VSS CH353 PRPC 19-20 Chap1

Petroleum Refining Processes
(NITW; CH353; 4-Credits)
Instructor
Vidyasagar Shilapuram
Email:vidyasagars@nitw.ac.in
Department of Chemical Engineering
National Institute of Technology, Warangal
“Chemical engineering is the only engineering discipline founded on
all three sciences, and mathematics. As such, it is well positioned
for exploring discoveries and advances in chemistry, biology and
physics to solve pressing problems in energy, the environment,
Biosciences, materials and other exciting areas. This makes ChE
very relevant and also a lot of fun.”
Gregory Stephanopoulos, Professor, MIT

“Chemical engineering is the only engineering discipline founded on
all three sciences, and mathematics. As such, it is well positioned
for exploring discoveries and advances in chemistry, biology and
physics to solve pressing problems in energy, the environment,
Biosciences, materials and other exciting areas. This makes ChE
very relevant and also a lot of fun.”
Gregory Stephanopoulos, Professor, MIT
“I became a chemical engineer because of the elegant way in which the

subject describes both molecular-level phenomena and large-scale
Processes - our intuition spans a vast range of length scales.”
Karthish Manthiram, Professor, MIT

COURSE OBJECTIVES
1. To explain the concepts of origin and formation of crude oil

COURSE OBJECTIVES
2. To explain the properties, testing methods of the raw crude and

various product fractions
COURSE OBJECTIVES

3. To explain various treatment techniques of the raw crude and

COURSE OBJECTIVES

3. To explain various treatment techniques of the raw crude and

4. To explain processes involved in converting the crude into various

useful fractions.
COURSE OUTCOMES
CO1: Characterize the petroleum and petroleum products

COURSE OUTCOMES
CO2: Identify the methods involved in crude preprocessing

COURSE OUTCOMES
CO3: Design the fractionating column for crude

COURSE OUTCOMES
CO4: Differentiate the treatment techniques involved in post processing

of crude
COURSE OUTCOMES
CO4: Differentiate the treatment techniques involved in post processing

of crude
CO5: Apply the process flow technologies for crude conversion to fuels
Course Outline
Course Outline
Origin, formation and composition of petroleum-
Origin and formation of petroleum
Reserves and deposits of world
Petro Glimpses and petroleum industry in India
Composition of petroleum
Course Outline
Petroleum processing data-

Evaluation of Petroleum
Thermal properties of petroleum fractions
Important products-properties and test methods
Course Outline
Petroleum processing data-

Evaluation of Petroleum
Thermal properties of petroleum fractions
Important products-properties and test methods
Fractionation of petroleum-
Dehydration and desalting of crudes
Heating of crudes
Distillation of petroleum
Blending of gasolines
Course Outline Continue…
Treatment techniques-
Fractions-Impurities
Gasoline treatment
Treatment of kerosene
Treatment of lubes
Wax and purification
Course Outline Continue…
Treatment techniques-
Fractions-Impurities
Gasoline treatment
Treatment of kerosene
Treatment of lubes
Wax and purification
Thermal and catalytic processes-

Cracking
Catalytic cracking
Catalytic reforming-introduction and theory
Naphtha cracking
Coking
Hydrogen processes
Alkylation
Isomerisation processes
Polymer gasolines
Course Outline (in short) Continue…
Origin, formation and composition of petroleum-Petroleum processing

data-Fractionation of petroleum-Treatment techniques-Thermal and
catalytic processes
Text Books:
1. B.K.Bhaskara Rao, Modern petroleum refining processes, 4th Edition,
Oxford&IBH publishing co.pvt.ltd.,2008.
2. J.G.Speight, and B. Ozum, Petroleum Refining Processes, Marcel Dekker,

2002.
3. Mohamed A. Fahim, Taher A. Al-Sahhaf, Amal Elkilani,

Fundamentals of Petroleum Refining, Elsevier Science, 2010
4. R. A. Meyers, Hand Book of Petroleum Refining Processes, McGraw

Hill, 3rd Edition, 2003.
Text Books:
1*. B.K.Bhaskara Rao, Modern petroleum refining processes, 4th Edition,
Text Books:
2002.
Text Books:
1*. B.K.Bhaskara Rao, Modern petroleum refining processes, 4th Edition,

