Chemical Process Technology:

Prof. Vimal Katiyar

Department of Chemical Engineering
Indian Institute of Technology Guwahati
 CL 402-Chemical Process Technology (3-0-0-6)
❑ Syllabus
Raw materials and principles of production of olefins and aromatics; typical intermediates from
olefins and aromatics such as ethylene glycol, ethyl benzene, phenol, cumene and DMT, dyes, and
pharmaceuticals; chemical processes based on raw materials sugar, starch, alcohol, cellulose,
paper, glyceride, oils, soaps, detergents; industrial processes for the production of inorganic heavy
chemicals such as acids, alkalis, salts, and fertilizers such as sulphuric, nitric, and phosphoric acids,
soda ash, ammonia, etc.

❑ Text:
1. C. L. Dryden, Outlines of Chemical Technology, Edited and Revised by M.Gopala Rao and S.
Marshall , 3rd Ed., Affiliated East West, New Delhi, 1997.

❑ References:
1. T. G. Austin and S. Shreve, Chemical Process Industries, 5th Ed., McGraw Hill, New Delhi, 1984.

2. R. E. Kirk, and D. F. Othmer, Encyclopaedia of Chemical Technology, 4th Ed., Interscience, New
York, 1991.

3. P. H. Groggins, Unit Processes in Organic Synthesis, 5th Ed., McGraw Hill, 1984.
Chemical Processing and the Work of the
Chemical Engineer:
 Chemical Technology

❑ Deals with chemical processing of raw materials into useful and profitable
products
▪ Products include both consumer goods and intermediates for further chemical
and physical modifications

❑ Chemical conversions: chemical reactions applied to industrial processing

❑ The subject deals with

▪ Basic chemistry involved
▪ Equipment in which the reactions take place
▪ Costs of the reaction materials, energy used in the process, and the effect of
efficiency
❑ Classification as “Unit Operations” & “Unit Processes”
Structure of the Chemical Industry
Evolution of the Chemical Industry

Evolution of engineering materials

 Chemical Industry
❑ History of the chemical industry.

Year Event
1746 Production of moderately concentrated sulfuric acid in the lead chamber
process on an industrial scale
1789 Process for converting sodium chloride to sodium carbonate was
developed
1831 Process for manufacturing concentrated sulfuric acid was developed

1850 The first oil refinery was built

1856 The first synthetic aniline dye, mauveine was developed from coal tar

1863 Better process for production of sodium carbonate

1864 Alkali Works Act passed by British government, the first example of
environmental regulation
1874 Development of the Deacon process for converting hydrochloric acid into
chlorine
~1900 Birth of chlor-alkali industry

1905 Development of the Haber process for producing ammonia

1907 Hydrogenation of fats

 Chemical Industry
❑ History of the chemical industry.

Year Event
1909 Patent on Bakelite, the first commercially important plastic

1920 Large-scale industrial production of isopropanol from oil

1923 Development of a high-pressure process to produce methanol and

development of the Fischer–Tropsch process, a method for producing
synthetic liquid fuels from coal gas.
1926 Development of a process for commercial fluidized-bed coal gasification

1930 First commercial steam reforming plant development, first commercial

manufacture of polystyrene and discovery of nylon
1931 Development of ethene epoxidation process for the production of ethene
oxide
1933 Polyethene discovery

1934 First American car tire produced from a synthetic rubber, neoprene

1936 Development of a method of industrial scale catalytic cracking of oil

fractions
1938 Commercialization of the alkylation process for the production of high-
octane alkylate and discovery of the hydroformylation for the formation of
aldehydes from alkenes
 Chemical Industry
❑ History of the chemical industry.

Year Event
1939 Start of large-scale low-density polyethene (LDPE) production and start of
large-scale poly(vinyl chloride) (PVC) production
1940 Development of catalytic reforming to produce higher octane gasoline

1953 Introduction of the Ziegler catalyst for the production of high-density

polyethene (HDPE).
1954 Introduction of chromium-based catalysts for the production of HDPE

1955 Start of large-scale production of poly(ethene terephthalate) (PET)

1957 First commercial production of isotactic polypropene

1960 Commercialization of two industrially important processes: ethene to

acetaldehyde (Wacker), and acrylonitrile production (SOHIO)
1963 Development of the first commercial methanol carbonylation process for
the production of acetic acid based on a homogeneous cobalt catalyst
1964 Many new catalysts and processes are developed, for example, a zeolite
catalyst for catalytic cracking and the metathesis of alkenes
1966 First low-pressure methanol synthesis commercialized
 Chemical Industry
❑ History of the chemical industry.

