Introduction: Composition of petroleum,laboratory

tests, refinery feedstocks and products

Introduction to petroleum refinery

 Petroleum refineries have goal to convert as much of the barrel of crude oil into transportation fuels
which is economically practical. Refineries produce many profitable products however, the high-volume
profitable products are the transportation fuel gasoline, diesel and turbine (jet) fuels, and the light
heating oils. These transportation fuels have boiling points between 25 and 350oC. Although products
such as lubricating oils, refrigeration and transformer oils, and petrochemical feedstocks are
profitable.They amount to less than 5 percent of the total crude oil charged to refineries. The processing
equipment indicated is for processing crude oils of average gravities and sulfur contents. Crude oils with
low API gravities (high specific gravities) and high sulfur contents require additional hydrotreating
equipment. The quality of crude oils processed by worldwide refineries is expected to worsen slowly in
the future with the sulfur contents and densities to increase. Therefore refineries will require processing
the entire barrel of crude rather than just the material boiling below (550 oC).Sulfur restrictions on fuels,
coke and heavy fuel oils affects the bottom-of-the-barrel processing as well. These factors requires
extensive refinery additions modernization the shift in market requirements among gasolines and
reformulated fuels for transportation challenges

Refinery Overview

The crude oil is heated in a furnace and charged to an atmospheric distillation tower, where it is
separated into light gas (C1-C4), light naphtha, heavy naphtha, kerosine, atmospheric gas oil, and reduced
(topped) crude . The reduced crude is sent to the vacuum distillation tower and separated into vacuum gas
oil stream and vacuum reduced crude bottoms (residua, resid). The reduced crude bottoms from the
vacuum distillation tower is thermally cracked in a delayed coker to produce gas, coker gasoline, coker gas
oil, and coke. The atmospheric and vacuum crude unit gas oils and coker gas oil are used as feedstocks for
the catalytic cracking or hydrocracking units where heavy molecules get converted into lower molecular
weight compounds boiling in the gasoline and distillate fuel ranges. The hydrocracked products are
saturated whereas catalytic cracker products are unsaturated and further need improvement in quality by
either hydrotreating or by reforming. The light naphtha streams from the crude tower, coker and cracking
units are sent to an isomerization unit to convert straight-chain paraffins into isomers which have higher
octane numbers. The heavy naphtha streams from the crude tower, coker, and cracking units are fed to the
catalytic reformer to improve octane numbers. The products from the catalytic reformer can be blended
into regular and premium gasolines for marketing. The wet gas streams from the crude unit, coker, and
cracking units are separated in the vapor recovery section (gas plant) into fuel gas, liquefied petroleum gas
(LPG), unsaturated hydrocarbons (propylene, butylenes, and pentenes), normal butane, and isobutane. The
fuel gas is burned as a fuel in refinery furnaces and the normal butane is blended into gasoline or LPG. The
unsaturated hydrocarbons and isobutane are sent to the alkylation unit to react olefins with isobutane to
yield isoparaffins. The alkylation is done at high pressure and low temperature in the presence of sulfuric or
hydrofluoric acid as catalyst. The product is called alkylated gasoline, which is a high-octane product
blended into premium motor gasoline and aviation gasoline. The middle distillates from the crude unit,
coker, and cracking units are blended into diesel and jet fuels and furnace oils. In some refineries, the heavy
vacuum gas oil and reduced crude from paraffinic or naphthenic base crude oils are processed into
lubricating oils. The asphaltenes are removed in a propane deasphalting unit, and the reduced crude from
bottoms are processed with the vacuum gas oils to produce lubeoil base stocks (LOBS). The vacuum gas oils
and deasphalted stocks are solvent-extracted to remove the aromatic compounds followed by dewaxing to
improve the pour point. These LOBS are further treated with acid clays to improve their color and stability
before being blended into lubricating oils. Each refinery has its own unique processing scheme which is
determined by the process equipment available, crude oil characteristics, operating costs, and product
demand.

Refinery Feed Stocks[19-20]

The basic raw material for refineries is petroleum or crude oil. The chemical compositions of crude
oils obtained from various sources are almost uniform although their physical characteristics vary
widely. The elementary composition of crude oil usually falls within the following ranges: C 84-88; H
11-15; S up to 5%, N up to 0.5 %. Crude oils are classified as paraffin base, naphthene base, asphalt
base, or mixed base depending upon the composition of the residue left after distillation. Crude oils
which have up to 80% aromatic content are known as aromatic-base oils. The U.S. Bureau of Mines
has developed a system which classifies the crude according to two key fractions obtained in
distillation: No. 1 from 250 to 275 oC at atmospheric pressure and No. 2 from 275 to 300 oC at 40
mmHg pressure. The API gravity of these fractions varies depending upon paraffinic and naphthenic
grade of the crude(Paraffin : API 40 for No. 1 and 30 for No. 2, Naphthene : API < 30 for No. 1 oil and
<=20 for No. 2 oil). The paraffinic and asphailtic classifications in common use are based on the
properties of the residuum left from nondestructive distillation and are more descriptive to the
refiner because they convey the nature of the products to be expected and the processing necessary.

Composition Of Petroleum[19-20]

Crude oils are composed of many members of homologous series of hydrocarbons. Petroleum is
essentially a mixture of hydrocarbons, and even the non-hydrocarbon elements are generally present
as components of complex molecules predominantly hydrocarbon in character, but containing small
quantities of oxygen, sulfur, nitrogen, vanadium nickel, and chromium. The composition of the total
mixture, in terms of elementary composition, does not vary a great deal, but small differences in
composition can greatly affect the physical properties and the processing required to production
marketable products. The hydrocarbons present in crude petroleum are classified into three general
types: paraffins, naphthenes, and aromatics. Olefins are generally not present in crude oil, however
these are formed during processing by the dehydrogenation of paraffins and naphthenes. The paraffin
series of hydrocarbons is characterized by the rule that the carbon atoms are connected by a single
bond and the other bonds are saturated with hydrogen atoms.The general formula for paraffins is
CnH2n+2. Crude oil contains molecules with up to 70 carbon atoms, and the number of possible paraffinic
hydrocarbons is very high. Olefins do not naturally occur in crude oils but are formed during the
processing. They are very similar in structure to paraffins but at least two of the carbon atoms are
joined by double bonds. The general formula is CnH2n. Olefins are generally undesirable in finished
products because the double bonds are reactive, and the compounds are more easily oxidized and
polymerized to form gums and varnishes. Olefins containing five carbon atoms have high reaction rates
with compounds in the atmosphere that form pollutants and, even though they have high research
octane numbers, are considered generally undesirable. Some diolefins (containing two double bonds)
are also formed during processing, but they react very rapidly with olefins to form high-molecular-
weight polymers consisting of many simple unsaturated molecules joined together. Diolefins are very
undesirable in products because they are so reactive, they polymerize and form filter and equipment
plugging compounds. Cycloparaffin hydrocarbons in which all of the available bonds of the carbon
 atoms are saturated with hydrogen are called naphthenes. There are many types of naphthenes
present in crude oil, but except for the lower-molecular-weight such as cyclopentane and cyclohexane,
are generally not handled as individual compounds. They are classified according to boiling range and
their properties determined with the help of correlation factors such as the characterization (Kw) factor
or correlation index ( CI) . The aromatic series of hydrocarbons is chemically and physically very
different from the paraffins and cycloparaffins (naphthenes). The cyclic hydrocarbons, both naphthenic
and aromatic, can add paraffin side chains in place of some of the hydrogen attached to the ring
carbons and form a mixed structure.

Petroleum /crude oil[19]

 Petroleum (also called crude oil) is a mixture of gaseous, liquid , and solid hydrocarbon
compounds.

 Petroleum occurs in sedimentary rock deposits throughout the world and also contains small
quantities of nitrogen oxygen and sulfur-containing compounds as well as trace amounts of
metallic constituents.

Petroleum[19]

 The fuels derived from Petroleum contribute approximately one-third to one-half of the total
world energy supply and are used for transportation fuels (gasoline,diesel fuel,and aviation
fuel,among others) and heating buildings.

 Petroleum products have a wide variety of uses that vary from gaseous and liquid fuels to near-
solid machinery lubricants. Residue of many refinery processes asphalt—is now a premium
value product for highway surfaces, roofing materials, and miscellaneous waterproofing uses.

 Crude petroleum is a mixture of compounds boiling at different temperatures that can be

separated into a variety of different generic fractions by distillation and the terminology of these
fractions has been bound by utility and often bears little relationship to composition.

Major Processes: [19-20]

 Desalting

 Sweetening

 Hydrogen Generation Unit

 DHDS/DHDT

 Reformer

 Isomerisation

 Amine Treating

 Sulphur Recovery Unit

  Bitumen Blowing Unit

 Lube and wax

 Solvent Extraction

 Solvent dewaxing

 Solvent Deoiling

 Solvent deasphalting

 Lube isomerisation

 Hydrodesulfurisation

Fig:1.3[15]A typical REFINERY PROCESS CHART

Typical Refinery Products

 LPG 2.1%
  NAPHTHA 5.0%

 MS 11.2%

 OTHERS 18.3%

 LIGHT DISTILLATE 36.6%

 ATF 9.0

Chemistry in Fuel refining

Key properties of Fuels

 MS: Octane number, Sulphur, distillation, Oxidation stability, Bz/ Aromatics/ Olefin content.

 HSD: Cetane number,Sulphur,distillation,lubricity.

 Kerosene: Smoke Point.

 ATF: Freezing point.

 Furnace oil: Stability.

 Bitumen: Penetration, viscosity, Softening point.

 LOBS: Viscosity, Viscosity Index.

Definations and Terminology [19,20]

Petroleum is a mixture of gaseous, liquid, and solid hydrocarbon compounds that occur in sedimentary
rock deposits throughout the world and also contains small quantities of nitrogen, oxygen, and sulfur-
containing compounds as well as trace amounts of metallic constituents.Petroleum is a naturally occurring
mixture of hydrocarbons, generally in a liquid state, which may also include compounds of sulfur, nitrogen,
oxygen, metals, other elements .Any naturally occurring hydrocarbon, whether in a liquid, gaseous, or solid
state may found explorations.

Complexity of a refinery [19,20]

The combination of refining processes and operations employed (complexity) varies from one refinery to
another.Modern refinery is highly complex, energy and capital intensive. Role of catalytic processes,
secondary processing and hydroprocessing is increasing .Factors deciding the complexity of a refinery.

 Nature/source of crude oils- flexibility to process variety of crudes.

 Demand pattern in the markets.

 Product quality - current/ future.

 Production of feedstocks for downstream units.

 Inter-fuel substitution.

Separation: Heavy on the bottom, light on the top

Classification of crude

Classification of crude

The hydrocarbons found in petroleum are classified into the following types: [19,20]

 Paraffins (CnH2n+2)saturated hydrocarbons with straight or branched chains, but without

any ring structure.

 Cycloparaffins (CnH2n)(naphthenes),saturated hydrocarbons containing one or more

rings, each of which may have one or more paraffin side-chains(also known as alicyclic
hydrocarbons).

 Aromatics (CnH2n-6)i.e,hydrocarbons containing one or more aromatic nuclei such as

benzene, naphthalene, and phenanthrene ring systems that may be linked up with
(substituted) naphthalene rings or paraffin side-chains.

Paraffins:

 Carbon atoms connected by single bond

 Other bonds saturated with hydrogen

Naphthene’s:

 Ringed Paraffins (Cycloparaffins)

 All bonds saturated with hydrogen

Aromatics:

 Six Carbon Rings (Multiple Bonding)

 All bonds unsaturated

Olefins:

 Usually not in crude oil

 Formed During Processing

At least two carbon atoms connected by double bond

 Fig:1.4 A typical example of n-butane, Cyclopentane, Decaline, Benzene, Napthalene, and
1-butene.

Paraffin /naphthene/Asphalt base crude (based on residue after distillation) [21]

 Paraffin base: The presence of paraffin wax in residue is reflected in the paraffin nature
of the constituent.

 Asphaltic base: high asphaltic content corresponds with the naphthene properties of the
fractions. Asphalt-base (black amorphous solid MW 600-30K) crude oils our mainly of
highly Aromatic (or naphthene) hydrocarbons.

Crude oil [19]

Color: Light brown to dark brown

Sp.gr: 0.81—0.985

Boiling range: 25 – 400oC

Hydrocarbons C1- C70 (4000 compounds)

Metals: V, Fe, Ni

S-( H2S, Thiols (mercaptans), sulfides, di sulfides, poly sulfides and thiophenes).

Cause corrosion of equipment, bad odour in products, catalyst poisoning, Air pollution.
 N –Indoles, pyridines and quinolines (Difficult to remove).

 Oxygen compounds: present as naphthenic acids and phenols

 Are corrosive in nature and cause odour.

 Metal: act as catalyst poisons

Crude composition

C: 84-87%, H: 11-14%,S: 0-5%,N: 0-1%,O: 0-2%.

Reservoirs/ sedimentary basin [19-22]

 Petroleum occurs underground, at various pressures depending on the depth.

 Because of the pressure, it contains considerable natural gas in solution. Petroleum

underground is much more amount of fluid with than the surface and is generally mobile
under reservoir conditions because of the elevated temperature phase(the geothermal
gradient) in subterranean formations decrease the viscosity.

 Petroleum is derived from aquatic plants and animals that lived and died hundreds of
millions of years ago. Their remains mixed with mud and sand in layered deposits that,
over the millennia, were geologically transformed into sedimentary rock.

Reservoirs and Oil field

 Gradually the organic matter decomposed and eventually formed petroleum (or a
related precursor), which migrated from the original source beds to more porous and
permeable rocks, such as sandstone and silt stone, where it finally became entrapped.
Such entrapped accumulations of petroleum are called reservoirs.

 A series of reservoirs within a common rock structure or a series of reservoirs in separate

but neighboring formations is commonly referred to as an oil field.

 A group of fields is often found in a single geologic environment known as a sedimentary

basin or province.

Estimations of Reserves [22]

Estimation of HC Content: Done by material balance

Estimation of fresh finding: by physical condition of the reservoir.

Porous sedimentary rocks: porosity(e)

Maximum amount of HC that can present in rock=e * (vol. of reservoir)

WATER present in oil=SW connate water

Total volume of HC deposited=vol.of reservoir.*e*(1-SW)( volume Deposited under reservoir

condition)

Generally, deposits are several meter deep where pressure >100atm.Lig/ gas volume expan-sion
factor Bg at surface conditions For liquid expansion factor is small but for gas it is high.

Thus Total vol.of deposit at surface condition=vol. of reservoir*e*(1-Sw)* Bg.

Table:1.2

Subdivision of Petroleum and Similar Materials into Various

Subgroups[19-22]

Derived Manufactured
Natural Materials
Materials Materials

Synthetic Crude
Natural Gas Saturates
Oil

Petroleum Aromatics Distillates

Heavy Oil Resins Lubricating Oils

Bitumena Asphaltenes Wax

Asphaltite Carbenesb Residuum

Asphaltoid Carboidsb Asphalt

Ozocerite(Natural Wax) - Coke

Kerogen - Tar

Coal - Pitch

Refinery Operation

 Crude oil is transported to refineries by pipelines, (more than 500,000 barrels per day), or by
ocean-going tankers.

 The basic refinery process is distillation, which separates the crude oil into fractions of
differing volatility.

 After the distillation, other physical methods are employed to separate the mixtures
including absorption adsorption solvent extraction and crystallization.
  After physical separation into such constituents as light and heavy naphtha, kerosene, light
and heavy gas oils selected petroleum fractions may be subjected to conversion processes such
as thermal cracking (i.e., coking;) and catalytic cracking.

 Cracking breaks the large molecules of heavier gas oils into the smaller molecules that form
the lighter, more valuable naphtha fractions.

 Reforming changes the structure of straight-chain paraffin molecules into branched-chain

iso-paraffins and ring-shaped aromatics. The process is widely used to raise the octane number
of gasoline obtained by distillation of paraffinic crude oils.

Table:1.3

Process Development Since The Commencement Of The Modern Refining Era [19,20]

Year Process Name Purpose By Product

Naphtha,Cracked
1862 Atmospheric Distillation Produce Kerosene
Residuum

1870 Vacuum Distillation Lubricants Asphalt,Residua

1913 Thermal Cracking Increase Gasoline Yield Residua,Fuel Oil

1916 Sweetening Reduce Sulfur Sulfur

1930 Thermal Reforming Improve Octane Number Residua

1932 Hydrogenation Remove Sulfur Sulfur

1932 Coking Produce Gasoline Coke

Improve Lubricant Viscosity

1933 Solvent Extraction Aromatics
Index

935 Solvent Dewaxing Improve Pour Point Wax

Petrochemical
1935 Catalytic Polymerization Improve Octane Number
Feedstocks

Petrochemical
1937 Catalytic Cracking Higher Octane Gasoline
Feedstocks

1939 Visbreaking Reduce Viscosity Increased distillate Yield

 High-Octane aviation
1940 Alkylation Increase Octane Number
Fuel

1940 Isomerization Produce Alkylation Feedstock Naphtha

Petrochemical
1942 Fluid Catalytic Cracking Increase Gasoline Yield
Feedstocks

1950 Deasphalting Increase Cracker Feedstock Asphalt

1952 Catalytic Reforming Convert Low-Quality Naphtha Aromatics

1954 Hydrodesulfurization Remove Sulfur Sulfur

1956 Inhibitor Sweetening Remove Mercaptans Disulfides and Sulfur

Convert To High Octane

1957 Catalytic Isomerization Alkylation Feedstocks
Products

Improve Quality And Reduce

1960 HydroCracking Alkylation Feedstocks
Sulfur

1974 Catalytic Dewaxing Improve Pour Point Wax

1975 Resid HydroCracking Increase Gasoline Yield Cracked Residua

 Fig:1.5[15]A typical REFINERY PROCESS CHART with both Atmospheric (ADU) and Vaccum
distillation process (VDU).

Classification of Crude as a hydrocarbon resource:[19,20]

Fossil energy resources divide into two classes:

  Naturally occurring hydrocarbons (petroleum, natural gas, and natural waxes)

 Hydrocarbon sources (oil shale and coal) which may be made to generate hydrocarbons
by the application of conversion processes. Oil Shale are argillaceous, laminated
sediments of generally high organic content that can be thermally decomposed to yield
appreciable amounts of oil.

 The classification of petroleum and natural gas as naturally occurring mixtures of

hydrocarbons occurs by they can be separated into their original hydrocarbon
constituents.

 The hydrocarbon constituents, separated from petroleum and natural gas, are the
hydrocarbon constituents that existed from the reservoir.

 Naturally occurring hydrocarbons are major contributors to the composition of

petroleum and natural gas.

 Coal and kerogen do not enjoy this by means of separation and methods of thermal
decomposition and it must be applied before hydrocarbons are produced.

 Kerogen is the complex carbonaceous (organic) material that occurs in sedimentary rocks
and shales.

Subdivision of the earth’s organic sediments [20]

 Fig:1.6

Classification of the earth’s organic sediments according to hydrocarbon occurrence and

production.[20]

Characterization of crude:

Crude Oil Properties

Crude of petroleum is very complex except for the low-boiling components, no attempt is made by
the refiner to analyze for the pure components that contained in the crude oil. Relatively simple
analytical tests are run on the crude and the results of these are used with empirical correlations to
evaluate the crude oils as feedstocks for the particular refinery. Each crude is compared with the other
feedstocks available and, based upon the operating cost and product realization, is assigned a value.
The useful properties are discussed.

API Gravity: The density of petroleum oils is expressed in the United States in terms of API gravity
rather than specific gravity; it is related to specific gravity in such a fashion that an increase in API
gravity corresponds to a decrease in specific gravity. The units of API gravity are API and can be
calculated from specific gravity (sp. Gr.) by the following:
API=141.5/Sp.Gr-131.5
 Sp. Gr. of crude oil may vary from less than 10oAPI to over 50oAPI but most crudes fall in the 20 to
45o API range. API gravity always refers to the liquid sample at 60 oF (15.6 oC). API gravities are not
linear and, therefore, cannot be averaged. For example, a gallon of 20o API gravity hydrocarbons when
mixed with a gallon of 30oAPI hydrocarbons will not yield two gallons of 25o API hydrocarbons but will
give two gallons of hydrocarbons with an API gravity different from 250 API. On the other hand, Specific
gravities of different oils can be averaged.

Sulfur Content, wt% [20]

Sulfur content and API gravity are two properties which have the greatest influence on the value of
crude oil, although nitrogen and metals contents are increasing in importance. The sulfur content is
expressed as percent of sulfur by weight and varies from less than 0.1% to greater than 5%. Crudes
with greater than 0.5% sulfur generally require more extensive processing than those with lower sulfur
content.

Pour Point [20]

The pour point of the crude oil, in oF or oC, is a rough indicator of the relative paraffinicity and
aromaticity of the crude. The lower the pour point, the lower the paraffin content and the greater the
content of aromatics.

Carbon Residue [20]

Carbon residue is determined by distillation to a coke residue in the absence of air. The carbon
residue is roughly related to the asphalt content of the crude and to the quantity of the lubricating oil
fraction that can be recovered. In most cases the lower the carbon residue, the more valuable the crude.
This is expressed in terms of the weight percent carbon residue by either the Ramsbottom (RCR) or
Conradson (CCR).

Salt Content [20]

If the salt content of the crude, when expressed as NaCl, is greater than 10 lb/ 1000 bbl, it is
generally necessary to desalt the crude before processing. If the salt is not removed, severe corrosion
problems may be encountered. If residua are processed catalytically, desalting is desirable at even lower
salt contents of the crude. Although it is not possible to have an accurate conversion unit between
lb/1000 bbl and ppm by weight because of the different densities of crude oils, 1 lb/1000 bbl is
approximately 3 ppm.

Characterization Factors [20]

There are several correlations between yield and the aromaticity and paraffin city of crude oils, but the
two most widely used are the UOP or Watson ‘‘characterization factor’’ (KW) and the U.S. Bureau of
Mines ‘‘correlation index’’ (CI).
KW= TB1/3/ G , Where,TB is the mean average boiling point, R and G is the specific gravity at 60 oF.
The Watson characterization factor :KW ~15 for highly paraffinic compounds , KW <10 for highly
aromatic materials and KW vary from 10.5 to 12.9. For a highly naphthenic crude it is 10.5 to 12.9 for a
paraffinic base crude.
 The correlation index is useful in evaluating individual fractions from crude oils. The CI scale is based
upon straight-chain paraffins having a CI value of 0 and benzene having a CI value of 100 and is defined
as follows:
C.I = 87552/TB + 473.7 G – 456.8
The CI values are not quantitative, but the lower the CI value, the greater the concentration of paraffin
hydrocarbons in the fraction; and higher the CI value, greater the concentration of naphthene and
aromatics.

Nitrogen Content, wt%

High nitrogen content is undesirable in crude oils because organic nitrogen compounds cause severe
poisoning of catalysts used in processing and cause corrosion problems. Crudes containing nitrogen
more than 0.25% by weight require special processing to remove the nitrogen. [19,20]

Distillation Range

The boiling range of the crude gives an indication of the quantities of the various products present.
The most useful type of distillation is known as a true boiling. point (TBP) distillation and generally
refers to a distillation performed in equipment that accomplishes a reasonable degree of fractionation.
There is no specific test procedure called a TBP distillation, but the U.S. Bureau of Mines Hempel and
ASTM D-285 distillations are the tests most commonly used. Neither of these specify either the
number of theoretical plates or the reflux ratio used and, as a result, there is a trend toward using the
results of a 15:5 distillation (D- 2892) rather than the TBP. The 15:5 distillation is carried out using 15
theoretical plates at a reflux ratio of 5: 1. The crude distillation range has to be correlated with ASTM
distillations because product specifications are generally based on the simple ASTM distillation tests
like D-86 and D-1160 etc.[20]

Metals Content, ppm

The metals content metals (nickel, vanadium, and copper) of crude oils vary from a few parts per million
to more than 1000 ppm. Minute quantities of some of these metals can severely affect the activities of
catalysts and result in a lower value product distribution. Vanadium concentrations above 2 ppm in fuel
oils can lead to severe corrosion to turbine blades and deterioration of refractory furnace linings and
stacks. Distillation concentrates the metallic constituents of crude in the residues, but some of the
organometallic compounds are actually volatilized at refinery distillation temperatures and appear in the
higher-boiling distillates. The metallic content may be reduced by solvent extraction with propane or
similar solvents as the organometallic compounds are precipitated with the asphaltenes and resins.

API GRAVITY (Indicates the crude sp.gr) (American petroleum Institute)

API=141.5/Spig. – 131.5

 Heavy oils: Petroleum- materials less than 200o API

 Heavy oils: API gravity range of 10o to 15oAPI

 Bitumen: API gravity 5o to 10oAPI

  Atmospheric residual: 10o to 15o API

 vacuum residua: 2o to 8o API

UOP Characterization Factor/ Waston Characterization Fator [23]

Characterization factors: K=(TB)1/3/d

(Correlates boiling point with sp.Gr.)

where TB is the average boiling point in degrees Rankine (= F + 460) and d is the specific gravity
60 oF/60 oF. (Also, Kuop= (Tk)3/0.827 G, if T in K)

K: additive on a weight basis.

Highly paraffin oils: K : 12.5 to 13.0

Cyclic (naphthene) oils have K: 10.5 to 12.5.

Aromatics: 9.0- 10.5

Correlation Index (C.I.)[23]

 According to the chemical composition of the 250 oC to 300 oC fraction has been used.

 But the difficulty is that in the fractions boiling above 200 oC (390 oF) the molecules can no longer
be placed in one group, because most of them are of a typically mixed nature.

 More direct chemical information is desirable and can be supplied by means of the correlation
index (CI).

 The CI, developed by the U.S. Bureau of Mines, is based on the plot of specific gravity vs the
reciprocal of the boiling point in Kelvin.

For pure hydrocarbons, the normal paraffin series is given value of CI=0 and for benzene CI = 100.

CI= 473.7d - 456.8 + 48,640/TK

Where, TK for a petroleum fraction is the average boiling point (K) and ‘d’ is the specific gravity

 CI Values between 0 and 15 : indicates a predominance of paraffin hydrocarbons in the

fraction.

 CI Values 15 to 50 : indicates predominance of either naphthene’s or of mixtures of paraffins,

naphthene, and aromatics.

 CI values more than 50 : indicates a predominance of aromatic species.

Physical properties

VISCOSITY [19,20]
  Materials having viscosity less than 10,000 centipoises (cp) are conventional petroleum
and heavy oil.

 Tar sand bitumen has a viscosity greater than 10,000 cp.

 In order to classify petroleum, heavy oil, and bitumen the use of a single parameter such
as viscoity is not enough.

Other properties such as API gravity, elemental analysis, composition, and the properties of
thefluid in the reservoir as well as the method of recovery need to be acknowledged

Fig.1.8 Classification of petroleum, heavy oil, and bitumen by API gravity and viscosity

POUR POINT [20]

 Tar sand bitumen is a naturally occurring material that is immobile in the deposit and
cannot be recovered by the application of enhanced oil recovery technologies, including
steam –based technologies.

 Heavy oil is mobile in the reservoir and can be recovered by the application of enhanced
oil recovery technologies,including steam–based technologies.

 Pour point is the lowest temperature at which oil will move, pour , or flow when it is
chilled without disturbance under definite conditions (ASTM D97).

 The pour point and reservoir temperature present a more accurate assessment of the
condition of the oil in the reservoir an indicator of the mobility of the oil in the reservoir.

 when used in conjunction with reservoir temperature, the pour point gives an indication
of the liquidity of the heavy oil or bitumen and, therefore the ability of the heavy oil or
bitumen to flow under reservoir conditions.

 In summary, the pour point is an important consideration because, for efficient

production, additional energy must be supplied to the reservoir by a Thermal process to
increase the reservoir temperature beyond the pour point.
  Pour point offers more general applicable to the conditions of the oil in the reservoir or
the bitumen in the deposit and comparison of the two temperatures(pour point and
reservoir temperatures) that shows promise and warrants for further consideration.

Crude oil; analysis and distillation

CRUDE DISTILLATION

Overview

Purpose

 To recover light materials.

 Fractionate into sharp light fractions.

Configuration —May be as many as three columns in series

 Crude Stabilizer/Preflash Column

Reduce traffic in the Atmospheric Column

 Atmospheric Column

 Vacuum Column

Reduced pressure to keep temperatures below 650o F

Crude Oil Fractionation / Distillation

 Crude oil is heated to 750 oF (400 oC)

 Heated crude is separated into rough "cuts “

 Different boiling point are drawn from the distillation tower.

  Light compounds (fuel gas and LPG) rise to the top of the tower, Heavy material (asphalt) falls to
the bottom of the tower.

Petroleum Refining Operations.

 Petroleum refining begins with the distillation, or fractionation, of crude oils into separate
hydrocarbon groups like Light ends, naphtha/gasoline kerosine diesel and residue etc.

 The resultant products are directly related to the characteristics of the crude processed.(T 650-
750 deg oF) or (310 oC-350 oC)

 Most distillation products are further converted into more usable products by changing the size
and structure of the hydrocarbon molecules through cracking, reforming, and other conversion
processes.

Fig 1.10 Atmospheric Distillation[19]

Fig:1.11 Typical Configuration Atmospheric Column w/o Preflash[19,20]
 Fig:1.12 ADU & VDU OVERVIEW [24,25]

Wash Zone

 Couple trays between flash zone & gas oil draw.

 Reflux to wash resins & other heavy materials that may contaminate the products.

Condenser

 Typically 0.5 to 0.2 psig.

 Balancing act

 Low pressure reduce compression on overhead system.

 High pressure decrease vaporization but increases flash zone temperature & furnance
duty: affects yields.

Pumparounds

 Reduces overhead condenser load & achieves more uniform tower loading.

 provides liquid reflux below liquid draws.

 Side draws & strippers cut point related to final boiling point of draw steam.

 Side strippers remove light component tail & return to main column.

 Steam strippers traditional.

 Reboiled strippers reduce steam usage & associated sour water.

Trays & pressure profile [19,20,24,25]

 Typically, 32 in tower 0.1 to 0.2 psi per tray.

 Condenser & accumulator 3 to 10 psi across condenser liquid static head in accumulator.

 Typically, 6 to 16 psi across entire column.

Fig:1.13 A typical configuration of Atmospheric column with stripping section and reflux drum
arrangement.
 Fig:1.14[19]A typical configuration of two stage hydrocracking unit.

Table:1.4

Typical Crude Tower Cut Points[19,20]

CUT TBP IBP(oF) TBP EP(oF)

Light Naphtha(LSR Gasoline) 80 to 90 180 to 220

Heavy Naphtha 180 to 220 330 to 380

Distillate (Kerosene) 330 to 380 420 to 520

AGO(Atm Gas Oil) 420 to 520 650

 LVGO(Light Vac Gas Oil) 650 800

HVGO(Heavy Vac Gas Oil) 800 950 to 1100

Vaccum Resid 950 to 1100 -

Introduction to refinery feed stocks and refinery products

REFINERY PRODUCTS

Generally,the products which dictate refinery design are relatively few in number, and the basic refinery
processes are based on the large-quantity products such as gasoline, diesel, jet fuel, and home heating oils.
Storage and waste disposal are expensive, and it is necessary to sell or use all of the items produced from
crude oil even if some of the materials, such as high-sulfur heavy fuel oil and fuel-grade coke, must be sold
at prices less than the cost of fuel oil. Economic balances are required to determine whether certain crude
oil fractions should be sold as is (i.e., straight-run) or further processed to produce products having greater
value. Usually, the lowest value of a hydrocarbon product is its heating value or fuel oil equivalent (FOE).
This value is always established by location, demand, availability, combustion characteristics, sulfur
content, and prices of competing fuels.

Low-Boiling Products

 The compounds which are in the gas phase at ambient temperatures and pressures methane,
ethane, propane, butane, and the corresponding olefins.

Methane (C1)

 It is usually used as a refinery fuel but can be used as a feedstock for hydrogen production by
pyrolytic cracking and reaction with steam.

 It is generally expressed in terms of pounds or kilograms, standard cubic feet (scf) at 60 °F and
14.7 psia, normal cubic meters (Nm3) at

 15.6 °C and 1 bar (100 kPa), or in barrels fuel oil equivalent (FOE) based on a lower heating value
(LHV) of 6.05 x106 Btu (6.38 x106kJ).

Refinery Gases

 Ethane (C2) can be used as refinery fuel or as a feedstock to produce hydrogen or ethylene,
which are used in petrochemical processes.

 Ethylene and hydrogen are recovered in the refinery and sold to petrochemical plants.

Refinery Products

 n-butane has a blending octane in the 90s and is a low-cost octane improver of gasoline.

 Isobutane used as a feedstock to alkylation units, where it is reacted with unsaturated materials
(propenes, butanes, and pentenes) to form high-octane isoparaffinic compounds in the gasoline
 boiling range.

Liquified Petroleum Gas (LPG)

Mixture of light HCs propane and butane,gases at ambient temperature but condensed to liquid state
by applying moderate pressure.

 Mainly consists of propane, propylene, butane, butene, and iso - butane.

 A significant amount of isobutane is converted to isobutylene which is reacted with methanol to
produce methyl tertiary butyl ether (MTBE).
 Used as an additive for gasoline.
 n-butane as LPG has the disadvantage of a fairly high boiling point [32 °F (0 °C) at 760 mmHg]
and during the winter is not satisfactory for heating when stored outdoors in areas which
frequently have temperatures below freezing.
 Isobutane has a boiling point of 11 °F (12 °C) and is also unsatisfactory for use in LPG for heating
in cold climates.
 Butane–propane mixtures are also sold as LPG, and their properties and standard test
procedures are also specified by the GPA.
  Use Domestic fuel, feed stock for various chemicals and fuel for IC engine.

Table:1.5[19,20]

Properties Of Comercial Propane And Butane

Property Commercial Propane Commercial Butane

Vapour Pressure,Psig

70oF(21.1oC) 124 31

100oF(38oC) 192 59

130oF(54oC) 286 97

Specific Gravity Of Liquid,60/60o 0.509 0.582

Intial Boiling Point At 1

-51(-47.4) 15
Bar oF(oC)

Dew Point At 1 Bar oF(oC) -46(-44.6) 24

Sp.ht.Liquid At 60oF,15.6oC

Btu/lb(oF) 0.588 0.549

 Kj/(kg)(0C) 2.462 2.299

Limits Of Flammability,Vol% Gas In Air

Upper Limits 2.4 1.9

Lower Limits 9.6 8.6

Latent Heat Of Vaporization At VP

Btu/lb 185 165

Kj/(kg) 430.3 383.8

Gross Heating Values

Btu/lb Of Liquid 21,550 21,170

Btu/ft3 Of Gas 2,560 3,350

Kj/(kg) Of Liquid 50,125 49,241

Kj/m3 Of Gas 9,538 12,482

LPG Production

Methods of Extraction of LPG from NG

 Compression and cooling.

 Adsorption.

 Absorption.

Cryogenic process:

 Refrigeration by direct expansion based on Joul Thomson effect.

 Cascade refrigeration using (C3) as refrigerant.

 Turbo expander

Gasoline /Motor Spirit[19,20]

  Gasolines are complex mixtures of hydrocarbons having typical boiling ranges from 100 to 400
°F (38 to 200 °C)as determined by the ASTM method.

 Hydrocarbon range:C5-C10(mainly n-paraffins, iso paraffins,naphthenes and aromatic

hydrocarbons)

 Components are blended to promote:

 high antiknock quality (High octane number)

 ease of starting

 quick warm-up

 low tendency to vapor lock

 And low engine deposits

Production of Gasoline

Fig:1.15

Gasoline Specifications

Most important properties wide greatest effects on engine performance are: Reid vapor
pressure,Boiling range,and Antiknock characteristics.

The Reid vapor pressure is approximately the vapor pressure of the gasoline at 100 °F (38 °C) in absolute
units (ASTM designation D-323).

The Reid vapor pressure (RVP) and boiling range of gasoline governs ease of starting, engine warm-up,
rate of acceleration, loss by crankcase dilution, mileage economy,and tendency toward vapor lock.

 Engine warm-up time is affected by the percent distilled at 158 °F (70 °C) and the 90% ASTM
distillation temperature.
 Warm-up is expressed in terms of the distance operated to deveop full power without excessive use of
the choke. A two-to four-mile (3 to 7 km) warm-up is considered satisfactory.

 Altitude affects several properties of gasoline, the most important of which are losses by evaporation
and octane requirement.

 Octane number: requirement is greatly affected by altitude and, for a constant spark advance, is about
three units lower for each 1000 ft(305 m) of elevation. In practice, however the spark is advanced at
higher elevations to improve engine performance and the net effect is to reduce the PON of the
gasoline marketed by about two numbers for a 5000- ft (1524-m) increase in elevation.

Octane Number [19,20]

 Octane numbers are obtained by two test procedures; those obtained by the first method are
called motor octane numbers (indicative of high-speed performance)and those obtained by the
second method are called research octane numbers (indicative of normal road performance).

 Octane numbers quoted are usually, unless stated otherwise, research octane numbers. In the
test methods used to determine the antiknock properties of gasoline,comparisons are made
with blends of two pure hydrocarbons, n-heptane and iso-octane (2,2,4-trimethylpentane).

 Octane numbers quoted are usually, unless stated otherwise, research octane numbers. In the
test methods used to determine the antiknock Properties

 Isooctane has an octane number of 100 and is high in its resistance to knocking; n-heptane is
quite low (with an octane number of 0) in its resistance to knocking.

Gasoline/ Motor spirit [19,20]

 Posted octane numbers (PON) are arithmetic averages of the motor octane number (MON) and
Research octane number (RON) and average four to six numbers below the RON.

 PON is the arithmetic average of the research and motor octane numbers [(RON +MON)/2].

 The posted method octane number (PON) of unleaded regular gasolines:~ 87 and

 premium gasolines: ranged from 89 to 93.

 For all gasolines, octane numbers average about two numbers lower for the higher elevations of
the Rocky Mountain states.

 The difference between the research and motor octane is an indicator of the sensitivity of the
performance of the fuel to the two types of driving conditions and is known as the ‘‘sensitivity’’
of the fuel.

 Aviation gasoline: higher volatility and higher-octane number

 Other Activity: antioxidants, metal deactivators, and anti-stall agents, are included with the cost
of the antiknock chemicals added.

 Light straight-run (LSR) : gasoline consists of the (C5)-190 °F (C5)-88 °C) fraction of the naphtha
 from the atmospheric crude still.

 (C5)-190 °F fraction means that pentanes are included in the cut but that (C4) and lower-boiling
compounds are excluded and the TBP end point is approximately 190 °F.