2002.
3. Mohamed A. Fahim, Taher A. Al-Sahhaf, Amal Elkilani,

Fundamentals of Petroleum Refining, Elsevier Science, 2010
4. R. A. Meyers, Hand Book of Petroleum Refining Processes, McGraw

Hill, 3rd Edition, 2003.
Additional Reading
1. James H.Gary, Glenn E. Handwerk, Petroleum Refining Technology
and Economic, 4th edition, Marcel Dekker, Inc, 2001.
2. http://nptel.ac.in/courses/103102022/ by Dr.KK Pant (IITD) &
Dr. D.Kunzru (Retd. IITK)
Method of Evaluation:
Surprise tests/Minor tests --- 20 Marks
Mid-Semester Examination --- 30 Marks

(10-15-Febraury-2020)
End Semester Examination --- 50 Marks

(13-27-April-2020)
Total --- 100 Marks

General Instructions
• Most of the time mode of teaching will be on ppt
• Course is purely theory
• Understand and revise many times for exam point of few
•After you go through basic courses of chemical engineering, when you

look at each chapter, course is more scientific, and conceptual oriented
• Some part of the course is given for self learning, also included in
exam
• CR make sure projector is on and every thing is set

General instructions
Day Time
75% attendance in the course is compulsory Mon 12-1
Tue 11-12
Latecomers are not entertained
Wed 11-12
4 classes scheduled per week Thu 9-10
14 weeks course

Extra classes will be conducted
Last working day: 03-April-2020
General instructions
Day Time
75% attendance in the course is compulsory Mon 12-1
Tue 11-12
Latecomers are not entertained
Wed 11-12
4 classes scheduled per week Thu 9-10
14 weeks course

Extra classes will be conducted
Last working day: 03-April-2020
8-9 9-10 10-11 11-12 12-1
Mon APC PRP
Tues PRP
Wed APC PRP
Thurs PRP APC
Fri
Class Representative
Coordinate with the students and teacher for
Announcements
Issues related to subject/class

Section-A Section-B
Name Anvesh Nikhil Reddy
Roll No. 176112 176211
Phone Number 9603075979 9701242537
Email dontulaanvesh@ nikhilreddy.d1999
@
1. Origin, Formation and Composition of Petroleum
 Overview of petroleum
 Origin and formation of petroleum
 Reserves and deposits of world (Self reading)
 Petro Glimpses and petroleum industry in India (Self
reading)
 Composition of petroleum
1. Introduction
1. Introduction
 Most of the countries are importers of energy.

 60% of the energy needs of the world are met by petroleum
1. Introduction

 The fossil fuels are irreversibly consumed at a rate more than million
times faster than they were formed.
 Insecure position especially for petroleum and its products.
1. Introduction

 The hike in price of petroleum and its products is for two reasons;
(a) Mounting demands
(b) Fast depletion of reserves
1. Origin and formation of petroleum

 The hike in price of petroleum and its products is for two reasons;
(a) Mounting demands
(b) Fast depletion of reserves
 Thus its competence to serve mankind is unquestionable

 According to Mayer and Hocott (1977) ‘there is no dearth of
petroleum and natural gas resources demanding in the earth. There is
no foreseen shortage of available supplies by present technology until
well into the next century’.
 The controversies may be serious by understanding the formation of

petroleum and rate at which these are conserved

 Perhaps resources may not be the problem, but availability may be


 Efforts are in progress

 To locate new perspective fields
 To identify uneconomical fields
 Innovations in search of secondary recovery techniques to lift the oil from
existing sources

 Efforts are in progress

 To locate new perspective fields
 To identify uneconomical fields
 Innovations in search of secondary recovery techniques to lift the oil from
existing sources
Que: Which companies working in this direction???
1.1.1 Occurrence of petroleum
 Petroleum occurs in the earth crust

 In all possible states
 Varies in colors from light brown to dark brown or black
 Exhibiting luminescence in some cases