Year Event
1970s Birth of environmental catalysis. Development of a catalytic converter for
Otto engine exhaust gas, Energy crises (1973 and 1979), Start of large-scale
bioethanol production
1980s The selective catalytic reduction (SCR) for controlling NOx emissions.
Development of a process for the production of linear low-density
polyethene (LLDPE)
1990s Discovery of carbon nanotubes. Improved NOx abatement in exhaust gases
by NOxtrap
2000s Introduction of soot abatement for diesel engines. Ultra-efficient
production of bulk chemicals. Green chemistry and sustainability, including
biomass conversion, become hot topics. New paradigms and concepts,
Product Technology, Process Intensification
 Chemical Industry
❑ Major Industries

Businesses in the chemical industry

Petrochemical Industry
 Market of the Chemical Industry

European Union (EU) sales figures for chemical industry, 2010

 Principal Chemical Conversions
Acylation  Fermentation

Alcoholysis  Fischer-Tropsch reaction

Alkylation  Fruedek0crafts (reactions)

Amination by reduction  Halogenation

Ammonolysis  Hydroformylation (oxo)

Aromatization  Hydrogenation, hydrogenolysis

Calcination  Hydrolysis and hydration (saponification,

alkali fusion)
Carboxylation
 Ion Exchange
Causticization
 Isomerization
Combustion (uncontrolled oxidation)
 Neutralization
Condensation
 Nitration
Dyhydration
 Oxidation (controlled)
Dehydrogenation
 Poymerization
Diazotization and Coupling
 Pyrolysis or cracking
Double decompostion
 Reduction
Electrolysis
 Silication formation
Esterification
 Sulfonation and sulfation
 Energy Consumption
❑ Fossil Fuel Consumption

Total world energy consumption in million metric tons oil equivalent

 Alternative of Fossil Fuels

❑ Energy production by photosynthesis and comparison with current and

future consumption

Energy Flow Remarks Years reserve

TW EJ/a (R/P)
Radiation reaching earth 125 000 4 000 000 1 kW/m2 sustainable

Natural photosynthesis 130 4000 sustainable

Energy consumption (2005) 14 440 mainly cooking,
heating
Biomass 1.5 50 sustainable
Coal 4.4 140 190
Oil 5.2 170 42
Natural gas 3.6 110 63
Energy consumption (2050 49 1550 3.5 times that of 2005
estimate)
 Alternative of Fossil Fuels
❑ Biomass

Oils and fats

Sugars

Lignocellulosic biomass
 Chemical Engineering Functional Areas

 Process Red ≈ 46%;

 Research and Development Blue ≈ 40%
 Administration
 Production
 Design
 Consulting
 Project management – construction
 Environmental engineering
 Education
 Product engineering
 Maintenance
 Quality Control
 Other
 Role of Process Engineer

❑ New process or product development

It consists of evaluating the performance of the process at the laboratory scale,

where its technical feasibility can be shown, moving on to the pilot plant, and finally

full industrial scale.

❑ Modification in existing process

Based on the experience, process parameters are modified to achieve better output

❑ Building capacity

Available plant facility is to be run at optimized condition to reach the maximum

production capacity

❑ Intelligence

To produce cheap and/or good quality products, always look for better alternatives
 Process Economics
Economically profitable process design is the driving force

An economic flowchart has to

be prepared based on:
▪ Financial sources
▪ Cost of finished product
▪ Market demand and sales
▪ Fixed and movable assets
▪ Operational cost
▪ Labor
▪ Cash outflow (tax, dividend etc.)

Business cash flowchart

 Chemical Process Selection, Design and Operation

❑ Modern chemical processes are often extremely complex operations

involving 100s of equipment

❑ The typical chemical process is analyzed with interdependent

considerations for plant operation, such as
▪ Mass & Energy Balance
▪ Thermo chemistry
▪ Unit Operations
▪ Plant Equipment
▪ Ancillary Equipment
▪ Process Plant Diagram
▪ Instrumentation & Control
▪ Economics
▪ Safety
❑ Pilot plants are designed to obtain the data for larger plants
 Chemical Process Selection, Design and Operation

❑ Design and operation of the chemical reactors is most critical in a plant

❑ The factors which have to be considered for chemical reactors are:

▪ Chemical Factors

This involves the kinetics of the reaction - whether it's first order or second

order; based on the chemical reaction engineering considerations, the design of the

reactor must provide sufficient residence time for the required degree of reaction,

and therefore, maximum conversion to product.

▪ Mass Transfer Factors

The reaction rate of homogeneous reactions may be controlled by the rate of

diffusion of reactants rather than by the chemical kinetics of Langmuir

isotherms and Freundlich isotherms.

 Chemical Process Selection, Design and Operation

▪ Heat Transfer Factors

These describe whether the reaction is exothermic or endothermic. In

Exothermic, heat is released to the environment, and in Endothermic, heat is

absorbed by the reactants. The value of heat of reaction is necessary to

operate the chemical reactor.

▪ Safety Factors

This involves the control and confinement of any hazardous reactants and

products as well as the control of reaction and process conditions.