Technological Option For MS Quality Improvement

Hydroprocessing:

 For Sulphur Reduction

 For Benezene saturation

 For Olefin Reduction

Isomerisation:

 For Ocatane Improvement

Reforming:

 For Ocatane Improvement

 Use Of Oxygenates For Octane Improvement

Table:1.6

WORLDWIDE - GASOLINE QUALITY

Attribute Japa Kore New South

Unit India Euroll China Taiwan
Zealand Africa

89/9 91/9 90/93/9

RON Min 91 91/95 91/95 92/95/98 95/97

PPM 350/15 80/120/18 1000/150

Sulphur 150 150 100 130 800
Min

Aromatic Vol 30 or
42 42 . 48/42 40 . .
%Max 35

Vol 21/1 23 or 20 or
Olefins 21/18 . 35 . .
%Max 18 25

35- 60&7 44- 70- 45 KPA

RVP KPA 88(W) 59/59/61 45-75
60 78 S,96-Wmin

Gasoline

 Catalytic reformate is the C5 gasoline product of the catalytic reformer(table 1.5).[19,20]

  Heavy straight-run (HSR) and coker gasolines are used as feed to the catalytic reformer, and
when the octane needs require, FCC and hydrocracked gasolines of the same boiling range may
also be processed by this unit to increase octane levels.

 The FCC and Hydrocracked gasolines: Generally used directly as gasoline blending stocks, but in
some cases are separated into light and heavy fractions with the heavy fractions upgraded by
catalytic reforming before being blended into motor gasoline.

 Motor gasoline is unleaded, and the clear gasoline pool octane is now several octane numbers
higher than when lead was permitted.

Gasoline/Motor spirit/Petrol

 The reformer increases the octane by converting low octane paraffins to high-octane aromatics.

 Some aromatics (e.g., Benzene) have high rates of reaction with ozone to form visual pollutants
in the air and some are claimed to be potentially carcinogenic by the EPA.

 This restricts the severity of catalytic reforming and will require refiners to use other ways to
increase octane numbers of the gasoline pool by incorporating more oxygenates in the blend
(Table 1.6).[19,20]

Table:1.7

GASOLINE QUALITY REQUIREMENTS(Euro Norms)

Property EURO-I(92) EURO-II(96) EURO-III(00) EURO-IV(05)

RON 95 95 95 95

MON 85 85 85 85

S% Wt,Max 0.05 0.05 0.015$ 0.005

Bz.,%Vol., Max 5.0 5.0 1.0+ 1.0

Arom.,%Vol., Max - - 42 35

Olef.,%Vol., Max - - 18 ?

Lead., gm/litre 0.013 0.013 0.005 0.005

Polymer gasoline :
 Manufactured by polymerizing olefinic hydrocarbons to produce higher molecular weight olefins in the
gasoline boiling range.

Refinery technology favors alkylation processes rather than polymerization for two reasons: [19,20]

1- Larger quantities of higher-octane product can be made from the light olefins available

2- The alkylation product is paraffinic rather than olefinic, and olefins are highly photo reactive and
contribute to visual air pollution and ozone production.

Alkylate gasoline:

It is the product of the reaction of isobutane with propylene, butylene, or pentylene to produce
branched-chain hydrocarbons in the gasoline boiling range.

Alkylation of a given quantity of olefins produces twice the volume of high-octane motor fuel as can be
produced by polymerization. In addition, the blending octane (PON) of alkylate is higher and the
sensitivity (RON -MON) is significantly lower than that of polymer gasoline.

 Normal butane is blended into gasoline to give the desired vapor pressure. The vapor pressure
[expressed as the Reid vapor pressure (RVP) of gasoline is a compromise between a high RVP to
improve economics and engine starting characteristics and a low RVP to prevent vapor lock and reduce
evaporation losses.

 Normal butane is blended into gasoline to give the desired vapor pressure. The vapor pressure
[expressed as the Reid vapor pressure (RVP)of Butane has a high blending octane number and is a very
desirable component of gasoline; refiners put as much in their gasolines as vapor pressure limitations
permit.

 Isobutane can be used for this purpose, but it is not as desirable because its higher vapor pressure
permits a lesser amount to be incorporated into gasoline than n-butane.

 Normal butane is blended into gasoline to give the desired vapor pressure.

 Concern over the effects of hydrocarbon fuels usage on the environment has caused changes in
environmental regulations which impact gasoline and diesel fuel compositions.

 The main restrictions on diesel fuels limit sulfur and total aromatics contents and gasoline
restrictions include not only sulfur and total aromatics contents but also specific compound limits (e.g.,
benzene), limits on certain types of compounds (e.g., olefins), maximum Reid vapor pressures,and also
minimum oxygen contents for areas with carbon monoxide problems.

Distillate Fuels[20,26,27]

Middle Distillate fuels can be divided into three types:

 Jet or turbine fuels,diesel fuels,and heating oils.These products are blended from a variety of
refinery streams to meet the desired specifications.

 Kerosine type jet fuels: mainly used in commercial jet airlines.

  Military jet aircraft use a 30:70 blend of a kerosine fraction and a low octane straight run heavy
naptha fraction. Butane is added for adjusting volatility.

Jet and Turbine Fuels

 Jet fuel is blended for use by both commercial aviation and military aircraft.

 Also known as turbine fuel and there are several commercial and military jet fuel specifications.

 For most refineries the primary source of jet fuel blending stocks is the straight-run kerosine
fraction from the atmospheric crude unit because

 Kerosene (kerosine): also called paraffin or paraffin oil, is a flammable pale-yellow or colorless
oily liquid with a characteristic odor.

 It is obtained from petroleum and used for burning in lamps and domestic heaters or furnaces,
as a fuel or fuel component for jet engines, and as a solvent for greases and insecticides.

 Kerosene is intermediate in volatility between gasoline and gas diesel oil. It is a medium oil
distilling between 150 oC and 300 oC(300 oF to 570 oF).(HC: C10-C14).

 Kerosene has a flash point of about 25 oC (77 oF) and is suitable for use as an illuminant when
burned in a wide lamp.

 Fuel oil: any liquid or liquid petroleum product that produces heat when burned in a suitable
container or that produces power when burned in an engine.

Kerosine Composition

 Chemically, kerosene is a mixture of hydrocarbons; the chemical composition depends on its

source, but it usually consists of about 10 different hydrocarbons, each containing from 10 to 16
carbon atoms per molecule; the constituents include n-dodecane (n-C12H26), alkyl benzenes, and
naphthalene and its derivatives.

 Kerosene is less volatile than gasoline; it boils between about 140 oC (285 oF) and 320oC (610 oF).

 Kerosene, because of its use as a burning oil, must be free of aromatic and unsaturated
hydrocarbons, as well as free of the more obnoxious sulfur compounds. The desirable
constituents of kerosene are saturated hydrocarbons, and it is for this reason that kerosene is
manufactured as a straight-run fraction, not by a cracking process.

 Typical hydrocarbon chain lengths characterizing JP-4 range from C4 to C16.

 Aviation fuels consist primarily of straight and branched alkanes and cycloalkanes.

 Aromatic hydrocarbons are limited to 20% to 25% of the total mixture because they produce
smoke when burned.

 A maximum of 5% alkenes is specified for JP-4. The approximate distribution by chemical class
is:
  straight chain alkanes (32%),

 branched alkanes (31%),

 cycloalkanes (16%), and

 aromatic hydrocarbons (21%).

 Jet fuel comprises both gasoline and kerosene type jet fuels meeting specifications for use in
aviation turbine power units and is often referred to as gasoline-type jet fuel and kerosene type
jet fuel.

 Jet fuel is a light petroleum distillate that is available in several forms suitable for use in various
types of jet engines.

 The major jet fuels used by the military are

 JP-4, JP-5, JP-6, JP-7, and JP-8.

 JP-4 is a wide-cut fuel developed for broad availability.

 JP-6 has a higher cut than JP-4 and is characterized by fewer impurities.

 JP-5 is specially blended kerosene, and

 JP-7 is high flash point special kerosene used in advanced supersonic aircraft.

 JP-8 is kerosene modeled on Jet A-l fuel (used in civilian aircraft).

 Usually, jet fuels sell at higher prices than diesel fuels and No. 1 and No. 2 heating oils, and it is
more profitable for the refiner to blend the kerosine fractions from the atmospheric crude unit
and the hydrocracker into jet fuel rather than other products.

 Commercial jet fuel is a material in the kerosine boiling range and must be clean burning.

Characteristics of ATF fuels

Table:1.8

Characterstics Of Aircraft Turbine Fuels(ASTM D-1655 and DERD 2494)

DERD
Property Jet A JP-5 JP-8
2494

Aromatics,Vol%,Max 20 25 22.0 22.0

Combustion Prop

Smoke Point,mm,min,or 25 19 - 25

Smoke 18v - 19 20
 Point,mm,min,and

Napthalenes,vol%,max 3.0 - 3.0 3.0

Distillation,D-86,oF(oC)

10%
400(205) 400(205) 401(205) 401(205)
Recovered oF(oC),max

50%
report report report report
Recovered oF(oC),max

FBP oF(oC),max 572(300) 554(290) 572(300) 572(300)

Flash point,oF(oC),min 100(38) 140(60) 100(38) 100(38)

Freeze point,oF(oC),max -40(-40) -51(-46) -52.6(-47) -52.6(-47)

Sulfur,wt%,max 0.30 0.4 0.3 0.3

Two of the critical specifications relate to its clean burning requirements and limit the total aromatics as
well as the content of double ring aromatic compounds are :

 Smoke point, expressed in mm of MAXIMUM flame height at which smoking is detected, and
the volume percent total aromatics and naphthalene.

 Specifications limit total aromatic concentration to 20% and the naphthalene content to 3% or
3.0% depending upon the specific specifications.

 Hydrocracking saturates many of the double ring aromatics in cracked products and raises the
smoke point. (Improves the quality)

 The desired freeze point specification is very low [-40 to -58 °F max (-40 to -50 °C max.)] and
hydrocracking is also used to isomerize paraffins and lower the freeze point.

 Jet fuel is blended from low sulfur or desulfurized kerosine, hydrotreated light coker gas oil, and
hydrocracked blending stocks.

 The smoke point and percent aromatics specifications limit the amount of cracked stocks which
can be blended into jet fuels.

 The two basic types of jet fuels are naphtha and kerosine.

 Naphtha jet fuel is produced primarily for the military and is a wide-boiling-range stock which
extends through the gasoline and kerosine boiling ranges.
  The naphtha-type jet fuel is more volatile and has more safety problems in handling.

 JP-8 jet fuel is being phased in for military application.

 The JP-8 jet fuels are blended from the various components to arrive at the lowest-cost blend
that meets specifications.

AUTOMOTIVE DIESEL FUELS

Volatility, ignition quality (expressed as cetane number or cetane index), viscosity, sulfur content,
percent aromatics, and cloud point are the important properties of automotive diesel fuels.

 No.1 diesel fuel (super-diesel) is generally made from virgin or hydrocracked stocks having
cetane numbers above 45.

 It is having a boiling range from 360 to 600 °F (182 to 320 °C) and is used in high-speed engines
in automobiles, trucks, and buses.

 High speed engines above 1500 rpm, need high C.N 45-50.

 No.2 diesel fuel is very similar to No. 2 fuel oil and has a wider boiling range than No.1.

 It usually contains cracked stocks and may be blended from naphtha, kerosine, and light cracked
oils from the Coker and the fluid catalytic cracking unit.

 Limiting specifications are flash point [125 °F (52 °C)], sulfur content (0.05% max.), distillation
range, cetane number or cetane index (40 min.), percent aromatics, and cloud point.

PRODUCTION OF DIESEL

Fig:1.16

DISTILLATE BLENDING
 Fig:1.17

Fuel Quality control

 The main restrictions on diesel fuels limit sulfur and total aromatics contents and gasoline
restrictions.

 Include not only sulfur and total aromatics contents but also specific compound limits (e.g.,
benzene).

 Limits on certain types of compounds (e.g., olefins), maximum Reid vapor pressures.

Diesel Cetane Number

 One key to diesel quality Measures the ability for auto-ignition

 Essentially the opposite of octane number May be measured but frequently approximated

 ASTM D 976 —Standard Test Methods for Calculated Cetane Index of Distillate Fuels

Trends

 High demand.

 Heavier crudes with narrow diesel cuts.

 More stringent emissions requirements necessitate higher cetane.

WORLDWIDE-DIESEL QUALITY

Table:1.9
 N
ew
E A Ind
urop
Zea
ustr
ia
SA lan
alia
(BIS) J
.Nttrib apa
Outes Di BB
JJ B
r.98/ harhar
an-
an-
har
70/ atat
04
02at II
EEC IIIIV

C
etan
5 4 4554
e1 -
Num
ber

C
etan
44 444
e2 -
Inde

D
88 8 8 8
ensit 8 8
3 20-20-
20-
20-
20-
y @45 60
860
860
860
845
845
15 oC

K 12 2 2 2
2
V@4 .5-
-.0-.0-.0-.0-
.7
40 oC 4.5
4.5
5.04.54.5

T
90 3
5 - -- -
deg 60

T
95 3 33 3 3 3
6
deg60 70
70706060

7T 5 35 3 55
otal0 &000
00#50 0/1
5
Sulfu
10
 00

Fl 3
66 33
ash
8 5/6
1.5
Point

P
olyar 1 11
9 -- - -
oma
tics

W
ater
1 0 022
-
Cont .02.05
0000
ent

L
1 44 4 4 4
ubric -
60
6060#
6060
ity

Table:1.10

Diesel Specification

NO.1 NO.2 NO.4

Minimum Cetane 40 40 30

Sulphur Current,wt% 0.5 0.5 2.0

Low Sulphur Diesel 500 ppm

Ultra Low Sulphur Diesel 15 ppm

Temp For 90% Recovery

MinimumoF 540

MaximumoF 550 640

Mostly From Virgin Stock."SuperDiesel"

NO.1
Used For Auto & High Speed Engines

NO.2 Wider Boiling & Contain Cracked

 Stock.Very Similar To Home Heating
Fuel(w/o additives)

Traditionally Largest Volume

NO.4 Produced.Used For Marine,Railroads,&
Other Low To Medium Speed Power Plant

Ignition Delay

 The time interval

between injection
and the onset of
the pressure rise.
Distillate fuels
having high
cetane number
will show a short
ignition delay
period while
those fuels with
poor cetane
number will give
long ignition
delay period.

 Self-ignition
temperature: low
for paraffins
(higher MW
paraffins have
lower ignition
temperature
(desired).
Aromatics have
high self-ignition
temperatures
(undesired).

 Rapid pressure
rises results from
the accumulation
of fuel in the
combustion
 chamber during
ignition delay
period. And large
number of
ignition points
occurring
throughout the
fuel/air mixture.

 With long ignition

delay time, rapid
rapid pressure
rise causes
uncontrollable
inefficient engine
smoking.

 Rapid pressure
rise results
undesirable
knocks, high
stresses, and
severe engine
vibration (Diesel
knocking).

Cetane number

 The ignition
properties of
diesel fuels are
expressed in
terms of cetane
number or cetane
index.

 These are very

similar to the
octane number
(except the
opposite) and the
cetane number
expresses the
volume percent
of cetane (C16H34,
high-ignition
 quality =>100 CN)
in a mixture with
alpha-
methylnaphthale
ne (C11H10,
(Aromatic)low
ignition quality
CN= 0).

 The fuel is used

to operate a
standard diesel
test engine
according to
ASTM test
method D-613.
Since many
refineries do not
have cetane test
engines, a
mathematical
expression
developed to
estimate the
cetane number is
used.

 High Cetane No:

shorter ignition
delay period, low
pressure rises
rates and hence
tend to cause less
combustion
noise.

 trembly high
cetane number
cause incomplete
combustion
because of
insufficient fuel
or air mixing due
to very short
ignition delay
 period

 The higher the

H/C ratio, the
better the
burning
characteristics
(i.e., the higher
the smoke point
and the higher
the cetane index)
To improve air
quality, more
severe
restrictions are
placed on the
sulfur and
aromatic
contents of diesel
fuels. As the
cetane index is an
indicator of the
H/C ratio, it is
also an indirect
indicator of the
aromatic content
of the diesel fuel.

 Therefore,
frequently a
minimum cetane
index
specification is
used an
alternative to
maximum
aromatics
content.
Lowering sulfur
and aromatics
contents
specifications also
lowers the
particulate
 emissions from
diesel engines.

 Aniline point:
Defined as
temperature at
which a liquid just
becomes
completely
miscible with
equal volume of
aniline.

 Aromatics are
easily miscible=>.
Low A.P

 Paraffins have
high A.P.

 Diesel Index= A.P.

(F)x Degree API/
100

Table:1.11

DIESEL QUALITY
REQUIREMENTS(Eu
ro Norms)

E E E E
Pro
UROURO URO- URO-
perty III(00
IV(05
I(92)
II(96)

Cet
ane 4 4 5 5
Numb9 9 1 4
er

S%
0. 0. 0. 0.
Wt.,M
20 05 035005
ax

T95 3 3 3 3
,Deg.c.
 Max 70 70 60 60

PA
Hs., 1 1
- -
%Wt., 1 1
Max

Future Strategy For

Deisel Quality Improvement

For Sulphur Reduction &

Cetane Improvement

 Setting Up High
Pressure DHDT
That Can Handle
Cracked Stocks
Also.

 Capacity
Expansion/New
Unit for
Hydrocracker.

 VGO
Hydrotreatment.

 Replacement Of
Catalyst by New
Highly Catalyst.

 Use Of High-
Performance
Internals In
Existing DHDS.

Fuel Quality
Improvement To Meet
Emission Norms

PETROL

 Reduction Of
Benzenes 5 To 1
(%V) Lower VOC
  Reduction Of
Olefins To 21(R),
(18)P Emission

 Reduction Of
Sulphur 500-150-
50ppm-Lower
SO2

 Increase In
Octane To 91-
Energy Efficiency,
Lower CO2

DIESEL

 Sulphur
Reduction 2500-
350-50ppm-
Lower SO2

 Cetane Increase
48-51-Better
Efficiency-Lower
CO2

 PAH Control 11%

max/mass-Lower
Hydrocarbon
Emission

 End Point and

Density
Reduction

Lower CO, NOx, VOCs,

SO2 Have Indirect Influence
on The Formation of GHGs

HEATING OILS

 The principal
distillate fuel
oils: No. 1 and
No. 2 fuel oils.

 No. 1 fuel oil:

very similar to
 kerosine, but
generally has a
higher pour point
and end point.
Limiting
specifications are
distillation, pour
point, flash point,
and sulfur
content.

 No. 2 fuel oil:

very similar to
No. 2 diesel fuel,
contains cracked
stock, and is
blended from
naphtha,
kerosine, diesel,
and cracked gas
oils. Limiting
specifications are
sulfur content,
pour point,
distillation, and
flash point.

Table:1.12

Heating oil
specifications

N N NN
O.1O.2O.4O.6

Flas
1 1 1 1
hPoint.
00(3
00(3
30(40(6
F(oC),
8) 8) 55)0)
min

Pou
9 2 2
rPoint.o
(- 8(-8(- -
F(oC),m
18)6) 6)
ax
 Distillation
TempoF(oC)

10%
4
Recove
19(2 - - -
red,
15)
Max.

90%
5
Recove
40(2
- - -
red,
82)
Min.

5 6
Max
50(2
40(3 - -
88)88)

Viscosity,mm2
/s at 104oF(40oC)

1 1 >
Min -
.3 .9 5.5

2 3 2
Max -
.1 .4 4.0

at
212oF(100oC)

1
Min - - -
5.0

5
Max - - -
0.0

Density,kg/m3
60 F(15oC)
o

Max 8 8
o
API 50(3
76(3 - -
min) 5) 0)

Ram 0 0 - -
 sbotto
mCarb
on
Residu
.15.35
e On
10%
btms,w
t%,max

Ash,
0
wt - - -
.10
%,max

Sulp
0 0
hur,wt
.50.50
%,max

Wat
er &
0 0 0 2
Sedime
.05.05.50.00
nt Vol
%,Max

Lube oils

 Principle
source: fraction
left after gasoline
kerosine and
diesel oil.

 ASTM Boiling
point>35 oC

 Mainly composed
of
paraffins,Naphthe
nes and
aromatics.

 Use: machine
engine oils,
turbine oils,
 Transformer oils

 Viscosity
Index: Change in
viscosity with
temperature

 V.I = (L-U)/ (L-H)

Atmospheric Gas Oil:

 ASTM end point

42oC

 Not a market
product

 VGO: Producr
obtained from
vacuum
distillation unit.
ASTM boiling
range 420-600 C.

Bitumen:

 Residue obtained
from CDU.

 Solid at room
temperature.
Highly viscosity.

 Asphalt: mixture
of bitumen in oil
containing
mineral matter.

Use: highway
construction, water proofing
coating

RESIDUAL FUEL OILS:

 Residual fuel oil:

composed of the
heaviest parts of
the crude and is
 generally the
fractionating
tower bottoms
from vacuum
distillation.

 Critical
specifications:
viscosity and
sulfur content.
Sulfur content
specifications are
generally set by
the locality in
which it is
burned. Only low
sulfur fuel oils
can be burned in
some areas and
this trend will
continue to
expand.

 Heavy fuel
oils: with very
low sulfur
contents are
much in demand
and sell at prices
near those of the
crude oils from
which they are
derived.

Asphalt

 Mixture of
Bitumen in oil
containing much
mineral matter

 Bitumen obtained
from distillation
column is poor in
quality.
  Air blowing is
done to obtain
suitable grade.

 Use: Highway
construction,
water proofing
coating etc.

Alternate Energy Sources

 World petroleum
demand is
growing at an
unsustainable
rate.

 Conventional oil
supplies are
defined.

 All available
carbon resources
need to be
considered,
engaged and
utilized.

 New technologies
need to be
deployed.

 Depending on
physical location
– GTL/CTL are
viable near-term
solutions.

Road Map Of Energy

Resources And Demanded
Product
 Fig:1.18

Alternative Energy and

Technology Option for
Transportation

Biofuels, Ethanol,

Ethanol

Biodeisel

Hydrogen Fueled Cars

Major Thrust is Currently

on Biofuel and Hydrogen

Major Thrust is Currently

on Biofuel and Hydrogen

Compressed Natural
GAS(CNG)

 Mixture of
hydrocarbons ~
80 to 90 %
methane.
  Compressed to a
pressure 200 to
250 kg/cm2( to
enhance the
vehicle onboard
in cylinder)

 Energy value:

43.6 Mj/kg (H2 = 140.4

Mj/kg)

6860 Mj/M3at 200 atm

and 15oC

(H2 = 1825 Mj/ M3)

 Better cold start

conditions than
gasoline.

WOBB INDEX: Indicates

the heat input to the engine.
Calculated by dividing the
heating value of the gas by
the square root of its gravity.

W.I = Heat of
combustion/ (sp. Gr)0.5

Desired value (NG) 48.5-

53 MJ/M3

LPG 72- 83 MJ/M3

Advantages of Natural
Gas

 Clean fuel
requiring little
processing.

 Easily transported
via pipelines.

 CO2 emission per

 unit of energy
lower than other
fossil fuels.

 Unburned
molecules
released into the
atmosphere
contribute less to
smog formation
than gasoline
molecules.

 methane’s single
C is reactive than
carbons of longer
hydrocarbon
chains.

Disadvantages of Natural
Gas

Table:1.13

ecially Cellulosic, are Cost competitive with oil & gas

Price

Common $/GJ

$50/bbl $8.80

$ 1.67/gala $13.80

$7.5/ scf $7.90

$20/ton $0.94
 $0.04/kWh $11.10

$0.23/lb $13.80

$2.25/ bu $6.50

$50/Ton $2.50

< crops b

Ethanol Feedstocks and

Processes

Process

Fermentation

her starchy sources) Enzyamatic Saccharification and Acidic Hydrolysis

Acidic Hydrolysis and Enzyamatic Saccharification

Fig:1.19

Table:1.14
 Biomass
Classification

Oxe G
Proc
genate
ener
ess
ation

Met 2n Ther
hanol mal

1st Biolo
Eth
and2
gical or
anol nd
Thermal

1st Biolo
But
and2
gical or
hanolnd
Thermal

Mix
ed 2n Ther
Alcoho mal
ls

DM 2n Ther
E mal

Hyd
rocarb
ons

Phys
Bio st
1
deisel Chemica

Ther
Syn n
2mal(Lon
thetic
g Term
Diesel
Bio

Syn 2n Ther
 thetic
Gasoli mal
ne

Ther
1st
Hyd mal or
and2
rogennd Biologic
al

Dehydration and desalting of crude

CRUDE OIL PRETREATMENT (DESALTING)

 Crude oil contains water, inorganic salts, suspended solids, and water-soluble trace metals.

 First step in the refining process is to remove salt and solids to reduce corrosion, plugging, and
fouling of equipment and to prevent poisoning of the catalysts in processing units.

 contaminants must be removed by desalting (dehydration).

 If the salt content of the crude is greater than 10 lb/1000 bbl (expressed as NaCl), the crude
requires desalting to minimize fouling and corrosion caused by salt deposition on heat transfer
surfaces and acids formed by decomposition of chloride salts.(<1000 lb/bbl).

Typical Configuration Atmospheric Column w/o Preflash[1,2]

Fig:2.1 Typical Configuration Atmospheric Column w/o Preflash[3]
 Fig:2.2 Atmospheric Distillation Unit Overview [3]

Most typical methods of crude-oil desalting:

 Chemical and Electrostatic separation:Washing of the salt from crude oil with water oil and
water phases are separated in a settling tank by adding chemicals to assist in breaking up
emulsion or by the application of electrostatic field to colapse the droplets of saltwater more
rapidly.

 Chemical desalting:Water and chemical surfactant (demulsifiers) are added to the crude, heated
so that salts and other impurities dissolve into the water or attach to the water, and then held in
a tank where they settle out.

 Electric desalting:Under charge condition polar molecules get oriented and get separated. More
than 90% of salt can be removed in just less than half an hour.
Desalting of Crude

Fig:2.3 Desalting of Crude

Electric Dehydration and desalting[1-3]

 Electrical desalting is the application of high-voltage electrostatic charges to concentrate

suspended water globules in the bottom of the settling tank.Either AC or DC fields may be used
and potentials from 12,000 to 35,000 volts are used to promote coalescence.

 Surfactants are added if the crude has a large amount of suspended solids.

 The feedstock crude oil is heated to between 150 and 350oF to reduce viscosity and surface
tension for easier mixing and separation of the water.

 The temperature is limited by the vapor pressure of the crude-oil feedstock.

Electric desalting[1]

 The dual field electrostatic process provides efficient water separation at temperatures lower
than the other processes and as a result,higher energy efficiencies are obtained.

 The salts are dissolved in the wash water and the oil and water phases separated in a settling
vessel either by adding chemicals to assist in breaking the emulsion or by developing a high-
potential electrical field across the settling vessel to coalesce the droplets of salty water more
 rapidly.

 Desired pH <6,at higher pH emulsion forms.

 Ammonia is used to reduce corrosion. Caustic or acid may be added to adjust the pH of the
water wash.

 Wastewater and contaminants are discharged from the bottom of the settling tank to the
wastewater treatment facility.

 The desalted crude is continuously drawn from the top of the settling tanks and sent to the
crude distillation (fractionating) tower.

Wash water and T requirement in Desalter:[1,2]

 (3-4vol%, T 240-260oF (API >30), to 7-10 vol%,T 280-300o F for API<30)

 For single-stage desalting units 90 to 95% efficiencies are obtained and two-stage processes
achieve 99% or better efficiency.

 Efficiencies of up to 99% water removal in a single stage are claimed for the dual field process.
About 90% of desalters use AC field separation only.

 Heavy naphthenic crudes form more stable emulsions than other crudes. Higher temperature is
required.

Crude Electrostatic desalting

Fig:2.4 Crude Electrostatic desalting[1,2]

Crude Assay, ASTM, TBP distillations, Evaluation of crude oil properties.

Crude Oil Distillation

 Crude oil distillation is an open art technology.

 The crude oil is distilled at atmospheric pressure and separated into various fractions as desired
in Crude oil distillation unit .
 The reduced crude oil is further fractionated under vacuum to produce vacuum gas oil (VGO) as
a feed to Hydrocracker or FCCU in a Fuel type Vacuum Unit,or distilled to produce Lube oil feed
stock in a Lube type Vacuum Unit.

Crude Oil Distillation Scheme[1,2]

Fig:2.5 Crude Oil Distillation Scheme

Crude Oil Properties

 Sulfur, nitrogen, and metals content.

 Sulfur.
 Sour vs sweet — ~0.5 wt% cutoff restrictions on sulfur in final products.
 Nitrogen
 Usually tolerate up to 0.25 wt%.

Nickel, vanadium, copper

 Can poison catalysts.

 Tend to be in the largest molecules/highest boiling fractions.

Properties appropriate for certain boiling point ranges[1,2]

 Octane number
 Cetane number
 Viscosities
 Carbon residue

Crude Assay
 The complete and definite analysis of a crude oil is called crude assay.A complete crude assay will
contain some or all of the following:

1. Whole crude gravity, Viscosity, ‘S’ content, pour point etc.

2. TBP curve, Mid Volume plot of gravity, Viscosity etc.
3. Light end analysis up to C8 and C9.
4. Properties of fractions. (naphtha, middle distillates, gas oil residue).Yield vs Vol.%, gravity, S,
viscosity, octane no., diesel index, Flash point , Fire point, Smoke point, Pore point, Vapor
Pressure etc.
5. Properties of lube distillates ( only if the crude is suitable for the manufacture of lube base
stocks).
6. Properties of asphalt (only if residue have suitable characteristics for preparation of asphalt.
7. EFV curve run at atm. Pressure. Not useful for design work but is of great importance to the
refinery or to a crude oil purchaser.

Crude Oil Characterization[1,2]

 Trading: Density,API Gravity

 Transportation: RVP,Pour Point,KV,Wax content
 Contamination: Salt content,BS&W
 Processability: Sulfur,Nitrogen,TAN,Asphaltene,MCR
 Cracking Point: ASTM Distillation
 LPG Potential: Light hydrocarbons(GC)
 Classification: Characterization factor

API & S, N & Asphaltene

API gravity Various average boiling points and mid

percent corves

Different types of boiling points/ functional values

Table:2.1 For narrow boiling cuts (TBP slope less than 2) all above
mentioned boiling points tend to equal. [1,2,6,7]
 Average Boiling
Physical property for which it is distinct.
Point

Volume Average Used for liquid viscosity, Specific gravity.

Weight Average Critical properties

Molal Average Characterization factor, Thermal Expansion of liquid.

Molecular weight, Sp. gravity, Heat of combustion, Sp.

Mean Average
heat etc.

For additive properties, viscosities are additive when

Cubic Average
expressed on cubic average.

Average Boiling Points: To specify certain properties of the fraction

1:Vol. Avg. - Based on the boiling temperature of different cuts.VABP

Used for distinguishing physical property like Liquid Viscosity, Specific Gravity.

2. Weight Average Boiling point- For Critical Temperature.

% calculation based on weight.

Mol. Average-based on boiling temperature of different mole fraction.

(Characterization factor, Thermal expansion of liquid, based upon boiling

temperature at different mole fraction.)Molal average

t1, t2, t3 are at respective mole fraction.

X1, X2, X3 are mole fraction

Mean Average Boiling Point

(For Estimating Mol.wt, Sp. Gravity, Sp.heat of fraction.)

Mean Avg B.P=(Molal avg. B.P + Cubic avg. B.P)/2

Cubic Avg. B.P:

Va= Vol. Fraction

Average Boiling Point for a Fraction (summary)

five types are defined in the API Technical Data Book :

Volume average boling point

Mass average boling point

Molar average boling point

Cubic average boling point

Mean average boling point

Will generally use boiling point at mid-cumulative yield

Interconversion of Boiling points

 Calculate slope of Distillation curve of a fraction.

 ASTM/TBP/EFV Slopes
 TBP Slope = (t70%– t10%/60)

70% and 10% are volumetric boiling points.

 Fig:2.8 Conversion of TBP slope to ASTM on EFV slope [1,2]

CRUDE OIL PROPERTIES

These are required for estimating property of cut ranges in the manual method.

 Mid percent API Gravity (density ) is drawn along with TBP

 Mid percent Mol. Wt. is drawn along with TBP

Evaluation of crude properties

 Calculate Mean average boiling point from TBP slope and correction factor
(From graph)

MABP = VABP+ Correction factor

 Calculate Characterisation factor (Kw) and API gravity for fractions.

 Kw is assumed constant for whole crude and its fraction.
 50% BOILING POINTS OF ASTM : Calculated from the slope of TBP Curve of
a crude and its 50% B.P.

For Fractions: Separate IBP and volume percent for crude fractions
 Calculate MABP (VABP, SLOPE and Watson Characterization factor)
 Calculate API of fractions
 Calculate Molecular weight of the fractions using graph
 Plot MID Volume percent vs API gravity and M.W

Mean AVG /Molal Avg BP

Fig:2.9 Mean AVG /Molal Avg BP [1,2]

 Fig:2.10 Molal Average Bolling Point [1,2]

50% Boiling Point on ASTM curve :can be calculated from the slope of TBP
curve of a crude and its 50% B.P can be estimated
Fig:2.11 50% Boiling Point on ASTM curve :can be calculated from the
slope of TBP curve of a crude and its 50% B.P can be estimated
Fig:2.12 Relationship between ASTM and TBP 50 volume points [1,2]
Fig:2.13 Characterization factor vs B.P and API gavity [1,2]

Calculation of Molecular weight

Fig:2.14 Calculation of Molecular weight
Fig:2.15 ASTM true boiling point and equillirium flash vaporisation
Distillation curves for a Naphtha kerosine Blend[1,2]
Fig:2.16 D1160 Temperature Difference[F] [1,2]
 Fig:2.17 TBP Temperature oF

Crude Oil Properties

Distillation analysis/Boiling point range

 Amount collected from batch distillation at the indicated temperature

 Most useful is TBP (True Boiling Point)
 Standardized tests —ASTM D86, D1160,

API gravity
Standard Conditions (Temperature & Pressure)

“Standard conditions” may vary between countries and even states within the US
Standard temperature 60°F.Other typical values are 14.73 psi & 14.503 psi.

Normal conditions

 0°C and 100 kPa (32°F and 14.50 psi)

 Almost exclusively used with metric units

Fig:2.6 API & S, N & Asphaltene

Crude Oil Assay

 Indicates distribution quantity and quality of crude oil feedstock based upon boiling point
temperature range.
 Represents expected products from crude and vacuum distillation.

Quality measures[1,2]
  Specific gravity and API gravity.
 Sulfur content.
 Octane number and Cetane number.
 Viscosity.
 Carbon residue.

TBP Curves

Fig:2.7 TBP Curves

Watson characterization factor.

 12 – 13 (Paraffinic) to 10 (Aromatic)

Laboratory Distillation[1-6]

 Helps to characterize a product and also helpful in data designing.

  Forms a basis of design of distillation.

Three different types:

A:True boiling point distillation (TBP) for crude used to obtain true boiling point distillation curve good
fractionation.

 Number of plates and amount of reflux must specified.

 True Boiling Point(TBP)(ASTM D2892)
 10 to 20 theroretical stages near infinite reflux.
 1 atm; no hotter than 650oF minimize cracking.

TBP DATA

 Large no. of stages and a high reflux to distillate ratio so as the temperature at any point on
temperature Vs volumetric yields curve represents the actual boiling (true boiling) points of
the hydrocarbon material present at the Vol. % point.
 Hempel Distillation:Semi fractionating type distillation, but can be used TBP data, where TBP
data are insufficient.

ASTM Distillation or Engler Distillation

 Simple distillation carried out with standard ASTM flask of 100, 200, 500 ml capacity.
 No reflux is provided.
 Rapid batch distillation employing no trays or reflux between the still pot and condensation.

Separation is poorer: more volatile and high volatile components are present in initial condition. So
IBP is higher than TBP.[1,7]

Distillation Analyses

 ASTM D86
 Low resolution - no packing reflux from heat loses.
 1 atm; no hotter than 650 oF minimize cracking.
 Correlation to correct to TBP basis.
ASTM Distillation Analyses

 ASTM D1160
 Used on Resids (650 oF).
 Relatively low resolution.
 Vaccum conditions- 10 to 40mmHg,no hotter than 1000oF AEBP.
 Correlations to correct to atmospheric pressure & TBP basis.

ASTM Distillation

 At the end in TBP only pure component less volatile component is present. Whereas in ASTM
more volatile components and less volatile both are present so FBP is lower in ASTM.
 Separation is poorer compared to TBP.
 IBP for ASTM is higher than that for the TBP.
 FBP for ASTM is lower than that for the TBP.

e.g. Kerosene TBP Range 135-300oC.

ASTM range 160-275oC.

Equilibrium Flash Vaporization[1,2,7]

 By conducting operation at a series of temperature,curve,% vaporized Vs temperature may be

plotted.
 Mixture is heated without allowing the vapor to separate from the remaining liquids, the
vapor assist in causing the high boiling point of the mixture to vaporize.
 Similar to ASTM but vapor and liquid are kept in contact till the desired degree of vaporization
is reached. Poorer separation. (Higher IBP LOWER FBP than ASTM).

Evaluation of properties of crude oil and its fractions

General Procedure for evaluation of crude oil/ fractions

1. From the crude distillation data,plot TBP and gravity- midpercent curves.

2. Select TBP cut-points of products to be made from atmospheric and vacuum pipe stills.

3. From TBP and gravity curves, determine percentages and gravities of fractions.
 4. Convert volumes percent to weight percents.

5. Determine weight of bottoms stream by difference.If the volume of bottom stream is taken
from the TBP curve, then gravity is calculated from weight and volume.

6. For crude oils containing significant amounts of sulfur or nitrogen, it is also necessary to make
sulfur and/or nitrogen balances around each unit.