 Petroleum occurs mostly in sedimentary rocks and it is more

homogenous than coal


 Petroleum is a mixture of various hydrocarbons of homologous

series namely paraffins, napthenes, and aromatics


 Petroleum is a mixture of various hydrocarbons of homologous

series namely paraffins, napthenes, and aromatics
 Thus main elements are

 C(84-86%),
 H2 (11-14%) and
 Other elements O2, N2, S including different metals in traces rarely contribute
about 8%
1.1.2 Origin and formation
 Scientists still not clear in successfully explaining the origin and
formation of huge hydrocarbon deposits
 Notably a sound theory has yet be evolved
 Scientists still not clear in successfully explaining the origin and
formation of huge hydrocarbon deposits
 Notably a sound theory has yet be evolved
 Different and conflicting theories appeared in large number to

explain the formation of petroleum deposits.
 Mendeleeff and Berthelot hypothesis (Inorganic Theory)

 Assumes the availability of carbides in earth’s crest
 Some carbides, based upon the inorganic reactions, produce
hydrocarbons when reacted with water, such as
CaC2+2H2O→C2H2+Ca(OH)2
Al4C3+12H2O→3CH4+4Al(OH)3

o The deposits of such magnitudes could never be balanced with the
hypothesis proposed

o The deposits of such magnitudes could never be balanced with the
hypothesis proposed
 V.D. Sokolov Hypothesis (Organic Theory)

 The hydrocarbon vapors were already in cosmic clouds
 Favorable conditions leading to precipitation of these clouds, rained
hydrocarbons, which were either adsorbed or entrapped in earth’s crest
 The inorganic basis of petroleum formation had to be given up in
favor of organic theory due to the following observations and facts
(as enumerated by J.D.Haun)
 The inorganic basis of petroleum formation had to be given up in
favor of organic theory due to the following observations and facts
(as enumerated by J.D.Haun)
(a) The homologous series present in petroleum are found only in organic matters
(b) Nitrogen compounds in petroleum, especially plant derived porphyrins,
comprise a very small amount but their significance is immense in the
formation of petroleum from life source
(c) The range of radio isotopes of carbon C12-C13 is within the range of natural
carbonaceous materials and not from inorganics, as they do not have any
chance to absorb radioactivity
(d) Optical activity, a pre-requisite of natural organics, is exhibited by petroleum
(e) Most organisms, like diatoms are found in petroleum
(f) Petroleum formation is a result of low temperature activity only
(g) Petroleum is always associated with sedimentary rocks, (even recent
formations too) and not with igneous rocks
(h) Small quantity of petroleum (hydrocarbons) in recent sediments suggest, that
the formation of petroleum is normal, continuous and does not require any
severe physico-chemical conditions
1.1.3 Organic Theories
 There are various schools with various thoughts concerning the
origin and formation of petroleum based on their
discovery/prediction/observation. Some of which are listed as:
 Engler (1886): After the natural extinction of mammoths, the body fat was
slowly converted to hydrocarbons
 Thomas-Graham (1843): Naphtha must be a product of action upon vegetable
matter of high temperature
 Chaptal(1845): When plants became entirely decomposed into vegetable moulds
these contained certain oil which escaped decomposition
 JW Draper (1846): Action of natural heat of earth on coal
 Popoff (1875): Methane could be produced by decomposition of cellulose
 Hopper Seyler (1886): Bacteria could produce methane, as is ever evident in
muddy areas
 Treibs(1934): Some of the plant pigments, microscopic organism, and biological
matter present in crudes.
 This prompted API to launch a project API 43* to investigate thoroughly
*API-American Petroleum Institute Standards. API 43 relates to the formation of organic material into
petroleum
As crude oil is a mixture of all sorts of hydrocarbons, it doesn't have a single molecular weight. API gravity
is just a measure of the of the relative density of the fluid.
 Mikhailovosky, N. Potering and N.C.Anderson (bright explanation near to the
goal) say that
 Source of petroleum was not a definite species of flora (plant life)
 Also the organic matter of sea oozes consisting of remains of plants and animal
organisms
o The initial decomposition of the vegetable and animal matter was a result of
activity of micro-organisms
o Later the organic matter underwent changes due to pressure and temperature of
the crest of the earth
o Petroleum take birth in argillaceous rocks1 enriched with organic matter and later
migrates and got stored in arenaceous rocks2
1,2 rocks formed from clay deposits/clay sediments. Find further details to
differentiate the same
goal) say that
 Also the organic matter of sea oozes consisting of remains of plants and animal
organisms
activity of micro-organisms;
the crest of the earth.
o Petroleum took birth in argillaceous rocks enriched with organic matter and later
migrated and got stored in arenaceous rocks.
 The extension works by other research group characterized the composition
and content of organic matter in rock of different ages
 Controversies always flare up,
 One school advocates-temperature-pressure distillation or by tectonic stress
 Another school advocates as a biochemical process;
 Yet another advocates it purely as a chemical or radioacivity reaction-and so on.
goal) say that
 Also the organic matter of sea oozes (comes out) consisting of remains of plants and
animal organisms
activity of micro-organisms;
the crest of the earth.
o Petroleum took birth in argillaceous rocks enriched with organic matter and later
migrated and got stored in arenaceous rocks.
 The extension works by other research group characterized the composition