 Utilities
Water Conditioning
 Water Conditioning

❑ Water conditioning has to be done by considering

▪ Quantity

▪ Quality

▪ Reuse

▪ Pollution

❑ Water Hardness
▪ Carbonate (temporary)
❖ Caused by bicarbonates of calcium and magnesium
❖ Can be reduced by heating
▪ Noncarbonate (permanent)
❖ Caused by sulfates and chlorides of calcium and magnesium
❖ Requires chemical agents for reduction
❑ Presence of sodium salts, silica, alumina, iron and manganese in water also
requires conditioning
 Methods

❑ Based on the need two types of conditioning is applied

▪ Softening

Process to remove or reduce hardness

▪ Purification

Process to remove organic matter and microorganisms from water

❑ Methods of softening
▪ Ion exchange
▪ Lime-Soda processes
▪ Phosphate conditioning
▪ Silica removal
▪ Deaeration
▪ Demineralization and desalting
❑ Purification is carried out in sequence with softening methods for waste
water treatment
 Ion Exchange

❑ Sequence of industrial ion exchangers development

▪ Zeolites

▪ Organic ion exchangers

▪ Sulfonated organic ion exchangers

❑ Sodium cation exchange process

▪ Softening
Ca/ Mg((HCO3)2 / SO4/ Cl2) + 2NaR → (Ca/ Mg)R2 + Na2((HCO3)2/ SO4/ Cl2)
(soluble) (insoluble) (insoluble) (soluble)
R – cation exchange radical
▪ Regeneration
(Ca/ Mg)R2 + 2NaCl → 2NaR + (Ca/ Mg)Cl2
❖ Polystyrene divinylbenzene (SDVB) sulfonated synthetic resins are used for the
application (pH 6-8 for regeneration)
❖ It has high temperature stability (up to 150°C) and pH stability (pH 0 to 14)
 Ion Exchange

❑ Sodium cation exchange process

 Ion Exchange

❑ Hydrogen cation exchange process

▪ Softening

Ca/ Mg/ Na2(HCO3)2 + 2HR → (Ca/ Mg/ Na2)R2 + 2H2O + CO2

(soluble) (insoluble) (insoluble) (soluble)

Ca/ Mg/ Na2(HCO3)2 + 2HR → (Ca/ Mg/ Na2)R2 + 2H2(SO4/ Cl2)

(soluble) (insoluble) (insoluble) (soluble)

▪ Regeneration

(Ca/ Mg/ Na2)R2 + H2SO4 → 2HR + (Ca/ Mg/ Na2)SO4

(insoluble) (soluble) (insoluble) (soluble)

❖ It can be employed to remove all cations
❖ Acidic water after regeneration is not desirable and either neutralized or
blended with sodium Zeolite treated water
 Ion Exchange

❑ Anion exchange process

▪ Softening

H2SO4 + 2R4NOH → (R4N)2SO4 + 2H2O

(soluble) (insoluble) (insoluble) (soluble)

R4N- anion exchanger radical
▪ Regeneration

(R4N)2SO4 + 2NaOH → 2R4NOH + Na2SO4

(insoluble) (soluble) (insoluble) (soluble)

❖ Two types of anion exchangers highly basic or weekly basic are used
❖ Both can be used to remove strongly ionized acids
❖ Only highly basic anion exchangers can remove weakly ionized acids
❖ Highly basic anion exchangers are regenerated by caustic soda, while weakly
ones are regenerated by caustic soda, soda ash, or ammonium hydroxide
 Lime-Soda Process

❑ Carbonate hardness removal

Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O

Mg(HCO3)2 + Ca(OH)2 → MgCO3 + CaCO3 + 2H2O

MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3

❑ Noncarbonate soluble calcium and magnesium salts

MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2

CaCl2 + Na2CO3 → CaCO3 + 2NaCl

CaSO4 + Na2CO3 → CaCO3 + Na2SO4

MgSO4 + Na2CO3 + Ca(OH)2 → Mg(OH)2 + CaCO3 + Na2SO4

▪ Cold-lime-soda and hot-lime-soda are the two processes available
▪ Cold-lime-soda process is employed for partial softening and ordinarily uses
▪ Disposal of high amount of sludge formed in the process is expensive and
 Lime-Soda Process

Output: 20-25 ppm

Hot-lime-soda process
 Lime-Soda Process

❑ Hot-lime-soda process
▪ Hot-lime-soda process is mostly employed for conditioning of boiler feed water
▪ The process is carried out in the following sequence:
❖ Analysis of the raw water
❖ Heating of the raw water by exhaust steam
❖ Mixing and proportionating of the lime and soda ash in conformance with the raw
water analysis
❖ Pumping of the lime slurry and soda
❖ Reaction of the lime and soda is facilitated by mixing with or without previous
heating
❖ Coagulation or release of the supersaturation by slow agitation or contact with
seeds (fresh surface) by sludge recirculation
❖ Settling or removal of the precipitate with or without filtration
❖ Pumping away the softened water
❖ Periodic washing way of the sludge from the tank bottom
 Other Conditioning Methods