Example: Whole crude TBP Data (API Gravity 36.3)

Table:2.2 Plot TBP, M.W , API AND Wt% CURVES FOR THE CRUDE oil

Volume percent 5 10 20 30 40 50 60

TBP Temperature (oF) 62 144 255 344 437 531 623

Volume percent 70 80 85

TBP Temperature (oF) 717 819 897

CALCULATIONS

SP.Gr.For whole crude = 141.5/ (131.5+ API)

Sp. Gr. = 0.84 (for the crude oil)

VABP for whole crude = (t20+t50 + t 80)/3

==>VABP =[ ( 255+ 531+819)/3 ]= 535 oF

TBP Slope =[ (t70- t10)/ 60 ]

= (717-144)/60

= [9.6 oF/%]

 Correction Factor (from graph ) = - 70 oF

  Mean Average Boiling Point ( MABP) = 535 - 70 = 465 oF

 Characterisation Factor Kw = 11.5 (Assumed constant) (From graph)

 Divide whole crude into various cuts

Basis :100 Barrel of crude oil ( 1bbl= 42 US gallon, 1 US Gallon= 3.78 L)

Basis 100 Barrel of crude oil( Weight of the crude = 100x0.843x 349.7=29500 Lb)

(density of water = 349.7 lb/bbl)

Table:2.3[1,2]

Boiling range (F) Cumulative vol.% VABP( F) MABP(F) API M.W Mid vol%

IBP-200 15 110 110 65 78 7.5

200-300 25 251 251 15 112 20

300-400 46.5 482 482 35 186 41.0

Calculation for weight percent

Table:2.4[1,2]

Density Wt.% of
Vol.%cuts API Sp.Gr weight Cumulative wt.%
(lb/bbl) cuts

15 65 0.72 251.7 3770 12.8 12.8

15-25 51 0.78 272.7 2727 9.2 22.0

25-35.5 44 0.81 283.2 2973 10.1 32.8

wt.%,calculated based on total mass of crude (29500 lb)[1,2]

Fig:2.18 wt.%,calculated based on total mass of crude (29500 lb)[1,2]

Exercise

 Complete the Table for other fractions (cuts).

 Plot API vs mid volume, Molecular weight vs MID Volume and weight percent vs mid volume for
these cuts.

 Calculate 50% ASTM and 50%EFV Boiling temperatures for each fraction and plot. Draw astm
 and EFV curves for the crude.

Fig:2.19

Crude Oil Assay Example-1

Table:2.5
Table:2.6
Table:2.7
 50% Boiling Point on ASTM curve :can be calculated from the slope of TBP curve of a crude and its 50%
B.P can be estimated

Fig:2.20
Fig:2.21 Different Slope and Interconversion

Table:2.8
Fig:2.22
Fig:2.23

Linearized Distillation Yield Curves

Fig:2.24 Linearized Distillation Yield Curves

Design concept of crude oil distillation column design.

Distillation Column Design

The design of a distillation can be divided in the following steps.

 Specify the degree of separation:- Set product specification.

  Select the operating conditions:- Operating pressure.

 Determine the stage and reflux requirement:- The number of equilibrium stages.

 Select type of contacting device:- Plates or packing.

 Size the column:- Diameter, number of real stages.

 Design the column internals:- Plates,Distributors,Packing Supports etc.

 Mechanical design:- Vessel and Internal fittings.

Arrangement of Towers

Three types of arrangements ( How heat is removed)

1. Top Tray Reflux : Reflux is only at top tray only

 Reflux is cooled and sent into the Tower.

 Heat input: Through Tower bottom.

 Removal: at the top.

 Thus requires large tower diameter.

 Improper reflux and poor quality of fraction. Economic utilization of heat is not possible.

2. Pump back reflux.

3. Pump around Reflux.

Fig:2.25 Vacuum Distillation Unit Overview [7]

Pump back Reflux:

 Reflux is provided at regular intervals.

 This helps every plate to act as a true fractionator.( because there is always good amount of
liquid).

 Tower is uniformly loaded, hence uniform and lesser diameter tower will do.

 Heat from external refluc can be utilised as it is at progressively higher temperatures.

 However design of such tower is costly, but provides excellet service.

 Most common in refineries.

Top Tray reflux

Fig:2.26 Top Tray reflux[1,2]

Pump Around Reflux:

 In this arrangement reflux from a lower plae is taken, cooled and fed into the column at a higher
section by 2 to 3 plates.

 This creates local problem of mixing uneven composition of reflux and liquids present on the
tray.

 Designers treat all the plate in this zone as one single platre, the result gives large number of
plates and high tower height.
Fig:2.27 Atmospheric Distillation Unit Middle [8]
Fig:2.28 Typical Configuration of Single Feed and Multiple Feed into Distillation Unit [1,2,11]

Some Basis

 Section above feed point-Rectifying/Enrichment Section

 Section below Feed-Stripping Section

 Reflux ratio R= Flow returned as reflux/Flow of top product design

 Minimum reflux Rmin:-Reflux below which stage required is infinity.

 Optimum reflux ratio typically lines between 1.2 to 1.5 times the minimum reflux ratio.

 Relative Volatility αij=Pi/Pj=Ki/Kj

 y=αX/(1+(α-1)x) for contruction of y-x diagram.

Fig:2.29 Stage Equations For Distillation Unit

Mesh Equations

Material Balance

Vn+1Yn+1 + Ln-1Xn-1 +FnZn =VnYn +LnXn +snXn............Equ 1

Energy Balance

Vn+1Hn+1 +Vn-1Hn-1 +Fhf +qn =VnHn +Lnhn +Snhn.........Equ 2

 Equilibrium Relation:

Yi =KiXi........Equ 3

Summation Equitation:For Liquid & Vapor composition

These Four equations are the called MESH EQUATION i:e Material Equilibrium, Summation and Heat
(Energy)Balance Equation.MESH Equation can be written for each stage and for reboiler and condenser.The
Solution of the set of equations forms the basis of rigorous methods.

Basic Processes

 Separation by Boiling point difference.

 Crude Assay provides estimates of various products obtainable from a particular crude.

Table:2.9[1,2]

Typical Products TBP CUT RANGE

Unstabilized Naphtha IBP-120oC

Heavy Naphtha 120oC-140oC

 Kerosene 140oC-270oC

Light Gas Oil 270oC-330oC

Heavy Gas Oil 330oC-370oC

Reduced Crude Oil 370oC +

Fig:2.30[1,2]
Fig:2.31 Atmospheric Distillation Unit Bottom [9]
Fig:2.32 Vacuum Distillation Unit Overhead [10]

Process Design Basics

Heat and material balance calculations

 Compute hydrocarbon material balancefor feed and products.

 Steam rates to stripping sections and steam distributions between overhead distillates vapors
and liquids.

 Hydrocarbon material balances around product strippers.

 Atmospheric EFV Temperatures for products corresponding to the estimated strip out for each
 product.

 Draw Tray locations, Number of trays in each sections and total number of trays in the Tower.

 Heat input to the base section of the tower from feed and bottoms stripping steam, heat
outflow in the bottoms liquid and external heat quantities at the flash zone.

Product Yield Determination

 Desired ASTM distillation of product(s) of interest is decided and ASTM is converted to

TBP.Product TBP is applied to the whole crude TBP cruve to eastimate volumetric yields TBP cut
volume is eastimate.

 ASTM(5-95) GAP/OVERLAP between adjacent cuts determined.

Separation Criteria

 DEGREE OF SEPARATION:Difference between ASTM- 5% of heavier distillate and ASTM -95%

point of lighter distillate.

 DEGREE OF DIFFICULTY OF SEPARATION:Difference between ASTM 50% point of the distillate

fraction in questions.

Separation Criteria

Degree of Separation

 Defined in terms of product purities or component recoveries.

 Greater the degree of separation, greater will be recovery of the light component in the
distillate and the heavy component in bottoms.

 Degree of difficulty of separation : Defined as the relative difficulty encountered in separating

the two compounds, regardless the purity requirements set by process specifications~ inversely
proportional to the relative volatility between the two components.

ASTM Gap and Overlap

  Fractionation is the difference between 5% ASTM curve of Heavy cut and the 95 % point on the
ASTM curve of a lighter cut of two adjacent side product.

 Positive difference is called Gap.

 Negative difference is called overlap.

 ASTM Boiling range gives general composition of fractions.

 5- 95 GAP: Defines the relative degree of separation between adjacent fractions.

 Determined by subtracting 95 vol.% ASTM Temperature of a fraction from the 5 Vol. % ASTM
temperature of the adjacent heavy fraction.

 (5-95) Gap = (t5H-T95L)ASTM

 5H=5% OF THE HEAVIER FRACTION

 95L= 95% OF THE LIGHTER FRACTION

 TBP CUT POINT = (TOH+ T100L)/2

 TBP Over lap= [T100L – TOH]

TBP CUT , GAP & OVERLAP

Fig:2.33 TBP Cut , Gap & Overlap[1,2]

General observation for separation

For a given system

 No. of trays required increases markedly as purity requirement increases, but reflux
requirements increases only a small amount.

 Tray and reflux requirements increases as relative volatility decreases i.e separation becomes
more difficult.

Separation Criteria

 For a fixed number of trays,reflux reqirement is directly proportional to the degree of difficulty
 of separation.

Qualitatively

 At reflux condition exceeding minimum requirements =>Tray requirements are directly

proportional to the required degree of separation.

 The degree of difficulty of separation inherent in the physical chemical system under
consideration.

Crude Column Design

INPUT REQUIRED

 Crude TBP (essential)

 Density/API gravity (essential)

 Molecular Weight(optional)

 Viscosity(optional)

SPECIFICATION REQUIRED

 Column Pressure

 Product specification can be given in terms of fix draw or distillation point.

 Pump around duties need to be specified.

 Column top temperature can be specified.

Process design

 Prepare TBP Distillation and equilibrium Flash Vaporisation curves of crude to be processed.

 Using crude assay data construct TBP curves for all products except gas and reduced crude.
Convert these to ASTM & EFV.

 Convert TBP data to EFV curves.

 Prepare material balance of crude distillation column, on both volume and weight basis.
 Fractionation requirements: ASTM gap and overlap

Knowing gaps as the design parameters correlate deviation or gap with F factor( product of number of
plates between two adjacent side draws off stream and internal reflux ratio.

Packie’s Method

 Degree of difficulty of separation : The difference between 50 vol.% temperatures of the

fractions under study.

 Convert 50% TBP temp to ASTM.

 Separation Capability (F):defined as the product of the reflux to feed ratio at the upper draw
tray as calculated on the volumetric basis and the number of actual trays in that section.(F,
Factor related to gap and overlap).

 Packie method: Based on Gap and overlap.

 Number of plates in particular section depends on gap and reflux ratio.

 F= Reflux ratio x Number of plates in that section.

F=(LN/DN)NT,(NT: No of trays of distillation column)

L/D= Reflux ratio

TBP VS ASTM 50% B.P

Fig:2.34 TBP VS ASTM 50% B.P[1,2]

Relation Between TBP and ASTM 50% Boiling Point

IBP AND FBP OF ASTM & TBP

Fig:2.35 IBP AND FBP OF ASTM & TBP[1,2]

Relation Between IBP and FBP of ASTM and TBP

 Fig:2.36 Relation Between IBP and FBP of ASTM and TBP[1,2]

EXAMPLE

In a refinery side stream operation the fraction to be collected is diesel. The diesel entering the side
stripper is 4000 bbl/h, the 50 percent point of the cut is 275 oC and contained with Kerosine whose mid
boiling point is 145 oC. If the stripper is having 4 plates find the actual amount of diesel coming out of the
stripper if the ASTM GAP is 20 o C.

SOLUTION

Calculate F Factor from Packie method for side stream stripper.

ASTM ΔT50%= 275- 145= 130oC (254 oF)

ASTM GAP= 20 oC = 36 oF
F= (L/D)NT=>L/D= 5/4= 1.25

V= L+D = 4000

Hence D( Actual amount of diesel )= 1778 bbl.

Calculation of minimum number of stage

Fenske equation is used for Nm

Calculation of minimum reflux ratio

Using Underwood Equation:

q = heat to vaporize 1 mole of feed / molar latent heat of vaporization.

θ = Root of underwood equation.

Calculate Rm using Erbar- Maddox(or Gilliland)correlation calculate R actual.

CALCULATION OF REFLUX RATIO

Fig:2.37 CALCULATION OF REFLUX RATIO[1,2]

Kirkbride equation is used for feed tray location.

log[Nr/Ns]= 0.206log[(B/D)(Xf.LK/Xd.HK)2].........Krikbride Equation

Where

Nr= Number of stages above the feed,including any partial condenser.

Ns= Number of stages below the feed,including the reboiler.

B= Molar flow bottom product.

D= Molar flow top product.

Xf.HK = concentration of the heavy key in the feed.

Xf.LK = concentration of the light key in the feed.

Xd.LK = concentration of the heavy key in the top product.

Xb.LK = concentration of the light key in the bottom product.

In simulation method,it is known as short cut mettod

Fig:2.38[1,2]

Optimization Criteria in Design

 Maximization of distillates.

 Maximization of desired product(s).

 Quality of reduced crude.

 Overflash control to optimize energy.

  Optimization of pumparound in yield.

Optimization of particular product(s).

Flash Zone operating conditions-FZ temperature is limited by advent of cracking.

 FZ pressure is set by fixing the reflux drum pressure and adding to it to the line and tower
pressure drop.

 Over flash:Over flash is the vaporisation of crude over and above the crude overhead and side
stream products.

 Over flash is generally kept in the range of 3-6 liquid volume %. Kept at minimum value as a
Larger over flash consumes larger utilities.

Over flash prevents coking of wash section plates and carryover of coke to the bottom side streams by
and the tower bottom by providing reflux to the plates between the lowest sidestream and the flash zone.

Flash Zone Temperature

 Crude TBP provides estimate of total distillate.

 EFV cruve of the crude is derived from the TBP and converted to the flash zone pressure.

 Overflash quantity is selected included this material balance and heat balance arount the
bottom section including feed section is done to fix the flash zone temperature.

 Flash zone temperature thus fixed ensures desired total distillate yield.

Product Yield Detrmination[1,2,6]

 From ASTM curve:1 ATM EFV curve are develoved and extrapolated to(-) 50% VOL% vaporized
as an initial estimate.

 Stripping steam to the stripper is set at about 10LB/BBL of stripped product bubble point of
unstripped side stream is estimated.
Fig:2.39

EFV TEMP VS DRAW TRAY TEMP

Fig:2.40 EFV TEMP VS DRAW TRAY TEMP[1,2]

FLASH ZONE
Fig:2.41 FLASH ZONE[1,2]

 D= Sum of all streams.

 V= % OF VAPORISATION in Flash zone.

 Lo = Overflash.

 SF= Total amount of hydrocarbons stripped out by steam.

 Thus V= D + Lo - SF

 From the flash curve(EFV) of the crude, the temperature at which this vaporisation is achieved
at the FZ Pressure is determined.

 This T should not exceed the maximum permissible temperature. If does quantities of Overflash
and stripping steam are changed until a permissible temp is obtained.

 Stripped out HC Fraction (Sf) depends on amount of stripping steam.

 W= Lofz- Vso,( W=Vol. % Feed leaving the bottom).

 Lofz= Lo (Overflash)+ W

 V= Lo+100- W/(1-Sf) vol.% of of feed flashed at FZ inlet.

 Sf= fraction of strip out vapor (Lofz(1-Sf)= W).

 EXAMPLE: It is planned to yield as a side stripper from an atmospheric crude tower, 100 bbl per hour of
a light distillate product having a TBP cut point range of 400-525 oF (volume range 27-39%, API 39.8). The
estimated draw tray temperature is 425oF. The liquid is to be stripped in a 4 tray column using 500oF Steam.
The stripping rate is 10 lb/bbl of stripped product. Calculate the temperature of stripped product stripping
the bottom of the stripper.

Solution:100 bbl of LD to be producd, TBP Cut 27-39 % =12 vol.%, Mid vol %33

 Strip out vapor= Sf= 23.8 vol.%.

 Feed (F)= w/1-sf.

 = 100/(1-238).

 = 131.2 bbl/h/ 100 BBL OF LD.

 Therefore Feed F= 12X1.312=15.74 % OF CRUDE.

Heat into FZ, QFZ1= V’H+W’H.

Selection of Column Pressure

Pressure to be adequate that dew point (for the composition of top product) is more than cooling hot
water temperature around 45oc + ΔT(15oc)=60oc with cooling water inlet temperature of 33oc with
condensate temperature of 40o - 45o can be obtained eith consideration of 10o- 15o ΔT .The column
pressure to be adequate that bubbles point of the top product is 40o - 45o.

i.e

at column pressure and drum temp of 45o

or
 ΣPi calculated at 45oC for all the components.

ΣPi=ΣXiPi or ΣYiPt=ΣXiPi

For crude Distillation Column

The top product is a mixture of light end and top naptha(C5-140o).The naptha TBP is subdivided 10oC or
20 C cuts eg.70o-80o,80o-90o,90o-100oetc and midpoint are tabulated.
o

K values estimated from de-priester chart.

Table:2.10

Comp./cut range(TBP) B.P.T Ki 45oC,1.6 Kg/cm2g Xi Ki Xi

C1 B1 K1 X1 K1 X1

C2 B2 K2 X2 K2 X2

C3 B3 - - - -

C4 B4 - - - -

C5 B5 - - - -

70o-90o 80o - - - -

90o-110o 100o - - - -

110o-130o 115o - - - -

130o-150o 140o Kn Xn Kn Xn

Σni=1KiXi
 It ΣKiXi=1 then the pressure is OK.

If not 1 then repeat trial with another value of pressure till ΣKiXi is 1.

Same method is applied for discrete component and mixture of pure component and fixes the reflux
drum pressure.

Top Temperature Estimation

Top temperature is dew point of top vapor at column top pressure.Once reflux drum pressure is fixed
D(say)the column top pressure is estimated after adding the pressure drop across condenser/OH

line.Typically 0.3kg/cm2-0.5 kg/cm2 is taken as pressure drop.

Column top pressure = PD+0.5

Again calculation is performed at top pressure for determining the dew point.Assume a top temperature
and calculate.

Σyi/Ki till it becomes 1.

Calculation of Vapor/Liquid Profile

Fig:2.42 Calculation of Vapor/Liquid Profile[1,2,11]

This is done by performing material balance & heat balance in envelopes.

Atmospheric distillation unit

 Tower Dia :5- 8 m.

 No.of Plates : 25-40(depends on No. of draws).

 Maxm.Allowable pressure drop per plate :0.015 kg/cm2).

 Pressure drop from furnace outlet to Flash zone : 0.3 – 0.4 kg/cm2.

 Pressure at top of the tower : 1.2 -1.4 kg/cm2

  No.of plates required for separation.

 LN – HN (80-130 C): 6-8

 HN- LD (180C): 5-6

 LD- MD (250C): 4-6

 MD- GAS OIL(330 C): 3-4

 Flash zone to First draw tray: 3

 FZ TO BOTTOM : 3

 Reflux drum pressure: 1.1-1.15 kg/cm2 abs.

 Steam rate /bbl of crude: 4-5 kgs

 Reflux ratios : 2-3 (for light fractions)for Heavy fractions 1.5- 2.5.

Contacting Device

 Cross Flow

 Counter flow

Cross Flow

Fig:2.43 Cross Flow

Counter Flow :Packing,Heat transfer trays.

H dry -->dry tray pressure drop,inches.

H dry = C1+C2V 2/2gC

ΔP dry=K2(VH)2DV/DL-unit full open.

Tray Pressure Drop

HT= H dry+ How+ Hw

ΔPT = ΔP dry +0.4(gpm/lwi)2/3+0.4 HW

Pumparound Duties

 Pumaround duties need to be maximized for energy efficiency point of view.

 This is limited by Gap/Overlap specification between adjacent products and minimum internal
reflux specification.

 Pumparound duties are maximized and reflux ratio is brought close to 1.5 to 1.8.

Vacuum Column

(ΔT)Hy.Diesel PA :70oC-90oC

(ΔT)LVGO PA :50oC

(ΔT)HVGO PA :55oC

Stages in vacuum column:-

Top PA =1 stage.

Top Hy.Diesel-LVGO =2-3 stage.

LVGO PA =1 stage.
LVGO-HVGO =1 stage.

HVGO PA =2-3 stage.

Wash =2-3 stage.

Wash liquid at bottom of wash bed˜0.3M3/hr/M2column C.S area.

Thermodynamics - BK10/GSI.

Transport Property - PETRO.

Density - API.

Vacuum Distillation Unit[1,11]

 The primary objective of a vacuum distillation is to produce either feedstock for FCCU or HCU.
This type of vacuum distillation units are termed as Fuel Type Vacuum Unit.

 The other kind of vacuum distillation unit is a Lube Type Vacuum Unit and deployed for
production of fractions for Lube Oil Base stocks.

 In a Fuel Type Vacuum distillation Unit the VGO TBP cut point is controlled for Maximizing
profitability while containing the level of contaminants acceptable by downstream secondary
Units.

VACCUM DISTILLATION
Fig:2.44 VACCUM DISTILLATION[1,2]

Vacuum Distillation unit:cont

Fig:2.45 Vacuum Distillation unit[1,2]

Different Configuration of Vacuum Column

1. Dry (no stripping, no coil steam).

2. Wet (Precondenser limiting column overhead pressure to cooling water temperature

limitations).

3. Dump column without stripping (no precondenser, coil steam used to adjust flash zone oil
partial pressure).

4. Dump column with stripping steam (no precondenser, coil and stripping steam used).

Different Configuration of Vacuum Column

 The first one operates typically at 8-12 mm Hg (a) at top. The vapour directly goes to ejectors.

 The second type operates at 60-70 mm Hg (a) at top and have a precondenser, the non-
condensable are pulled by ejector.

 The third type of operation is done at 18-25 mm Hg (a) at top.

 Without stripping steam has a booster ejector followed by condenser.

  This fourth type again operates with a top pressure of 18-25 mm Hg (a) and uses stripping steam
and Coil steam both. This type is considered best to increase cut point of VGO limiting the
contaminants like V, Ni etc. in VGO with same number of stages in wash section as compared to
other configurations.

Furnaces

1.Introduction:

Furnaces are used throughout the industry to provide the heat, using the combustion of fuels. These
fuels are solid, liquid or gaseous. Furnaces consist essentially of an insulated, refractory lined chamber
containing tubes. Tubes carry the process fluid to be heated, and sizes are device for burning the fuel in air
to generate hot gases. A great variety of geometries and sizes are used, and much of the skill employed in
their design is based on experience. However, all furnaces have in common the general feature of heat
transfer from hot gas source to a cold sink, and in the past few decades theoretical models of increasing
complexity and power have been developed to aid the designer.[1,2,3]

2.Types of furnaces used in process plant[1-6]

An industrial furnace or direct fired heater is equipment used to provide heat for a process or can serve
as reactor which provides heats of reaction. Furnace designs vary as to its function, heating duty, type of
fuel and method of introducing combustion air. However, most process furnaces have some common
features. Fuel flows into the burner and is burnt with air provided from an air blower. There can be more
than one burner in a particular furnace which can be arranged in cells which heat a particular set of tubes.
Burners can also be floor mounted, wall mounted or roof mounted depending on design. The flames heat
up the tubes, which in turn heat the fluid inside in the first part of the furnace known as the radiant section
or firebox. In this chamber where combustion takes place, the heat is transferred mainly by radiation to
tubes around the fire in the chamber. The heating fluid passes through the tubes and is thus heated to the
desired temperature. The gases from the combustion are known as flue gas. After the flue gas leaves the
firebox, most furnace designs include a convection section where more heat is recovered before venting to
the atmosphere through the flue gas stack. (HTF=Heat Transfer Fluid. Industries commonly use their
furnaces to heat a secondary fluid with special additives like anti-rust and high heat transfer efficiency. This
heated fluid is then circulated round the whole plant to heat exchangers to be used wherever heat is
needed instead of directly heating the product line as the product or material may be volatile or prone to
cracking at the furnace temperature.)

The radiant section is where the tubes receive almost all its heat by radiation from the flame. In a
vertical, cylindrical furnace, the tubes are vertical. Tubes can be vertical or horizontal, placed along the
refractory wall, in the middle, etc., or arranged in cells. Studs are used to hold the insulation together and
on the wall of the furnace. The tubes are a distance away from the insulation so radiation can be reflected
to the back of the tubes to maintain a uniform tube wall temperature. Tube guides at the top, middle and
bottom hold the tubes in place. The convection section is located above the radiant section where it is
cooler to recover additional heat. Heat transfer takes place by convection, and the tubes are finned to
increase heat transfer. The first two tube rows in the bottom of the convection section and at the top of the
radiant section is an area of bare tubes (without fins) and are known as the shield section, so named
because they are still exposed to plenty of radiation from the firebox and they also act to shield the
convection section tubes, which are normally of less resistant material from the high temperatures in the
firebox. The area of the radiant section just before flue gas enters the shield section and into the
convection section called the bridge zone. Crossover is the term used to describe the tube that connects
from the convection section outlet to the radiant section inlet. The crossover piping is normally located
outside so that the temperature can be monitored and the efficiency of the convection section can be
calculated.

In petrochemical industries, furnaces are used to heat petroleum feedstock for fractionation, thermal
cracking, and high-temperature processing. Usually, these furnaces are fired by oil or gas. They have to be
designed to ensure that the fluid receives the correct amount of heat and has sufficient residence time
within hot zone. While at the same time excess temperatures have been avoided. These excess
temperatures lead to degeneration of the product or damage to the furnace. The balance is achieved by
appropriate disposition of the tubes carrying the fluid within the furnace, and careful control of firing rate
and fluid flow Calculations are required to determine the fuel consumption and the maximum
temperatures of the tube and walls. Tube temperatures in some plant may be as high as 900 °C, and
combinations of high pressure (e.g., 200 atm) and relatively high temperatures (e.g., 450 °C) are not
uncommon. Process heaters come in many shapes and sizes; Figures 3.1, 3.2 and 3.3 show typical
arrangements.Fig.3.1 is a vertical cylindrical process heater with a band of vertical tubes in the radiation
zone and a bank of horizontal tubes at the outlet that receive heat mainly by convection. The latter may
have fins attached to enhance heat transfer, except for the base of the furnace and the flames are vertically
oriented. Typical heat transfer rates for the vertical tubes in the radiation zone are about 50 kW/m2, and
the total heat rating is usually in the range 3 to 60 MW.
 Fig.3.2[1]shows an alternative arrangement, where the tubes are horizontal and cover not only the
vertical walls but also the sloping roof of the “cabin”. Units of this type are used for a similar range of duty
as is the aforementioned vertical cylinder. Fig.3.3[1] shows the more unusual design for smaller heat loads,
where a single central wall of horizontal tubes is heated on both sides by two sets of burners set in the
base.

3.Furnace heat transfer[1-8]

A fuel-fired furnace consists of a gaseous heat source, a heat sink, and a refractory enclosure, as
illustrated diagrammatically in Fig.3.4.[1] Heat is transferred to the heat sink by radiation and convection
from the hot gases and by reradiation from the refractory walls. In developing any model of the process, it
is necessary to consider two heat transfer phenomena:

 The heat emission from hot gases containing combustion products, i.e. the heat source.
  The heat absorbed by the tubes, taking into account their geometrical configuration and
material properties (the heat sink), composed of primary heat transfer from hot gases and
secondary heat exchange with the refractory walls.

3.1.Furnace heat balance

Heat is released in a fuel-fired furnace as a result of combustion, and the rate of heat generation, Qf, is
equal to the rate of combustion of fuel, Mf, multiplied by its lower calorific value, Δhf:

Qf = Mf Δhf...............................(1)

The heat generated by the combustion process appears initially as sensible heat in the steam of hot
gases, consisting of combustion products and excess air, passing through the furnace at a rate Mg. Part of
this heat is transferred to the heat sink at a rate Qg, part is lost through the furnace walls at a rate Ql, and
the remainder is carried out of the furnace through the exhaust stack as the sensible heat of the partially
cooled combustion products at a rate Qp. As illustrated in Fig. 3.5[1] the heat balance for this process may be
expressed as:

Qf = Qg + Ql +Qp...............................(2)

If there were no heat sink and no losses, all the heat released by combustion would go into heating the
gases produced, which would then attain a temperature, Tf, known as the adiabatic flame temperature. The
adiabatic flame temperature is, therefore given by:

Qf = Mgcpg (Tf-To)...............................(3)

Where To is the air inlet temperature and cpgis an appropriate average value of the gas specific heat for
the range To to Tf.

In a real furnace the gases do not attain the adiabatic flame temperature, due to the heat sink and wall
losses. For example, neglecting losses but allowing for heat removal by the sink at a rate of Qg), the
theoretical gas temperature, Tg) is given by

Qf -Qg=Mgcpg Tg-To...............................(4)

Hence, combining equations (3) and (4)

This equation shows how the gas temperature, Tg is related to the rate of heat transfer of the sink, Qg, by
heat balance. However, Qg is also related to Tg by the heat transfer characteristics of the hot gas and of the
sink. A solution of the problem requires a combination of these two sets of equations.
 3.2 Hot gases as heat source

The chemical composition of the gases produced by the combustion of hydrocarbons depends upon the
choice of fuel and the amount of excess air employed above the stoichiometric requirements. In practice,
excess air is required to ensure complete combustion; typical values are 10% for gaseous fuels, 15 to 20%
for liquid fuels, and 20% for pulverized fuel, although lower percentages can be achieved with efficient
burners.

As we know, gaseous combustion products radiate heat when raised to temperatures above their
surroundings. When solid particles are present in the furnace gas stream they become incandescent,
radiating both heat and light, so producing a glowing or luminous flame. Gaseous fuels burn with a
nonluminous flame, but liquid and solid fuels produce luminous flames due to the presence of particles of
carbonaceous material. For example, soot or coke resulting from the incomplete combustion of the
hydrocarbons and mineral matter originally in the fuel. In general, solid fuel produces a more luminous
flame than does liquid fuel.

Carbon dioxide and water vapor are the main sources of radiation for nonluminous flames, and the total
emissivity εg of a volume of combustion gases is dependent upon the temperature Tg and product of partial
pressure and effective path length PL . The total absorptivity of a gas also depends upon its temperature
and partial pressure path length product, but in addition upon the temperature Ts of the source of the
radiation that is being absorbed.[1,9,10]

3.3 Heat Sink

The rate at which heat is transferred by radiation from the hot gases to sink depends not only upon the
emissivity of the gas and emissivity of the sink surface, but also upon the relative size of the sink. This is
because the unconverted refractory lining radiates back into the furnace heat that it has received from the
flame, and some of this is absorbed by the heat sink.

This compound effect is illustrated in Fig. 3.6, where two extreme cases are shown. The diagram on the
left represents the case in which the sink area is very small, and that on the right represents the case in
which the sink is very large and completely covers the furnace walls.

In the case of refractory surface, assuming no heat loses, is in equilibrium with the gases and reradiates
all the heat falling upon it. The total radiation flux within the enclosure is equal to that emitted by a
blackbody at temperature Tg . Under these circumstances the heat flux to the sink is independent of the gas
emissivity, depending only on the emissivity of the sink itself. The rate of heat transfer to a very small sink
at temperature T1 is therefore

QgA1-->0 = A1ε1σ(Tg4-T14)....................(6)

In the second case,where the sink covers the whole of the interior of the furnace, the situation is
analogous to the exchange between two parallel party reflecting surfaces. It was already known that the
rate of heat transfer is given by

Intermediate situations can be estimated by using the equation for the simple case when the sink and
the refractory are intimately mixed (Hottel and Sarofim, 1967). This is called the speckled surface equation
and is quite adequate for preliminary estimates of furnace performance. It gives
 Where C is the ratio of the sink area to the total area, i.e. A1/At.

Fig. 3.6 shows an example of the way of the effective emissivity (the term in the curly braces in Equation
8) varies with C. The example assumes a gas emissivity is close to that of the gas, εg of 0.3 and a sink
emissivity, ε1 , 0f 0.85, the latter being typical of tube surfaces. For large values of C the effective emissivity
is close to that of gas, εg , and is intensive to the value of the sink emissivity, ε1 . For this reason the
emissivity of tube surfaces in the fire tube boilers, where the sink entirely encloses the hot gas stream, may
often be taken as unity for calculation purposes.

Fig:3.6[1]
 Fig. 3.6 Effect of heat sink area on effective emissivity. (a) small heat sink area; (b) large heat sink area;
(c) blackbody analogous to (d) exchange between reflecting surfaces;

Fig:3.7

Fig (3.7) an example(εg, ε1) speckled surface equation.[1]

εc=(1/(1/ε1+C(1/ εg)-1)),C=A1/At

3.4 Effect of tube geometry on the heat sink characteristics

So far the heat sink has been treated as a plain surface. In practice, however, it consists of one or more
banks of tubes usually mounted close to the refractory wall, as shown diagrammatically in Fig.
3.7. Normally there is a space between the tubes and consequently some of the radiation from the hot
gases is not intercepted and impinges on the refractory wall behind the tubes. Most of this heat is
reradiated and part contributes to the heat flow to the sink. This is a complex situation and complete
formal analysis is very difficult. Because of mutual shielding effects of adjacent tubes, the radiation heat flux
varies circumferentially around the tubes, as shown diagrammatically in Fig. 3.8.[1] The surface of the tube
facing inward (position 1 in the figure) receives maximum heat flux because it is subject to radiation from a
total angle of 180°. Point 2 receives radiation from a smaller angle and point 3 only from a very narrow
beam; beyond this point there is an area of the tube that receives no direct radiation from the hot gases.
There is, of course, an additional component of heat flux, mainly on the back of the tubes, due to
reradiation, but this is much smaller in magnitude.

The ratio of peak to mean heat flux is a function of tube pitch to diameter ratio, B, as shown
in Fig.3.9[1] for three typically configurations. This factor is important in assessing the permissible heat
rating of a furnace, because it is the peak heat flux, which is usually the limiting factor. A simplification of
this complex situation was proposed by Hottel in which the heat sink is defined as an equivalent plain
surface having an area equal to that covered by the tubes, as shown in Fig. 3.10, and an effective emissivity,
eeff, which would give the same radiative heat transfer as the tube bank.

The first step in calculating the equivalent emissivity of the plain surface is to determine the fraction, F,
of radiation intercepted by the tubes. The equation for F is based on optical path geometry, namely,

F = 1-(1/B){(B2-1)1/2-cos-1(1/B)}..............(9)

This function is plotted in Fig.3.11[1] for a single and a double row of tubes.

The interception factor, F,can then be used in calculating the effective emissivity of the tube bank,
including radiation from an adiabatic refractory backing,as:
 εeff= 1/{(1/F(2-F)) + ((B/π)(1/ε1-1))}..................(10)

Effective emissivity based on this equation is plotted in Fig. 3.12[1] as a function of tube pitch to diameter
ratio for a tube material emissivity of 0.85. It is clear from the form of the equation and the shape of the
curve that tube spacing has a very powerful effect. This is partly due to the fact that the actual tube surface
area per unit of total projected area, A, is proportional to 1/B, a fact reflected in the reduction in the
fraction, F, of radiation intercepted, which plays a predominant role in determining eeff. The foregoing
equations apply to true banks adjacent to the refractory wall. A similar approach can be made to the case
of a centrally mounted tube bank, but here a different form of equivalent plain area has to be used.
Procedures for this type of furnace geometry are outlined in the Heat Exchanger Design Handbook
(Truelove, 1983).
 4. Furnace models

The full mathematical description of practical furnaces is exceedingly complex, combining aerodynamics,
chemical reactions, and heat transfer, and computer programs are necessary for detailed solutions.
Advanced methods of calculation may be divided into zone methods and flux methods.

Zone methods are employed when the heat release pattern from the flame is known. They start by
dividing the furnace and its walls into discrete zones. The effective exchange areas between zones are
determined, and the radiative heat transfer corresponding to the prescribed heat release pattern is
calculated. In flux methods, instead of dividing the space into zones the radiation arriving at a point in the
system is itself divided into a number of characteristic directions, representing averages over a specified
solid angle. Flux methods are well suited for use in combination with modern methods of prediction of fluid
flow and mixing pattern. Simultaneous solutions of the radiative heat transfer equations using flux methods
and turbulent flow models are feasible.

4.1 “Well Stirred” furnace model[1-16]

This is the simplest approach to the assessment of furnace performance. One of the first versions is the
method of Lobo and Evans (Lobo and Evans, 1939), which was used in Process Heat Transfer (Kern, 1986).
Subsequently an improved version, expressed in nondimensional terms, which made the calculations
easier, was presented in the book Radiative Heat Transfer (Hottel and Sarofim, 1967). These authors also
introduced additional terms to allow for incomplete mixing and wall losses. Their model, later reviewed by
Hottel (1974), still forms the basis of most simple calculation procedures (e.g., Truelove, 1983).

The furnace is modeled in three zones as shown, Fig.3.13[1] namely, the central hot gas zone, the heat
sink, and the refractory walls. The combustion region and the space occupied by hot products of
combustion are lumped together in the central hot gas zone (hence the alternative title “lumped model”),
which transfers heat by radiation to the heat sink, here shown diagrammatically as a tube bank, and to the
refractory walls containing the furnace.

The following simplifying assumptions are made:

 The hot gases are perfectly mixed and at a uniform temperature, Tg.

 The heat sink is gray and has a uniform temperature, T1.

 The refractory surface is radiatively adiabatic, that is to say it radiates all the heat that is
receives.

The “well stirred” furnace model is based on a combination of the balance equation for the furnace
(Equation 5), namely.

(Qf-Qg)/Qf=(Tg-To)/(Tf-To)..................................(11)

And the expression for heat transfer to the sink based on the“specked surface” model (Equation
8),namely.

Qf= A1{1/((1/εeff) + C(1/εg-1))} σ (Tg4-T14)=gr σ (Tg4-T14).....................(12)

Where, gr, the total heat transfer factor for radiation from gas to sink, is

gr= A1/{1/eeff+C(1/εg-1)}....................................(13)
 Note that εeff(Equation 10) has replaced ε1, because the model is using
the projected area, A1, of the tube bank as illustrated in Fig. 3.10.

If the furnace contains a convectively heated section, the total heat transfer factor can be modified to
introduce both radiation and convection,as

Qg =gr σ(Tg4-T14) +αAc(Tg-T1)................................(14)

Where,gr = total heat transfer factor for radiation from the gas to the sink, including reradiation from
the refractory walls and multiple reflection.

α= convective heat transfer coefficient from the gas to the sink.

Ac = area of the sink subject to convective heat transfer.

Because the convective component is usually small compared with that of radiation it may be submitted
in the gr,term as follows.Let

αAc (Tg-T1)= (αAc/4σT3g1)σ(T4g-T41)..........................(15)

where

Tg1≈(Tg+T1)/2........................................................(16)

Then

Qg=grc σ(Tg4-T14).....................................................(17)

where

grc=gr+(α Ac/4σT3g1).................................................(18)
 Fig. 13 Simple well stirred Furnace model

Equations (11) and (17) can be combined to give

(Qg/σ grc)+T41=T4f{1-(Qg(Tf-To)/QfTf}4...........................(19)

It is convenient to apply this expression in a nondimensional form

involving the terms:

Q,g =Qg(Tf-To)/QfTf =reduced furnace density ..................(20)

D, =Qf/σ grc3f(Tf-To) =reduced firing density......................(21)

T,1 =T1Tf =reduced sink temperature................................(22)

Equation (19) then reduced to

Q,gD,+(T,1)4) =(1-Q,g)4...................................................(23)

Coking and Thermal process, Delayed coking

Coking and Thermal Process, Delayed Coking

Fig:4.1 Simplified Refinery Flow Diagram [1,2]

 Treatment processes : To prepare hydrocarbon streams for additional processing

and to prepare finished products.