and content of organic matter in rock of different ages.
 Controversies always flare up,

 One school advocates-temperature-pressure distillation or by tectonic stress
 Another school advocates as a biochemical process;
 Yet another advocates it purely as a chemical or radioacivity reaction-and so on.
 However, biochemical theory has been received with some favor, as it

concerned with low temperature and pressure, and bacteria of versatility
 However, biochemical theory has been received with some favor, as
it concerned with low temperature and pressure, and bacteria of
versatility
 Thus it may be concluded that the petroleum formation from

organic mass is via combination of physical and biological processes
rather than individual
 In other words, may be explained by two distinct processes namely

physical and biological
Assignment for next class
Que 0: What is OPEC?
Que 1: What are the objectives of OPEC?
Que 2: Are we (Indians) are the mebers of OPEC or not?
Que 3: Who are the members of OPEC?
Que 4: What is the MMTPA of crude India processes?

 However, biochemical theory has been received with some favor, as
it concerned with low temperature and pressure, and bacteria of
versatility
 Thus it may be concluded that the petroleum formation from

organic mass is via combination of physical and biological processes
rather than individual
 In other words, may be explained by two distinct processes namely

physical and biological
1.1.4 Physical Methods
 Depends upon the factors like;
1. Heat 2. Pressure 3. Catalysts 4.Radio activity
1.1.4 Physical Methods
 Depends upon the factors like;
1. Heat 2. Pressure 3. Catalysts 4.Radio activity
1.1.5 Biological Methods

 All biologic methods are governed by source and environments
1. By preservation of hydrocarbons synthesized by the source sediment
organisms
2. Biological reduction (anerobic or aerobic) of sources being (a) fatty
acids (b) proteins and amino acids (c)Carbohydrates
3. Biological and physical methods, such as
(a) By condensation of bacterially produced methane under high
pressure and temperature in the presence of catalysts
(b) By bacterial modification of sediments
Martins R et al1
 Evidence in biogenicity* showed that petroleum formation does not
differentiate vegetable and animal source
*Biogenicity refers to any chemical and/or morphological signature preserved over

a range of spatial scales in rocks, minerals, ice, or dust particles that are uniquely
produced by past or present organisms. This includes elemental and isotopic
signatures diagnostic of life, which cannot be formed by purely abiotic processes.
These may be accompanied by textural remains with shapes, orientations, and
abundances that uniquely result from the growth or decay of (once) living
organisms. Further support for biogenicity can be shown if the distribution and
abundance of this evidence is controlled by biologically significant primary
variables such as light, temperature, and nutrient gradients.
1,2…n superscript with number indicates theories or observations by various researchers

Martins R et al1
 Evidence in biogeneicity showed that petroleum formation does not
Burton D2
 Origin of petroleum is from
 Fish mollusks, lamellibranches, diatoms foraminiferae and other sea creatures
 Ancient biological matter-particularly from lipid rich lower marine plants such as
plankton
 Terrestrial plants supply terpens
 Biogenic origin- reason being presence of odd carbon numbers

Martins R et al1
Burton D2
 Fish molluscs, lamellibranches, diatoms foraminiferae and other sea creatures as
suggested by close classification of crude oil with marine
plankton