❑ Phosphate conditioning

▪ Used in conjunction with one of the previous method

▪ Used for internal conditioning of the boiler water as well as conditioning of

cooling and process water

▪ Orthophosphates and complex phosphates are used in steam boilers to

precipitate the amount of calcium present

▪ Complex phosphate sodium hexametaphosphate is advantageous for boiler

systems which tends to become alkaline, as it can revert back to an acid

orthophosphate

▪ Sodium hexametaphosphate helps in iron removal and corrosion prevention as

well
 Other Conditioning Methods

❑ Silica removal

▪ Silica is removed by dolomitic lime or activated magnesia in the softener

▪ Ferric coagulates are also used for preliminary coagulation and settling

▪ Demineralization is used to have only trace amount of silica

❑ Deaeration
▪ Deaeration is done to condition water for industrial boiler
▪ Presence of oxygen increases the corrosion rate by various reactions depending
upon conditions
▪ Corrosion of iron due to formation of OH‾ by O2 and H2O reaction is well known
▪ Removal of the dissolved oxygen can inhibit it
▪ Deaeration is done by spraying or cascading the water down over a series of
trays contained in a pressurized vessel
▪ Remaining trace amount of oxygen is removed by oxygen scavengers such as
sodium sulfite hydrazine hydrate
 Demineralization and Desalting

❑ Demineralization

▪ Demineralization is employed to various processes including conditioning of

water for high pressure reactors

▪ Ion exchange system for demineralization is chosen based on:

❖ Volume and composition of the raw water

❖ The effluent quality requirement

❖ Comparative capital and operating cost

▪ Demineralization system with silica removal will consists of:

▪ Hydrogen cation exchange unit

▪ Strongly basic anion exchanger unit

▪ Degasifier between the units

Demineralization and Desalting

Demineralization system
 Demineralization and Desalting

❑ Desalting

▪ Desalting or desalinization is applied to partial or complete demineralization of

highly saline waters

▪ Methods used for desalting are:

❖ Electrodialysis

❖ Reverse osmosis

❖ Multistage flash evaporation

❖ Vertical tube evaporation

❖ Vapor compression

❖ Vacuum freeze vapor compression

▪ Desalting by reverse osmosis is 20-30% less costlier than thermal desalting

units
 Demineralization and Desalting

Electrodialysis system

▪ Electrodialysis utilizes ion exchange membranes in electric field, which under

electric field provides less desalinated water in one compartment

▪ Reverse osmosis uses the pressure above osmotic pressure to force pure water

through a semipermeable membrane from concentrated brine solution

▪ Cellulose acetate or polyamide is used for membrane in reverse osmosis

 Purification

❑ Purification is done by three major processes:

▪ Coagulation and filtration through sand or hard coal

▪ Oxidation by aeration

▪ Treatment with chlorine

Municipal water treatment flowchart

 Purification

▪ Purification is done in sequence to softening of the water

▪ Aeration is done to remove iron, odor and taste

▪ The aerated water is partly softened by lime and the precipitate coagulated and

filtered

▪ Chlorine is added to destroy the pathogenic microorganisms

▪ Activated carbon is employed to remove odors and to improve the flavor

 Water in Petroleum Refinery

❑ Water is required in refinery for:

▪ Cooling (91% of the water in refinery is required for cooling)

▪ Boiler feed

▪ Processing

▪ Sanitary services

▪ Fire protection

▪ Miscellaneous purposes

❑ Water quality

▪ Most of the part of cooling system does not require high quality water

▪ Mostly high quality demineralized water is used for high pressure boilers

▪ But complete treating and softening of all cooling water is profitable

 Water in Petroleum Refinery

❑ Source and use of water in refinery

 Water in Petroleum Refinery

❑ Effects of water constituents and method of removal

Water in Petroleum Refinery
 Water in Petroleum Refinery

❑ Quality tolerances of cooling water suggested by American Water

Works Association

Constituent or property Limiting values (ppm)

Hardness as CaCO3 50

Iron 0.5

Manganese 0.5

Iron plus manganese 0.5

Turbidity 50

Corrosiveness None

Slime formation None

 Water in Petroleum Refinery

❑ Boiler feed water makeup

Figures refer to frequency of use of various types of water treatment

 Water in Petroleum Refinery

❑ Water quality tolerance for boiler-feed water

 Water in Petroleum Refinery

❑ Treatment of makeup for boiler-feed water

Figures refer to frequency of use of various types of water

 Water in Steam Power Plant

❑ Water treatment for steam power plants is conducted to Prevent problems

such as

▪ Carryover to the turbine components

▪ Corrosion

▪ Scale formation/deposition in the boiler turbine systems

❑ Improved water treatment methods are required in power plant to

▪ To prevent the fast aging

▪ To achieve higher operational efficiency

▪ Better environmental conservation

 Water in Steam Power Plant

❑ Steam Power Plant

 Water in Steam Power Plant

❑ Water systems at steam power plants

 Water in Steam Power Plant

❑ Problems at steam power plant from abnormal water quality data

 Water in Steam Power Plant
❑ Problems at steam power plants and the relevant solution for water

treatment
 Water in Steam Power Plant

❑ Water quality control criteria during combined water treatment operation

Constituent or property Recommended value

pH 8.5-9.3 (9.0)