 Treatment: It include the removal or separation of aromatics and naphthenes as

well as impurities and undesirable contaminants.

 Treatment involve:chemical or physical separation such as dissolving, absorption,or

precipitation using a variety and combination of processes including
desalting,drying,hydrodesulfurizing,solvent refining,sweetening,solvent extraction,
and solvent dewaxing.
 Fig:4.2 Thermal Processes [2,6]

Delayed Coking

Using time and high temperature one can break large asphalt molecules into gasoline and
diesel.Petroleum coke is a solid by product and is blended with coal to use as a solid fuel in
power plants.[5,8]

Fig:4.3
 Cracking

Dissociation of high molecular weight hydrocarbon into a smaller fragments through agency
of heat alone is termed as thermal cracking or pyrolysis.

Can also be done in presence of catalyst.

CnH2n+2 Cn/2Hn+2 + Cn/2Hn (T= 400o C)

12 C6 + C6
6 C4 + C2 /C3 + C3

Cracking proceeds via free radical mechanism.

RCH2.CH3 RCH2 + CH3

Unsaturated (olefins) obtained in the process crack again.[3,6]

 C4H8 C2H6 + H2/C2H4 + CH4 + C

 C4H8 CH4 + C3H4 (diolefins / alkynes)

 C2H4C3H4 C + H2

Olefins cracks on dehydrogenation to diolefin or an alkyne.[1,2,6]

 Hydrogenation also occur but to less extent.

 C3H4 + H2 C3H6

Saturates are converted to unsaturates:

Ring opens in the extreme conditions of cracking

Chemistry of Catalytic Cracking[1-2,6-8]

Paraffins Paraffins + Olefins

 Thermal cracking operation[1,2]

Tab:4.1

Cracking temperature
Nature of operation Products
(C)

425-460 Visbreaking Fuel oil

Gas, gasoline, Tar oils, circulating

460-520 Thermal cracking
oils

520-600 Low temperature coking Gas, asoline , soft coke

800-1000 High temperature Gas , heavy aromatics

Above 1000 decomposition H2, gas, carbon black

Thermal cracking[1,2,6-8]

Properties of cracked materials

Product properties are extensively dependent on the conditions of cracking.The properties

that undergo changes during cracking are:

a) Characterisation factor (decreases due to high aromatic content)

b) Boiling point , viscosity, pour point decreases.
c) Unsaturation and Aromatisation increases.
d) Octane number of gasoline increases.
e) Sulphur content in the cracked product increases as the rule although the maximum amount
in heavier portion only.

Cracking[1,2,6-8]

It is a endothermic process , so external heat is required.

 Main parameters affecting cracking:

 Pressure

 Temperature

 and time of cracking.

Pressure has no direct effect on velocity of the reaction. If more gases to be produced then
low pressures are desirable.

 With higher pressures gas to gasoline ratio becomes less.

 Reaction velocity is directly dependent upon temperature .

Fig:4.4

Visbreaking[1,2,8]

 Reduction in viscosity is Visbreaking.

  Materials like residuums are not of direct utility or stocks decided with difficulties
due to high pour point , from palapable feed stock for this operation.

 Liquid products may be used as cycle stocks for crackers commercially valuable
main products know as fuel oil.

 Light fraction gas and gasoline.

Basic parameters:

Cracking temperature and residence time Soaker type (more gas) or coil type
visbreaker(more gasoline due to for short residence time)

High temperature soaker visbreaking[1,2,9-12]

Soaker drum : Large vessel designed to allow for a long residence time for the feedstock.
Cracking in the furnace is minimised by using high liquid velocity and steam injection.

With increase in T and cracking time : light fraction increase => fuel oil yield decrease.

High conversion soaker visbreaking

 Gives higher conversion and more stable residue compare to conventional soaker
visbreaking.

 Feed stocks : Heavy crude oil, oil shale, long and short residue, visbroken residue.
Fig:4.5

Operating conditions and products:[1,2,9-16]

 Increase in cracking time and temperature increases the lighter fraction and
decreases the fuel oil yield.

 Pressure has negligible effect on velocity of reaction. At high pr. gas / gasoline ratio
is less.

 Pressure retards cracking reactions

 Fig:4.6

Visbreaking Operation[1,2]

Feed stock: Asphalt, Short residuum to residuums,and medium oil

Steps:

1) Preheating of feed upto 250oC

2) Heating in furnace up to 470o C.
3) Pressure 10-15 kg/cm2 necessary to avoid coke formation.
Steam admission in to feed stocks also checks coke formation.
4) Fraction (Light and heavy) from quencher goes to distillation column.

Theory of cracking:
 Thermal cracking proceeds via free radical machanism.[1,2,8-17]

Free radicals : atom or group of atom with bare unpaired electron.

RCH2CH3 RCH2O + CH3O

Unpaired electrons are very active and try to form stable compound by acquiring unpaired
electrons from sources available.
HC (charged) ions are usually referred as carbonium ions.

 Paraffins rate of reaction increases with increase in carbon number.

 olefins cracks much faster compared to paraffins.

Chemistry of catalytic cracking[1,2,3-14]

Large molecules smaller Fragments with double bond

Hydrogen demand net through creation of double bond by means of :

 Hydrogen Transfer

 Cyclization

 Aromatization

Effect of pressure on cracking:

Pressure retards cracking reactions. But in practice a positive pressure of 10 to 15

Kgs/cm2 is used to minimize coke formation.Recycling increases refractory nature of stocks and
 hence recycling should not exceed 2 to 3 times of fresh stock for economic operation.

Catalytic Cracking[3-16]

 Catalytic Cracking is the most widely used refinery process for converting heavy oil
into gasoline of high octane value.

 Catalyst Cracking is distinguished from Thermal Cracking in the reaction mechanism

Which is called carbonium- ion mechanism.

 Carbonium ion mechanism gives more stable saturated compounds.

Protonation of an olefins:[1,2,5-13]

RCH:CH2 + H+ RCH+.CH3 / RCH2CH2+

Bronsted Acid

Catalytic cracking, Cracking reactions, Zeolite catalysts

Catalytic Cracking Reactions:

H vary depending upon the compound:

 Cracking:(+ve) endothermic

 H-Transfer:(-ve) Exothermic

 Isomerization mildly:Exothermic

 Cyclization :(-ve) Exothermic

 Cyclization :Dealkalization :(+ve)

 Catalytic cracking, Main Catalysts: Acidic catalysts.[1,2,6-18]

Fig:4.7 The typical sketch and relationship between the Acid strength of different catalyst versus
different reaction carried out for different hydrocarbon products.

Addition of Lewis Acid:

 RCH:CH2 + BF3 / AlCl3 / FeCl3 RCHF.CH2+ + BF2-

 Life time of a Carbonium ion may vary from a fraction of second to minutes.

 Tertiary Carbonium ion is stablest one followed by secondery and primary Carbonium ion.

 When protonation takes place, a Carbonium Ion may result.

Paraffin Reactivity:
 Rate of reaction increases with carbon number but rate of coke formation also increases with (carbon
number) molecular weight characterized by high production of C3 and C4 in the cracked gas.

Olefin Reactivity:

These cracks at a much faster rate compared to paraffins and subject to rapid isomerization.

Naphthene Reactivity:

They cracks at a faster rate compared to corrsponding paraffins.

Aromatics:

Alkyl Aromatics

Stability of the ring:

So ring does not crack because of alkyl group. But removal of alkyl group is easy and it is again by ß-
scission.

Cracking reactions:[1,2,9-20]
Alkyl Naphthene Naphthene + Olefin

Alkyl Aromatic Aromatic + Olefin

N-Octane cracking, C8H18 (where R= CH3CH2CH2CH2CH2----)

Step1: mild thermal cracking initiation reaction.

nC8H18 CH4 + RCH=CH2

Step2: Proton shift

Step3:

Step4: Rearrangement towards more stable structure

stability tertiary > secondary > primary

Step5: Hydrogen ion transfer

Cracking Catalyst
Acidic catalyst : which can supply proton.

 Acid treated natural alumino silicates.

 Amorphous synthetic silica-alumina catalyst.

 Crystalline (aluminosilicates) synthetic. Silica alumina ctalyst zeolite or moleculor sieve.

 Zeolites have more active sites and adsorption capacity which helps in faster cracking rate.

Advantages of zeolite catalyst:[1,2,8-20]

1. Zeolite has tremendous advantages over amorphous silica-alumina.

2. Higher activity: factor of 100 higher than amorphous silica-alumina catalyst.

3. Higher gasoline yield at a given conversion however octane number of gasoline obtained from
zeolite cracking is lower by 2-3 numbers compared to amorphous catalyst.

4. Production of gasoline containing a large number of paraffin and aromatic hydrocarbons.

Tab:4.2

Paraffin Aromatics Naphthenes Olefins

Amorphous 38 10 0.45 10

Zeolite 45 20 0.15 20

Olefins are lower & paraffins and aromatics are higher. This is because of superior Transfer
facility of zeolites.

 O+N P+A

 O P+A

 Cyclo-olefins N+A
 Gasoline yield is higher with zeolite. This is because of:

 C16 C16+

 C16+ C16+ + C3

5. Lower coke yield.

6. Increased iso- butane production.( this is again because of H- Transfer)

7. Increased iso- butane production.( this is again because of H- Transfer)

8. Lower dry gas yield.( C1-C4 HC’s) [more gasoline, less coke and less gas yield are its main
advantages.]

Characteristics

 Residence time ~ 1 -4 sec.

 Zeolite – Y : generally used as a cracking catalyst.

 Faujasite: naturally occuring crystalline alumino-silicates.

 Zeolite –Y : synthetic form of Faujasite.

 Composition: 0.9 ± 0.2 Na2O . Al2O3.wSiO2.xH2O (sodium form of zeolite.)

3<w<6 ,x<9
but Na is poison to cracking reaction. So it must be in ion form. So converted to acidic form.

 Cation exchange with a medium containing rare earth cation ( cesium, lanthanum etc.)

Catalytic Cracking processes

 Fixed bed , Houdry

 Moving bed- Air lift- Thermofer catalytic cracking

 Fludised bed:

 FCC , UOP, Texaco

  Kellog (Orthoflow)

 Fexi cracking

Cracking Feedstocks and reactors, Effect of process variables

REFINING[1,2,12]

 Process to produce useful fuels from crude oil.

 Separation, Conversion, Treatment and Blending.

 Primary processes- fractionation

 Secondary Processes-conversion processes

 improve the product quality.

 upgrade heavier ends to lighter products.

 Predominantly catalytic processes.

Fig:4.8 A typical sketch of refinery operations integrated with its profit margin, product pattern
shift, with deteriorating crude quality and stringent emission control parameters.

 Crack carbon-carbon bonds in gas oils.

 Fine catalyst in fluidized bed reactor allows for immediate regeneration.

  Lowers average molecular weight and produces high yields of fuel products.

 Produces olefins.

 Attractive feed characteristics.

 Small concentrations of contaminants Poison the catalyst.

 Small concentrations of heavy aromatics Crack and deposit coke on catalyst.

 Products may be further processed.

 Further hydrocracked.

 Alkylated to improve gasoline antiknock.

 Early Fixed and Moving Bed Catalytic Cracking.

 Cyclic fixed bed catalytic cracking commercialized in late 1930s.

 Houdry Process Corporation formed in 1930.

 First Houdry catalyst cracker started up at Sun Oil’s Paulsboro, New Jersey,
refinery in June 1936.

 Three fixed bed reactors and processed 2,000 barrels/day 12,000 barrels/day
commercial unit went on stream at Sun’s Marcus Hook Refinery in 1937.

 Other adoptees: Gulf, Sinclair, Standard Oil of Ohio, and The Texas Company.

 Sun & Houdry Process Corporation started development on a moving bed process in
1936.

 Pilot Thermofor catalytic cracker was started in 1941.

 First commercial 20,000-barrel/day unit commissioned at Magnolia’s Beaumont

Refinery in 1943.

Catalytic cracking[1,2,12]

 The process flows of both types of processes are similar. The hot oil feed is contacted
with the catalyst in either the feed riser line or the reactor.

 As the cracking reaction progresses, the catalyst is progressively deactivated by the

formation of coke on the surface of the catalyst.

 The catalyst and hydrocarbon vapors are separated mechanically, and oil remaining on
the catalyst is removed by steam stripping before the catalyst enters the regenerator.

 The oil vapors are taken overhead to a fractionation tower for separation into streams
 having the desired boiling ranges.

 The spent catalyst flows into the regenerator and is reactivated by burning off the coke
deposits with air. Regenerator temperatures are carefully controlled to prevent catalyst
deactivation by overheating and to provide the desired amount of carbon burn-off.

 This is done by controlling the air flow to give a desired CO2/CO ratio in the exit flue
gases or the desired temperature in the regenerator.

 The flue gas and catalyst are separated by cyclone separators and electrostatic
precipitators.

 The catalyst in some units is steam-stripped as it leaves the regenerator to remove

adsorbed oxygen before the catalyst is contacted with the oil feed.

FLUIDIZED-BED CATALYTIC CRACKING [1,2,12]

The FCC process employs a catalyst in the form of very fine particles [average particle size about
70 micrometers (microns)] which behave as a fluid when aerated with a vapor.The fluidized catalyst
is circulated continuously between the reaction zone and the regeneration zone and acts as a
vehicle to transfer heat from the regenerator to the oil feed and reactor.

 Two basic types of FCC units in use today are:

 side-by-side type,where the reactor and regenerator are separate vessels adjacent to
each other,and the Orthoflow, or stacked type, where the reactor is mounted on top of
the regenerator.

One of the most important process differences in FCC units relates to the location and control of
the cracking reaction. Until about 1965, most units were designed with a discrete dense-phase
fluidized-catalyst in the reactor vessel.The units were operated so most of the cracking occurred in
the reactor bed

The extent of cracking was controlled by varying reactor bed depth (time) and temperature.
Although it was recognized that cracking occurred in the riser feeding the reactor because the
catalyst activity and temperature were at their highest there, no significant attempt was made to
regulate the reaction by controlling riser conditions.After the more reactive zeolite catalysts were
adopted by refineries, the amount of cracking occurring in the riser (or transfer line) increased to
levels requiring operational changes in existing units.

The fresh feed and recycle streams are preheated by heat exchangers or a furnace and enter the
unit at the base of the feed riser where they are mixed with the hot regenerated catalyst.The heat
from the catalyst vaporizes the feed and brings it up to the desired reaction temperature. The
mixture of catalyst and hydrocarbon vapor travels up the riser into the reactors. The cracking
reactions start when the feed contacts the hot catalyst in the riser and continues until the oil vapors
are separated from the catalyst in the reactor. The hydrocarbon vapors are sent to the synthetic
crude fractionator for separation into liquid and gaseous products.

The catalyst leaving the reactor is called spent catalyst and contains hydrocarbons adsorbed on
its internal and external surfaces as well as the coke deposited by the cracking. Some of the
adsorbed hydrocarbons are removed by steam stripping before the catalyst enters the regenerator.
In the regenerator, coke is burned from the catalyst with air.

The regenerator temperature and coke burnoff are controlled by varying the air flow rate. The
heat of combustion raises the catalyst temperature to 1150 to 1550oF (620oC–845oC) and most of
this heat is transferred by the catalyst to the oil feed in the feed riser. The regenerated catalyst
contains from 0.01 to 0.4 wt% residual coke depending upon the type of combustion (burning to CO
or CO2) in the regenerator.

The regenerator can be designed and operated to burn the coke on the catalyst to either a
mixture of carbon monoxide and carbon dioxide or completely to carbon dioxide.Older units were
designed to burn to carbon monoxide to minimize blower capital and operating costs because only
about half as much air had to be compressed to burn to carbon monoxide rather than to carbon
dioxide.Newer units are designed and operated to burn the coke to carbon dioxide in the
regenerator because they can burn to a much lower residual carbon level on the regenerated
catalyst. This gives a more reactive and selective catalyst in the riser and a better product
distribution results at the same equilibrium catalyst activity and conversion level.

For units burning to carbon monoxide, the flue gas leaving the regenerator contains a large
quantity of carbon monoxide which is burned to carbon dioxide in a CO furnace (waste heat boiler)
to recover the available fuel energy.The hot gases can be used to generate steam or to power
expansion turbines to compress the regeneration air and to generate electric power.
Fig:4.9 Older fluid catalytic-cracking (FCC) unit configurations [1,2]
 Fig:4.10 UOP reduced crude cracking(RCC)[1,2]

NEW DESIGNS FOR FLUIDIZED-BED CATALYTIC CRACKING UNITS [1,2,12]

Zeolite catalysts have a much higher cracking activity than amorphous catalysts, and shorter
reaction times are required to prevent overcracking of gasoline to gas and coke. This has resulted in
units which have a catalyst-oil separator in place of the fluidized-bed reactor to achieve maximum
gasoline yields at a given conversion level. Many of the newer units are designed to incorporate up
to 25% reduced crude in the FCC unit feed. Schematic drawings of Exxon Research and Engineering’s
FLEXI CRACKING IIIR design.
 These units incorporate a high height-to-diameter ratio lower regenerator section for more
efficient single-stage regeneration and an offset side-by-side or stacked vessel design. UOP-designed
units utilize high velocity, low inventory regenerators, and Kellogg-designed units use plug valves to
minimize erosion by catalyst containing streams . All units are now designed for both complete
combustion to CO2 and CO combustion control.

The large differential value between residual fuel and other catalytic cracking feed stocks has
caused refiners to blend atmospheric and vacuum tower bottoms into the FCC feed. Residual feed
stocks have orders of magnitude higher metals contents (especially nickel and vanadium) and
greater coke forming potential(Ramsbottom and Conradson carbon values) than distillate feeds.
These contaminants reduce catalyst activity, promote coke and hydrogen formation, and decrease
gasoline yield. It has been shown that catalyst activity loss due to metals is caused primarily by
vanadium deposition, and increased coke and hydrogen formation is due to nickel deposited on the
catalyst.

The high coke laydown creates problems because of the increase in coke burning requirement
with the resulting increased air or oxygen demand, higher regenerator temperatures, and greater
heat removal. For feeds containing up to 15 ppm Ni V, passivation of nickel catalyst activity can be
achieved by the addition of organic antimony compounds to the feed with reductions in coke and
hydrogen yields up to 15% and 45%, respectively. For feeds containing 15 ppm metals and having
Conradson carbon contents above 3%, hydroprocessing of the FCC feed may be required to remove
metals, reduce the carbon forming potential, and to increase the yield of gasoline and middle
distillates by increasing the hydrogen content of the feed.

Feeds for Catalytic Cracking[1,2,12]

 Aromatic rings typically condense to coke

 No hydrogen added to reduce coke formation.

 Amount of coke formed correlates to carbon residue of feed normally 3-7 wt%
CCR.

 Catalysts sensitive to heteroatom poisoning

 Sulfur and metals (nickel, vanadium, and iron).

 Feeds normally hydrotreated.

  Atmospheric and vacuum gas oils are primary feeds

 Could be routed to the hydrocracker for diesel production Not as expensive a

process as hydrocracking.

 Dictated by capacities of gasoline/diesel economics.

Fig:4.11 FCC Products[1,2]

Fig:4.12 FCC unit with coke productions during cracking reactions [1,2]
Fig:4.13 FCC regeneration unit[1,2]

PRODUCT YIELDS

 Produces high yields of liquids small amounts of gas coke Mass liquid yields are usually
90%-93%; liquid volume yields that are often more than 100%(Rule of thumb) Remaining
mass yield split between gas and coke.

 The yield pattern is determined by complex interaction of feed characteristics and

reactor conditions that determine severity of operation.
  Conversion defined as relative to what remains in the original feedstock boiling range of
Conversion =100%-(Gas Oil Yield).

Catalytic Cracking Catalysis & Chemistry [1,2,8-19]

 Zeolite catalysts

 High activity.

 Good fluidization properties.

 High gasoline and low coke yields.

 Acid site catalyzed cracking and hydrogen transfer via carbonium mechanism.

 Basic reaction —carbon-carbon scission of paraffins, cycloparaffins aromatics to

form olefins lower molecular weight paraffins.

 Olefins exhibit carbon-carbon scission and isomerization with alkyl paraffins to

form branched paraffins.

 Cycloparaffins will dehydrogenate (condense) to form aromatics.

 Small amount of aromatics and olefins will condense to ultimately form coke.

 Research continues by catalyst suppliers and licensors

 Recognition that both crackability of feed and severity of operations are factors.

 Theoretical basis for cracking reactions lead to more precise catalyst formulation.

 Catalyst can be tailored to maximize gasoline yield or increase olefin production.

CATALYTIC CRACKING[1,2,12]
Fig:4.14 Catalytic Cracking[1,2]
 Fig:4.15 Exxon FLEXCRACKING IIIR FCC unit(courtesy of Exxon Research and Engineering)

FCC Cracking, Catalyst coking and regeneration, Design concepts, New Designs for Fluidized-Bed
Catalytic Cracking Units

FCC Cracking, Catalyst coking and regeneration, Design concepts, New Designs for Fluidized-Bed
Catalytic Cracking Units

 Refining Process and Catalysts.[1,2,21,22]

 Fluid Cracking Catalyst (FCC).

 FCC additives.

 Reforming Catalyst.

 Catalyst Characterization.
  R & D & Commercialization Status in India.

 Conclusion.

FCC SCENARIO IN INDIA

 FCC Units in Operation :15

 Total FCC Capacity ~ 26 MMTPA

 Future FCC Capacity ~ 42 MMTPA

FCC PROCESS

Fig:4.16 FCC PROCESS

FCC RISER/REGENARATOR COMBINATION

Fig:4.17 FCC/RISER/REGENARATOR COMBINATION

KELLOG DESIGN RISER UNIT

Fig:4.18 KELLOG DESIGN RISER UNIT[1,2]

KELLOG RESID FLUID CATALYTIC CRACKING(RFCC)

Fig:4.19 KELLOG RESID FLUID CATALYTIC CRACKING(RFCC) [1,2]

ZEOLITE STRUCTURE[23]
Fig:4.20 Zeolite Structure

FCC: Some Interesting Facts

 Nearly 20% of crude is being processed at FCC.

 Larger FCC units holds about 400 Tonnes of catalyst.

 Four major manufactures (Grace Davision, Engelhard, Akzo Nobel, CCIC)supply 1400 tons of
catalyst daily to process 12 million barrels per day (600 MMT/day).

 400 FCC units in world.

PROCESS VARIABLES
 In addition to the nature of the charge stock, the major operating variables effecting the conversion and
product distribution are the cracking temperature,catalyst/oil ratio, space velocity,catalyst type and
activity, and recycle ratio. For a better understanding of the process, several terms should be defined.
Activity :Ability to crack a gas oil to lower boiling fractions.
Catalyst/oil ratio (C/O) =lb catalyst/lb feed.
Conversion =100 (volume of feed volume of cycle stock)/volume of feed.
Cycle stock :Portion of catalytic-cracker effluent not converted to naphtha and lighter products [generally
the material boiling above 430°F(220°C)]
Efficiency =(% gasoline)conversion.
Recycle ratio=Volume recycle/volume fresh feed.
Selectivity:The ratio of the yield of desirable products to the yield of undesirable products (coke and gas).
Space velocity:Space velocity may be defined on either a volme (LHSV)or a weight (WHSV) basis. In a
fluidized-bed reactor, the LHSV has little meaning because it is difficult to establish the volume of the
bed.The weight of the catalyst in the reactor can be easily determined or calculated from the residence
time and C/O ratio.
LHSV = Liquid hour space velocity in volume feed/(volume catalyst)(hr).
WHSV =(Weight hour space velocity in lb feed)/(lb catalyst) (hr).

Within the limits of normal operations, increasing[1,2,23]

1. Reaction temperature

2. Catalyst/oil ratio

3. Catalyst activity

4. Contact time

Results in an increase in conversion, while a decrease in space velocity increases conversion. It should be
noted that an increase in conversion does not necessarily mean an increase in gasoline yield, as an increase
in temperature above a certain level can increase conversion, coke and gas yields, and octane number of
the gasoline but decrease gasoline yield . In many FCC units, conversion and capacity are limited by the
regenerator coke burning ability. This limitation can be due to either air compression limitations or to the
after burning temperatures in the last stage regenerator cyclones. In either case FCC units are generally
operated at the maximum practical regenerator temperature with the reactor temperature and throughput
ratio selected to minimize the secondary cracking of gasoline to gas and coke. With the trend to heavier
feedstocks, the carbon forming potential of catalytic cracker feeds is increasing, and some units limited in
carbon burning ability because of limited blower capacity are adding oxygen to the air to the regenerator to
overcome this limitation. Oxygen contents of the gases to the regenerator are being increased to 24–30%
by volume and are limited by regenerator temperature capability and heat removal capacity
GROWTH OF CATALYSTS IN FCC

Fig:4.21 Growth of catalysts in FCC

Fluid Catalytic Cracking

Reactions in FCC[1,2,21,22]
  Paraffins are cracked to give olefins and smaller paraffins.

 Olefins are cracked to give smaller olefins.

 Napthenes (cycloparaffins) are cracked to olefins.

 Alkyl aromatics lose their side chains.

 Isomerisation of olefins to iso-olefins.

 H-transfer reactions.

Acidity of solid catalysts

FCC Catalyst

 Catalyst Components

 Zeolite

 Matrix
  Binder

 Filler

Structure of Zeolite[23]

Fig:4.22 Structure of Zeolite

Zeolite
Fig:4.23 Zeolite

Further treatments of NaY zeolite

 Ion Exchange.

 RE Exchange.

Preparation methods of High-Silica Y zeolites[23]

 Thermal and hydrothermal modification..

 Chemical modification.

 Combination of hydrothermal and chemical modification.

Ion Exchange
Thermal and hydrothermal modification

Fig:4.24

Framework Stabilization:
 Fig:4.25 Framework Stabilization

Zeolite properties[23]

1. Introduction

The word ‘Zeolite’ is derived from the Greek word, which means ‘boiling stone’[24] (2002). Zeolites are
water-containing crystalline aluminosilicates with highly ordered structures. They can be of naturally
originated or synthesized and consist of SiO4 and AlO4- tetrahedra. These tetrahedras are interlinked
through common oxygen atoms to give a three-dimensional network through which long channels
run[25] (2006).

A representative empirical formula for a zeolite can be written as Mx/n [(AlO2)x (SiO2)y]mH2O. Where, M is
the cation of valency n; x and y represents Si/Al ratio and having value from 1 to 8. When M cations are
replaced by H+ions, the active catalysts can be generated and used in the petroleum industries for cracking,
hydrocracking and isomerization reactions[26] (1982). Zeolites provide excellent shape selectivity and acidic
sites. Due to these characteristics, zeolites have dominant applications in petroleum industries.

Hydrocracking and hydroisomerization are the two of the most important processes of the petroleum
refineries, which are not possible without application of suitable catalysts (Fig.4.26). The continuous
increase in global demand of the petroleum products increases the valuation of these processes in modern
refineries. Hydroisomerization is termed as the isomerization of n-paraffins into branched isomers.
Hydroisomerization of C4–C7 hydrocarbons has been applied for the production of gasoline with a high
octane number. Hydroisomerization of C7 –C15 paraffins applies to improve diesel fuel cold flow properties,
such as viscosity, pour point and freezing point. The hydroisomerization reaction is always accompanied by
a hydrocracking reaction that lowers more or less the yield of that the isomerized feed molecules[27] (2005).

Catalysts used for hydroisomerization reactions are bifunctional in nature. They generally contain metal
such as Pt, Pd, Ni etc. dispersed on acidic supports. While hydroisomerization and hydrocracking reactions,
metals are responsible for hydrogenation-dehydrogenation agent and acidic supports are responsible for
isomerization and cracking of the substances[28] (2003). Zeolite acidity (number and strength distribution)
and pore structure play important role in overall reactions.

Typical acidic supports of bifunctional catalysts used are amorphous oxides or mixture of oxides (i.e. HF-
treated Al2O3, SiO2–Al2O3, ZrO2/SO42-); zeolites (Y, Beta, Mordenite, ZSM-5, ZSM-22, ZSM-12 etc.);
silicoaluminophosphates (SAPO-11, SAPO-31, SAPO-41) and mesoporous materials (MCM-41, AlMCM-41)
(Deldari, 2005).

Gasoline and diesel are the most important and valuable fractions generated by petroleum refineries.
The demand of these two fractions have globally increased since last few years. The average demand for
diesel will be almost twice than that of the demand of gasoline in next few years (Fig.4.27). So, major part
of the investments of the petroleum refineries have covered processes for production or upgrading of
middle distillate fractions to make them suitable for diesel blendstock[29] (2010).

So, objective of this work is to develop suitable molecular sieve based catalysts for the
hydroisomerization of middle distillate fractions. The catalyst should provide transition shape selectivity for
branched isomers. Also, the catalyst should provide good mechanical strength during reaction conditions
and structure (especially in the case of molecular sieves) should not collapse at reaction conditions. The
zeolite molecular sieves successfully fulfilled all these criterions and have been commercially used since
their invention. Therefore, development of the noble metal (i.e. Pt, Pd etc.) loaded zeolite (i.e. ZSM-12,
ZSM-22, ZSM-48) supported catalysts, is the major objective. Also, development of kinetic model for
hydroisomerization followed by hydrocracking reactions will also be performed.
Fig:4.26 Schematic flow diagram of a modern refinery [29](2010)
 Fig:4.27 Incremental transportation fuel demand from 2008 to 2015 [29](2010)

2.1 Introduction to molecular sieves and zeolites (Szostak, 1989)

In 1932, McBain proposed the term “Molecular Sieve” for the materials which have selective adsorption
properties and these materials separate components of a mixture on the basis of difference in molecular
size and shape. The different classes of molecular sieves are listed in Fig.4.28 Structure of many of these
materials are analogous, but all are different in terms of elemental composition and aluminosilicates have
been given the classical name ‘Zeolites’.

Structurally zeolites are the crystalline aluminosilicates with a framework based on an extensive three-
dimensional network of oxygen ions. The AlO2- tetrahedra in the structure determine the framework charge
and is balanced by cations, which occupy non-framework positions. The crystalline framework structure
contains voids and channels of discrete size. The pore opening ranges from 3 to 8Ao. The negative charge
has been created by AlO2- tetrahedra and balanced by cations like alkaline (Na+, K+, Rb+, Cs+), alkaline earth
(Mg+2, Ca+2), NH4+, H3O+ (H+), TMA+ (Tetramethylammonium), other nitrogen containing organic cations, and
rare-earth and noble metal ions. All aluminosilicates are molecular sieves but not zeolites. An
aluminosilicate is called zeolite if it contains at least one aluminium ion per unit cell based on the bulk
composition of the sample, with no allowance made for inhomogeneities within the individual crystal on
the microscopic level.
 Fig:4.28 Classification of molecular sieve materials indicating the extensive variation in
composition[30] (1989)

Fig:4.29 Examples of pore opening in the zeolite molecular sieves [25] (2006)

Zeolites have been classified on the basis of different structural elements. The kind of building unit most
suitable for the classification of the zeolites depends on the property under consideration. If we are able to
identify ability of a perticular zeolite to selectively adsorb one component of a mixture over another,
understanding of the detailed complex structure of that perticular zeolite would not be necessary. Size of
the pore opening of the perticular zeolite is responsible for selective adsorption of perticular components.
So, we can classify zeolite from on the basis of pore size to sequence of building blocks which form the
regular network pattern characteristic of the zeolite. Each level acts as a model to understand, describe or
visualize a specific aspect of a material.

The first level of classification is based on pore size. All the zeolites used for catalytic or adsorption
operations can be classified by the number of T atoms, where T is Si or Al that define pore opening. Till date
only three types of pore openings are known and of practical interest. They are 8-member ring (small pore),
10-member ring (medium pore) and 12-member ring (large pore) zeolites (Fig.4.29). The distribution of
products for different zeolites depends upon difference in their pore sizes. Example of 8-member ring
zeolites are Erionite, Chabazite and Type A. ZSM-5, ZSM-11, ZSM-22, EU-1 and Theta-1 comes under the
category of 10-member ring zeolites. Whether Type Y, Mordenite (synthetic), ZSM-12 and ß are the
examples of 12-member ring zeolites.

Second level of classification is based on the number of dimensions encompassed by the pores and
shape of the pore mouth. There are one-, two- and three-dimensional tubes or channels can be viewed in
the zeolite structures. Analcite is the example of one-dimensional channels, while Mordenite has two-
dimensional intersectig channel system. ZSM-5 and ZSM-11 contain intersecting three-dimensional 10 ring
channel system. The difference in shape and size of channel interaction are responsible for subtle
difference in selectivity between different zeolites. The size and shape of the pore opening can be
determined by configuration of T and O atoms relative to each other, Si/Al ratio, size and location of the
cation and temperature.

Pore openings and channel systems determine catalytic and adsorptive properties of the zeolites. But, as
also mentioned earlier they don’t provide any information on structural properties of the zeolites. Lack of
information on structural properties of the zeolites led to develoment of Structural Building Units. The
Structural Building Units can be classified into Primary Building Units, Secondary Building Units, Extended
Chain Building Units and Sheet Building Units. A primary building unit is the individual tetrahedral TO4 unit,
where T is either Si or Al. A secondary building unit (SBU) is the geometric grouping of those tetrahedra.
These SBU’s contain 4, 6, and 8-member single rings; 4-4, 6-6, and 8-8 member double rings; and 4-1, 5-1,
and 4-4-1 branched rings. Most of the zeolites frameworks can be generated by the arrangement of
different SBU’s. ZSM-5 and Ferrierite can be described by their 5-1 building uits. Offretite, zeolite L,
Cancrinite, and Erionite are generated using only single 6-member rings. Some zeolite structures can be
generated by various SBU’s. For example, the sodalite structure can be built from either the single 6-
member or the single 4-member ring (Fig.4.30).
 Fig:4.30 Generation of sodalite structure from either 6-member rings or 4-member rings [30] (1989).

Arrangement of the secondary building units in space generates chain building units, which add further
dimensions to secondary building units. Various types of chains found in the zeolite structures is shown in
Fig.4.31.

Fig:4.31 Chains found in zeolite structures: (a) zig-zag (b) sawtooth (c) double crankshaft (d)
narsarsukite (e) natrolite 4=1 and (f) pentasil chains [29](2010).
 Chain building units rearrange and form the sheet building units. Generally, chain building units are one-
dimensional and sheet building units are two-dimensional. In Fig.4.32 successive built up of the ZSM-5
(MFI) is shown.

Fig:4.32 The ZSM-5 (MFI) structure can be built up successively: (a) the pentasil unit; (b) chains of
pentasil units; (c) layers of these chains; and (d) layers linked across inversion centres [29] (2010).

2.2 Hydrothermal synthesis of zeolites (Cundy[31] Cox, 2005)

In late 1940s, Richard Barrer and Robert Milton have started synthesis of zeolites by conversion of
known mineral phases under the action of strong salt solutions in the temperature range of 170 to 270oC.
By 1953, Milton and his colleagues had synthesized 20 zeolites including 14 unknown as natural minerals.
Initially the aim of study was to understand complex synthesis processes and later it has been shifted to
discoveries of new materials, advances in synthesis techniques, innovations in theoretical modelling
methods, development of new techniques for the investigations of reaction mechanisms and development
of the new techniques for the characterization of the materials.

A typical hydrothermal zeolite synthesis can be described in brief as follows:

 Silica and alumina sources in the amorphous form have been mixed together in the alkaline pH
and in an aqueous medium with a cation source.

 The reaction mixture has been heated in a sealed autoclave at temperature above 100oC and
autogeneous pressure.

 After reaching the appropriate temperature, reactants remain amorphous for some time and
 this time is known as “induction period”. Crystallization starts after this period of time.

 After appropriate time period, all the amorphous materials will be converted into zeolite
crystals. These crystals are recovered by filtration, washing and drying.

The Si and Al sources have been used in an oxide form and these amorphous precursors contain Si-O
and Al-O bonds. At the end of the hydrothermal synthesis crystalline zeolite products containing Si-O-Al
linkages has been created in the presence of “mineralizing” agent (generally alkali metal hydroxide). The
bond type of the product is very similar to the bond types of precursor oxides. So, it can be concluded that,
no great enthalpy changes has been takes place. In fact, overall free energy change of the reaction is small
enough to become the overall reaction kinetically controlled. This gives the benefit of generation of
metastable products. To make the synthesis process industrially important, the product must contain
reproducibility and the same specification each time. This needs to develop exact conditions for product
optimization. This influences the choice of starting reagents from wide varieties of simple oxides or
hydroxides to sodium silicate solution and solid sodium aluminate. Usage of sodium silicate solution or solid
sodium aluminate gives not only benefits in terms of cost or ease of operation but also they offer optimum
routes to particular materials. Flexibility in the choice of reagents enables equilibria to be approached from
various directions. We may also get the kinetic benefits like preferred nucleation of one phase over another
in the situations of possibility of co-crystallization of the materials.

Now let’s come to the synthesis mechanism for zeolites. The most probable pathways can be given as
induction period, nucleation and crystal growth in sequence. Induction period is the time (t) between the
notional start of the reaction and the point at which the first crystal formation can be observed. According
to the classical nucleation theory, the induction period has been divided into three subunits as relaxation
time (tr), time for formation of stable nucleus (tn) and time for the nucleus to grow to a detectable size (tg).
‘Nucleation’ is defined as the series of atomic or molecular processes by which the atoms or molecules of a
reactant phase rearrange into a cluster of the product phase large enough as to have the ability to grow
irreversibly to a macroscopically larger size. The ‘cluster’ is defined as nucleus or critical nuclei. The rate of
nucleation (i.e., the number of nuclei formed per unit time per unit volume) can be expressed by an
Arrhenius-type equation[29] (2010):

J = A exp (-ΔG*/kT).................(1)

Where, ΔG* is the critical Gibb’s free energy, k is rate constant at temperature T. Cations and organic-
structure-directing agents also involved in the nucleation process by surrounding themselves with metal-
oxide species in preferred geometries. Crystal growth is considered as one of the most important step and
studies tell that zeolite growth increases linearly during most of the crystallization process for both gel and
clear solution synthesis. Temperature, gel composition, agitation and aging are the various parameters
which affect the zeolite growth[29] (2010).
 2.3 Characterization of zeolites

Characterization of the synthesized zeolites is very important aspect. A particular zeolite must contain
good crystal structure, required Si/Al ratio, desired BET surface area and pore size, desired acidic and metal
sites, good dispersion of metal sites, proper crystal morphology etc. for particular application. Each of the
above mentioned properties can be verified by various characterization techniques like X-Ray Diffraction
(XRD), BET surface area analyzer, Solid state Nuclear Magnetic Resonance (Solid NMR), NH3 or Pyridine
Temperature Programmed Reduction (NH3 -TPD or Pyridine-TPD), H2 -Chemisorption or CO-Chemisorption,
Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) (both normal and high
resolution) etc.