Martins R et al1
Burton D2
 Fish molluscs, lamellibranches, diatoms foraminiferae and other sea creatures as
suggested by close classification of crude oil with marine
plankton
 Organic matter accumulates and will be mixed with various
proportions of inorganics i.e. sedimentary soils is converted to
kerogen during diagenesis
 Above matters is referred as kerogens or mother substances for
shale
Diagenesis: The physical and chemical changes occurring during the conversion of sediment to
sedimentary rock.
 Kerogen is a mixture of organic chemical compounds, having
high molecular weight (upwards of 1,000 daltons or 1000 Da; 1Da=
1 atomic mass unit) that make up a portion of the organic matter
in sedimentary rocks.
 Diagenesis is the change of sediments into a different sedimentary
rock during and after rock formation (lithification), at temperatures
and pressures less than that required for the formation of
metamorphic rocks.
 Kerogen is divided into three classes (Type-I, II & III) based on the
nature of original organic source material
 Hydrogen rich straight chain groups usually are from algae, lipids and planktons
These contribute to Type-I and Type-II forms of kerogen
 Type-III kerogen is oxygen rich cyclic carbon structures obtained from higher
plants, known as lignines.
 The sedimentary deposit is classified both in terms of proportion of

kerogen and amounts type-I and type-II
 The sedimentary deposit is classified both in terms of proportion of

kerogen and amounts type-I and type-II
 If the kerogen% in sedimentory deposit is

 <1 the bearing sedimentary rock is oil source rock
 above 1 and upto 50 the rock is an oil shale
 >50 (known as humic kerogen): Found to contain higher plant materials
kerogen to coal, gas
Kenneth kobe3
 Petroleum results from a series of biochemical and chemical reactions
 Starts with organic remains of dead micro-organisms
 Bacteria are involved in transformation of the constituents of decaying
microorganisms into hydrocarbons and also decompose organic matter to CO2,
H2S, etc.
 No bacteria can produce more than C2 compounds
 Thus C11 to C14 compounds must have been formed from marine life (as is evident
from certain Gambian crudes)
 Most organisms are found to generate petroleum in their metabolic processes
too
 Anaerobic conditions keep porphyrins to remain in crude
Kenneth kobe3
 Petroleum results from a series of biochemical and chemical reactions
 Starts with organic remains of dead micro-organisms
 Bacteria are involved in transformation of the constituents of decaying
microorganisms into hydrocarbons and also decompose organic matter to CO2,
H2S, etc.
 No bacteria can produce more than C2 compounds
 Thus C11 to C14 compounds must have been formed from marine life (as is evident
from certain Gambian crudes)
 Most organisms are found to generate petroleum in their metabolic processes
too
 Anaerobic conditions keep porphyrins to remain in crude
McNab et al.4
 Crudes are divided into three types depending upon the time of
deposit
 Tertiary crudes: 11X106-74X106 years of age (asphaltic crude)
 Mesozoicera oil: 75X106-200X106 years of age
 Paleozoic crudes: 200X106-500X106 years of age (paraffinic crudes)
Brooks and Frost5
 Organic matter decomposed under the action of natural catalyst as
well as bacteria
 Evidence of bacteria in sedimentary rocks is positive
 Organics are initially decomposed to acids and gases (CH4), till the
activity of bacteria ceases
Brooks and Frost5
well as bacteria
Gubkin6
 Formation of petroleum and gas is from organics i.e. may be fat or
carbohydrate
 Scattered in argillaceous rocks is a local process
 Started with accumulation of organic matter in sea oozes
Brooks and Frost5
well as bacteria
Gubkin6
 Formation of petroleum and gas is from organics i.e. may be fat or
carbohydrate
 Scattered in argillaceous rocks is a local process
 Started with accumulation of organic matter in sea oozes
Others7
 The hydrogenation of carbon oxides result in –CH2-Chains
 This is taking place under the catalytic activity of earth’s crest due to
favorable conditions of temperature and pressure
Thus every new thought resulted is more sterile addendum in better understa…
Overall Conclusions of origin and formation of petroleum
Compare all the organic/biological theories discussed and correlate with the overall conclusions
 Petroleum formation is from biological origin
 Because of the oil association with sediments containing a relatively large
amount of organic matter
 The presence of optically active compounds and complex substances of
biological origin
Continue…
biological origin
 Petroleum formation is at low temperature, usually less than 200OC
(or even 100OC)
Continue…
biological origin
 Petroleum formation is at low temperature, usually less than 200OC
(or even 100OC)
 The thermophilic bacteria (bacteria that can survive at high
temperature) place the major role in conversion of this organic mass
into liquid hydrocarbons
 The overall explanation until now may be summed up in two steps:

 First: Action of bacteria is contributing the lighter fractions
 Secondly: Continuous catalytic action of earth at depths of 1-2 Km to yield
heavier hydrocarbons
 These are all possible natural reactions occurring over the ages
Continue…
 Petroleum hydrocarbons might have been formed by many processes
each contributing its own share, may be small
 API gravity of crude and paraffinicity increase with the depth of mine
and time of formation and storage because severity of reaction
 API gravity of crude and paraffinicity increase with the depth of mine
and time of formation and storage because severity of reaction
 Age of the oil is indicated by CPI (Carbon Preference Index)

 Hydrocarbons of recent origin show CPI of 4 to 5
 Ancient bitumen show about 1
 Odd carbon number is dominant in recent formations i.e. as the oil ripens the
oddity decreases
Assignment-1
Q1: Systematically collect extensive information, understand and
differentiate between various rocks viz., Sedimentory rocks,
argillaceous rocks, arenaceous rocks, etc, responsible for petroleum
formation?
Q2: Elaborate what is Kerogen. Classify kerogens with significant

similarities and differences. Elaborate classification of sedimentory
rocks for oil source/oil shale based on Kerogens?
Q3: Differentiate Petroleum/crude oil/coal/natural gas and shale oil?

1.4 Composition of Petroleum
 Petroleum occurs in all three possible states: Liquida, Solidb, and Gasc
 The liquid petroleuma
o Usually colored from dark brown to bluish black or black
o Exhibiting some times bloom or fluorescence
 The semi solid or solid petroleumb
o Such deposits are formed after the evaporation or migration of lighter fractions
o Known as pitch
o pitch usually black in color
 gasc mainly in the dissolved form in liquid petroleum
 The gaseous deposits of petroleum are known as natural gas deposits

o some times gasoline is also accompanied.
Gas from condensate reservoir contain a good portion of lighter
fractions of a boiling points upto 30 OC
 The bulk of petroleum is a homogenous mixture, made up of
hydrocarbons of
 Saturated compounds like paraffins, naphthenes and
 Unsaturated cyclic compounds mainly aromatics (ring structures)
 The average ultimate composition of petroleum is mainly given in

terms of constituents of hydrocarbons, namely
 Carbon and hydrogen: Carbon: 84-86%, Hydrogen:11-14%
 The other major elements of importance are sulfur, oxygen and nitrogen
o Generally these three elements combined do not exceed 5% on an average
o However, exception to this statement can be traced in some crudes of some
particular origin
o These elements are treated as impurities because of their inherent properties
like odor, color, corrosiveness, etc.
 The highest carbon atom present in the crude is C70

 Further, except first few hydrocarbons, all other hydrocarbons
exhibit isomerism
 Composition of petroleum depends not very much on the origin of
formation4, but certainly change with the time of formation1, storage2
and different layer through which it migrated3
The general properties of these homologous series are
1.4.1 Paraffins
 CnH2n+2 is the general formulae
 First three compounds are gases
 Compounds upto C16 are liquids and
 Beyond C16 upto C30 assume semisolid consistency
 Well beyond C30 assume the shape of solid blocks, some times even crystalline
forms
The general properties of these homologous series are
1.4.1 Paraffins
 CnH2n+2 is the general formulae
 First three compounds are gases
 Compounds upto C16 are liquids and
 Beyond C16 upto C30 assume semisolid consistency
 Well beyond C30 assume the shape of solid blocks, some times even crystalline
forms
 There are number of isomeric compounds for each compound,
profoundly differing in properties
 Upto C3 no isomers are possible
 C4 exhibit only two isomers
 C5 exhibit three isomers
 The number of isomers increases as the number of carbon atoms increase
 C13H28 exhibit 802 isomeric forms
 Paraffins are stable, not attacked by sulphuric acid or other oxidizing
agents
 However, paraffins of higher order>C30 are prone to oxidation
 Higher paraffins are very much insoluble in water; though the lower
ones are soluble in ethers and alcohols
 Paraffins upto 3 carbon atoms have inclination to form hydrates
(Recent research) such as CH47H2O,C2H67H2O and these hydrates
offer clogging and corrosion difficulties
 The specific gravity of the series increase with molecular weight
 still paraffins have less specific gravity and boiling point than aromatics
 Viscosity of paraffins is less but viscosity index is high, with poor
illuminating characteristics
 The pour point of paraffins is usually high
 Due to this characteristic paraffin rich crudes and products bring
difficulties in transportation and storage
 Isomers differ from n-paraffins by having slightly low boiling points,