Iron (μg/l) 2 or less (1 or less)

Dissolved oxygen (μg/l) 20-200 (50 ± 30)

Electrical conductivity (mS/m) 0.02 or less

( ): Target value
Chemical Process Technology:
Petroleum Processing
 Origin

❑ Vegetation origin

▪ Theories considers that any organic matter can be converted into petroleum

under suitable conditions

▪ Petroleum was formed from organic matter near shore and in marine deposits

▪ Deficiency of oxygen and high pressure application for long time are considered

as major reason for conversion of organic matter into petroleum

▪ Theories also considers the migration of petroleum gas liquids to favorable

retention

▪ Carbohydrates and proteins are considered to be destroyed by bacterial action

leaving the fatty oil behind

 Exploration

Process schematic of oil

Subdivision of recovery methods
Recovery is site specific and depends upon several
variable factors
Effect of reservoir depth on recovery
Effect of oil viscosity on recovery
Effect of permeability on oil recovery
Positions where asphaltenes (and wax) deposition
can occur
Oil recovery by thermal methods
The THAI process
Cyclic steam injection (huff and puff)
Steam assisted gravity drainage (SAGD)
Cyclic microbial oil recovery
Oil recovery by microbial flooding
Microbial Products and Their Contribution
to Enhanced Oil Recovery
 Exploration
❑ Surface geological methods:
The presence of volatile hydrocarbons near the surface is an indication of oil formations at
some distance beneath.
▪ Sensitive gas chromatography used to detect as low as 1 × 10-4 vol. % conc.
▪ Microbiological flora of the hydrocarbon oxidizing type in water wells is usually
evidence of hydrocarbon deposits
▪ Radioactive isotopic exchange of carbon with rock deposits gives lower C-14 assay
where gaseous hydrocarbons are seeping
❑ Geophysical methods:
▪ Extensive: Seismic survey measures shock wave patterns and characterizes strata
(impervious shale, gas, oil, salt water, etc.); Air surveys from 250-300 kmph low
flying planes with magnetometer for magnetic survey and scintillation counter for
radioactive survey
▪ Intensive: Sonic and ultrasonic probing during core sampling to measure porosity;
Neutron reflecting measurements with scintillating detector which increase in the
vicinity of hydrocarbons.
 Production
❑ Worldwide oil production in 2018 Source: U.S. Energy Information Administration
Country Total Petroleum and Other Country Total Petroleum and Other
Liquids Production (Thousand Liquids Production (Thousand
Barrels Per Day) Barrels Per Day)
Algeria 1577 Iraq 4615
Angola 1655 Italy 156
Argentina 678 Japan 127
Australia 369 Kazakhstan 1959
Azerbaijan 808 Korea, South 114
Bolivia 77 Kuwait 2869
Brazil 3427 Libya 1073
Brunei 111 Malaysia 749
Canada 5295 Mexico 2084
Chad 132 Nigeria 2057
China 4816 Norway 1863
Colombia 889 Oman 988
Peru 140
Congo (Brazzaville) 347
Qatar 1943
Denmark 120
Russia 11401
Ecuador 517
Saudi Arabia 12418
Egypt 667 South Africa 110
Equatorial Guinea 184 South Sudan 125
France 120 Thailand 497
Gabon 195 Turkmenistan 279
Germany 205 United Arab Emirates 3790
Ghana 173 United Kingdom 1162
India 1011 United States 17885
Indonesia 891 Venezuela 1526
Iran 4468 Vietnam 253
 Consumption

❑ Top 10 total world oil consumers Source: U.S. Energy Information Administration
Country Million barrels per day Share of world total

United States 19.69 20%

China 12.79 13%

India 4.44 5%

Japan 4.01 4%

Russia 3.63 4%

Saudi Arabia 3.30 3%

Brazil 2.98 3%

South Korea 2.61 3%

Canada 2.47 3%

Germany 2.38 2%

Total top 10 58.31 60%

World total 96.92

 Crude-oil Constituents

❑ Chemical composition of petroleum

Composition by weight%

Element Percent range

Carbon 83.9-86.8

Hydrogen 11.0-14.0

Nitrogen 0.02-1.70

Oxygen 0.08-1.82

Sulfur 0.06-8.00

Metals 0.0-0.14
 Crude-oil Constituents

❑ Paraffins or alkanes

▪ Saturated hydrocarbons with straight or branched chains which contain only

carbon and hydrogen and have the general formula CnH2n+2

▪ They generally have from 5 to 40 carbon atoms per molecule, although trace

amounts of shorter or longer molecules may be present in the mixture

▪ Comprise the largest fraction of petroleum crudes

▪ Branch chain alkanes are known as iso- or neo- paraffins alkanes

▪ Branched chain alkanes perform better in internal combustion engine

▪ Only small amount of isoalkanes exist in crude

▪ They may be formed by catalytic reforming, alkylation, polymerization or

isomerization
 Crude-oil Constituents

❑ Olefin or alkenes

▪ Unsaturated hydrocarbons with straight or branched chains with general

formula CnH2n

▪ They are generally absent in crude oil and formed by refining process

▪ They are relatively unstable and improves the antiknock quality of gasoline

▪ On storage they polymerize and oxidize

▪ The unstable nature is useful for forming other petrochemicals

❑ Naphthenes or cycloalkanes

▪ Saturated hydrocarbons which have one or more carbon rings to which

hydrogen atoms are attached according to the formula CnH2n

▪ Cycloalkanes have similar properties to alkanes, but have higher boiling points