2.4 Classification of zeolites

Zeolites are comprehensively classified on the basis of their morphology, crystal structure, Chemical
composition, effective pore diameter, origin of trivalent species donor.

2.4.1 Morphology

Fibrous: Tetrahedra linked more numerous in one crystallographic .Lamellar (Open framework):
Tetrahedral linkages within similar plane.Zeolites have been structurally classified on the basis of Secondary
Building Unit (SBU). They can be explained as cage, ring or cage like structures which forms the basic
architecture of zeolites. Fig.4.33 shows some of the SBU.
 4.33 SBU in zeolite skeleton.

2.4.2 Unit cell size:

It is an elementary building block of the zeolite crystal.

It is a measure of aluminium sites or the total potential acidity.
si + NAi = 192

Al/Unit cell= 111.52 (UCS – 24.191) developed by Breck and Flannigan.

Tab:4.3

cell UCS(oA) Al/Unit

NaY (As synthesized) 24.64 – 24.67 54

USY 24.50 – 24.54 40

Equilibrated USY 24.25 – 24.30 2 - 13

2.4.3 Rare earth level:

Rare earth elements serve as a bridge to stabilize aluminium atoms in the zeolite structure.

Tab:4.4

Rare earth exchanged zeolite(oA) USY

High UCS Low

High Zeolite activity Low

High Gasoline selectivity Low

Low RON High

 High Hydrogen transfer Low

High Hydrothermal stability Medium

2.4.4 Chemical Constitution

Zeolites are classified on the basis of their framework silicon and aluminum constitution. This
classification is mainly done on the basis of the Silicon to Aluminum ratio and was introduced by
Flanigen[32] (1982). Table 1 vividly describes some of the zeolites.

Tab:4.5 Silica rich and poor zeolites.

Si/Al = 8 Si-MEL (silicalite-2), Si- MFI (silicalite-1), Si-FER etc

Si/Al = 5-500 MFI, BEA, FER etc.

eSilica Zeolites Si/Al = 2-5 Erionite, Chabazite, MOR, L, X, Y etc.

Si/Al = 1-1.5 A, X, Sodalite, etc.

2.4.5 Pore Size Diameter

Different zeolites have different opening ring combination. Such as Fig.4.34 a) displays the graphical
view of MFI zeolite with 10 Member Ring (M.R.) opening structure. While Fig.4.34 b) displays dimensions of
LTA zeolite with 8 M.R. Structure. Fig.4.34 c) elaborates dimensions of VPI-5 with 18 M.R. Some example s
of different zeolites containing.
 Fig:4.34 Ring opening structures along [001] of some zeolites. (Units mentioned in fig are in Angstrom
unit)

Tab 4.6 Classification based on ring opening

Medium Pore10 M.R. Medium Pore 12, 14 M.R. Large Pore18, 20 M.R.

MOR CIT-5 (14) VPI-5 (18)

VPI-8 UTD-1F (14) Cloverite (20)

ZSM-22 AlPO-5 (12)

ZSM-18 ZSM-12 (12)

2.5 Characteristics and Physicochemical properties of zeolites (Deldari, 2005)

Global rise in demand of zeolites can be justified with the help of some following properties of zeolites
followed by discussing the chief properties of zeolites. High surface area, uniform micropore size, high
hydro thermal stability, intrinsic acidity, ability to accommodate active metal species, introducing
constraints to undesired species by molecular sieving effect (shape selectivity), environmentally harmless,
non-corrosive, show ease of separation from reaction mixture compared with homogeneous catalysts.
 2.5.1 Framework Cation Exchange

4.35 Fixed pore opening[25] (2006)

The zeolite framework is comprised of Silicon and Aluminum linked together with oxygen atoms to form
tetrahedra. To stabilize the structure or to compensate negative charge imparted by aluminum due to its
valency, a cation is required. Cation exchange properties of zeolite is function of its intrinsic properties like
(i) Framework topology (ii) Ion size and shape (iii) Charge density of anionic framework (iv) Ion valence (v)
Electrolyte concentration in aq. Phases.

2.5.2 Size Constraints or Molecular sieving or Shape selectivity

Due to rigid skeletal system, zeolite window has intact window size due to which molecules having size
larger than this window dimensions often experience constraints in accessing the intrinsic sites. Thus,
prevents undesired large molecules to enter network. Depending upon this shape selectivity is being
classified into three main subdivisions as described in brief below.

2.5.2.1 Reactant Shape selectivity

 This refines the accessibility molecules inside pore geometry of zeolite by imparting the fixed window
opening, thus limits the diffusion of molecules with kinetic diameter larger than this window. This allows
shape selective entrance of molecules, activity of such molecules is often hindered. Fig.4.36 shows the
shape selectivity of n- butane and iso-butane over zeolites.

4.36 Shape selectivity of hydrocarbon reactants on to zeolite framework.

2.5.2.2 Transition Shape selectivity

Transition shape selectivity refers to curbing of intermediate compounds formed therin the framework
whose size is larger than skeleton size. Fig.4.37 shows formation of small sized isomer compared to bulky
ones.
 4.37 Shape selective transition compound formation restriction.

2.5.2.3 Product Selectivity

Due to restricted pore size products diffusing through these materials experience constraints and so
product formed is also selective in nature. But however sometimes this bulky products accumulate over a
position of zeolite blocking the accessibility of virgin molecules resulting into coking or deactivation of
catalyst.

4.38 Shape selective product formation

2.5.2.4 Molecular Traffic Control

In case of some selected zeolites, having multi dimensional channels, in such cases reactants access
pores other than what product diffuse out. This becomes easier as counter diffusion is prevented. Several
probing techniques are investigated for having clear idea on shape selectivity of zeolites amongst which
some includes: (i) Constraint Index (ii) Refined constraint index (iii) Spacious Index, o-p index.
 2.6 Applications of zeolites

2.6.1 Ion-exchange

Natural zeolites have a very gifted tendency to ion exchange some water pollutants. Clinoptilolite is
successfully employed for removing Ammonium from municipal sewages. Regeneration is performed by
NaCl and CaCl2. Ammonia is air stripped in regeneration and absorbed by sulphuric acid to give ammonium
sulphate, a kind of fertilizer. An advantage of zeolites for elevated resistance compared to organic resins for
wastewaters of nuclear industry has been investigated.

2.6.2 Agricultural Uses

Soils of volcanic origin are prone to have some fraction of natural zeolites, so they give some indications
for their application in improving soil fertility. Natural zeolites helped many plants including spinach, radish,
sugar beet, tomato, maize, rice, potato and cucumber[33] (2011).

2.6.3 Adsorption

Most of the applications are based on water vapour adsorption. Based upon such properties zeolites are
used as drying media for air, sour natural gas and other artificial gas streams. Water adsorption-desorption
cycles chabazite, clinoptilolite gave some good inferences in air conditioning and refrigeration. Their
applications based on adsorption of pollutants gas such as SO2 from gas effluents attributed to the fact that
selectivity was found to be good for polar molecules rather than non-polar molecules. Gas separation
technologies are also under investigation, of these O2 from air by pressure swing adsorption method are
employed using mordenite rich tuffs. Some lab scale investigations of water-ethanol vapour separations by
Phillipsite were performed knowing that it provides selectivity to ethanol.

2.6.4 Catalysis: Petroleum Refining and Petrochemistry, Application to Hydroisomerization and

Hydrocracking[29] (2010)

Due to stupendous shape selectivity and acidic sites provided by zeolites they have found their
dominant applications in petroleum industry, especially for hydrocracking and hydroisomerization. As
mentioned earlier, long-chain n-paraffins present in the petroleum products, have bad effect on some
properties like octane number of gasoline and cold-flow properties of diesel fuel. It is desired to remove or
convert them into isomers. Conventionally hydroisomerization process has been used for this. The
isomerization process usually takes place in the presence of hydrogen, and in this case it is referred to as
hydroisomerization [27](2005).

The term cold-flow properties refer to the flow characteristics of a diesel fuel after at low temperature
range. If cold-flow properties don’t change with respect to temperature, it is termed as good. It is the ability
to operate under cold weather conditions. Petroleum products contain different hydrocarbons like n-
paraffins, i-paraffins, olefins, naphthenes, and aromatics. Among these, normal and slightly branched
paraffins have relatively high melting points in the typical range of 250–360 oC. The melting point of normal
paraffins ranges between 10 and 40oC, while the melting point of the heaviest methyl paraffin present (C21)
is, depending on the position of the branching, between –4 and 13 oC. The extent of decrease in the melting
point significantly depends on the degree, the position, and the length of the branching. Branching
positions in the middle of the chain have a higher effect than those near the end of the chain, while longer
side chains lead to a higher decrease of melting point.

Engines running on diesel should be able to operate even in cold weather conditions where temperature
can reach values well below 0oC. On the basis of the data presented above it is evident that such
temperatures may cause the crystallization of those compounds presenting the highest melting points,
thereby affecting the flow characteristics, and ultimately may lead to solidification of the product. Standard
test methods for determining these properties are cloud point (CP; ASTM D2500), pour point (PP; ASTM
D97), and cold filter plugging point (CFPP); IP 309). The CP is the temperature at which a haze of wax
crystals is formed; PP is the highest temperature at which the product still flows, while CFPP is the highest
temperature at which the wax crystals severely reduce the flow through a filter. Different options are
available to improve the cold-flow properties of gas oil:

 The simplest is to reduce the backend cutpoint and add kerosene blendstock. This action
removes the heavier paraffinic molecules that tend to precipitate at higher temperatures.
However, reduction of the end point results in significant reduction of diesel yield from the
crude.

 Removal of wax-forming components by crystallization after dilution of the feedstock with a

suitable solvent and chilling (i.e., solvent dewaxing). This option is generally economical only for
feedstocks with a high content of paraffins, and it is mainly used for the production of
lubricating oil base stocks.

 Usage of cold-weather additives to meet seasonal low-temperature.

 Catalytic dewaxing process wherein the waxy paraffin are selectively cracked or isomerized.

All of above mentioned techniques; catalytic dewaxing process is of our interest. Catalytic dewaxing is a
process where the products are removed which are responsible for the degradation of the cold-flow
properties. They are removed by selective cracking to lighter compounds, by boiling in the gasoline and LPG
range (i.e., cracking dewaxing), or by isomerization into more branched lower melting point structures
minimizing as much as possible the cracking (i.e., isomerising dewaxing).

The detailed mechanism of the hydroisomerization and hydrocracking of n-alkanes on bifunctional

catalysts is shown in Fig.4.39

4.39 Proposed mechanisms for hydroisomerization and hydrocracking of n-alkanes on bifunctional

catalysts[29] (2010)

A catalyst can be used for hydroisomerization, if it contains following properties [27](2005):

 It should provide good selectivity of isomerized products.

 It should have proper balance of acidic and metal sites.

 It should be able to withstand high pressure and temperature.

 The pore opening of the catalyst is small enough to restrict the larger isoparaffins from reacting
at the acidic sites inside the pore.
2.6.5 Matrix

 Physical functions

 Binder

 Diffusivity

 Diluting medium

 Sodium sink

 Heat transfer

 Manufacturing
4.40 Main Reactions in FCC Catalysis

FCC Catalyst
4.41 FCC Catalyst

ROLE OF ADDITIVES

4.42 Role of Additives

FCC Additives
4.43 FCC Additives

ZSM-5 additive

 Octane boosting.

 Increase in C3 and C4 olefins and LPG maximization.

 Preference for higher butylene yield.

 Initially ZSM-5 cracks paraffins and olefins. As cycle time increases, olefin isomerisation
dominates while gasoline loss and octane improvement is minimum.
 Fig 4.44 A typical flow sheet for higher molecular hydrocarbons (feed) cracking with ZSM-5 towards
propylene and butylenes.

How to Maximize Propylene Yield?

 Fig 4.45 A typical flow sheet for higher molecular hydrocarbons (feed) cracking with ZSM-5 towards
lighter olefins, napthenes, paraffins and aromatics.

Cracking by ZSM-5 favored by:[23]

 Low pressure

 High Tempreature

 Fast diffussion of primary cracking product from the catalyst.

Secondary catalyst reactions

 Hi-transfer.isomerization,cyclization favored by:

 High host catalyst ZM

 High zeolite acid strengh,high UCS.

 Slow diffusion of primary cracking product from the catalyst.

Suppressing competitions from secondary reaction is the major key for maximizing propylene.

Hydrogen Transfer Index

 The relative activity of the host FCC catalyst for secondary reactions can be quantified using the
 Hydrogen Transfer Index (HTI):

Designing a Max C3= Catalyst for Resid[23]

REQUIREMENTS:

 Minimize Hydrogen Transfer to increase C3= plateau.

 Vanadium tolerance for good hydrothermal stability.

 Good bottoms cracking ability.

 Low coke selectivity.

 High accessibility reduces HTI. Primary cracking products can diffuse from the catalyst faster and
are less likely to undergo secondary reactions.

Balance between HTI and Activity

 Low Hydrogen Transfer maximizes propylene.

 If achieved by reducing Rare Earth, activity is lower.

 There is a limit to how much zeolite can be used in catalyst to compensate for activity loss.

 Dilution effects from large amounts of ZSM-5 must also be overcome.

 The challenge, particularly for Resid, is achieving high propylene yield AND good conversion with
acceptable catalyst addition rate.

Vanadium

 At regenerator conditions, Vanadium on equilibrium catalyst exists as V+5.

 In the regenerator ‘V’ presented on the catalyst converted Vanadium pentoxide (V2O5).

 Under regenerator conditions V2O5 is mobile because it melts at regenerator conditions.

 In the presence of steam V2O5 is converted to Vanadic acid H3VO4.

Ni passivators
  ‘Ni’ passivating agents are antimony, bismuth and rare earth compounds (Ce, La, etc…).

 Antimony: This is a first commercially used additive.Ni-Sb alloys formed.

1. Antimony will block ‘Ni’ active sites.

2. Alternation of electronic and chemisorption properties.

3. The amount of antimony available to passivate nickel will be determined by the

equilibrium between antimony and nickel.

Draw back:Antimony effects on CO combustion promoters.

Vanadium Passivators[1,2,23]

 Vanadium passivating agents are Tin, Titanium, Zirconium and rare earth compounds.

 Other than the above stated passivating agents there are other passivating agents are also
reported. They are germanium, gallium, indium, tellurium, aluminium, barium, zinc, boron,
phosphorous, tungsten, tantalum, lithium and cadmium.

Metal traps

 Metal traps are added to the FCC Catalyst as separate particle or incorporated directly into the
catalyst particle.

 These metal traps react with incoming metals like nickel and vanadium and form an inert
compounds.
 Fig 4.46 A typical FCC flow sheet in petroleum refining system which incorporates an FCC to distill
high-octane gasoline and LPG from the heavy contents of the crude oil with sulphur

Catalyst/Additives for Sulphur Control

 Grace

 GSR Technology for sulphur reduction 15-25%

 Sulphur reduction is achieved mainly from front end .

 For Gasoline.

 AKZO

 Resolve FCC catalyst selective matrix activity

 15-30% Sulphur reduction.

 Optimized access.

 For Gasoline.

 BCA Additive

 20-30% achieved pesovskite /Spinel.

  Alumina Matrix.

 Sulphur capture by Matrix.

Objective and application of catalytic reforming process, reforming catalyst

 Fundamental of Catalytic Reforming[1-4]

 Objective.

 Reaction-Desirable & Undesirable.

 Process

 Semi Regenerative Reforming.

 Dualforming.

 Continuous Catalytic Regenerative Reforming.

 Process Variable.

 Reforming Catalytic

 Types.

 Poisons.

 Some Recent Advance in Reforming

 Semi Regenerative Reforming.

 Update on CCR Technology/Catalyst.

 Update on SR Technology/Catalyst Debottlenecking Option.

Introduction of Catalytic Reforming[1-4]

Catalytic reforming is a chemical process used to convert petroleum refinery

naphthas, typically having low octane ratings, into high-octane liquid products called
reformates which are components of high-octane gasoline (also known as petrol).
Basically, the process rearranges or restructures the hydrocarbon molecules in the
naphtha feedstocks as well as breaking some of the molecules into smaller molecules.
The overall effect is that the product reformate contains hydrocarbons with more
complex molecular shapes having higher octane values than the hydrocarbons in the
naphtha feedstock. In so doing, the process separates hydrogen atoms from the
hydrocarbon molecules and produces very significant amounts of byproduct hydrogen
gas for use in a number of the other processes involved in a modern petroleum
refinery. Other byproducts are small amounts of methane, ethane, propane and
butanes. This process is quite different from and not to be confused with the catalytic
steam reforming process used industrially to produce various products such as
hydrogen, ammonia and methanol from natural gas, naphtha or other petroleum-
derived feedstocks. Nor is this process to be confused with various other catalytic
reforming processes that use methanol or biomass-derived feedstocks to produce
hydrogen for fuel cells or other uses.

History[5-11]

Universal Oil Products (also known as UOP) is a multi-national company developing

and delivering technology to the petroleum refining, natural gas processing,
petrochemical production and other manufacturing industries. In the 1940s, an
eminent research chemist named Vladimir Haense working for UOP developed a
catalytic reforming process using a catalyst containing platinum. Haensel's process
was subsequently commercialized by UOP in 1949 for producing a high octane
gasoline from low octane naphthas and the UOP process become known as the
Platforming process.The first Platforming unit was built in 1949 at the refinery of the
Old Dutch Refining Company in Muskegon, Michigan. In the years since then, many
other versions of the process have been developed by some of the major oil
companies and other organizations. Today, the large majority of gasoline produced
worldwide is derived from the catalytic reforming process.

To name a few of the other catalytic reforming versions that were developed, all of
which utilized a platinum and/or a rhenium catalyst:

Rheniforming:Developed by Chevron Oil Company.

Powerforming:Developed by Esso Oil Company, now known as ExxonMobil.
Magnaforming:Developed by Englehard Catalyst Company and Atlantic Richfield Oil
Company.
Ultraforming:Developed by Standard Oil of Indiana, now a part of the British
Petroleum Company.
Houdriforming:Developed by the Houdry Process Corporation.
CCR Platforming:A Platforming version, designed for continuous catalyst regeneration,
developed by UOP.
Octanizing:A catalytic reforming version developed by Axens, a subsidiary of Institut
francais du petrole (IFP), designed for continuous catalyst regeneration.Chemistry

Before describing the reaction chemistry of the catalytic reforming process as used
in petroleum refineries, the typical naphthas used as catalytic reforming feedstocks
will be discussed.Typical naphtha feedstocks.A petroleum refinery includes many unit
operations and unit processes. The first unit operation in a refinery is the continuous
distillation of the petroleum crude oil being refined. The overhead liquid distillate is
called naphtha and will become a major component of the refinery's gasoline (petrol)
product after it is further processed through a catalytic hydrodesulfurizer to remove
sulfur-containing hydrocarbons and a catalytic reformer to reform its hydrocarbon
molecules into more complex molecules with a higher octane rating value. The
naphtha is a mixture of very many different hydrocarbon compounds. It has an initial
boiling point of about 35 °C and a final boiling point of about 200 °C, and it contains
paraffin, naphthene (cyclic paraffins) and aromatic hydrocarbons ranging from those
containing 4 carbon atoms to those containing about 10 or 11 carbon atoms.

The naphtha from the crude oil distillation is often further distilled to produce a
"light" naphtha containing most (but not all) of the hydrocarbons with 6 or less carbon
atoms and a "heavy" naphtha containing most (but not all) of the hydrocarbons with
more than 6 carbon atoms. The heavy naphtha has an initial boiling point of about 140
to 150 °C and a final boiling point of about 190 to 205 °C. The naphthas derived from
the distillation of crude oils are referred to as "straight-run" naphthas.

It is the straight-run heavy naphtha that is usually processed in a catalytic reformer

because the light naphtha has molecules with 6 or less carbon atoms which, when
reformed, tend to crack into butane and lower molecular weight hydrocarbons which
are not useful as high-octane gasoline blending components. Also, the molecules with
6 carbon atoms tend to form aromatics which is undesirable because governmental
environmental regulations in a number of countries limit the amount of aromatics
(most particularly benzene) that gasoline may contain.It should be noted that there
are a great many petroleum crude oil sources worldwide and each crude oil has its
own unique composition or "assay". Also, not all refineries process the same crude oils
and each refinery produces its own straight-run naphthas with their own unique initial
and final boiling points. In other words, naphtha is a generic term rather than a
specific term.The table just below lists some fairly typical straight-run heavy naphtha
feedstocks, available for catalytic reforming, derived from various crude oils. It can be
seen that they differ significantly in their content of paraffins, naphthenes and
aromatics:

Tab:5.1

Typical Heavy Naphtha Feedstocks[5-11]

Crude oil name => Barrow Island Mutineer- CPC Blend Draugen
Location => Australia Exeter Kazakhstan North Sea
 Australia

Initial boiling point, oC 149 140 149 150

Final boiling point, oC 204 190 204 180

Paraffins, liquid volume

42 62 57 38
%

Naphthenes, liquid
42 32 27 45
volume %

Aromatics, liquid volume

12 6 16 17
%

Purpose of Reformer

 The purpose of Reforming process is to produce high octane number

reformate reformate, which is a main component for motor, fuel,aviation
gasoline blending or aromatic rich feedstock.Hydrogen rich gashydrogen
gas Due to the nature of the reactions, reforming process produces :LPG

 Reformer Feed of Either:

-Low Quality straight Run Naphtha.
-or cracked naphtha generally mixed with straight Run Naphtha.

 Reformer Feed Pretreatment:

Due to the Presence Contaminants in all cases and to specific characterstics
of cracked naphtha .Naphtha Pretreating Unit(s) ios are always necessary.

 Refining Process & Catalysts

 Fluid Cracking Catalyst (FCC)

 FCC additives

Reforming Catalyst[1-13]

 Catalyst Characterization

 R & D & Commercialization Status in India

  Conclusion

Catalytic reforming

Chemical process to convert petroleum refinery naphthas, typically having low

octane ratings, into high-octane liquid products called reformates which are
components of high-octane gasoline (also known as petrol).Process re-arranges or re-
structures the hydrocarbon molecules in the naphtha feedstocks Breakes some of the
molecules into smaller molecules.

Overall effect

Product reformate contains hydrocarbons with more complex molecular shapes

having higher octane values than the hydrocarbons in the naphtha feedstock.

By-products

The process separates hydrogen atomsfrom the hydrocarbon molecules and

produces very significant amounts of byproduct hydrogen gas for use in a number of
the other processes involved in a modern petroleum refinery.Other byproducts are
small amounts of methane,ethane.

CATALYTIC REFORMING[5-7,9-11]

 A major conversion process in petroleum refining and petrochemical

industries.

 Process converts straight run naphtha (C6-C10, Straight chain paraffins and
naphthenes) to gasoline components of high antiknock quality.

 Manufacture of Hydrogen and LPG as bye-products.

 The octane of reformate is provided mainly by aromatics having 6 to 10

carbon atoms and light iso paraffins.

 Alkanes and cycloalkanes are selectively converted to aromatic

hydrocarbons.
  Transforms low octane naphtha to high octane reformate.

 Reaction temperature 700-800 oK,pressure 70-450 psi

 Reaction is carried out in hydrogen atmosphere even though the hydrogen

is one of the product.

 Reforming is primarily endothermic.

Reforming Reactions[6-13]

Some refinery naphthas include olefinic hydrocarbons, such as naphthas derived

from the fluid catalytic cracking and coking processes used in many refineries. Some
refineries may also desulfurize and catalytically reform those naphthas. However, for
the most part, catalytic reforming is mainly used on the straight-run heavy naphthas,
such as those in the above table, derived from the distillation of crude oils.There are a
good many chemical reactions that occur in the catalytic reforming process, all of
which occur in the presence of a catalyst and a high partial pressure of hydrogen.
Depending upon the type or version of catalytic reforming used as well as the desired
reaction severity, the reaction conditions range from temperatures of about 495 to
525oC and from pressures of about 5 to 45 atm.The commonly used catalytic
reforming catalysts contain noble metals such as platinum and/or rhenium, which are
very susceptible to poisoning by sulfur and nitrogen compounds Therefore, the
naphtha feedstock to a catalytic reformer is always pre-processed in a
hydrodesulfurization unit which removes both the sulfur and the nitrogen compounds.

The four major catalytic reforming reactions are: [1-7,11-13]

1:The dehydrogenation of Naphthenes to convert them into aromatics as

exemplified in the conversion methylcyclohexane (a Naphthenes) to toluene (an
aromatic), as shown below:
 2:The dehydrogenation of naphthenes to convert them into aromatics as
exemplified in the conversion methylcyclohexane (a naphthene) to toluene (an
aromatic), as shown below:

3:The dehydrogenation and aromatization of paraffins to aromatics (commonly

called dehydrocyclization) as exemplified in the conversion of normal heptane to
toluene, as shown below:
 4:The hydrocracking of paraffins into smaller molecules as exemplified by the
cracking of normal heptane into isopentane and ethane, as shown below:[1-7,11-13]

The hydrocracking of paraffins is the only one of the above four major reforming
reactions that consumes hydrogen. The isomerization of normal paraffins does not
consume or produce hydrogen. However, both the dehydrogenation of naphthenes
and the dehydrocyclization of paraffins produce hydrogen. The overall net production
of hydrogen in the catalytic reforming of petroleum naphthas ranges from about 50 to
200 cubic meters of hydrogen gas (at 0 oC and 1 atm) per cubic meter of liquid
naphtha feedstock. In the United States customary units, that is equivalent to 300 to
1200 cubic feet of hydrogen gas (at 60 oF and 1 atm) per barrel of liquid naphtha
feedstock. In many petroleum refineries, the net hydrogen produced in catalytic
reforming supplies a significant part of the hydrogen used elsewhere in the refinery
(for example, in hydrodesulfurization processes). The hydrogen is also necessary in
order to hydrogenolyze any polymers that form on the catalyst.

Process description[9-13]
 The most commonly used type of catalytic reforming unit has three reactors, each
with a fixed bed of catalyst, and all of the catalyst is regenerated in situ during routine
catalyst regeneration shutdowns which occur approximately once each 6 to 24
months. Such a unit is referred to as a semi-regenerative catalytic reformer
(SRR).Some catalytic reforming units have an extra spare or swing reactor and each
reactor can be individually isolated so that any one reactor can be undergoing in situ
regeneration while the other reactors are in operation. When that reactor is
regenerated, it replaces another reactor which, in turn, is isolated so that it can then
be regenerated. Such units, referred to as cyclic catalytic reformers, are not very
common. Cyclic catalytic reformers serve to extend the period between required
shutdowns.

The latest and most modern type of catalytic reformers are called continuous
catalyst regeneration reformers (CCR). Such units are characterized by continuous in-
situ regeneration of part of the catalyst in a special regenerator, and by continuous
addition of the regenerated catalyst to the operating reactors. As of 2006, two CCR
versions available: UOP's CCR Platformer process[13] and Axen's Octanizing process.
[14] The installation and use of CCR units is rapidly increasing. Many of the earliest
catalytic reforming units (in the 1950's and 1960's) were non-regenerative in that they
did not perform in situ catalyst regeneration. Instead, when needed, the aged catalyst
was replaced by fresh catalyst and the aged catalyst was shipped to catalyst
manufacturer's to be either regenerated or to recover the platinum content of the
aged catalyst. Very few, if any, catalytic reformers currently in operation are non-
regenerative.
 Fig:5.1 The process flow diagram below depicts a typical semi-regenerative
catalytic reforming unit

Schematic diagram of a typical semi-regenerative catalytic reformer unit in a

petroleum refinery The liquid feed (at the bottom left in the diagram) is pumped up to
the reaction pressure (5 to 45 atm) and is joined by a stream of hydrogen-rich recycle
gas. The resulting liquid-gas mixture is preheated by flowing through a heat
exchanger. The preheated feed mixture is then totally vaporized and heated to the
reaction temperature (495 to 520 °C) before the vaporized reactants enter the first
reactor. As the vaporized reactants flow through the fixed bed of catalyst in the
reactor, the major reaction is the dehydrogenation of naphthenes to aromatics (as
described earlier herein) which is highly endothermic and results in a large
temperature decrease between the inlet and outlet of the reactor. To maintain the
required reaction temperature and the rate of reaction, the vaporized stream is
reheated in the second fired heater before it flows through the second reactor. The
temperature again decreases across the second reactor and the vaporized stream
must again be reheated in the third fired heater before it flows through the third
reactor. As the vaporized stream proceeds through the three reactors, the reaction
rates decrease and the reactors therefore become larger. At the same time, the
amount of reheat required between the reactors becomes smaller. Usually, three
reactors are all that is required to provide the desired performance of the catalytic
reforming unit.

Some installations use three separate fired heaters as shown in the schematic
diagram and some installations use a single fired heater with three separate heating
coils. The hot reaction products from the third reactor are partially cooled by flowing
through the heat exchanger where the feed to the first reactor is preheated and then
flow through a water-cooled heat exchanger before flowing through the pressure
controller (PC) into the gas separator. Most of the hydrogen-rich gas from the gas
separator vessel returns to the suction of the recycle hydrogen gas compressor and
the net production of hydrogen-rich gas from the reforming reactions is exported for
use in other the other refinery processes that consume hydrogen (such as
hydrodesulfurization units and/or a hydrocracker unit). The liquid from the gas
separator vessel is routed into a fractionating column commonly called a stabilizer.
The overhead offgas product from the stabilizer contains the byproduct methane,
ethane, propane and butane gases produced by the hydrocracking reactions as
explained in the above discussion of the reaction chemistry of a catalytic reformer,
and it may also contain some small amount of hydrogen. That offgas is routed to the
refinery's central gas processing plant for removal and recovery of propane and
butane. The residual gas after such processing becomes part of the refinery's fuel gas
system. The bottoms product from the stabilizer is the high-octane liquid reformate
that will become a component of the refinery's product gasoline.

REACTOR DESIGN[1-2,11-13]

Fixed-bed reactors used for semiregenerative and cyclic catalytic reforming vary in
size and mechanical details, but all have basic features as shown in Figure. Very similar
reactors are used for hydrotreating, isomerization, and hydrocracking.The reactors
have an internal refractory lining which is provided to insulate the shell from the high
reaction temperatures and thus reduce the required metal thickness. Metal parts
exposed to the high temperature hydrogen atmosphere are constructed from steel
containing at least 5% chromium and 0.5% molybdenum to resist hydrogen
embrittlement. Proper distribution of the inlet vapor is necessary to make maximum
use of the available catalyst volume. Some reactor designs provide for radial vapor
flow rather than the simpler straight-through type.

Fig:5.2 Typical fixed-bed downflow catalytic reformer

The important feature of vapor distribution is to provide maximum contact time

with minimum pressure drop. Temperature measurement at a minimum of three
elevations in the catalyst bed is considered essential to determine catalyst activity and
as an aid in coke burn-off operations.

CATALYTIC REFORMERS IN INDIA[1-2,11-15]

 14 plants having capacity of 4.5 MMTPA are operating.

 Four SR and three CCR plants have been licensed jointly by IIP-IFP in India

 IIP-IPCL state of art bimetallic Pt-Re catalyst in two reformers.

OCTANE NO. OF GASOLINE

 What is Octane Number?

 An empirical number measuring anti-knocking capacity .

 RON (research): Represents low speed driving.

 MON (motor): Repressents high speed driving.

 Average = (MON+RON)/2

OCTANE NO Vs CARBON NO

Fig:5.3 Octane NO Versus Carbon No for important Hydro carbon group in

Reforming

Reforming Catalyst

 First recognized dual function catalyst.

 Cracking/hydrogenation/dehydrogenetaion.
  Isomerization.

 Sulfur tolerant.

 Low coke generation.

CATALYST COMPOSITIONS[1-2,11-18]

 Pt/Alumina (Chlorinated Gamma alumina).

 Pt-Re/Alumina (Decreased coke formation than Pt/Alumina).

 Pt-Ir/Alumina

 Hydrogenation and dehydrogenation activities are associated with

metal component.

 Activity for acid catalysis resides on the carrier surface.

 Performance depends on Pt crystallite size and promoter metals.

Catalyst Mechanism[19-21]

Most catalytic reforming catalysts contain platinum or rhenium on a silica or silica-

alumina support base, and some contain both platinum and rhenium. Fresh catalyst is
chlorided (chlorinated) prior to use. The noble metals (platinum and rhenium) are
considered to be catalytic sites for the dehydrogenation reactions and the chlorinated
alumina provides the acid sites needed for isomerization, cyclization and
hydrocracking reactions. The activity (i.e., effectiveness) of the catalyst in a semi-
regenerative catalytic reformer is reduced over time during operation by
carbonaceous coke deposition and chloride loss. The activity of the catalyst can be
periodically regenerated or restored by in situ high temperature oxidation of the coke
followed by chlorination. As stated earlier herein, semi-regenerative catalytic
reformers are regenerated about once per 6 to 24 months.Normally, the catalyst can
be regenerated perhaps 3 or 4 times before it must be returned to the manufacturer
for reclamation of the valuable platinum and/or rhenium content.

 Platinum or rhenium on a silicaor silica-alumina support base.

 Some contain both platinum and rhenium.

 Fresh catalyst is chlorided(chlorinated) prior to use.

 The noble metals are considered to be catalytic sites for the

 dehydrogenation reactions and the chlorinated alumina provides the acid
sites needed for isomerization, cyclization and hydrocracking reactions.

 The LIFE of the catalyst is reduced over time during operation by

carbonaceous coke deposition and chloride loss.

 Catalyst can be periodically regenerated or restored by in situ high

temperature oxidation of the coke followed by chlorination.

 Normally, the catalyst can be regenerated perhaps 3 or 4 times before it

must be returned to the manufacturer for reclamation of the valuable
platinum and/or rhenium content.

Catalyst Manufacture[1-2,19-21]

 Acidic Support(Alumina from Aluminium chloride).

 Spray drying of aluminum hydroxide solution to produce alumina .

 Removal of excess chloride by slurrying.

 Spray dried or extrudates formed.

 Impregnation of metals, e.g PtCl3.

 drying.

 Refining Process & Catalysts.

 Fluid Cracking Catalyst (FCC).

 FCC additives.

 Reforming Catalyst.

Catalyst Characterization:

 R & D & Commercialization Status in India

 Conclusion.

Octane Rating

 The octane rating is a measure of the autoignition resistance of gasoline

 and other fuels used in spark-ignition internal combustion engines. It is a
measure of anti-detonation of a gasoline or fuel.

 Octane number is the number which gives the percentage, by volume, of

iso-octane in a mixture of iso-octane and normal heptane, that would have
the same anti-knocking capacity as the fuel which is under consideration.
For example, gasoline with the same knocking characteristics as a mixture
of 90% iso-octane and 10% heptane would have an octane rating of 90.

Research Octane Number (RON)

RON is determined by running the fuel in a test engine with a variable compression
ratio under controlled conditions, and comparing these results with those for mixtures
of iso-octane and naphthenes.

Motor Octane Number (MON)

MON testing uses a similar test engine to that used in RON testing, but with a
preheated fuel mixture, a higher engine speed, and variable ignition timing to further
stress the fuel's knock resistance. Depending on the composition of the fuel, the MON
of a modern gasoline will be about 8 to 10 points lower than the RON.

Tab:5.2

CATALYTIC REFORMERS IN INDIA

S.N CAPACITY TYPE OF CATALYST

REFINERY DUTY
O MMTPA PROCESS BY

1 BPCL 0.33 SR Benzene Procatalyse

2 BRPL 0.11 SR Xylenes Procatalyse

3 CPCL 0.09 SR Octane IPCL-IIP

4 IOCL, Barauni 0.3 SR Octane Procatalyse

 5 IOCL, Digboi 0.09 SR Octane Procatalyse

6 IOCL, Haldia 0.196 SR Octane Procatalyse

7 IOCL Mathura 0.5 CCR Octane Procatalyse

8 IOCL, Panipat 0.5 CCR Octane Procatalyse

Aroma-
9 IOCL, Vadodara 0.33 SR Procatalyse
tics

10 IPCL, Vadodara 0.11 SR Xylenes IPCL-II

11 KRL 0.248 SR Benzen Criterion

12 MRPL 0.3 CCR Octane UOP

13 RIL, Patalganga 0.233 CCR Xylenes UOP

14 RPL, Jamnagar - CCR Octane UOP

Reformer feed, Reforming reactor design, Continuous and semi regenerative process

Reformer feed, Reforming reactor design, Continuous and semi regenerative process.

FEED[1-2]

 Reformer feed, Reforming reactor design, Continuous and semi regenerative process.

 Naphtha from thermal & catalytic crackers can also be used.

Tab:5.3

Characteristic of Typical Reformer Feeds

PARAMETERS PARAFFINIC NAPHTHENIC

RONC 50 66
 P/N/A(%vol) 66.8 /21.8/11.4 29.3/61.85/8.85

ASTM Distillation - -

IBP 92 88

30 115 115

50 123 123

70 133 132

90 147 145

95 152 150

- 155 161

Chemical Reactions

 Two types of reaction involved in the octanizing process:

 Desirable Reaction which lead to higer octane number and to higher purity hydrogen
production.They are the reaction to promote.

 Adverse Reaction which lead to decrease of octane no and a decrease in hydrogen purity.They
are the reaction to minimize.

RON:Research Octane Number

MON:Motor Octane Number

Tab:5.4 [1-2,19-21]

RON MON
 Cyclohexane 83 77.2

MethlyCyclohexane 74.8 71.1

1.3 Dimethlycyclohexane 71.7 71

Benzene 114.8 100

Toluene 120 103.5

m-Xylene 117.5 115

Desirable reactions with H2 production[1-5,12,17-21]

 Naphthenes dehydrogenetion

 Naphthenic compound dehydrogeneted into aromatic with production of 3 moles of

H2 per mole of napthene.

 Promoted by the metallic function.

 Highly Endothermic.