low pour points, high viscocity, and viscosity index
 Usually i-paraffins are more reactive than n-paraffins but burn like n-paraffins
without much illumination and smoking
 High molecular compounds (>/C20) may be of saturated or

unsaturated nature and decompose if exposed to a temperature of
above 370OC
 Isomers differ from n-paraffins by having slightly low boiling points,

low pour points, high viscocity, and viscosity index
 Usually i-paraffins are more reactive than n-paraffins but burn like n-paraffins
without much illumination and smoking
 High molecular compounds (>/C20) may be of saturated or

unsaturated nature and decompose if exposed to a temperature of
above 370OC
Que: Qualitatively differentiate the parafins, olefins, aromatics, napthenes w.r.to

properties discussed
 Viscosity is defined as the force in dynes required to maintain 1 sq.
cm plane, with a unit velocity gradient from another similar plane
separated by a distance of 1 cm
 The relative viscosity is the ratio of the viscosity to that of water at
standard temperature
 In all refinery operations instead of absolute viscosity kinematic
viscosity is used.
 Viscosity index indicates the variation characteristics of viscosity with

temperature
 Evaluated with the following formulae
Where L=viscosity of a reference oil of zero viscosity in deg. at 37.8OC
H=viscosity of a reference oil of 100 viscosity index at 37.8OC
U=viscosity of test sample at 37.8OC
 The minimum ambient temperature at which fuel must be free

flowing is called pour point
Assignment-1*
Q1:Systematically collect extensive information, understand and differentiate
between various rocks viz., Sedimentory rocks, argillaceous rocks,
arenaceous rocks, etc, responsible for petroleum formation?
Q2: Elaborate what is Kerogen. Classify kerogens with significant similarities
and differences. Elaborate classification of sedimentory rocks for oil
source/oil shale based on Kerogens?
Q3: Differentiate Petroleum/oil/crude oil and shale oil?
Q4: Tabulate the characteristics of petroleum that posses on a relative

scale w.r.to homologous series paraphenes, napthenes and aromatics?
 Note: This table must be updated during the entire course as an when discussed
Characteristics Significance Paraffins Napthenes Aromatics Remarks
Pour Point Difficult/ease in Very high compared
transportation to rest
Specific Gravity <Aromatics >Paraffins
Example Medium High Low
* source must be mentioned (Book, journal, website (link must be provided))

1.4.2 Unsaturates (Olefines and Properties)
 Unsaturated compounds like olefines, diolefines do not appear in
crude to measurable quantities, however, they are detected in some
crudes
 These unsaturates are mainly formed during cracking operations
 The absence of unsaturates to a large extent can be best judged by