▪ These are the second most abundantly occurring series in crudes

 Crude-oil Constituents

❑ Aromatic or benzenoids

▪ Unsaturated hydrocarbons which have one or more planar six-carbon rings

called benzene rings, to which hydrogen atoms are attached with the formula

CnH2n-6.

▪ They have good storage stability and desirable due to high antiknock value

❑ Other components

▪ After carbon and hydrogen sulfur is most abundant compound in crude oil and it

is highly undesirable due to corrosion, pollution, catalyst poisoning and bad odor

▪ Nitrogen compounds are found in low amount and do not create much trouble

▪ Trace amount of metals such as Fe, Mo, Na, Ni, V etc. is found in the crude oil

▪ These metals are strong catalyst poisons and removed from the crude oil

▪ Salts are also found in crude oil and they create corrosion problem
 Refining Processes
❑ Overview of oil refining

Flow scheme of a typical complex oil refinery

 Refining Processes

❑ Typical physical and chemical processes in a complex oil refinery

Chemical processes
Physical Processes
Thermal Catalytic
Desalting Visbreaking Hydrotreating

Dehydration Delayed coking Catalytic reforming

Distillation Flexicoking Catalytic cracking

Solvent extraction Hydrocracking

Propane deasphalting Catalytic dewaxing

Solvent dewaxing Alkylation

Blending Polymerization

Isomerization
 Physical Processes

❑ Desalting and dehydration

▪ First step in the refining process is desalting and dehydration

▪ Accomplished by adding hot water with added surfactant to extract the

contaminants

▪ Oil and water phases are separated by phase separation

▪ Desalted crude is sent to the crude distillation tower

❑ Electrical Desalting
 Physical Processes

❑ Crude Distillation

Fractional distillation
 Physical Processes

❑ Crude Distillation

D-4m, L-20-30m, T: 15-20

Can not operate more than 630 K
Thermal cracking, Pyrolysis
Carbonaceous materials: Coke
Low HTC

Pipe Still Heater

D-1m, L-4m
Simple atmospheric crude distillation
 Physical Processes

❑ Crude Distillation

15m

610K

Modern crude distillation unit consisting of atmospheric and vacuum distillation

 Physical Processes

❑ Common refinery fractions

Light end Intermediate Heavy Distillates Residues

distillates
Natural gasoline and Heavy fuel oils Heavy mineral oil Lubricating oils
natural gas

LPG Diesel oils Heavy flotation oils Fuel oils

Light Gas oils Lubricating oils Petroleum
H2, H2S, SO2 Waxes Road oils
Motor gasoline Asphalts
Solvent Naphtha Coke
Jet fuel Greases
Kerosene
Light heating oil
 Physical Processes
❑ Deasphalting

Propane deasphalting process

▪ Coke formation tendency in heavy distillates is reduced by removal of

asphaltenic materials

▪ Liquid propane is the most suitable solvent

▪ Butane and pentane are also used for this purpose

 Thermal Processes

❑ Visbreaking

Schematic of the visbreaking process

▪ Visbreaking is viscosity reduction process of vacuum residue by mild thermal

cracking process

▪ The main product (about 80 wt%) is the cracked residue

 Thermal Processes
❑ Delayed Coking

Schematic of the delayed coking process

▪ It is a thermal cracking process with long residence time, resulting in formation

of petroleum coke
 Thermal Processes
❑ Flexicoking

▪ It is a done to minimize coke production

Schematic of the Flexicoking process

 Catalytic Processes
❑ Catalytic cracking

▪ Catalytic cracking is required to increase gasoline production

▪ Here thermal cracking is catalyzed by solid acids, which promote the rupture of

C–C bonds

▪ The crucial intermediates of the catalytic reaction are carbocations

▪ Besides C–C bond cleavage a large number of other reactions occur:

❖ Isomerization

❖ Protonation, deprotonation

❖ alkylation

❖ polymerization

❖ cyclization, condensation (eventually leading to coke formation)

▪ Zeolites and amorphous silica-aluminas are used as catalyst

 Catalytic Processes
❑ Catalytic cracking mechanism

Mechanism for catalytic cracking of alkanes, including isomerization

 Reaction

❑ Cracking reactions
C2 H6 ↔ C2H4 + H2
C3H8 ↔ C3H6 + H2
C4H10 ↔ C4H8 + H2

▪ High reaction temperature is favorable

for higher conversion

▪ Forward reaction is also favored if the

alkanes have a low partial pressure

▪ A process under vacuum is desirable

▪ Smaller alkane needs higher

temperature for a given conversion

Equilibrium conversion of alkanes as

function of temperature at 1 bar
 Reaction Mechanism

❑ Cracking reactions

Mechanism of ethane dehydrogenation

 Catalytic Processes
❑ Catalytic cracking process

Flow scheme of a modern fluid catalytic cracking (FCC) unit

 Catalytic Processes

❑ Catalytic reforming (1950 on wards..)