 Thermodynamically favored by high temperature,low pressure and high number of

carbons.

 Kinetically favored by high temperature ,high no. of carbons;not affected by hydrogens

partial pressure.

 At the selecting operating conditions,reaction is very fast and almost total.

Desirable reactions

 Paraffin's Dehydrocyclization

 Multiple step reaction.

 Promoted by both acidic and metallic function.

 Kinetically favored by high temperature and low temperature.

 Dehydrogenation step become easier as paraffin molecular weight increases but is

competed by Hydro cracking.

 At the selected operating condition much lower rate than that of Dehydrogenetionm.

 Linear Paraffin Isomerization

 Promoted by acidic function.

 Slightly Exothermic.
  Fast.

 Thermodynamically dependant on temperature:pressure has no effect.

 Kinetically favored by high temperature:not effected by the hydrogen partial pressure.

 Naphthenes Isomerization

 Desirable reaction because the subsequent dehydrogenation of the alkylcyclohexane

into an aromatic.

 Difficulty of ring rearrangement and high risk of ring opening (paraffin formation).

 At the selected operating condition.theoretically low rate but subsequent

dehydrogenation shift the reaction towards the desired direction.

 Slightly endothermic.

 Easier reaction for higher carbon number.

Naphthenes isomerisation

Tab:5.5

RON MON

Ethylcyclopetane 67.2 61.2

MethlyCyclohexane 74.8 71.1

Toluene 120 103.5

Adverse reactions[1-2,15-22]

 Hydrocraking

 Hydrocracking effect either paraffin and olefins.

 Promoted by both acidic and metallic functions.

 Favored by high temperature and high pressure.

 Exothermic risk of runaway reaction.

 At the selected operating condition,hydro cracking reaction could be complete but is

limited by kinetics.

Adverse reaction

 Consequences of Cracking

 Decreases of paraffins and increases of aromatics proportion(i.e increases in octane)in

the reformate and a loss of reformate yield.
  Decreases in hydrogen production(cracking reaction consuming hydrogen).

 Increase of light end production and low molecular weight paraffins.

 Hydrogenolysis

 Promoted by metallic function.

 Favored by high temperature and high pressure.

 Exothermic(risk of runaway reaction).

 Hydrodealkylation

 Breakage of the branched radicial of an aromatic ring.

 Promoted by metallic function.

 Favored by high temperature and low temperature.

 Consumes hydrogen and produces methane.

 But at selected operating condition and with the selected catalyst,this reaction is not
significant.
 Alkylation

 Additioh of an olifen molecule on an aromatic ring.

 Promoted by metallic function.

 Lead to heavier molecules which may increase the end point of the product.

 High tendency to form coke must be avoided.

 TransAlkylation(alkyl disproportionation)

 Dismutation of 2 toulence ring to produce benzene and xylene.

 Promoted by metallic function.

 Favored by very serve condition of pressure and temperature.

 At the selected operated conditions,and with the selected catalyst this reaction is
negligible.

 Coking
  Result from complex group of reaction.Deatailed machanism not fully known yet.

 Linked to heavy unsaturated products(polynuclear aromatics) and heavy olifins traces or

diolefins present in the feed or in CCR reaction.

 Coke deposit reduces active contact area and reduces catalyst activity.

 Favoured by low pressure:In octanizing operating conditions necessity of a continous

regeneration to maintain a low level of coke.

Chemical Reaction[1-2,24-26]

All these reaction occur in series and parallel to each other producing a complicated reaction scheme.In
an effort to simplify the scheme according to the reaction rates the main reaction take place in the
following order:

Tab:5.6

1 1st Reactor Dehydrogenetion/Isomerization

Dehydrogenetion/Isomerization/Cracking and
2 2nd and 3rd Reactor
Dehydrocyclization.

3 4th Reactor Cracking/Dehydrocyclization.

 The catalyst distribution is:

 R1= 10%

 R2= 15%

 R3= 25%

 R4= 50%

Tab:5.7

Reactions Heat of Relative

 Reaction(1)KCAL/MOLE Rate(2)Approx

Naphthenes dehydrogenetion -50 30

Paraffin dehydrocyclization -60 1 base

Isomerization:paraffins +2
3
Naphthenes +4

Cracking +10 0.5

Heat of reaction <0 = endothermic reaction

For pressure below 15kg/cm2

Conventional unit[1-2,15-25]

Fig 5.4 Conventional unit

Fig 5.5

Continuous catalytic regenerative reforming

Fig 5.6 Continuous catalytic regenerative reforming

Continuous catalytic regenerative reforming

Fig 5.7 Continuous catalytic regenerative reforming

Objective of regenerative unit

Recover initial catalyst activity

 Coke Removal -2 Burning Zones

 Metal Redistribution & chloride adjustment -Oxychlorination

 Catalyst drying -calcination

Fig 5.8 A typical FCC flow sheet to regenerate catalyst from spent catalyst (Regeneration process)

Catalyst regenerator
Fig 5.9 Catalyst regenerator

Process variables[1-2,22-29]

 Pressure

 Temperature

 Space velocity

 Hydrozen partial pressure(H2/HC)

 Quality of the feed

 Operating parameters summary.

Process variables

 Each of them can be fixed by operator within the operating range of the equipment
 independently from the others.

 For one set of independent variable for same feed characterstics there is only one performance
of the unit i.e one set of value for:

 Product yields

 Product quality(octane)

 Catalyst stability(coke make)

 Pressure is the basic variable because of its inherent effect on reaction rates.

 Effect of pressure on reactions

 Low pressure enhance hydrogen production by these reactions:dehydrogenations

dehydrocyclisation coking.

 Cracking rate reduces.

 The lower the pressure the higher the yields of reformate and hydrogen for a given
octane number.But it developer high coking rate(compensated by continous
regeneration).

 Average catalyst pressure used is close to last reactor inlet pressure.

 During transient condition(startup,shutdown,upset)it is recommended to increase the pressure

to lower coke formation.

 Limit of operation action.

 Pressure rise limited by equipments design pressure.

 Pressure lowering limited by recycle compressor design for power and intake volume.

Effect of temperature

 Most important and used operating parameter is space velocity.

 Catalyst activity is directly related to reactor temperature.By simply raising or lowering reactor
inlet temperature operator can raise or lower product quality and yield.

 It is commonly accepted to consider the weight average inlet temperature(WAIT).

where Ti 1,Ti 2 .......are inlet tempreature of reactor

(wt catalyst of R1)....... are weight of catalyst in reactor

 An increase of temperature (i.e WAIT) has the following effect.

 Increase octane.

 Decrease of yield (of C5+Fraction).

 Decrease of H2 purity.

 Increase of coke deposit.

 A slight increase of temperature(WAIT) through the life of the catalyst make up for this activity
loss.

 Larger and temporary changes in temperature required.

 To change octane-at contant feed quality and quantity.

 To change feed quantity and still maintain octane

 To change feed quality and still maintain octane

Space velocity

 Linked to resident time of feed in the reactor and effect the kinetics of the reforming reaction.
  Operator must careful in mind that each time liquid feed rate is changed a temperature
correction must be applied if octane is to be maintained.

 Important Recommendation

 Always decrease reactor inlet temperature first and decrease feed flow rate afterward.

 Always increase feed flow rate first and increase reactor inlet temperature afterward.

Effect of Hydrogen to Hydrocarbon Ratio

where R is the recycle flow in Kg l h (or lb l h)

M is the recycle gas molecular weight

F is the feed rate in kg l h(or lb l h)

m is the feed molecular weight

Y vol fraction of H2in the recycle gas

 The recycle gas MW is obtained by chromatographic analysis as well as the H2 vol fraction(Y)

 The feed MW is obtained by chromatographic analysis or by correlation from its distillation

range and specific gravity.

 Operator can change H2/Hc ratio by lowering or increassing the recycle compressor flow.

 For a given unit the amount of recycle is limited by the recycle compressor characterstics(power
suction flow).
  The H2/Hc ratio has no obvious impact on the product quality or yield.

 But a high H2/Hc ratio reduces the coke build up.

 It is stirctly recommended to operate with a H2/Hc ratio equal to (or higher than) design figure.

Effect of feed quality chemical composition

 Characterization of the Feedstocks:0.85 N + A

 With a higher 0.85 N + A .

 The same octane content will be obtained at a lower severity(temperature)and the

product yield will be higher.

 Or the same severity temperature the octane content will be higher.

 The endothermic reaction heat increases and the feed flow rate will be limited by the
heater design duty.

 With a higher 0.85 N + A .

 Higher paraffin and napthanic content obtained.The hydrogen purity of the recycle gas
decrease and operation will be limited by the recycle compressor capacity.

 Impurities

 Temporary or permanent reduction of catalyst activity by poisons contained in the feed.

Feed quality

 The feed distillation range is generally as follows:

 IBP (Initial Boling Point) 70-100oc

 EP(End Boiling Point)150-180oc

 Light fraction:
Cyclization of c6 more difficult than that of C7-C8.The lighter the feed,the higher the required
severity for a given octane.

 Heavy Fraction:
High naphthenic and aromatic content.Lower severity to obtain good yield.But polycyclic
compounds which favor coke deposit.
EP higher than 180oc are generally not recommended.
Operating parameters summary

 Here after the theoretical effect on the unit performance of each independent processes
variable taken separately:

catalyst[21-30]

 Reforming of catalyst are bimetallic catalyst consisting of platinum plus promoters on alumina
support, rhenium being essentially used.

 The main features of these catalyst are:

 High purity alumina support-High mechanical resistance.

 Platinum associated with Rhenium high stability and selectivity.

 High regenerability.

 The combination of these qualities give the following advantage:

 High Reformate Yield.

 High Hydrogen yield.

  High on stream Factor.

 Low Catalyst Inventory.

The main characterstics of catalyst other than it physical and mechanical properties are: [1-2,25-32]

 The Activity

 Catalyst increase the rate of desired reaction.

 Is measured in term of temperature

 The Selectivity

 Catalyst ability to favor desirable reaction.

 Practicle measured by the C5 + Reformate and hydrogen yield.

 The Stability

 Change of catalyst performance(activity,selectivity) with time.

 Caused chiefly by coke deposit and traces of metal in feed.

 Measured by the amount of feed treated per unit weight of catalyst.C5 + Wt reformate
yield is also an indirect measure of the stability.

 Platinum (pt) plus other promoter(s) impreganted on to gamma alumina containing around 1%
wt chloride provide to acidity.

 Since 1967 bimetallic catalysts have been widely used.

 The second metal come from the group of metal like:

 Rehinium(Re)

 Tin(sn)

 Iridium(Ir)

 Germanium(Ge)

Selection of metal
  Depend on what you want from the catalyst:The Objectives

 Stability and Cycle life

 Selectivity towards

 Hydrogen H2

 Liquid Reformate(C5 + Reformate)

 Benzene yield in C5 + Reformate

 Normal causes foa catalyst ageing/deactivation

 Mental sintering

 Temperature

 Metallic Phase

 Presence of Chloride

 Deposition of coke on metal and acid sites.Coking effect can be split.

 Degree of poisoning of deposited coke.

 Relative coking rate

 The relative rate of coking is proportional to the hydrogenation function of the catalyst this is
dependant on the metallic phase.

Fig 5.10
selectivity[1-4,12-22]

 Desired yields are:

 Hydrogen

 C5 + Reformate

 Low benzene

 Benzene

 Yield can be minimised by pre-factionnating the precursors (MCP,CH,nC6P)which are

present in the fraction boiling between 70 to 85oC.

 Benzene is also produced by the hydro alkylation of alkyl benzenes.

 Loss of desired yield is caused by cracking

 Hydrocracking involving the metal plus acid sites.

 Hydrogenolysis involving the metal in the presence of hydrogen.

Catalytic Reforming
 Types of Catalytic Reformers[1-4,25-34]

 Steam reforming Catalyst regenerated in-situ during shut-downs(6-24 months)

 CCR

 Continuous Catalyst Regeneration.

 In-situ regeneration of part catalyst in a special regenerator.

 Continous addition of regenerated catalyst.

Fig 5.11 A typical FCC flow sheet integrated with CDU, HDSD, VRDS, FCC to generate different
hydrocarbons from crude oil

Tab 5.8

RON & MON OF VARIOUS MOTOR FUEL STOCKS

 Stock RON MON

Butane 95 92

Iso-pentane 92 89

Medium pressure reformate 94 85

Low pressure reformate 99 88

Heavy reformate 113 102

FCC gasoline 91 80

Alkylate 95 92

Isomerate 85 82

MTBE 115 99

Important Properties of FCC catalysts

 Surface Area /Pore Size Distribution

 Zeolite Area

 Matrix Area

 Pore Volume

 Crystallinity

 Unit Cell Size

 Silicon-Alumina ratio

 Particle Size Distribution and Average particle Size

 Attrition Resistance

 Thermal properties/ Hydrothermal properties

 Metal Content

 Density
  Carbon and Sulphur Content

 Acidity

Surface Area / Zeolite to Matrix ratio, Pore size distribution

 Scope

 Measurement of SA, Z/M ratio and Pore size distribution of fresh/equilibrium FCC
catalysts/additives, zeolite, clay, alumina, etc.

 Principle

 Nitrogen at various pressures are adsorbed at liquid nitrogen temperature on the

samples and isotherms are generated.With the help of BET, BJH, T-Plot etc., the above
mentioned properties are measured.

 Instruments

 Flowsorb-2300, ASAP2010 of M/s Micromeritics,USA.

 Typical range of SA for FCC catalysts 80-300 m2/g.

Implications of SA

 Surface Area (Fresh=175-300, E-cat: 80-150).

 Indirect measurement of activity and stability of the catalysts.

 Z/M ratio gives information about SA of zeolites (small pores of <20 Ao)and SA of matrix,
(large pores>20 Ao).

 Matrix area does not tell whether the matrix is active or non-active.

 Loss of SA due to

 Hydrothermal deactivation (zeolite destruction).

 Thermal deactivation (high regn. Temp.).

 Increased metal deposition on catalyst.

 Reduced Fresh catalyst addition rate.

 SA of 10 units can decrease the MAT activity by about 2-5 units.

Pore Volume by Water Titration

 Scope: Measurement of Pore volume of Fresh and equilibrium catalysts.

 Principle: Catalyst is titrated by water until the fluidity of the sample is destroyed. Pore volume
is calculated as volume of water titrated over weight of catalyst.

 Procedure: Sample calcined to remove carbon and moisture.Titrated with distilled water or DM
water.

 Typical range: 0.15-0.45 cc/g Simple method, PV measurement can be done at Refinery

Pore Volume[19-21]

 Indications/Directions: Generally, higher pore volume in fresh catalyst means higher levels of
active matrix components.

 Decrease in pore volume in e-cat means

 Thermal deactivation.

 Hydrothermal deactivation of catalyst has little effect on pore volume.

 Changes in Unit operation .

 May indicate damage in the regenerator air grid/ catalyst distributor.

X-RAY Diffraction (XRD) Analysiss[19-21,33-36]

 Scope

 To identify and quantify crystalline phase, to detect impurities, to measure crystallite

size, UCS and Silica-alumina ratio.

 Principle

 X-ray patterns of test and standard samples are compared. Integrated intensities of the
peaks provide quantitative data.

 Instruments

 Rigaku, Japan XRD equipment.

  Typical Range

 Zeolite in FCC catalyst from 5-40%; Fresh catalyst: 15-40% E cat: 5 - 15 %.

UCS of Y Zeolite[19-21,33-36]

 It is a measure of aluminium sites or the total potential acidity per cell.UCS is a indicator of
zeolite acidity. As the UCS decreases, acid sites become further apart since Al4+ion is bigger than
Si4+ion.

 SiO2/Al2O3 mol ratio =2, UCS=25 Ao;

SiO2/Al2O3 mol ratio =15, UCS=24.4 Ao

 Lower UCS means fewer active sites per unit cell.The fewer acid sites are further apart and
therefore inhibit hydrogen transfer reactions,which in turn increases gasoline octane as well as
production of C3 and lighter components.

PSD by Micromesh[19-21,33-36]

 Scope

 Determination of Particle size and average particle size of FCC catalysts in the range of
20-150 microns.

 Principle

 Dry sieving procedure for determination of particle size in FCC catalysts by means of
calibrated sieves of uniform and precise square opening.

 Procedure

 Sample placed on top sieve, set shaken for specified time. Each sieve is weighed.

 Instrument

 Robot shifter RPS 75,Japan.

 Typical Range

 APS= 80 microns

Significance of PSD
  PSD is an indicator of fluidisation properties of catalyst. 0-40 micron particles (5-20 wt%)
improves the fluidisation.

 PSD is a function of cyclone performance, catalyst properties, catalyst make-up rate and unit
operating conditions.

 Case-1: A decrease in the percentage of smaller particles (fines) possibly due to (a) deteriorating
cyclone performance. (b)Reduced Catalyst attrition (c) Lower fines in the fresh catalyst.

 Case-2: An increase in fines may indicate increased catalyst attrition possibly due to (a) changes
in the fresh catalyst composition, (b) increased fines in the fresh catalyst (c) internal damage
such as air distributor or slide valve.

Attrition Resistance[19-21,33-36]

 Scope

 To measure ability of the catalyst to maintain integrity in the FCC system.

 Principle

 Calcined catalyst microspheres are subjected to high velocity air jet.Catalyst fines are
removed from the attrition zones and weighed.Attrited catalyst is expressed as weight
percentage and termed as Attrition Index (AI).Higher the index lower is the attrition
resistance.

 Instrument

 In house fabricated.

 Typical Range

 AI of FCC catalyst 5-15%.

 Increased attrition possibly due to

 Problem in the regenerator air grid.

 Large amounts steam to the regenerator/regenerated catalyst line.

 Excessive velocities (>300 FPS) in the feed nozzle can also cause attrition.

 Problem in the catalyst.

Apparent Bulk Density

  Scope

 Apparent Bulk density (ABD) of fresh, equilibrium FCC catalyst having size less than 150
microns.

 Principle

 Calcined catalyst sieved and taken into cylinder kept under given vibration to increase
the packing efficiency, mass/unit volume is calculated to get ABD.

 Instruments

 Bulk density meter, Model 1H 2000, Seishin, Japan.

 Typical Range

 0.7 -0.9 g /CC.

Significance of ABD[19-21,33-36]

 ABD is a also function of catalyst composition, manufacturing process and other physical
properties such PV and PSD. Generally does not change unless the catalyst type changes.

 Normally ABD of E-cat is higher than the fresh catalyst due to thermal & hydrothermal changes
in the pore structure that occur in the unit and also due to catalyst loss.

 If we compare one catalyst with other, slightly higher ABD catalyst can increase the pressure
drop across the slide value and improve the catalyst circulation.

 High ABD (>1.0) can restrict fluidisation.

 Low ABD (<0.6) indicates A) Change in Catalyst B) Fines loss.

Hydrothermal treatment of FCC Catalyst and additives [1-3,19-21,33-36]

 Scope

 Fresh catalysts can be hydrothermally deactivated to simulate equilibrium catalysts.

 Principle

 Hydrothermal deactivation of fresh FCC catalysts is done at 788 oC for 3 hours at 100%
steam whereas 750 oC for ZSM-5 additive.
  Instruments

 Xytel and In house fabricated.

Significance of Metal Analysis

 Alumina (Al2O3) content and Rare earth content is determined by catalyst formulations.Changes
in Alumina/ Rare earth content can be used to track catalyst change out.Unexpected change
indicate a change in catalyst formulations.

 The alumina content (25-55%)indicate the in-active alumina and active alumina i.e. Alumina
from clay, binder and zeolite.CO Promoter additive and SOx additives.

 The Sodium (Na) in the E-Cat is the sum of sodium added from the feed and sodium in the fresh
catalyst. Severe problem if the Na >>0.5%; Lower in unit conversion &loss in Octane Number. A
Increase in Na level of 0.1 unit can decrease MAT conversion by 3 units.

 Ni, V, Fe & Cu has the gas making tendencies of the catalyst, when deposited on FCC
catalysts.These metals originate from the FCC feed.

Carbon on FCC Catalyst[14-21,33-36]

 Scope

 To measure percent Carbon content of regenerated or spend catalyst.

 Principle

 Carbon is determined by combustion in a stream of dry oxygen and measuring carbon

dioxide by IR analyser.

 Instruments

 Lebold Heraus,Germany;Analysis time: >1 minute Carbon range from 0.001-6 wt%.

 Carbon level on the E-cat is the indicator of the regenerator effectiveness.

 Carbon on the catalyst:

For complete combustion mode: 0.05% wt.
For partial combustion mode: 0.1 or higher.

Contents
  Refining Process and Catalysts.

 Fluid Cracking Catalyst (FCC).

 FCC additives.

 Reforming Catalyst.

 Catalyst Characterization.

 R & D & Commercialization Status in India.

 Conclusion.

Catalyst Changeover

 FCC Daily charge for replenishment, reactor- regenerator cycle.

 Hydrocracking- total charge, regeneration every 2-3 yrs.

 Reforming- total charge, regeneration every 3 or more yrs.

Wide Range of Catalysts[14-21,33-36]

 All units do not use same catalyst.

 Requirement of each unit are different in terms of catalyst requirement for different setup
reaction scheme.

 Custom catalyst- need of the day.

Catalyst & Additive Sourcing – Needs Consideration [11-21,33-36]

 India is totally dependant of overseas supply.

 R & D have acquired many patents for catalys and additive formulations as well as
manufacturing process.

 Since Large amount of catalyst is required for a plant trial, decent size manufacturing facility is
to be created at first.
  Most of the refining catalysts are imported.

 Catalyst consumption is increasing.

 No major manufacturing facilities in the country.

 Research and development confined to isolated pockets.

 Urgent need to bridge gaps in scale-up and commercial activities.

Catalyst & Additive Sourcing – Needs Consideration

 Excellent Knowledge base.

 Laboratory stage developments.

 Large gap between laboratory to plant.

Tab 5.9

Olefin yield comparison off Indmax with FCC & DCC

Process FCC DCC INDMAX

Yield,Wt%

Ethylene - 5.1 3.1

Propylene 3.6 17.4 23.2

Isobutylene 1.2 4.8 10.0

Total butylene -- 11.0 18.9

Gaps to be bridged for catalyst breakthrough

 Rigorous evaluation under simulated conditions in association with user.

 Manufacturing Facility-to solve problems of

  catalyst manufacture.

 scale-up.

 Willingness to take risk by refineries.

Objectives & Hydrocracking Reactions,Hydrocracking feedstocks,Modes of Hydrocracking,Effects of

process variables

Hydroprocessing : Hydrocracking & Hydrotreating

Purpose

 Hydrotreating[1,2]

 Remove hetero atoms and saturate carbon-carbon bonds

 Sulfur, nitrogen, oxygen, and metals removed

 Olefinic and aromatic bonds saturated

 Reduce average molecular weight & produce higher yields of fuel products

 Minimal cracking

 Minimal conversion – 10% to 20% typical

 Products suitable for further processing or final blending

 Reforming, catalytic cracking, hydrocracking

 Hydrocracking

 Severe form of hydroprocessing

 Break carbon-carbon bonds

 Drastic reduction of molecular weight

 50%+ conversion

 Products more appropriate for diesel than gasoline

Hydroprocessing Trends[1-6]

 Hydrogen is ubiquitous in refinery and expected to increase

 Produces higher yields and upgrade the quality of fuels

  The typical refinery runs at a hydrogen deficit

 As hydroprocessing becomes more prevalent, this deficit will increase

 As hydroprocessing progresses in severity, the hydrogen demands increase dramatically

 Driven by several factors

 Heavier and higher sulfur crudes

 Reduction in demand for heavy fuel oil

 Increased use of hydrodesulfurization for low sulfur fuels

 More complete protection of FCCU catalysts

 Demand for high quality coke

 Increased production of diesel

Sources of Hydrogen[2-4,6-15]

Catalytic Reforming from steam reforming of NG and Naptha reforming methods and also from the
catalytic reformer one at Al2O3.

Cryogenic Pressure swing adsorption Membrane separation.

 Steam-Methane Reforming

 Most common method of manufacturing hydrogen

 90 to 95 vol% typical purity

 Synthesis Gas

 Gasification of heavy feed

 Hydrogen recovery – pressure swing adsorption or membrane separation

 More expensive than steam reforming but can use low quality by product

 Steam-Methane

 Reforming. Endotherm catalytic reaction 1400-1500 °C.

  Steam-Methane

 Shift conversion. Exothermic fixed-bed catalytic reaction 650°C.

 Gas Purification:Absorption of CO2 in amine or hot K2CO3 solution.

 Methanation. Trace amounts of carbon monoxide & carbondioxide removed. Exothermic fixed-
bed catalytic reactions,700-800 °C.

Hydrogen (H2) is identified to be an ideal energy carrier with high efficiency, since it possesses LHV of
121 MJ/kg compared to any other known fuels and burns cleanly, without generating any environmental
pollutants. H2 production is an attractive subject of current interest for fuel cell applications which are
considered to have the potential to provide a clean energy source for automobile as an alternative to
gasoline or diesel engines. H2 is also one of most important chemicals and is widely used for ammonia
production, oil refineries, and methanol production etc. In view of growing environmental concerns, such
as global warming and the depletion of fossil fuel, major efforts are being dedicated to develop the
utilization of renewable energy sources. Bio oil produced from biomass has been proposed as an alternative
to produce hydrogen; because this renewable rich energy resource does not contribute to a net increase in
atmospheric CO2. Bio-oil is a dark brown organic liquid. Bio-oil exhibits a complex composition with more
than 200 different compounds including acids, alcohols, aldehydes, ketones as well as lignin derived
oligomers, which are emulsified with water hence difficult to reform. In general, the steam reforming of
bio-oil is simplified in terms of the oxygenated organic compounds (CnHmOk) by the following reactions:

The above reaction is followed by the water–gas shift reaction:

 The overall process can be represented as followes:

Steam reforming of the main component in bio-oil such as acetic acid (12-14 by wt %) can offer the
information for active catalyst preparation and the knowledge about the potential catalytic behaviour of
bio-oil in steam reforming.

Reaction involved in steam reforming of acetic acid

Reforming of acetic acid for H2 production can be summarized as followes: First, Steam reforming of
acetic acid reaction has discussed as stated below:-

Followed by water gas shift reaction

The overall steam reforming reaction of acetic acid is

The maximum stoichiometric yield of H2 for acetic acid reforming is 2 mole to mole of carbon. However
some undesired reactions take place inside the reactor. Hence there is large possibilities of decomposition
of acetic acid to lower molecular weight oxygenates, lighter hydrocarbons (CH4, C2H4) and coke.
 Some amount of coke can also be formed via Boudouard reaction.

The desired gaseous product i.e. hydrogen is lost through methanation reaction and reverse water gas
shift reaction.

Small amount of acetone may be formed by ketonization reaction of acetic acid.

The terms % H2 yield, % acetic acid (acetic acid) conversion and % selectivity of gaseous product
distribution were used to describe the catalytic results in reforming of the oxygenate. The definitions are
given below.
Where RR is H2/CO2 reforming ratio and RR=4/2.

Fig:6.1 Transportation Fuel Evolution [1-2,12-16]

TRANSPORTATION FUELS

 Exhaust from automobiles major pollutant

 Strict emission norms all over the world

 Corresponding changes in fuel quality specifications

  Indian fuel quality standards following Euro norms

Table:6.1 [1-6]

WORLD CRUDE OIL QUALITY °C

Proprties of Crude Oil 1985 1990 1995 1999 2010

S in crude oil(wt%) 1.14 1.12 1.31 1.41 1.51

API Gravity Of Crude Oil 32.7 32.6 32.4 32.2 31.8

Residue in Crude Oil(vol%) 19 19.4 19.8 20.2 21.3

Metals in crude oil Residue 275 286 297 309 320

S in crude oil(wt%) 3.07 3.26 3.61 3.91 4.0

Table:6.2 Key Specifications of MS [1-6]

Euro-III Equ Euro-IV Equ

BIS 2000 BS-II
Regular Premium Regular

1000 500 150 150 50

88 88 91 95 91

No spec No spec 81 85 81

84 84 No spec No spec No spec

5 3 1 1 1

No spec No spec 42 42 35

No spec No spec 21 18 21
 Table:6.3 DIESEL SPECIFICATION IN INDIA[16-19]

BIS-2000 Bharat-II Bharat-III EURO-IV

2500 500 350 50

Cetane Number(*) 48 48 51 51

Density,kg/m3 820-860 820-860 820-845 820-845

95% Recovery,oC 370 370 360 360

11 11

Metros 2000-2001 April 1,2005 April 1,2010

Year of implementation Mega Cities April 1,2003 April 1,2005 April 1,2010

Rest of india April 1,2000 April 1,2005 April 1,2010

Fig.6.2 Future Production of Clean MS [1-6,12-19]

Fig.6.3 Steam-Methane Reforming[1-2,11-18]
Catalyst

 Catalyst is a material that can influence a chemical reaction without changing itself chemicallly
  It makes reaction faster by reducing activation energywithout affecting equillibrium

 Can selectively favor a certain over other

 Key Factors

 Activity(reaction temperature)

 Selectivity(desired product)

 Stability(deactivation rate)

 Hardness/crushing strength

Fig.6.4 Hydrocracking Catalyst[1-6,15-25]

Catalyst Charateristics

Important characteristics of catalysts which influence its performance are :-

 Partical size

 Pore volume
  Size distributor

 Pore diameter

 Surface area

 Shape of catalyst particles

Catalyst

Catalyst used in hydroprocessing

 Typical composition

 CoO 2-6wt%

 MoO3 10-25wt%

 Al2O3

 Factor helping catalyst activity

 Higher H2 partial pressure

 Lower liquid hourly space velocity(LHSV)

 Lower H2 recycle gas

Fig.6.5 Catalyst[1-5,15-25]

Catalyst Loading

 Special technique is used to load catalyst into reactor to maximise bulk density.This is callled
dense loading

 Dense loading helps in

 Liquid distribution in the bed

 Minimising bed slumping

 Achieving longer cycle length

 Maintaining lower operating temperture for same hetero atom removal and saturation

 Reducing deactivation rate

Catalyst Deactivation[1-6,12-16,26-30]

 Catalyst activity gradually reduce with time

 If reacting molecules cannot reach all catalyst active sites,rate of reaction decreases.It is called
catalyst deactivation.

 Catalyst Deactivation study necessary at higher reactor temperature for same S,N,O
removal/saturation

 Two types of deactivation temporary and permanent

 Major cause of temporary deactivation is coke deposition in catalyst due to undesireable side
reaction

 Coke can cover active catalyst sites and block the entrance of pores leading to active sites

 During plant upsets,coke deposition acclerates

 When temperory deactivation reaches the limits,catalyst regeneration is necessary.

 Permanent deactivation is caused due to metal accumulation in catalyst

 Metals like Pb,Fe,As,P,Na,,Ca,Mg and orgonomettalic compounds are poisonous to catalyst

 Process parameter which significantly influence catalyst deactivation

 Reactor temperature

 Feed boiling range/°API

 Feed Rate

 H2 partial pressure

 Recycle gas rate

 Feed contamination

Catalyst Regenration[1-6,20-28]

 Hydroprocessing catalyst cost is a significant fraction of unit cost processing

 To reduce operating cost it is better to regenerate

 Strict environmental norms for disposing spent catalyst also encourage regeneration of catalyst
and reuse
  Normally two regeneration are allowed and its impart total life of 3-5 years to catalyst

 Catalyst regeneration involves removal of deposited coke in oxidised atmoshere using stem/airs.

Diesel Hydrotreating[1-2,24-30]

 Feed

 Straight run:SRGO(HGO and LGO),VLGO,SRVD,SO

 Cracked stock VBGO,LCO

Typical Operating condition :-

 Temperature 320-400°C

 H2 pressure 40-100 bar

 LHSV 0.5-3.5h-1

 H2:Oil Ratio 160-550Nm3/m3

 Catalyst Ni/Mo/Al2O3 CoMoAl2O3

Hydrocracking[1-6,20-28]

 Feed :VGO,RESID,DISTILLATES

 Typical operating condition

o Conversion 50-100%(Normally low for once thru and high for recycle configuration)

o Temperature 350-425° C

o H2 pressure 100-200 bar

o LHSV 0.5-2.0 h-1

o H2 oil ratio 700-2000 Nm3

 Catalyst Ni/Mo or Ni/W on Amorphous Si/O2/Al2O3 or zeolyte

Table:6.4 Hydroprocessing Reaction-Effects Of Operating Condition

Fig.6.6 Diesel Quality Issues[17-19]

Effect of Process Variables on Cetane Index[17-19]

Fig.6.7 Effect of Process Variables on Cetane Index

Hydrocracking - Feeds[17-19]

1. Hydrocracking does a better job of processing aromatic rings without coking than catalytic
cracking.

2. Hydrogen used to hydrogenate polynuclear aromatics (PNAs)

3. Reduces frequency of aromatic condensation.

4. Hydrocracking more severe for resids high in resins, asphaltenes and heteroatom compounds.

5. Heteroatoms and metals prevalent in resins & asphaltenes poison hydroprocessing catalysts.

6. Feedstock selection in much more sophisticated than mare determination of CCR

7. Distribution of aromatic, naphthenic, and paraffinic structures important

Hydrocracking - Products[1-6,17-18]

1. Hydrocracking primary to make distillates

2. Intent is to minimize the production of heavy fuel oil

1. Lights ends are approximately 5% of the feed

2. Middle distillates<(kerosene,jet fuel,diesel,heating oil) still contain uncracked

polynuclear aromatics

3. All liquid fraction are low in sulphur and olefins

Hydrocracking - Chemistry[1-8]

Cracking Reaction

1. Saturated Paraffins cracked to form lower molecular weight olefins and paraffins

2. Side chain cracked off small ring aromatics(SRA) and cycloparaffins(napthenes)

3. Side chained cracked off the resins and asphaltenes heaving thermally stable polynuclear
aromatics(PNAs)

4. But condensation(dehydrogenation) also occurs if not limited by hydrogenation

Isomerization Reactions[1-4]

 Isomerisation provides branching of alkyl groups of paraffins and opening of naphtic rings

 Condensation Reaction

 Suppresed by hydrogen

Hydrogen - H2 Consumption[7-19]

Carbons bonds with hetero atoms and saturated

 Create lights ends

 Heavier distillates make more lights from breakings more complex molecules
  Sulphur converted to hydrogen sulfide

 Nitrogen converted to ammonia

 Oxygen converted to water

 Organic chlorides converted to hydrogen chloride

Typical chemical hydrogen consumption 2-3 wt% on feed

Hydrcracking catalyst[1-19]

Hydrocracking catalyst generally a crystalline silica alumina base with rare earth metal deposited in
lattice

 Acid function is provided by silica alumina base

 Chloride not required in catalyst formation

Feed stock may be hydrotreated

 Acid function is provided by silica alumina base

 Chloride not required in catalyst formation

 Catalyst suspectible to sulphur poisioning if hydrogen sulphide is present in large quantities

 Catalyst activity affected by ammonia if present in large quantities

 Something necessary to remove moisture to protect the crysatlline structure of catalyst

 Hydrocracking with a mettalic hydrogenation function is sensitive to matal contamination

Hydrocracking catalyst Deactivaton & Regeneration [1-19]

Catalyst deactive and coke does from even from hydrogen present

 Hydrocracker reqires peroidic regenration of fixed bed catalyst system.Typical catalyst cycle
length is 2 years

Channeling caused by coke accumulation a moajor concern

  Can create hot spot that can leads to temperature runaway

Continuous withdrawal of catalystfrom an expanded circulating bed for regeneration

 For use in hydrocracking whole crude or short resid

Hydrocracking Effect of Process Variables[7-19,22-30]

Crackability of feed desired yields of products determine operating severity.Operating Severtiy

 Catalyst

 Space Velocity

 Total Pressure

 Hydrogen partial pressure

Severe operation needed to significantly reduce molecular weight of feed & increase the
hydrogen:carbon ratio in product

Severity

 Mild operation for diesel or fuel oil from heavy gas oil

 Severe operation for kerosene or naphtha from light gas oil

Temperature

 Temperature not used to increase severity

 Temperature adjusted to offset decline in catalyst activity

 Consider 343°C to 400°C as a description of mild operation and 400°C to 450°C to severe
operation

Hydrocracking process

Single stage or two stage process

  Unit size

 Severity of operation

 Product desired

 Nature of feedstock

 Feed pretreating for conntaminant removal

Single stage Hydrocracking[11-27]

Simple hydrocracker single reactor combining modest desulphurization with hydrocracking of gas oil to
distillates

 Hydrogen sulfide must be relatively low and not be a problem for these catalysts

 Desulphurisation catalyst in the top bed and sulphur intensitive hydrocracking catalyst in lower
bed

Oleffins saturation can be a problem in term of heat release

 Hydrogen quence

 Additional quence netween hydrocracking catalyst beds

Single stage Hydrocracking

Fresh feed recycle feed,and hydrogen heated in furnace to reactor temperature approx 700&d
F.Operating pressure1,200 psig or more.1000 scl/bblor more hydrogen for combined desulphurization and
hydrocracking

Product Separation

 Reactor product is flashed to recycle hydrogen as high a pressure as poosible

 Minimize recompression horsepower

 Gas from low pressure(50 to 75 psig) flash to gas plant

liquid from flash fractionated overhead condition

 Straight run gasoline

  Naphtha siuitable for reforming

 Distillates either jet fuel/kerosene or diesel treating oil

 Bottom for recycle

 Some bottom may be pursed to fuel oil,which would reduce severity

Fig.6.8 Single Stage Hydrocracking with Recycle [1-2]

Two Stage Hydrocracking[1-2]

Use separate reactor with desulphurisation and olefins saturation in 1st reactor and hydrocracking in
2nd reactor

 1st reactor removes contaiminats and saturate aromatics

  It Can also do part of th hydrogenation conversion

Effluent from 1st reactorsent to fractionator - fractionator bottoms sent to 2nd stage hydrocracking
reactor.May need a separate internal hydrogen sulphide removal

Fig.6.9 Two Stage Hydrocracking with Recycle & Separator System [1-2]

Hydro treating process and catalysts Resid hydro processing,Effects of process variables,Reactor
design concepts

Hydro treating process and catalysts Resid hydro processing,Effects of process variables,Reactor
design concepts.