▪ Catalytic reforming is used for production of gasoline components with a high
octane number
▪ Also used for production of aromatics for the chemical industry

Reactions occurring during catalytic reforming

 Catalytic Processes

❑ Catalytic reforming products

Component Feed Product

Alkanes 45–55 30–50

Alkenes 0–2 0

Naphthenes 30–40 5–10

Aromatics 5–10 45–60

 Catalytic Processes
❑ Catalytic reforming process
▪ Semi-regenerative reforming
▪ Fully-regenerative reforming
▪ Continuous-regenerative reforming

Flow scheme of the semi-regenerative catalytic reforming process

 Catalytic Processes

❑ Catalytic reforming process

▪ It employs a moving bed, which enables continuous regeneration of catalyst
instead of the fixed bed reactor used in semi or fully regenerative system

Flow scheme of the continuous-regenerative reforming process

 Applications

❑ Ethene is the most common alkene

Ethene uses in year 2008

 Industrial Process

❑ Requirements of steam reforming process

▪ Considerable heat input at a high temperature level

▪ Limitation of hydrocarbon partial pressure

▪ Very short residence times (<1s)

▪ Rapid quench of the reaction product to preserve the composition

Simplified flow scheme of a steam cracker for naphtha cracking

 Industrial Process

❑ Composition of naphtha feed for yield patterns

Hydrocarbon type wt% of total

n-Alkanes 36.1

iso-Alkanes 36.6

Alkenes 0.2

Naphthenes 21.1

Aromatics 6.0

Total 100
 Industrial Process

❑ Commercial naphtha cracking yield patterns for different residence times

and steam dilution ratios

 Industrial Process

❑ Furnace

Typical two-cell cracking furnace configuration

 Industrial Process

❑ Coke formation during the cracking process causes undesired

phenomena:

▪ Reduced heat transfer rates

▪ Increased pressure drop

▪ Lowered yields

▪ Reduced selectivity towards alkenes

❑ Reducing coke formation

▪ Pretreatment of cracking tubes to create inert barrier

▪ Passivation of the tubes by chemical treatment prior to start-up or during

operation

▪ Applying a catalytic coating to the cracking tubes

Ammonia-Urea Process
Urea Production flowsheet
 Industrial Process

❑ Product processing

Simplified process flow diagram for producing ethene via gas cracking
 Industrial Process

❑ Product processing

Simplified process flow diagram for producing ethene via liquid cracking
 Selective Dehydrogenation of Light Alkanes

❑ Several catalytic dehydrogenation processes commercially available

▪ UOP Oleflex process

▪ Catofin process

▪ STeam active reforming (STAR)

▪ Snamprogetti fluidized bed reactor design (FBD)

Performance comparison of various dehydrogenation processes

 Selective Dehydrogenation of Light Alkanes

Commercial reactors for alkane dehydrogenation: (a) adiabatic moving bed reactors
Oleflex); (b) parallel adiabatic fixed bed reactors (Catofin); (c) tubular fixed bed reactors in
furnace (STAR); (d) fluidized bed reactor and regenerator (FBD).
 Metathesis of Alkenes

❑ Metathesis

▪ It is a reaction for conversion of alkenes to produce alkenes of different size

CH2=CH2 + CH3CH=CHCH3 ↔ 2CH3CH=CH2

Metathesis of alkenes; R1, R2, R3, R4 = H, CH3, CH2CH3 and so on

 Metathesis of Alkenes

❑ Metathesis process

▪ Olefins Conversion Technology (OCT) process

▪ Meta-4 process

Typical flow scheme of the OCT metathesis process

 Metathesis of Alkenes

❑ Comparison of metathesis technologies

OCT Meta-4
Reactor fixed bed Hydrotreating

Catalyst WO3/SiO2+MgOa Re2O7/Al2O3

Phase gas liquid

Temperature (K) 530 310

Pressure (bar) 30–35 60

Butene conversion (%) 60–75 63

Propene selectivity (%) 95 Not available

 Production of Light Alkenes from Synthesis Gas

❑ Fischer–Tropsch process

nCO + 2n H2 → CnH2n + nH2O

❑ Methanol-to-olefins process (MTO)

Reactions in the conversion of methanol to light alkenes and gasoline components

Production of Light Alkenes from Synthesis Gas

Flow scheme of the MTO process

 Other Methods

❑ Ethene by the catalytic dehydration of bioethanol

2CH3CH2OH ↔ CH3CH2OCH2CH3 + H2O

CH3CH2OCH2CH3 → 2CH2=CH2 + H2O

❑ Direct conversion of methane

2CH4 + 1/2O2 → C 2 H6 + H 2 O

C2H6 + 1/2O2 → C2H4 + H2O

Ethene/ Ethylene
 Ethene/ Ethylene Feedstocks

❑ Feedstocks

Total of ethylene
Feedstock Yield of ethylene, %
production, %
Ethane 35.6 45-50

Propane 11.2 30-32

n-Butane 3.0 30-31

Naphtha 47.0 23-33

Gas oil 3.2 19-22

 Ethylene Through Cracking of Naphtha

❑ Chemistry

C5H12 → C2H˙5 + C3H˙7 C5H˙11 → CH˙3 + C 4H8

C7H16 → C3H˙7 + C4H˙9 CH˙3 + CH˙3 → C2H6
C2H˙5 → C2H4 + H˙ CH˙3 + H˙ → CH4
C3H˙7 → C2H4 + CH˙3 H˙ + H˙ → H2
C3H˙7 → C3H6 + H˙ CH˙3 + C3H˙7 → C4H10
C4H˙9 → C 3 H6 + CH˙3 C4H10 → C4H8 + H 2
C4H˙9 → C4H8 + H˙ C4H8 → C4H6 + H2
CH˙3 + C4H˙9 → CH4 + C5H˙11 C4H6 + C2H4 → C6H10
C3H˙7 → C3H6 + H˙ C6H10 → C 6H 6 + 2H2
 Ethylene Through Cracking of Naphtha

❑ Composition of pyrolysis products from Naphtha steam cracking

Components Amount, % w/w

Hydrogen 1.0

Methane 14.0

Ethylene 23.5

Ethane 6.0

Propylene 17.5

Propane 1.0

Butadiene (1,3- & 1,2-) 3.5

Other C4’s 7.0

Gasoline 23.0

Heavy products 3.5

 Ethylene Through Other Processes

❑ Ethane cracking

▪ Ethane cracking yields 97% ethylene

▪ Cracking parameters are: 820°-870°C temperature, 2-3 bar pressure, ethaneto

steam ration 2.5–6

❑ Dehydration of ethyl alcohol

▪ Till recent times in India ethylene is produced by catalytic dehydration of ethyl

alcohol

𝑨𝒍𝟐 𝑶𝟑 (𝟑𝟐𝟎℃)
CH3 – CH2OH CH2=CH2 + H2O
 Purification of Ethylene

❑ Impurities present in ethylene after Naphtha cracking and removal

Impurity Removal

Acid impurities e.g., CO2, H2S, CO, SO2, Alkali washing and subsequently water
etc. washing

Moisture Alumina is used for drying

Acetylene Selective hydrogenation using palladium

based catalyst

Ethane Fractionation at 20 bar pressure

 Ethylene Derivatives

❑ Ethylene derivatives
 Major Marketing Products of Ethylene

❑ Ethylene market

Polyethylene and ethylene polymers 52%

Ethylene oxide 15%

Ethylene dichloride (for vinyl chloride) 14%

Ethyl benzene (for styrene) 8%

Linear alcohols 6%

Miscellaneous 5%
 Ethylene for Polymers

❑ Specification of polymer grade ethylene

Impurity Concentration
Ethylene > 99.9%

Methane < 1 ppm

Ethane < 1 ppm

Propylene < 250 ppm

Acetylene < 10 ppm

Sulphur < 10 ppm

Water < 10 ppm

Oxygen < 5 ppm

Carbon monoxide < 10 ppm

Propylene
 Propylene Production

❑ Production

▪ The source of propylene are gas streams of refinery and naphtha cracking

▪ Catalytic cracking of heavy distillate for producing gasoline serves as major

source of propylene

R-CH2+ + CH3CH2CH2CH2CH2CH3 → RCH3 + CH3C+HCH2CH2CH2CH3

CH3C+HCH2CH2CH2CH3 → CH3CH=CH2 + CH3CH2C+H2

CH3CH2C+H2 + R1H → CH3CH2CH3 + R 1+

 Yield

❑ Relative yield of ethylene and propylene from cracking various

hydrocarbons
Hydrocarbon Propylene/ ethylene wt. ratio
Ethane 0.04

Propane 0.33

Butane 0.58

n-pentane 0.81

Napata 0.57

Gas oil 0.62

Crude oil 0.60

 Propylene Derivatives

❑ Propylene derivatives
 Propylene for Polymers

❑ Specification of polymer grade propylene

Impurity Concentration
Propylene > 99.5%

Ethylene < 150 ppm

Butadiene < 10 ppm

Propadiene < 5 ppm

Propane < 5000 ppm

Sulphur < 1 ppm

Carbon dioxide < 5 ppm

Oxygen < 1 ppm

Carbon monoxide < 5 ppm

 Major Marketing Products of Propylene

❑ Propylene market

Isopropyl alcohol 8%

Propylene oxide 12%

Acrylonitrile 15%

Polypropylene and propylene polymers 38%

Cumene 9%

Oxo alcohols 6%

Miscellaneous 12%