Table:6.5

Technology to Improve HSD Quality[1-2,17-19]

 DHDS(35+bar pressure) When one sulfur reduction is required

Large sulfur reduction & high cetane gain coupled with T-95
DHDT(85+bar pressure)
point improvement

For middle distillate maximisation along with cetane

Hydrocracker
improvement & very high sulfur reduction

Purpose

 Hydrotreating[1-2]

 Remove hetero atoms and saturate carbon-carbon bonds Sulfur, nitrogen, oxygen, and
metals removedOlefinic & aromatic bonds saturated

 Reduce average molecular weight & produce higher yields of fuel products

 Minimal cracking

 Minimal conversion – 10% to 20% typical

 Products suitable for further processing or final blending

 Reforming, catalytic cracking, hydrocracking

 Hydrocracking

 Severe form of hydroprocessing

 Break carbon-carbon bonds

 Drastic reduction of molecular weight

 50%+ conversion

 Products more appropriate for diesel than gasoline

Hydroprocessing Trends[1-2,17-18]

 Hydrogen is ubiquitous in refinery and expected to increase

 Produces higher yields and upgrade the quality of fuels

 The typical refinery runs at a hydrogen deficit

 As hydroprocessing becomes more prevalent, this deficit will increase

  As hydroprocessing progresses in severity, the hydrogen demands

 increase dramatically

 Driven by several factors

 Heavier and higher sulfur crudes

 Reduction in demand for heavy fuel oil

 Increased use of hydrodesulfurization for low sulfur fuels

 More complete protection of FCCU catalysts

 Demand for high quality coke

 Increased production of diesel

Increased production of diesel[17-20]

 Catalystic Reformer

 The most important source of hydrogen for the refiner

 Continuously regenerated reformer: 90 vol%

 FCCU Offgas

 5 vol% of hydrogen with methane, ethane and propane

 Several recovery methods (can be combined)

 Cryogenic

 Pressure swing adsorption

 Membrane separation

 Steam-Methane Reforming

 Synthesis Gas

 Gasification of heavy feed

 Hydrogen recovery – pressure swing adsorption or membrane separation

 More expensive than steam reforming but can use low quality by product streams

Sources of Hydrogen[1-2,15-16]

 Catalytic Reformer
  The most important source of hydrogen for the refiner

 Continuously regenerated reformer: 90 vol%

 Semi-continuously regenerated reformer: 80 vol%

 FCCU Offgas

 5 vol% hydrogen with methane, ethane and propane

 Several recovery methods (can be combined)

 Cryogenic

 Pressure swing adsorption

 Membrane separation

 Steam-Methane Reforming

 Synthesis Gas

 Gasification of heavy feed

 Hydrogen recovery – pressure swing adsorption or membrane separation

 More expensive than steam reforming but can use low quality by product streams

 Reforming Endotherm catalystic reaction 750-815°C

 Shift Conversion.Exothermic fixed bed catalystic reaction 650°C

 Gas purification.Absortion of CO2 in amine or hot K2CO3 solution

 Methanation.Trace amount of carbon monoxide and carbon dioxide removed.Exothermic fixed-

bed catalystic reaction,700-800°C

Table:6.6

Technologies to Improve MS Quality[1-2,17-20]

Separation of Benzene rich light cut from rest of

Reformate Splitter
reformate
 Isomerisation Benzene Saturation & Octane increase

Continuos catalystic Reforming Octane increase

FCC Gasoline Spiltter Separation of light cut,mid cut & heavy cut

Selective desulpurisation Sulphur reduction

Hydroprocessing Catalysts

 Hydrotreating

 Desired function Cobalt molybdenum : sulfur removal and olefin saturation Nickel
molybdenum: nitrogen removal & aromatic saturation

 Reactor configurationFixed bed – temperature to control final sulfur content

 Selective catalysts for sulfur removal without olefin saturation Maintaining high octane
rating

 Hydrocracking

 Crystalline silica alumina base with a rare earth metal deposited in the lattice Platinum,
palladium, tungsten, and/or nickel

 Feed stock must first be hydrotreated

 Catalysts deactivate and coke does form even with hydrogen present Hydrocrackers
require periodic regeneration of the fixed bed catalyst systems Channeling caused by
coke accumulation a major concern Can create hot spots that can lead to temperature
runaways

 Reactor configuration Ebullient beds – pelletized catalyst bed expanded by upflow of

fluids Expanded circulating bed – allows continuous withdrawal of catalyst for
regeneration

Hydrodesulfurization[1-2,31-33]

 Sulfur

 Sulfur converted to hydrogen sulfide (H2S) Added hydrogen breaks carbon-sulfur bonds
and saturates remaining hydrocarbon chains
  Form of sulfur bonds Sulfur in naphtha generally mercaptans (thiols) and sulfides In
heavier feeds, more sulfur as disulphides and thiophenes

 Light ends Heavier distillates make more light ends from breaking more complex sulfur
molecules

 Unsaturated carbon-carbon bonds

 Olefins saturated – one hydrogen molecule added for each double bond Olefins
prevalent in cracked streams – coker or visbreaker naphtha, catalytic cracker cycle oil,
catalytic cracker gasoline

 Aromatic rings hydrogenated to cycloparaffins (naphthenes) Severe operation Hydrogen

consumption strong function of complexity of the aromatics prevalent in heavy distillate
hydrotreating, gas oil hydrotreating, hydrocracking

 Selective catalysts available for hydrotreating cat gasoline for sulfur removal but not saturate
olefins

 Maintain high octane ratings

Hydrogen Consumption[1-2,12-16]

 Chemical consumption due to hydrogenation reactions

 Cracking reactions of carbon-carbon bonds minimal in hydrotreating, even during

aromatic saturation

 Hydrogen is lost in equilibrium with light gases

 Amount is significant and may double amount required for sulfur removal

 Hydrogen absorbed in liquid products

 Usually small compared to sulfur removal needs – 1 lb/bbl

 Hydrogen removed with purge gas

 Used to maintain a high purity of hydrogen — light ends dilute the hydrogen
concentration

 Usually small compared to sulfur removal needs

General Effects of Process Variables[1-2,12-16]

  Reactor inlet temperature and pressure

 Increasing temperature increases hydrogenation but decreases the number of active

catalyst sites

 Temperature control is used to offset the decline in catalyst activity

 Increasing pressure increases hydrogen partial pressure and increases the severity of
hydrogenation

 Recycle hydrogen

 Require high concentration of hydrogen at reactor outlet Hydrogen amount is much

more than stoichiometric High concentrations required to prevent coke laydown &
poisoning of catalyst Particularly true for the heavier distillates containing resins and
asphaltenes

 Purge hydrogen

 Removes light ends and helps maintain high hydrogen concentration

 Naphtha hydrotreated primarily for sulfur removal

 Mostly mercaptans (RSH) and sulfides (R2S)

 Some disulfides (RSSR), and thiophenes (ring structures)

 Cobalt molybdenum on alumina most common catalyst

 Chemical hydrogen consumption typically 50 to 250 scf/bbl

 For desulfurization containing up to 1 wt% sulfur — 70 to 100 scf/bbl

 Significant nitrogen and sulfur removal — 250 scf/bbl

Naphtha Hydrotreating Process[1-2,12-16]

Fig:6.10 Naphtha Hydrotreating Process

 Liquid hourly space velocity ~ 2

 Hydrogen Recycle about 2000 scf/bbl

 Stripper overhead vapour to saturate gas plant

 Recovery of light hydrocarbons and remove H2S

 Fractionator Pentane/hexane overhead to isomerization

 Bottom to reformer

Hyrdoprocessing Basics[1-2,12-16,31-33]
Fig:6.11 HydroProcessing Family

INTRODUCTION

 Why Hydro processing ?

 Need to increase automotive fuel yield and quality

 Petroleum fractions contain organic Sulfur, Nitrogen etc. which cause Increased air pollution
Equipment corrosion

 Difficulties in further processing (catalyst poisoning etc.)

 Stringent Government regulation for Sulfur in fuel.

What is Hydroprocessing[1-2,31-35]

Hydrotreating

 Remove hertro atoms and saturation of carbon-carbon bonds

  Nitrogen,oxygen and metals removed

 Olefinic and Aromatic bonds saturated

 Reduced average molecular weight and produce higher yields of fuel products

Hydrotreating[1-2,30-35]

 Catalystic Hydrogenation process to remove contaminats(S,N,O) to upgrade fuel quality with

negligible effect on their boiling range

 Also saturate olefins/aromatics to improve Cetane

 Degree of hydroprocessing depends uppon the nature of feedstock & extends of pollutants
removal required

 Used to upgrade Gasoline,Diesel and Lube base stocks.

Hydrotreating[1-2,30-35]

 Sulphur is converted to hydrogen sulphide H2S

 Added hydrogen breaks carbon-sulphur bonds & saturates remainining hydrogen

carbons

 Creates some light ends

 Heavy distillates makes more light ends from breaking more complex sulphur molecules

 Form of sulphur bonds

 Sulphur is naphtha Mercaptans(Thiols) and sulfides

 In heavier feeds,more sulphur as Disulphides and Thiopenes

 Nitrogen is converted to ammonia(NH3)

 Pyridines and Pyyroles are nitrogen containing componds

 Nitrogen removal minor in naphtha hydrotreating

 As the feeds become heavier de-nitrogenation becomes more significant,such as heavy distillate
and gas oil hydrotreating

 Nitrogen removal requires about 4 times as much hydrogen as equivalents of sulphur removal
Major Hydrotreating Reactions[1-2,30-35]

Removal of Hetro Atoms

Major hydrotreating reaction[1-2,30-35]

Hydrotreating-Effect of Process Variables[1-2,30-35]

Reactor inlet temperature and pressure

 Increasing temperature increases hydrogenation but decreases the number of active catalyst
sites

 Temperature control is used to offset the decline in catalyst activity

 Increasing pressure increases hydrogen partial pressure and the increases the severity of
hydrogenation

Recycle Hydrogen

Requires high concentration of hydrogen reactor outlet

 Hydrogen amount is much more than stoichiometric

 High concentration require to prevent coke laydown and poisoning of catalyst

  Particularly true for the heavier distillate containing resins and asphaltenes

Pure Hydrogen

 Help to maintain high hydrogen concentration

Increases severity

 Naphtha Hydrotreating

 Distillate(Light and Heavy) hydrotreating

 Gas oil hydrotreating

Fig:6.12 Hydrogen Consumption

Fig:6.13 HydroProcessing Catalyst share in Refinery

Hydrotreating Trends[1-2,24,30-35]

Trend is more hydroprocessing is driven by several factors :-

 Heavier and higher sulphur crudes

 Reduction in demand for heavy fuel oil

 Increased used of hydrodesulfurization for low sulphur fuels

 More complete protection Of FCCU cactalyst

 Demand of high quality coke

Fig:6.14 Catalyst in DHDS/DHDT Reactor
Fig:6.15 Catalyst in Hydrocracking Reactor

Challenges in HydroProcessing[1-2,30-35]

 Design of new catalyst formulation for :-

o Diesel end point reduction

o Selective ring opening for cetane improvement with less hydrogen consumption

 Design of improved reactor internals

 Process and catalyst for slurry reaction based hydroprocessing

Table:6.7

Reaction Chemistry-Indicative Quality Changes

Reaction Hydrogen Density Boiling Point Cetane

moles kg/m3 °C Number

1-2 2 -40 -16.5 +10

1-2-3 3 -110 -28 +45

1-2-4 5 -90 -16.5 +30

Good Distributors
  Decrease radial thermal distributions

 Increase volume for catalyst loading

Leading to

 Increased cycle length

 Higher throughput

 Increase conversion

 Improved product quality

 Improved product consistency

Naphtha Hydrotreating-Hydrogen Consumption[1-2,30-35]

 For desulphurisation containing upto 1 wt% sulphur 70 to 100 scf/bbl

 Higher nitrogen levels increase hydrogen consumption proportionately

 Signifant nitrogen and sulphur removal-250 scf/bbl

This is chemical hydrogen consumption

 Add for mechanical loss and loss with the light hydrocarbon vapours
Fig:6.16 Naphtha Hydrotreating-Process

Naphtha Hydrotreating - Process[1-2,30-35]

 Feed & hydrogen fed to furnace

 Vapors passed down - flow over the catalyst bed

 Outlet vapors about 370°C

 Outlet cooled and flashed at 370°C to separate light ends

 Exchange with feed(for heat integration)

 Final exchange with cooling water

 Single stage flash adequate

  Bulk of flash gas recycled

 Flashed liquid fed to stripper for removal of light ends of hydrogen sulphide and sour water

Distillate Hydrotreating

 In general , all liquid distillate Streams contain sulfur compounds that must be removed needs
the treatment.

 Saturation of aromatics in diesel is essential to improve the cetane number.

Distillate Hydrotreating-Hydrogen Consumption[1-2,30-35]

 Light distillate hydrotreating (kerosene and jet fuel) requires more hydrogen than Naphtha
hydrotreating.

Heavy distillate (diesel) hydrotreating consumption quite variable

 Can consume considerable quantities of hydrogen at higher severity

 Hydrogen consumption and operating pressure are a function of the stream being treated, the
degree of sulfur and nitrogen removal, olefin saturation, aromatic ring saturation,…..

Typical conditions – 300oC – 425oC ; 300 psig and greater Modest temperature rise since reactions are
exothermic

 Hydrogen recycle rate starts at 2,000 scf/bbl;

 Consumption of 100 to 400 scf/bbl

 Conditions highly dependent upon feedstock

 Distillate (jet fuel & diesel) with 85% - 95% sulfur removal

 300 psig & hydrogen consumption of 200-300 scf/bbl

 Saturation of diesel for cetane number improvement

 over 800 scf/bbl hydrogen & up to 1,000 psig

Fig:6.17 Typical Distillate Hydrotreater for Base Metal Catalyst

Gas Oil Hydrotreating[1-2,30-35]

 Catalystic cracker feed stocks (atmospheric gas oil, light vacuum gas oil, solvent deasphalting gas
oil) hydrotreated severely Sulfur removal Opening of aromatic rings removal of heavy metals

 Desulphurization of gas oil can be achieved with a relatively modest decomposition of structures
Gas oils can be contaminated with resins and asphaltenes deposited in hydrotreater.

 Require catalyst replacement with a shorter run length than determined by deactivation

 Guard chamber may be installed to prolong bed life Nickel Molybdenum catalyst system from
severe hydrotreating

Gas Oil Hydrotreating - Process[1-2,30-35]

  Normally requires two reactors with two beds

 Effluent from the second reactor is flashed in to two stages

 High-pressure flash provides recycle of hydrogen gas

 Low-pressure flash separates light ends for hydrogen sulfide recovery

 Low-pressure flash liquid is treated as gas oil and sent to catalyst cracker

 The initial temperature is expected to be of the order of 350°C

 Hydrogenation highly exothermic-care must be taken to avoid runaways

Hydrocracking Trends[1-2,30-35]

Hydrocracking does a better job of processing aromatic rings without cooking than catalystic cracking

 Hydrogen reduced to hydrogenate polynuclear aromatics(PNAs)

 Reduce the frequency of aromatic considensation

 Hetroatom and metals prevalents in resins and asphaltenes poison hydroprrocessing catalyst

Feedstock selection is much more sophisticated than determination of CCR

 Distribution of aromatic,naphthenic and paraffinic structure is important

Hydrocracking Feeds

 Typical Feeds

 Cat cracker "cycle oil"

 Cat cracker "cycle oil"

 Highly aromatic with sulphur,small ring and polynuclear aromatics,catalyst fines usually
has high vescosity

 Hydrocracked to form high yield of jet fuel,kerosene,diesel & heating oil

 Gas oil from visbreaker

 Aromatic
  Gas oil from delayed cocker

 Aromatic olefinic with sulphur

Residue Hydrotreating[1-2,30-35]

Residuum technology is widely used for pretreating residuum to produce RFCC feed,hydrotreating coker
feed,hydrotreating visbreaker/FCC feed or to produce Low sulphur Fuel Oil(LSFO)

Most new residuum hydrotreating units pretreat for an RFCC,allowing a very high conversion to high
value product with this combined processing

The RDS process reduces metals,sulphur,nitrogen and carbon residue in the residuum

By pretreating the residuum with an RDS,the yields and quality of RFCC products are greatly improved

Residue Hydrocracking

This technology provides the means to convert residuum to lighter petroleum fraction such as naphthna
and distillates are greater than 70% conversion of heavy residual 975° F (524° C) material

The unconverted residue is usually blended as fuel oil as if the conversion is less than 80%

Conversion greater than 80% & as high as 97% has been achieved commercially but the unconverted
residue may be unstable as a fuel oil blend stock

Along with high conversion,feed desulphurization of 80-85% is typical for most designs

Hydrotreating of Diesel[1-2,30-35]

Unionfining

Fixed bed catalysic process developed by UOP

Adopted for diesel Hydro-desulphurization

Key Features

 Operates at about 36 Kg/cm2

  Operates at about 360-400°C temperature

 Hydrogen is consumed

 Heat is released

 Products are saturated

 Products are nearly free of hetero atoms(S,N,O)

HYDROTREATING FLOW SHEET[1-2,30-35]

Fig:6.18 Hydrotreating Flow Sheet

DHDS Process Variable[1-2,30-35]

 Some important process variable affects the catalyst stability and product quality

 These variable needs to be monitored regularly for consistent operation & longer cycle length

 The Process Variables :-

  Reactor temperature

 Feed rate quality

 Liquid Hourly Space Velocity

 Recycle gas rate

 H2S partial pressure

DHDS Process Variable

Reactor Temperature

 Temperature of the reactor effluent is more than that of the reactor inlet stream

 The hydesulphurisation reaction are exothermic

 The reactor temperature is most vital control parameter

 Best way to control reactor temperature is to control WABT by adjusting quench flow

 Increasing reactor temperature increases severity of reaction of constants like H2 partial

pressure

 Higher reactor temperature causes more hetero atom(S,N,O) removal and saturation

 Higher reaction leads to higher catalyst deactivation (more coke deposit) and lower cycle time of
plant

 Higher reactor temperature may have adverse impact on treated diesel color stability

Feed Quality & Rate

 DHDS feed streams are SR Gas oil,LCO from FCCU,gas oil from CIDW,kerosene cuts etc.

 Straight run components are easier to treat

 Cracked product /unsaturated are difficult to process as they require more heat during reaction

 Regular monitoring of SG,sulphur contents of feed is vital

 Higher S content in feed requires more severity,H2 consumption and H2S reaction

 Liquid hourly space velocity is defined as M3/Hr of feed (at 15°C)per M3 of catalyst

 Design value of LSHV depends upon feed stock quality,product quality stipulation and
channeling that may occur inside reactor,leading to unusual deactivation of catalyst bed
  Operate near design value,do not go below trundown ratio

H2 Partial Pressure[1-2,30-35]

 This is the design criteria and critical process variable for good hetero atom(S,N,O) removal

 It is defined as System Pressure * H2 Purity

 Lower H2 partial pressure reduces reaction rate

 Lower H2 partial pressure increases rate of coke deposition on catalyst

 Lower H2 partial pressure leads to higher reactor temperature the (S,N,O)removal and reduce
cycle length

Recycle Gas Rate

Higher Recycle Gas Flow Rate Helps in

 Supplying excess H2 is to ensure reaction completion

 Absorbing heat of reaction to control bed temperature

 Ensuring good linear velocity in heater and exchange to control temperature

 Another related process variable is gas-to oil ratio and has same effect.It is defined as Total gas
flow(NM3/Hr)/Feed rate(NM3/Hr)at 15°C

Hazards of Hydrogen[1-2,13-16,30-35]

Hydrogen gas is colorless and odorless and not detectable by human senses

Properties of Hydrogen

What Is Hydrogen?

Hydrogen is a colorless, odorless, tasteless, flammable nontoxic gas. It is the lightest of all gases, with a
specific gravity of 0.0695. The hydrogen content of atmospheric air at sea level is 0.5 ppm. Hydrogen has
two isomers (forms): ortho-hydrogen, in which the two atomic nuclei spin in the same direction; and para-
hydrogen, in which they spin in opposite directions. There is no difference in the chemical properties of the
two forms of hydrogen, but there are slight differences in physical properties. Gaseous hydrogen is a
mixture of 75% ortho-hydrogen and 25% para-hydrogen at room temperature; this mixture is called normal
hydrogen (CGA G5 1991).

Hydrogen Has Unique Properties[1-2,13-16]

Several unique properties contribute to the hazards associated with gaseous and liquid hydrogen
systems:

 Hydrogen is flammable over a wide range of concentrations.

 The ignition energy for hydrogen is very low.

 A single volume of liquid hydrogen expands to about 850 volumes of gas at standard
temperature and pressure when vaporized. At 7,000 ft elevation, this expansion rate is
increased to approximately 1,000 volumes of gas at standard temperature.

 Hydrogen is able to reduce the performance of some containment and piping materials, such as
carbon steel.

Properties of Hydrogen continued[13-16]

Flammability

Hydrogen burns with a nearly invisible bluish flame, unless it is contaminated with impurities, in which
case a pale-yellow flame is easily visible in the dark. The temperature of burning hydrogen in air is high
2050 oC (3,713 oF), as compared with 1250 oC (2,276 oF) for gasoline), and warm hydrogen gas rises rapidly
because of its buoyancy. Hydrogen forms a flammable mixture over a wide range of concentrations in air
and requires a minimum ignition source, only one-tenth of the energy required for gasoline vapors. It is the
combination of these factors that contributes to the flammability hazard associated with hydrogen gas.
(See the table below for a summary of the physical properties of hydrogen.)

Embrittlement

Because of its small molecular size, hydrogen can easily pass through porous materials and is capable of
being absorbed by some containment materials, which can result in loss of ductility or embrittlement. At
elevated temperatures, this process is accelerated. Because of the possibility of hydrogen embrittlement of
some materials, piping and component materials that are not subject to this form of degradation should be
selected.Recommended materials include 300-series stainless steels, copper, and brass.
 Properties of Hydrogen continued

The following table lists the physical properties and characteristics of hydrogen and their values.

Table:6.8

Physical Properties and Characteristics of Hydrogen

Property/Characteristic Values(approximate)

None

None

Toxicity Nontoxic

Density/Liquid(boiling point) 4.4lb/ft3 (0.07 g/cm3)

Boiling Point(1atm) -423.2 F (-252.9°C)

Critical Temperature(188.2 paisa) -400.4 F(-240.2°C)

stoichiometric mixture in air 29 vol %

Flammability limits in air 4-75 vol %

Detonation limits in air 18-60 vol %

Minimum ignition energy in air 20 uj

Autoignition temperature 1,085 °F(585 °C)

Volume Expansion
1:53
Liquid(-252.9°C) to gas (-252.9°C)
1:16
gas(from -252.9°C to 20 °C)
1:848
liquid(-252.9°C)to gas (20°C)

Hazards of Hydrogen[13-16,36]

Flammability and Explosivity are Primary Hazards

The primary physical hazards associated with hydrogen gas are its flammability and explosivity. This is
because hydrogen can form a flammable mixture with air over a wide range of concentrations (4%Ð75%),
and very low energy is needed to ignite hydrogen-air mixtures. Once hydrogen is ignited, the reaction can
proceed either by deflagration (subsonic propagation) or detonation (supersonic propagation). Deflagration
in a closed volume can cause a pressure increase of almost eight times the initial pressure. Detonation from
a low-energy ignition source is possible in hydrogen-air mixtures of 18 to 60% vol% that are well mixed and
confined. Although hydrogen - air mixtures have the same calorific value per pound as TNT, the rate of
energy release is much slower for hydrogen-air mixtures.

Hydrogen detonations, although rare, are characterized by pressure increases so rapid that pressure-
relief devices are usually ineffective. When using hydrogen in enclosed areas, consult National Fire
Protection Association documents 68 and 69.

Effects on Health

Hydrogen is nontoxic and has even been used as a filler for oxygen sources for underwater diving. The
primary health effect associated with hydrogen is the possibility that it could displace air in a poorly
ventilated or confined space, resulting in asphyxiation. However, because it is flammable at only 4% in air,
the most significant concern should be the physical hazard of flammability and the possibility of burns
resulting from fires and explosions. When working with liquid hydrogen, there is an additional health
hazard of cryogenic burns.

Table:6.9

Flammability Limits

Hydrogen Propane

LFL 4.1% 2.1%

UFL 75% 9.5%

Explosive Limits

LEF 18.3 UEL 59

Average velocity in air at 20°C

Hydrogen Oxygen
 39MPH 10MPH

Auto ignition temperature °C

Hydrogen Propane

400 450

An invisible spark or static spark from a person can cause ignition

 Hydrogen therefore easily ignited and burns rapidly

 Hydrogen-pure air flames are colorless

 Colorless Hydrogen flames can cause severe burns

 For occuptional exposure H2 is classed as as aphyxiant

Isomerization process, Reactions, Effects of process variables

Isomerization process, Reactions, Effects of process variables.

Isomerization[1-3]

The octane numbers of the LSR naphtha [C5-180oF (C5-82oC)] can be improved by
the use of an isomerization process to convert normal paraffins to their isomers.This
results in significant octane increases as n-pentane has an unleaded (clear) RON of
61.7 and isopentane has a rating of 92.3. In once-through isomerization where the
normal and iso compounds come essentially to thermodynamic equilibrium, the
unleaded RON of LSR naphtha can be increased from 70 to about 82–84. If the normal
components are recycled, the resulting research octane numbers will be about 87–93
RONC.

Reaction temperatures of about 200–400oF (95–205oC) are preferred to higher

temperatures because the equilibrium conversion to isomers is enhanced at the lower
temperatures. At these relatively low temperatures a very active catalyst is necessary
to provide a reasonable reaction rate. The available catalysts used for isomerization
contain platinum on various bases. Some types of catalysts require the continuous
addition of very small amounts of organic chlorides to maintain high catalyst activities.
This is converted to hydrogen chloride in the reactor, and consequently the feed to
these units must be free of water and other oxygen sources in order to avoid catalyst
deactivation and potential corrosion problems. A second type of catalyst uses a
molecular sieve base and is reported to tolerate feeds saturated with water at
ambient temperature.

A third type of catalyst contains platinum supported on a novel metal oxide base.
This catalyst has 150oF (83oC) higher activity than conventional zeolitic isomerization
catalysts and can be regenerated. Catalyst life is usually three years or more with all of
these catalysts. An atmosphere of hydrogen is used to minimize carbon deposits on
the catalyst but hydrogen consumption is negligible .The composition of the reactor
products can closely approach chemical equilibrium. The actual product distribution is
dependent upon the type and age of the catalyst, the space velocity, and the reactor
temperature. The pentane fraction of the reactor product is about 75 to 80 wt% iso-
pentane, and the hexane fraction is about 86 to 90 wt% hexane isomers .

Isomerization Processes[1-5]

 Vapor phase process

 Hydrogen used to suppress the dehydrogenation and coking.

 High yields and high selectivity to high-octane isomeric forms.

 Provides moderate (but important) contribution to the gasoline

pool.

 Catalyst types

 Chloride alumina catalyst.

 Organic chloride deposited on active metal sites.

 High temperature treatment with carbon tetrachloride.

 Chlorides are sensitive to moisture – drying of feed & hydrogen.

 Make-up essential

 Acidic zeolite with noble metal catalyst.

 Platinum catalyst.

 Does not require activation by hydrogen chloride.

Isomerization Processes[1-7]

 Pros

 Reforming conditions not appropriate for the paraffinic

components in SRG.

 Essentially zero benzene, aromatics, & olefins.

 Very low sulfur levels.

 Cons

 High vapor pressure.

 Moderate octane levels — (R+M)/2 only 85.

Feedstocks

 Lightest naphtha feed stock (SRG) with pentanes, hexanes, and small
amounts of heptanes.

 Feed often debutanized —"Debutanized Straight Run".

 Sulfur and nitrogen must be removed since catalysts employ an ‘acid site’
for activity.

 Merox

 Clay treating

 Hydrotreating

 Common for Straight Run Gasoline and Naphtha to be hydrotreated as one

stream and then separated.

Products

 Products

 Isoparaffins and cycloparaffins.

 Small amounts of light gasses from hydrocracking .

 Unconverted feedstock.

 Increased severity increases octane but also increases yield of light ends.
  Yields depend on feedstock characteristics and product octane.

 Poor quality feeds might yield 85% or less liquid product.

 Good feeds might yield 97% liquid product.

Catalytic Reforming and Isomerization [3-9]

If the normal pentane in the reactor product is separated and recycled the product
RON can be increased by about 3 numbers (83 to 86 RONC).If both normal pentane
and normal hexane are recycled the product clear RON can be improved to about 87
to 90. Separation of the normals from the isomers can be accomplished by
fractionation or by vapor phase adsorption of the normals on a molecular sieve bed.
The adsorption process is well developed in several large units.

Some hydrocracking occurs during the reactions resulting in a loss of gasoline and
the production of light gas. The amount of gas formed varies with the catalyst type
and age and is sometimes a significant economic factor. The light gas produced is
typically in the range of 1.0 to 4.0 wt% of the hydrocarbon feed to the reactor. For
preliminary estimates the composition of the gas produced can be assumed to be 95
wt% methane and 5 wt% ethane. For refineries that do not have hydrocracking
facilities to supply isobutane for alkylation unit feed, the necessary isobutane can be
made from n-butane by isomerization. The process is very similar to that of LSR
gasoline isomerization but a feed deisobutanizer is used to concentrate the n-butane
in the reactor charge. The reactor product is about 58 to 62 wt% isobutane. A
representative flow scheme for an isomerization unit is shown in Figure below.
Fig:7.1 A representative flow scheme for an isomerization unit

Isomerization Chemistry

 Primary reaction is to convert normal paraffins to isomeric paraffins.

 Olefins may isomerize and shift the position of the double bond.

 1-butene coluld shift to a mixture of cis-2-butene and trans-2-

butene

 Cycloparaffins (naphthenes) may isomerize and break the ring forming an

 olefin.

 Cyclobutane to butene.

Example

Cost Included

1. Feed Drying

2. Drying of hydrogen makeup

3. Complete preheat reaction and hydrogen circulation facilities

4. Product stabilization

5. Sufficient heat exchange to cool product to ambient temperature

6. Central control

7. Paid up royality

Cost not Included

1. Hydrogen source

2. Cooling water,steam and water supply

3. Feed desulfurization

4. Intial catalyst charge about $100/BPD of reactor feed

Royalities

 Paid up rayalty is about $90 to$160/BPD

Utility data(per bbl,"fresh"feed)

Power Kwh -1.0
Cooling water gal(0CoF) 600-1000
Fuel(LHV),MMBtu 0.20
Catalyst replacement,$ 0.05
Hydrogen makeup,sef 40

Example Problem

Calculate the length of time between regeneration of catalyst in a reformer

operating at the following conditions:

Liquid hourly space velocity (LHSV) = 3.0 v/hr/v

Feed rate = 5000 BPSD
 Feed gravity = 55.0oAPI
Catalyst bulk density =50 lb/ft3
Hydrogen-to-feed ratio = 8000 scf/bbl
Number of reactors =3
Catalyst deactivates after processing 90 barrels of feed per pound of catalyst.If the
catalyst bed is 6 ft deep in each reactor, what are the reactor inside diameters?
Assume an equal volume of catalyst in each reactor.

Solution

Time between regenerations:

5000 BPD =1170 ft3/hr
Total catalyst = 1170/3 = 390 ft3
(390 ft3) (50 lb/ft3) = 19,500 lb
(19,500 lb) (90 bbl/lb)/5,000 bbl/day = 351 days
Inside diameter:
Volume of catalyst per reactor = 390/3 = 130 ft3
Inside area = (130 ft3)/(6 ft) = 21.67 ft2
Inside diameter = 5.25 ft

Alkylation process, Feedstocks, reactions, products, catalysts and effect of process variables

Catalytic Alkylation[1-7]

Catalytic alkylation process is used in refineries to upgrade light olefins (produced

from catalytic crackers as well as from cokers viz breakers) and isobutene into a
highly branched paraffins. In petrochemical industry it is used to produce alkylate
benzenes and other petrochemical products.

The alkylation reaction involves the addition of photon H+( supplied by an acid
catalyst),to the double bond of an olefin to form carbonium ion. This ion then adds
to another olefin molecule to form a new carbonium ion which abstracts a hydride
ion, H-, and from isobutene to become a paraffin. At the same time new carbonium
ion is produced to continue the reaction.

STEP 1: Addition of proton H+(supplied by Acid catalyst to propagate double bond

of olefin)

Carbonium ion Formation[5-12]

STEP 2: Addition of this ion to another olefin.

STEP 3: Abstraction of Hydride ion H- from olefin.

Alkylation process are conducted by Lewis acids like sulphuric acid, hydrofluoric
acid, aluminium chloride (obsolete). Highly exothermic reaction HP = - ( 630 to 700
Btu/lb for isobutane alkylation).

Side Reactions

Feed Stocks

i-butane, Propenes, butenes.(olefins and isobutenes are alkylation feed stocks)

T = 10-20o C for H2SO4 alkylation.
Low temperature required for H2SO4 because at higher temperature tar formation
occurs due to oxidation-reduction reactions.
Acid strength 88-90% .High Acid concentration – for alkylation reaction.Weaker
acid gives polymerization reaction.

For HF, temperature is higher T ~ 38oC .Liquid phase reaction in both cases.

Process for H2SO4 alkylation:[5-12]

Fig:7.2 Sulphur Acid Alkylation Processes

Process has been applied to isobutanes and butenes.

Important features:

Absorption of olefinic HC occurs hundred times faster as fast as the absorption of

paraffins and sent to the stabilizer hence in order to maintain proper concentration
of the two HC in the acid. It is necessary to recycle large access of saturated HCs
through the system. Higher the ratio of paraffin to olefin in the feedstock, greater
the yield, higher O/W and smaller the acid consumption.

Operating Variables:
Acid concentration is kept high because of strong acid catalyst alkylation reaction
where as acid catalyst polymerization reaction occurs.

Cascade Refrigeration Process

Fig:7.3 Cascade Refrigeration Process

Uses of multistage reactors with mixers at each stage is to emulsify the

hydrocarbon and mixture of olefin in split in parallel in various reactions occurs
whereas i-butane in series feed to the system. This increases i-butane to olefin
ratio. Refrigeration by vaporization of a portion of hydrocarbon in each reaction is
necessary.
H F alkylation:

 Highly successful process for combining isobutane and isobutene.

 No refrigeration.

 Feed is dried.

Special material of construction is required (monel) because HF is very much

corrosive.
HF process is favorable for small plant but for large plant H2SO4 catalytic process is
used.

Process Variables (Alkylation):

(for both process) Major Variables are:- Reaction T, Acid strength, I-butane
concentration, olefin space velocity.

Reaction Temperature:

Low T increases octane number & reduces H2SO4acid requirements.Unfortunately

low T also requires higher refrigeration investment & operating cost. Miixing is
difficult.

High T ---> acid attacks the olefins significant sensitive to temp.

HF alkylation ---> less sensitive to temperature. Increase in T from 30Co to 100oC.

Isobutane Recycle Rate:

High isobutane recycle rate increases the octane number and lowers acid
requirements. However high isobutane rate also increases the investment required
for deisobutanizer and increase the operating cost of the tower because of the
higher steam requirements.

Space Velocity:

velocity of olefin/h / velocity of acid in reactor.Low space velocity increases octane

number and lowers acid requirements.High space velocity increases formation of
acid sulphates which are corrosive to downstream fractionation facilities.

Spent acid strength:

High spent acid strength tends to increases octane No, but also increases make up
acid requirements. Low spent acid strength tends to decrease make up acid
requirements, it increases risk of acid runaway.93-95% acid by weight, 1-2% water
remainder, Hc diluents. Some water is initially added to the acid which promotes
the proton transfer for alkylation reaction. Lowering olefin space velocity reduces
the amount of High boiling hydrocarbon produced, increases the product octane
and lowers acid consumption.

Contact Time:

Residence time of (fresh feed + external recycled i-butane in the reactor.)

5-25 minute-->HF alkylation
5-40 minute-->H2SO4 alkylation
Isobutane concentration:

Excess of i-butane/olefin ratio desirable. It increases the octane number. Catalytic

consumption is less.

Miixing:

i-butane solubility in H2SO4--> 0.1% by weight

i-butane solubility in HF-->3% by weight
solubility of i-butane in acid is very small (sparingly soluble) Olefins relatively
soluble in acids. So proper mixing is required otherwise polymerization will take
place instead of alkylation.

IE ---> isobutane in reactor effluent.

(I/O)F ---> (value of isobutane/olefin) in feed.
(SVo) ---> olefin space velocity

F = 10-40
Higher the 'F' better is the Quality product.

Alkylation of benzene:

With ethylene -----> gives ethylbenzene Starting material for styrene production cat
AlCl3
CH2= CH2 + HCl -----> CH3CH2Cl
HCl is used as promoter for Aluminium Chloride and lowers its consumption.

Exothermic reaction ΔH = 110 KJ/mol

Dehydration of ethylbenzene gives styrene.
Cat Fe2CO3 with metallic oxide or ZnO
T = 600Co – 630oC
Addition of K2CO3 reduces coke on catalyst.

Cumene:By alkylation of propylene with benzene yields Isopropylbenzene.

Cumene is used for production of phenol and methyl styrene.

Alkylation and polymerization[1-2,7-12]

The addition of an alkyl group to any compound is an alkylation reaction but in

petroleum refining terminology the term alkylation is used for the reaction of low
molecular weight olefins with an isoparaffin to form higher molecular weight so
araffins Although this reaction is simply the reverse of cracking, where as that of
paraffin hydrocarbons are chemically inert and belived to be delayed in its
discovery until 1935. Although alkylation can take place at high temperatures and
pressures without catalysts, the only processes of commercial importance involve
low temperature alkylation conducted in the presence of either sulfuric or
hydrofluoric acid. The reactions occurring in both processes are complex and the
product has a rather wide boiling range. By proper choice of operating conditions,
most of the product can be made to fall within the gasoline boiling range with
motor octane numbers from 88 to 94 and research octane numbers from 94 to 99.

Alkylation of olefins was developed to improve the octane of aviation

gasoline.Catalyst: aluminum chloride

 FCC significantly increased the production of light ends. High concentration

of the C2, C4, & C5 isomers, both olefinic & paraffinic which led to
development of both catalytic polymerization and alkylation.Processes are
used to make gasoline components from materials that are too light to
otherwise be in gasoline.

 Alkylation forms a longer chain highly branched isoparaffin by reacting an

alkyl group ( isobutane) with a light olefin ( butylene). This process
produces high-octane gasoline.

 Polymerization is the formation of very short chains product is nearly all

olefinic high research octane but moderate motor octane number. Sulfuric
acid, hydrogen fluoride, and aluminum chloride are the main catalysts used
commercially. Sulfuric acid is used with propylene and higher- boiling
feeds, but not with ethylene because it reacts to form ethyl hydrogen
sulphate and a suitable catalyst contains a minimum of 85% acidity. The
acid is pumped through the reactor and forms an air emulsion with
reactants. The emulsion is maintained at 50% acid. The rate of deactivation
varies with the feed and iso-butane change rate. Butene feedstocks cause
less acid consumption than propylene feeds. Aluminum chloride is not
widely used as an alkylation catalyst , but when employed hydrogen
chloride is used as a promoter and water is injected to activate the
catalyst .

 The form of catalyst is an aluminum chloride–hydrocarbon complex, and

the aluminum chloride concentration is 63% to 84%. The advantage of
hydrogen fluoride is that it is more readily separated and recovered from
the resulting product. The usual concentration is 85% to 92% titratable
acid, with about 1.5% water.

Sulfuric Acid Alkylation

 A consortium of major refiners and contractors developed process with

sulfuric acid as the catalyst.

 Sulfuric acid alkylation required access to acid regeneration on a large

scale.
  Most sulfuric acid alkylation plants were located on deep water for
barge transport of spent acid to regeneration at acid plants &
return of fresh acid.

HF Acid Alkylation

 Phillips Petroleum & UOP developed process using hydrofluoric acid as a

catalyst.

 HF could be readily regenerated in alkylation plant facilities.

 No need to transport catalyst in large quantities for regeneration.

 HF alkylate in general was not quite as high quality as sulfuric acid alkylate.

Feedstocks

 Olefinic stream from the catalytic cracker.

 Butylene is the preferred olefin since it produces the highest

octane number & yields.

 Isobutane & isopentane can be reacted with the olefin- Isopentane

not usually used since it is a good gasoline blend stock.

 High octane number & low vapor pressure.

 Catalytic cracker feed contains significant sulfur.

 Treating unit often precedes alkylation unit.

Products

 Alkylate desirable component for high performance automotive fuels.

 Very high octane index (R+M)/2 of 95.

 Low vapor pressure.

 Vapor pressure is adjusted for final boiling point.

 IBP adjusted for addition of normal butane.

 Low sulfur levels.

  Essentially no olefins, benzene or aromatics.

 Contributes large volume to the gasoline pool (19% vol).

 Catalytic cracker (34% vol).

 Reformer (28% vol).

 Isomerization unit (15% vol).

Process Chemistry

 Propylene, butylene, & pentenes are olefins used —butylene preferred.

 High octane isooctane alkylate produced.

 Lower reactant consumption.

 Alkylation reactions have complex mechanisms & it may produce many

different varieties.

Alkyaltion and Polymerisation Reaction [5-15]

  Formation of tert-butyl carbonium ion:

Operating Variables & Their Effects

 Capacity is expressed in terms of alkylate product, not feed capacity.

 Most important variables are type of olefin (Propylene, butylene, or

pentene), Isobutane concentration, Olefin injection & mixing, Reaction
temperature, and Catalyst type and strength.The critical measures for
success is based on the Alkylate octane number, volume olefin and
 isobutane consumed per volume of alkylate produce, degree of undesirable
side reactions, and acid consumption.

These effects are briefly discussed below:

 Type of Olefin

 Butylene is preferred.

 Produces the highest isooctane levels.

 Resulting Research Octane Numbers of 93-95 (with

isobutane).

 RON and MON are about equal for alkylation.

 Amounts of butylene consumed per alkylate produced is

the lowest.

 Side reactions are limited.

 Propylene is worse.

 Octane numbers are low (89-92 RON).

 Propylene and acid consumption are high.

 Pentene results are mixed.

 Side reactions are frequent

 Isobutane concentration.

 Excess isobutane required —normal volume ratio of isobutane to

olefin in the feed is 6-10.

 Limited isobutane solubility in acid phase.

 Olefins need to be surrounded by isobutane exposed to

acid — if not, olefins will polymerize instead of alkylate.

 Newer plants have multi injection and vigorous mixing systems.

 Effect of isobutane is expressed in terms of concentration

in the reaction zone

 Isobutane to olefin ratios maintained at 10,000 to 1.

 Isobutane/Olefin Injection and Mixing.

 More important in sulfuric acid systems.

  Acid viscosity at operating temperatures.

 Provide optimal reaction conditions for the very fast reaction.

 Inject olefin feedstock in incremental fashion to increase

isobutane/olefin ratios

 Newer plants designed for multi-injection locations into an

agitated emulsion to disperse olefin as rapidly as possible.

 Systems with single point injection can easily have an overload of

olefin in the emulsion.

 Leads to lower quality & higher acid consumption from

esterification reactions.

 Reaction Temperature

 Most noticeable variable in both reaction systems.

 Increasing temperature reduces octane number.

 HF systems run at 35oC.

 Sulfuric acid systems run at 7oC.

 Often employ auto refrigeration of the reactant mass to

provide coolant for the reactors.

 Acid Type and Strength

 HF acid strength is not an important variable in the range of 80% to

95%.

 Sulfuric acid strength is somewhat a function of the diluent.

 Water lowers acid activity 3 to 5 times as fast as

hydrocarbon diluents.

 Acid is considered "spent" at around 88% sulfuric acid.

Sulfuric vs HF Acid Alkylation[1-2,5-19]

 Principal difference is operating temperature.

 Sulfuric acid alkylation — refrigeration required

 HF alkylation – can operate at cooling water temperatures.

 Sulfuric acid alkylation is dominant process.

 Sulfuric acid plants require extensive recuperation of the spent acid

 —generally done off site.

 Larger coastal refiners tend to have sulfuric acid alkylation plants

with barge or short haul transportation to acid regeneration
facilities.

 HF plants generally smaller and catalyst regeneration is done inplant with a

small acid makeup.

 Urban community concerns to hazards of HF escape.

Table:7.1

Operating conditions in Alkylation

Variables H2SO4 HF

Iso butane concentration (Vol.%) 40-80 30-80

Total HC contact time (s) 1200-1800 500-1200

Temperature(oC) 2-16 16-46

Acid(Concentration wt.%) 88-95 80-95

Acid in emulsion (vol.%) 40-60 25-80

Polymerization: Objectives, process, Reactions,catalysts and effect of process variables

Polymerisation[1-2,14-21]

Polymerization is a process in which a substance of low molecular weight is

transformed into one of the same composition but of higher molecular weight,
maintaining the atomic arrangement present in the basic molecule. It has also been
described as the successive addition of one molecule to another by means of a
functional group, such as that present in an aliphatic olefin. In the petroleum
industry, polymerization is the controlled process by which olefin gases are
converted to liquid condensation products that may be suitable for gasoline (hence
polymer gasoline, polymerate) or other liquid fuels. The feedstock usually consists
of propylene, propene (CH3-CH=CH2), and butylenes (butenes, various isomers of
C4H8) from cracking processes or might even be selective olefins for dimer, trimer,
or tetramer production:

nCH2=CH2-->H-(CH2CH2)n-H

In this process, n is usually 2 (dimer), 3 (trimer), or 4 (tetramer); the molecular size

of the product is limited to give products boiling in the gasoline range constituents.
Thus, in polymerization all attempts are made to terminate the reaction at the
dimer or trimer (three monomers joined together) stage. The four-carbon to
twelve-carbon compounds that is required as the constituents of liquid fuels are
the prime products. Polymerization may be accomplished thermally or in the
presence of a catalyst at lower temperatures. Thermal polymerization is regarded
not as effective as catalytic polymerization but has the advantage that it can be
used to polymerize saturated materials that cannot be induced to react by
catalysts.

The process consists essentially of vapor-phase cracking of, say, propane and
butane followed by prolonged periods at high temperature (51oC to 59oC)for the
reactions to proceed to near completion. On the other hand, olefins can be
conveniently polymerized by means of an acid catalyst. Thus, the treated olefin-rich
feed stream is contacted with a catalyst (sulfuric acid, copper pyrophosphate, or
phosphoric acid) at 15oC to 22oC and 150 to 1200 psi, depending on feedstock and
product requirement. The reaction is exothermic, and the temperature is usually
controlled by heat exchange. Stabilization and fractionation systems separate
saturated and unreacted gases from the product. In both thermal and catalytic
polymerization processes, the feedstock is usually pretreated to remove sulfur and
nitrogen compounds.

Polymerization ties two or more olefins together to make polymer gasoline. The
double bond in only one olefin is changed to a single bond during each link
between two olefins. This means the product will still have a double bond. For
gasoline, these polymer stocks are good for blending because olefins tend to have
higher octane numbers than their paraffin homologs. However, the olefinic nature
of polymer gasoline can also be a drawback. During long storage in warmer
climates, the olefins can continue to link up to form bigger molecules of gum and
sludge. This effect, though, is seldom important when the gasoline goes through
ordinary distribution systems.

Thermal polymerization is regarded not as effective as catalytic polymerization but

has the advantage that it can be used to polymerize saturated materials that
cannot be induced to react by catalysts. The process consists essentially of vapor-
phase cracking of, say, propane and butane followed by prolonged periods at high
temperature (50oC to 59oC) for the reactions to proceed to near completion.

Polymerization reaction and operating condition[1-2,20-27]

Typical Operating conditions for polymerisation reaction are as follows:

T: 175-240 0C,P:400-1500 psia, space velocity:l/kg-h

SOLID PHOSPHORIC ACID CONDENSATION[1-2]

The catalytic polymerization process operates upon olefin-containing gases at 70C

and 200 pounds pressure, producing a liquid boiling in the gasoline range. Catalytic
dehydrogenation of paraffin gases such as propane and butanes takes place at
350oC. and atmospheric pressure with a yield of over 90 per cent olefins.
Comparison of the various methods of producing gasoline from propane and
butanes shows that two steps are desirable-( 1) dehydrogenation to produce
olefins that readily polymerize and (2) catalytic polymerization of these olefins. The
mildest operating conditions and maximum yields of polymer gasoline are obtained
when each of these operations is carried out under its respective optimum
conditions in the presence of catalysts.

The catalytic gas polymerization process of the UOP operates on olefin-containing

gases. The source of these gases may be the cracking process or the catalytic
dehydrogenation or cracking of propane butanes into olefins. The liquid product
from the polymerization process - within the gasoline range and. As produced, has
an octane rating of 80 to 83 or, on a blending basis, an octane number up to 135,
depending upon the percentage used in the blend and the octane rating of the
gasoline to which it is added. The catalytic polymerization process is carried out to
 polymerise selectively the isobutene present to isooctane in which, it
hydrogenation to yield 95 to 100 octane gasoline. Olefins can be conveniently
polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream
is contacted with a catalyst (sulfuric acid, copper pyrophosphate, or phosphoric
acid) at 15oC to 22oC and 150 to 1200 psi, depending on the feedstock and the
desired product(s). The reaction is exothermic, and temperature is usually
controlled by heat exchange. Stabilization and fractionation systems separate
saturated and unreacted gases from the product. In both thermal and catalytic
polymerization processes, the feedstock is usually pretreated to remove sulfur and
nitrogen compounds. This process converts propylene and butylene to high-octane
gasoline or petrochemical polymers.

Fig:7.4 process converts propylene and butylene to high-octane gasoline or

petrochemical polymers

Lube oil processing:propane deasphalting Solvent extraction, dewaxing,Additives production from

refinery feedstocks

Solvent selection criterion:

Y = extract
X = Raffinate
B = aromatics
A = Non aromatics

Solvent power -> should have high power for aromatics would lead to lower S/F for given
aromatics extraction capability.
Solvent Power generally decreases with increasing selectivity.
T increases the solvent power (exception is propane deasphaltive).
Corrosion -> It should not be corrosive.
Liquid SO2 (for H2O extraction)
70.05 wt% H2O causes severe corrosion.

Toxicity = should not be toxic

 Liquid SO2 need replacement with H2O solvent.

 Phenol extraction of lubes is being displaced by NMP.

Melting point(MP):

MP should be lower than ambient temperature for easy handling.

Interfacial Tension (IFT)[2-6]

 High IFT permits rapid settings due to easier coalescence.

 Low IFT facilitates dispersion (drops are smaller and more interfacial area for mass
transfer) whereas too low IFT lead to emulsification and coalescence.

 Density difference between disperse and continuous phase S must be large for ease of
setting of phases.

 Viscosity: High viscosity of either phase reduces master efficiency.

 Low viscosities are preferred for rapid setting of phases ( more viscosity phase is usually
dispersed).

 Low viscosity is preferred for ease of pumping.

Dewaxing:

Waxes are large MW Paraffinic compounds having melting point 32- 100 °C.
High viscosity Index lube oil cuts: contain large amount of wax.

 Lower wax content: lower the pour point

 Dewaxing is done to lower the pour point.

 All heavy fraction of crude oil contains at least some amount of waxy material.

 Waxes: It can not be distilled as it boils in the range of lubricating oils( can not be distilled)

 Classified based on penetration index and melting point

Dewaxing Process:[6-12]

1. Chilling and Pressing (Filteration).

2. Solvent Dewaxing.

3. Urea Dewaxing- Urea forms complex compound with large chain paraffin i.e wax range
higher molecular weight of HCs but not within the lubrication oil ( some m.w paraffins).

Dewaxing method without soluent (chilling and pressing)

Dewaxing method is simple process but time consuming.Based on the principle of decreases
solubility of wax in cold setting process.

Dilutant such as naphtha added to speed setting.

1. Paraffins wax cannot be separated by setting on certifying.

2. Filteration can be used.

Cold pressing
T= -17 °C (O° F)
P=35°C to 300°C

For microcrystalline wax cold pressing cannot be used because these wax either pass through
filter on may clog it.

Lighter change-Pressing.
Heavier change-Setting.
Solvent dewaxing :[9-15]

Most widely used solvent are MEK or propane .

Expensive process for separating lube oil.

MEK Dewaxing :Two components

Aromatic components – benzene or Toluene Maintains good oil solubility and Dewaxing
temperature.Ketone (MEK) – used to maintain wax solubility. It Causes the wax to solidify in a
easy of filterable form.In absence of MEK , it spread between filtration temperature and
pourpoint of dewaxed oil.
Solvent concentration: Maximum MEK concentration required in order to obtain highest filtration
rate.

Iso dewaxing:[6-12,16-18]

 Isomerizes a significant portion of the wax to lubes.

 Selective for mid distillates By products.

 Isodewaxing has a VI and yield advantage.

Fig:8.1 Propane Dewaxing
Propane Dewaxing: Same as MEK.Propane is cheaper easily available.

Urea Dewaxing:[1-2,16-19]

Urea forms solid filterable complex ( adducts) at room temperature with large paraffic ( > C18 )
HCs with no branching. To increase the rate of adduct formation some activator ( methanol) is
added.

Urea Dewaxing is more effective with lighter stocks.

Fig:8.2 Urea Dewaxing

Additives:

 VI improver ( poly isobutlene, poly methyl methacrlyates (PMMA)

 Pour point depressants ( Poly alkylated condensed aromatics).

  Anti oxidants – phenols, N compounds.

 Detergency dispersants – alkyl phosphates, petroleum sulfonates.

Iso Dewaxing:

Advantages of Iso dewaxing Technology:

 Has much lower capital and OP cost than solvent dewaxing.

 Give higher VI base oils than solvent and catalytic dewaxing.

 Has flexibility to handle or broad range of wax content in feed.

 Increases lube yields and extends catalyst life in Lube hydrocrackers.

 Can produce ultra low pour point base oils.

Iso Dewaxing Process Conditions (depend on feed and product requirement)

LUBE OIL PROCESSING

The lube oil base stocks are prepared from selected crude oils by distillation and special
processing to meet the desired qualifications. The additives are chemicals used to give the base
stocks desirable characteristics which they lack or to enhance and improve existing properties.
The properties considered are:

1. Viscosity

2. Viscosity change with temperature (vicosity index)

3. Pour point

4. Oxidation resistance

5. Flash point

6. Boiling temperature

7. Acidity (neutralization number)

Viscosity index is the most important characterisitics of a lube oil. It is defined as the rate of
change of viscosity with temperature is expressed by the viscosity index (VI) of the oil. The higher
 the VI, the smaller its change in viscosity for a given change in temperature. The VIs of natural oils
range from negative values for oils from naphthenic crudes to about 100 for paraffinic crudes.
Specially processed oils and chemical additives can have Vis of 130 and higher. Additives, such as
polyisobutylenes and polymethacrylic acid esters, are frequently mixed with lube blending stocks
to improve the viscosity– temperature properties of the finished oils. Lube oil blending stocks
from paraffinic crude oils have excellent thermal and oxidation stability and exhibit lower acidities
than do oils from naphthenic crude oils. The neutralization number is used as the measure of the
organic acidity of an oil; the higher the number, the greater the acidity.

Lube oil treatment[1-4,20]

The first step in the processing of lubricating oils is the separation of the crude oil distillation units
for the individual fractions according to viscosity and boiling range specifications. The heavier lube
oil raw stocks are included in the vacuum fractionating tower bottoms with the asphaltenes,
resins, and other undesirable materials. The raw lube oil fractions from most crude oils contain
components which have undesirable characteristics for finished lubricating oils. These must be
removed or reconstituted by processes such as liquid–liquid extraction, crystallization, selective
hydrocracking, and/or hydrogenation. The undesirable characteristics include high pour points,
large viscosity changes with temperature (low VI), poor oxygen stability, poor color, high cloud
points, high organic acidity, and high carbon- and sludge-forming tendencies.

The processes used to change these characteristics are:

1. Solvent deasphalting to reduce carbon- and sludge-forming tendencies

2. Solvent extraction and hydrocracking to improve viscosity index

3. Solvent dewaxing and selective hydrocracking to lower cloud and pour points

4. Hydrotreating and clay treating to improve color and oxygen stability

5. Hydrotreating and clay treating to lower organic acidity

Xem xét sinh thái trong nhà máy lọc dầu,Xử lý nước thải,kiểm soát ô nhiễm không khí,Xu hướng mới
trong nhà máy lọc dầu,Nguồn năng lượng thay thế,Dầu diesel sinh học,Năng lượng hydro từ sinh khối

Sulphur Recovery Process:-[1-4]

Major cause of air pollution because of S compounds

HDS to H2S can be converted to S.
S recovery process from acid gas (H2S).
Claus process :- H2S oxidation process)

Overall reaction H2S + 1/2 O2 -> S + H2O

In two step:

H2S+3/2 O2-> SO2 + H2O

2H2S+SO2 3S+2H2O Clave reaction exothermic
As 22% solution of KOH in water.For maximum sulphur recovery H2S/SO2 mole
reaction. S recovery efficiency for 3 cascade reactor stage is 96-97% With rich acid
gas feed(~50%H2S) reaction became exothermic where T reactor ~ 1200oC(thermal
process)

Clause Process :-

Work well for gas strem containing greater than 20% H2S(by value) and less than
5% HCS .When reaction is.

1. Heat is recovered from the reaction gases in the waste heat boiler by
generating high pressure steam.

2. Reaction gases leaving the waste heat boiler are then passed to a
condenser where cooling to 150-190oC result in condensation to elemental
S formula.

3. The gases containing unconverted H2S passed to a reactor containing bed

of bauxite cat.

4. Finally waste gases are incinerated to oxidize the last traces of H2S and
elemental S and then vented to atmosphere via stack.

Total S recovery with the subsequent class stages ranges from 94 to 96

percent.Complete conversation of H2S to SO2 elemental sulphur is not possible due
to thermodynamic chemical equilibrium of class reaction. Selective oxidation of H2S
to sulphur can be thermodynamically complete by reaction:
H2S +1/2 O2 S+H2O
Series of proprietary catalyst for direct oxidation of H2S to elemental S are used (Hi
activity process).
Sweetening process

Alkyl & aromatic mecaptans :-

Important S compounds distributed in petroleum products.Cause foul odour

oxidative determination towards metals. Also mercaptans cause oxidation
determination as well as inhibit the performance of various
additives(TEL,antioxidants) in finished products.Removal of is essential (sweetening
process).

Mercaptas removal Process

1. Caustic scrubbing, merox extraction.

2. Convation of mercaptous to disulfide include doctor sweetenies ,merox

sweetening ,copper chloride sweetening.

3. Acid treating ,clay treating ,catalytic process.

Doctor 2 Sweetening-A

Feed:All naphthas.
mercaptan level :no limits.
Very versatile process.
Disadvantages:Polysulfide formation

Copper Sluxry :[1-2,5-8]

Feed :Most cracked & straight from napththas . mercaptons level = up to 0.04%

Doctor Treating Process:

(Also caleed sodium plumbite treating)Na2PbO2.

Doctor solution:Active reagent sodium plumbite in aqueous caustic soda.Doctor

solution reacts with mercaptans to form lead mercaptides .Sulphur reacts and leads
mercaptides and gives disulphide’s and lead sulphide.Lead sulphide is regenerated
by air , NaOH to sodium plumbite again.

Disadvantage :Difficulty of controlling poly sulphide formation , which reduces

octane number,gum content and color stability.

Reaction Involved:

 PGO + 2NaOH -> Na2PGO2 + H2O

 2RSH + Na2PGO2 ->(RS)2p +2NaOH

 (RS)2PG + S -> R2S2 +PGS

Aesenuation def:

PGS + 2NaOH +1/2 O2->-> Na2PGO2 +S + H2O

Coppa Chloride Sweetening

Used to sweeter gasoline and kerosene by direct oxidation of mercaptons to

disulfides by direct oxidation of mercaptans to disulfides by using cupric chloride
oxidation as oxidizing agents.

Fundamental reaction invalid are:

 2RSH + CuCl2 -> (RS)2 Cu + 2HCL.

 (RS)2 CU + CuCl -> RSSR + Cu2Cl2

 Cu2Cl2 + 2HCL -> C42CL2 2HCL

 Cu2 Cl22HCL + ½ O2 -> 2C4Cl2+H2O

Water produced must be removed continuously to maintain connect reaction

condition.

Advantage:

No loss of octane no.

Alternative source of Energy[3-4]

  Due to world population growth and the advance of technologies that
depend on fossil fuels, reserves of fossil fuel eventually will not be able to
meet energy demand.

 Energy experts point out that reserves are less than 40 years for
petroleum, 60 years for natural gas and 250 years for coal.

 Fossil fuel costs are likely to increase in the near future. This will allow
renewable energy sources such as solar, wind, hydrogen, etc., to be
utilized.

Ethanol Production From Sugar Crops

Fig:9.1 Ethanol Production From Sugar Crops[4-9]

Table:9.1

Properties Of Conventional and Alcohol Fuels

Gasolin Methan Ethano

Characterstics Diesel
e ol l

Energy 42.5 44.0 20.0 26.9

 Content(MJ/Kg)

140-
Bioling Point,oC 37-205 65 78
360

Reaserch Octane No - 87-98 106 107

Motor Octane No - 80-90 92 89

Cetane No 45-55 0-5 5 5

Emissions with Ethanol Gasoline Blends

Fig:9.2 Emissions with Ethanol Gasoline Blends[8,9]

Ethanol as Transport Fuel[3-7,9-14]

Ethanol Advantage as Transport Fuel

 Octane Enhancer

 No engine modification required for E10 and lower blend

  Higher compression operation of the engine feasible

Environmental Benefits

 Lower emission of CO,VOC and Hydrocarbons

 Lower CO2 emission with higher compression ratio

 Complete CO2 cycle

 Higher biodegradability and low toxicity

5% Ethanol blending in gasoline is mandatory in india.

Further,BIS is examining the issues related to E10 blending.

CO2 Cycle of Ethanol Production From Sugarcane

Fig:9.3 Cycle of Ethanol Production From Sugarcane

Observation of Physico-Chemical Properties of Blend

  Octane number of gasoline increases with ethanol blending which offer
apportunities to refineries for reducing benzene and MTBE.

 Copper impurity in the anhydrous ethanol act as precursor for oxidation of

the blend.

 Additional dosage of anti-oxidants will be required to meet potential gum

specification and engine deposit formation.

 Addition of corrosion inhibitor required as blend have been reported to

cause problem on carburetor needles of two wheelers.

BIO-DIESEL[7-9]

Biodiesel is a monoalkylester of long chain fatty acids

produced from the trans-esterification reaction of vegetables
oils with alcohol in presence of catalyst and can be used as a
fuel.

Fig:9.4

BIODIESEL-Fuel From Oil Crops

Feed Stocks

Rapeseed Oil (Europe) Palm Oil (Malaysia)

Sunflower Oil (Italy & France) Linseed,Olive Oil (Spain)

Soybean Oil (USA & Brazil) Jatropha & Karanjia (India)

Production Process:Transesterification Path

.High Cetane
.Better Lubricity
.No Sulphur
.Can be directly used in diesel engine
.Environment Friendly
.Complete CO2Cycle

Fig:9.5

Table:9.2 Transesterification Reaction for Biodiesel Production [8,9]

Wide Global Acceptance of Biodiesel

 Zero Emissions

 By leading automobile manufacturers Audi, BMW, Kubota, Massey-

fergusan, Mercedes-Benz, Nissan Peugeot, Renault, Skoda,
Volkswagen,Volvo etc.

 By the Fuel Trade:Chevron-Texaco,Shell,TOTAL,Exxaon Mobile,BP etc

  By end user enterprises:Bus companies,taxi-fleets,forestry
enterprises,railroad,boat owners etc

Raw Material for Biodiesel Production

 Rapeseed Oil (Europe)

 Sunflower Oil (Italy & France)

 Soybean Oil (USA & Brazil)

 Palm Oil (Malaysia)

 Linseed,Olive Oil (Spain)

 CottonSeeds oil(Greece)

 Jatropha & Pongamia (Karanja) in India

 Jatropha (Nicaragua & SouthAmerica)

Impact of Bio-diesel on Emissions

Fig:9.6 Impact of Bio-diesel on Emissions

2nd Generation Biofuels[3-6]

 2nd generation biofuels have high emissions reduction potential.

 Biomass to be used include woody crops and grasses(not competitive with

food crops).

 High yield/Hectare as compare to first generation biofuels (BTL>3100 L/HC

oo HSD equivalent)

 BTL result in designer fuels compatible with new technologies

 Technology option for 2nd generation fuels:

 Direct fired combustion

 Gasification

 Pyrolysis
  Cofiring

Various Biomass Conversion Technologies

Fig:9.7 Various Biomass Conversion Technologies

Hydrogen as Future Fuel

 Available from water using non petroleum fossil fuel or renewable energy
resourse.

 Recycle rapidly and cleanly from hydrogen to water.

 Clean burning-potiential enviornmental benefits.

 Provides High efficiency energy conversion process

 Compatiable with all energy uses.

Table:9.3

Compansion of key properties for hydrogen and other fuels

Energy Per Specific Carbon

Energy Per Unit Motivity
Fuel type Unit Emission(kg C/kg
Volume(j/m3) Factor
Mass(j/kg) fuel)

Liquid
141.90 10.10 1.00 0.00
Hydrogen

Gaseous
141.90 0.013 1.00 0.00
Hydrogen

Fuel Oil 45.50 38.65 0.78 0.84

Gasoline 47.50 34.85 0.76 0.86

Jet Fuel 46.50 35.30 0.75 -

LPG 48.80 24.40 0.62 -

LNG 50.00 23.00 0.61 -

Methanol 22.30 18.10 0.23 0.50

Ethanol 29.90 23.60 0.37 0.50

Bio diesel 37.00 33.00 - 0.50

Natural gas 50.00 0.04 0.75 0.46

Charcol 30.00 - - 0.50

Current & Future Hydrogen Production Options[8-9]

Thermal Processes

Reforming of Natural Gas/Naptha

Gasification of Extra Heavy Oil /Coal/Biomass

 High-Temperature Water Splitting

Eletrolytic Processes

 Electricity from renewable sources like wind,solar,hydel etc.

Photolytic Processes

 Photobiological Water Splitting

 Photoelectrochemical Water Splitting

Other Options

 Chlor-Alkali Plants

 Co-generation electricity from Bagasse at sugar mills

H2PRODUCTION-GASIFICATION OPTION

Fig:9.8 H2 PRODUCTION-GASIFICATION OPTION

Fuel Cells[18-19]
  Fuel cell is essentially a battery that does not need recharging. As long as
hydrogen and oxygen fuel are supplied, it can continue to supply heat and
an electrical current indefinitely.

 Fuel cell consists of an electrolyte(a conductor of charged particles)

between an anode(negatively charged electrode)and a cathode (a
positively charged electrode).

 Once activated by a catalyst, the hydrogen gas separates into protons and
electrons, and the electrons are conducted through a wire, forming an
electrical current.

 The protons move through the electrolyte, where they combine with
oxygen and other electrons to produce heat and a water by product.

FUEL CELL[18-22]

Fig:9.9 Fuel Cell

Fuel Cell Benefits[18-22]

 Zero Emissions

High Efficiency

Enviornmentally Benign

Quiet and Quick and Easy Refueling

Wide Range of Operating Temperatures

Minimal Maintainence

Reliability and Quick Startup

Load Following

Ultimate Solution for Hydrogen Commercialization

Pollution control in Refining[22-24]

A petroleum refinery is generally considered as a single energy object, the energy

efficiency of which is approximately17 -20%. This is primarily due to the inadequate
utilization of secondary energy resources in the process units (30-35%) and the
almost complete loss of low-potential heat. To do enhance the energy recovery ,
energy-technological schemes must be introduced more widely, process units must
be fitted with boiler utilizers, the energy from liquid and vapor streams must be
used to produce electric power, and the efficiencies of heat exchange equipment
must be increased. A considerable fuel saving can be achieved by the use of low-
potential heat in heat pumps. Possibilities are available for the reduction of
discharges of sulfur dioxide, hydrogen sulfide, and other sulfur compounds that
pollute the biosphere. Coming into petroleum refineries every year along with the
crude oil is up to five million metric tons of sulfur, which is a raw material in short
supply for the production of sulfuric acid. However, thus far no more than 10% of
this sulfur has been recovered from petroleum. The remain'rag sulfur either passes
into the petroleum products, is partly burned in flares with the acid gases, is
discharged to the atmosphere, or is dissolved in the wastewater. On the average, in
the combustion of medium- sulfur fuel in tube furnaces, the combustion of product
vapors in flares, and the burnoff of coke in catalytic cracking units, theprocessing of
one metric ton of crude oil results in the discharge of up to 14 kg of sulfur dioxide
and 0.23 kg of hydrogen sulfide to the atmosphere.

Sources of waste water generated from Refineries [22-25]

Refinery waste waters can be characterized as:-

 Cooling Towers

 Boiler Feed water treatment units

 Process Units

 Desalter brine

 Tank Farms

 Chemical waste

 Sanitary and miscellaneous use

 Fire protection

The capacity of the environment to absorb the effluents and other impacts of
process technologies is not unlimited, as some would have us believe. The
environment should be considered to be an extremely limited resource, and
discharge of chemicals into it should be subject to severe constraints. Indeed, the
declining quality of raw material s, especially petroleum and fossil fuels that give
rise to many of the gaseous emissions of interest in this text, dictates that more
material must be processed to provide the needed fuels .

Oil from subterranean and submarine reservoir extraction can be environmentally

damaging. Crude oil and refined fuel spills from tanker ship accidents have
damaged fragile ecosystems. Burning oil releases carbon dioxide into the
atmosphere, which contributes to global warming. Thus, both the production and
processing of crude oil involve the use of a variety of substances, some toxic,
including lubricants in oil wells and catalysts an d other chemicals in refining. The
amounts used, however, tend to be small an d relatively easy to control. M ore
detriment al to the environment is the spillage of oil, which has been a particularly
common event.

Minor losses from truck and car accidents can affect rivers and streams. Leakage
from underground gasoline storage tanks, many abandoned decades ago , has
contaminated some local water sup plies and usually requires expensive operation
s either to clean or seal off. Both the production and processing of crud e oil involve
the use of a variety of substances, some toxic, including lubricants in oil wells and
catalysts and other chemic also in refining. The amounts used, however, tend to be
small and relatively easy to control. More detrimental to the environment is the
spillage of oil, which has been a particularly common event.

Minor losses from truck and car accidents can affect rivers and streams.A pollutant
is a substance present in a particular location (ecosystem) when it is not indigenous
to the location or is present in a greater-than-natural concentration. The substance
is often the product of human activity.

Pollutants are subdivided into two classes: primary and secondary.

Source -> Primary pollutant -> Secondary pollutant

GASEOUS EMISSIONS[24-26]

Gaseous emissions from petroleum refining create a number of environmental

problems.During combustion, the combination of hydrocarbons, nitrogen oxide,
and sunlight results in localized low-levels of ozone, or smog. This is particularly
evident in large urban areas and especially when air does not circulate well.
Petroleum use in automobiles also contributes to the problem in many areas. The
primary effects are on the health of those exposed to the ozone, but plant life has
been observed to suffer as well.Refinery and natural gas streams may contain large
amounts of acid gases, such as hydrogen sulfide (H2S) and carbon dioxide (CO2).

Hydrogen chloride (HCl), although not usually considered to be a major pollutant in

petroleum refineries can arise during processing from the presence of brine in
petroleum that is incompletely dried. It can also be produced from mineral matter
and other inorganic contaminants and is gaining increasing recognition as a
pollutant which needs serious attention. Acid gases corrode refining equipment,
harm catalysts, pollute the atmosphere, and prevent the use of hydrocarbon
components in petrochemical manufacture. When the amount of hydrogen sulfide
is large, it may be removed from a gas stream and converted to sulfur or sulfuric
acid. Some natural gases contain sufficient carbon dioxide to warrant recovery as
dry ice, that is, solid carbon dioxide. And there is now a conscientious effort to
mitigate the emission of pollutants from hydrotreating process by careful selection
of process parameters and catalysts.
The terms refinery gas and process gas are also often used to include all of the
gaseous products and by-products that emanate from a variety of refinery
processes. There are also components of the gaseous products that must be
removed prior to release of the gases to the atmosphere or prior to use of the gas
in another part of the refinery, that is, as a fuel gas or as a process feedstock. In
addition to the gases obtained by distillation of petroleum, more highly volatile
products result from the subsequent processing of naphtha and middle distillate to
produce gasoline.Hydrogen sulfide is produced in the desulfurization processes
involving hydrogen treatment of naphtha, distillate, and residual fuel; and from the
coking or similar thermal treatments of vacuum gas oils and residual fuels. The
most common processing step in the production of gasoline is the catalytic
reforming of hydrocarbon fractions in the heptane (C7) to decane (C10) range.

Natural gas is also capable of producing emissions that are detrimental to the
environment. While the major constituent of natural gas is methane, there are
components such as carbon dioxide (CO), hydrogen sulfide (H2S), and mercaptans
(thiols; R–SH), as well as trace amounts of sundry other emissions. The fact that
methane has a foreseen and valuable end-use makes it a desirable product, but in
several other situations it is considered a pollutant, having been identified a
greenhouse gas.

In addition to the corrosion of equipment of acid gases, the escape into the
atmosphere of sulphur containing gases can eventually lead to the formation of the
constituents of acid rain, that is, the oxides of sulfur (SO2 and SO3). Similarly, the
nitrogen-containing gases can also lead to nitrous and nitric acids (through the
formation of the oxides NOx,) which are the other major contributors to acid rain.
The release of carbon dioxide and hydrocarbons as constituents of refinery
effluents can also influence the behavior and integrity of the ozone layer. Gases
such as sulfur oxides (usually sulfur dioxide, SO2) as well as nitrogen oxides (NOx)
react with the water in the atmosphere to form acids. Acid rain has a pH less than
5.0 and predominantly consists of sulfuric acid (H2SO4) and nitric acid (HNO3). As a
point of reference, in the absence of anthropogenic pollution sources the average
pH of rain is 6.0 (slightly acidic; neutral pH 7.0).

In summary, the sulfur dioxide that is produced during a variety of processes will
react with oxygen and water in the atmosphere to yield environmentally
detrimental sulfuric acid. Similarly, nitrogen oxides will also react to produce nitric
acid. Hydrogen chloride, if produced during refining, quickly picks up moisture in
the atmosphere to form droplets of hydrochloric acid and, like sulfur dioxide, is a
contributor to acid rain. However, hydrogen chloride may exert severe local effects
because, unlike sulphur dioxide, it does not need to participate in any further
chemical reaction to become an acid and under atmospheric conditions that favor a
buildup of stack emissions in the area of a large industrial complex or power plant,
the amount of hydrochloric acid in rainwater could be quite high.

Liquid Effluents

Crude oil, as a mixture of hydrocarbons, is (theoretically) a biodegradable material.

However, in very general terms, petroleum is a mixture of: (a) hydrocarbons, (b)
nitrogen compounds, (c) oxygen compounds, (d) sulfur compounds, and (e)
metallic constituents. It is convenient to divide the hydrocarbon components of
petroleum into the following three classes: Crude oil also contains appreciable
amounts of organic no hydrocarbon constituents, mainly sulfur, nitrogen, and
oxygen-containing compounds and, in smaller amounts, organometallic
compounds in solution and inorganic salts in colloidal suspension. These
constituents appear throughout the entire boiling range of the crude oil but tend to
concentrate mainly in the heavier fractions and in the non-volatile residues.

Air Quality Standards:

They are the standards that specify allowable emission.

It can either be related to:

1. Quality of the air in the surrounding atmosphere (ambient air quality) –

Useful for the protection of the health of living populations, animals and of
property.

2. Gaseous emissions from a particular unit ( emission standard) - used for

planning pollution control strategy.

Ambient Air Quality Standards:

In India, for AAQS, various areas have been classified into 3 categories:
 1. Category A:covers Industrial and mixed – use areas.

2. Category B:Covers residential and Rural areas.

3. Category C:Covers sensitive areas such as sanctuaries, national parks, hill

stations etc.

Table: 9.4 Ambient Air Quality Standards: India

Category/ Area Concentration in micrograms/ m3

SPM SO2 NOx CO

A.Industrial & Mixed Use 500 120 120 2000

B.Residential & Rural 200 80 80 1000

C.Sensitive 100 30 30 500

Supporting Processes

 Not directly involved in the processing of petroleum based fuels

 Processes

 Hydrogen production and purification

 Gas processing units

 Acid gas treating

 Sulfur recovery

 Water treatment

Hydrogen Production & Purification

 Sources of hydrogen

 Catalytic Reformer

Majority of hydrogen used in refinery

 FCCU Off Gas

  Steam-Methane Reforming

Most common method of manufacturing hydrogen Methane, ethane, or heavy

components reformed to hydrogen, carbon dioxide, & water in a series of three
reactions .Hydrogen purity typically 90 to 95 vol%

 Synthesis Gas

Chemical solvent processes

 Amine sweetening (MEA, DEA, MDEA, DGA)

 Hot potassium carbonate

 Physical solvent processes

 Selexol

 Propylene carbonate

 Sulfinol

 Rectisol

 Dry absorbents

 Molecular sieve

 Activated charcoal

 Iron sponge

 Zinc Oxide