the probable catalytic activity of the earth’s crust in converting
unsaturates to saturates and ring structures
1.4.2 Unsaturates (Olefines and Properties)
 Olefines are represented by the general formulae CnH2n
 The first four are gases
 Upto C15 are liquids and
 Beyond C15 are solids
 The boiling points of olefines are generally lower by few degrees than
the saturated compounds of the same carbon number
 Chemically olefines differ very much from paraffins
 They are easily attacked by sulfuric acid and some of them even polymerize
 Treatment
 with sulfuric acid and subsequent hydrolysis yields alcohols (e.g. isopropyl
alcohol)
 with permagnate oxidation glycerols are formed
1.4.3 Acetylene and properties (Alkynes)
 The general formulae for this series is CnH2n-2
 These are isomeric with diolefines
 Acetylene yield crystalline compounds with ammoniacal solution of
copper salts and are attacked by sulfuric acid
 Acetylenes can be hydrogenated to give stable compounds
1.4.3 Acetylene and properties (Alkynes)
 The general formulae for this series is CnH2n-2
 These are isomeric with diolefines
 Acetylene yield crystalline compounds with ammoniacal solution of
copper salts and are attacked by sulfuric acid
 Acetylenes can be hydrogenated to give stable compounds
1.4.4 Diolefines
 These are represented by the formulae CnH2n-2
 Like other unsaturates, these are produced during cracking reactions
 They do not form salts with ammoniacal solution of copper salts
hence can be distinguished from acetylenes
 With mercuric chloride these form precipitates
 With sulfuric acid polymerizes these unsaturates
1.4.5 Naphthenes
 These are unsaturated ring compounds having general formula CnH2n
 Although C3 and C4 ring structures, are in existence, their stability is decreased
because of excessive strain (Bayer’s Strain Theory)
 The prominence of ring structure starts with five carbon atoms
 Napthenes are isomeric with olefines but differ greatly in properties
 Napthenes exhibit both the properties of saturated paraffins and
unsaturated aromatics
 Properties like specific gravity, viscocity, pour point, thermal characteristics lie
in between the two mentioned homologues i.e. saturated paraffins and
unsaturated aromatics
 Ring structures are having branched chains, where the isomeric
character predominantly occurs, followed by positional isomerism in
rings
1.4.6 Aromatics
 The first and smallest of the aromatics is benzene
 Other simple aromatics to follow are toluene, xylene, cumene, etc.
 Even though benzene is unsaturated, yet it follows the principles of substitution
with halogens rather than addition.
o This is mainly due to symmetric grouping of closed ring structure and resonance
 Aromatics are usually

 having high boiling points,
 low pour points (freezing points),
 high octane numbers,
 high viscosity and low viscosity index and
 burn characteristically with a red flame with much soot
 Aromatics resist oxidation since they behave like saturates

1.4.6 Aromatics
 In petroleum fractions
 Aromatics beyond 3-ring structure (Anthracenes) are probably non-existent
 Aromatics usually extend their presence from a temperature of 80 OC onwards
 Well dominate in lower middle cuts and heavy cuts
 The light aromatics (BTX) do not exceed even 5% of crudes of general nature
 Bulk of the aromatics are with side chains together with naphthenic exist in
heavier portion of crudes
1.4.7 Inorganics
Sulfur compounds:
 Sulfur is found in most of the crudes in variable amounts
 Usually the sulfur content does not exceed 5%
 Rare exemptions in some crudes of different origins
 Sulfur in crude occurs in different forms like

 Free sulfur
 H2S
 Mercaptents, and
 thiophenes, etc.
o These are frequently occurring compounds in almost all fractions of the crude
though to a different degree
 Mostly these are present in more quantities in higher molecular

weight stocks
Sulfur compounds:
 Heavier fractions contain
 Sulfides
 polysulfides
 Sulphonates and
 Sulphates
Consequences of sulfur compounds in crude
 Sulfur occupies prominent position in refining due to its threatening
problems of corrosion1 and odour2
 Pollution problems3 and following cost of waste treatment4 is

penalizing for all refiners with high sulfur stocks
 However, refiners remove habitually more detrimental sulfur compounds and
leave the less harmful ones into the products
o Ex: As seen in the case of sulfides converted to disulfides in gasolines
 Some of the sulphonates are regarded as good emulsifiers and detergents, hence
promptly extracted for use in cutting oils
 Prominent effect of sulfur is reflected in increasing the density of

crude5
 Further sulfur containing residuums when cracked leaves cross linked
structures6
 Offer continuing problems in desulfurization6a
 Its presence in different fractions complicates the refining and

treatment methods7
 It stops the effect of additives8
 Sulfur in gas inevitably depress the effect of lead8a and demands more
amount of additive8b
 Free hydrogen sulfide is available in some crudes which naturally

promotes corrosion1.
 The crudes containing sulfur compounds other than H2S and
exceeding 0.5% are denoted as high sulfur crudes. Such crudes are
classified as sour crudes, else, called sweet crude.
 Different crudes are presented in Table 1.1.
 Also shows effect of sulfur on API gravity of crude and pour point of crude.
 All sulfur crude mysteriously exhibit low pour points.
1.4.8 Oxygen and Nitrogen
 Oxygen and nitrogen do not occur in free state either in crudes or in
fractions.
1.4.8 Oxygen
 Oxygen and nitrogen do not occur in free state either in crudes or in
fractions.
 Oxygen occurs as oxyganated compounds like phenols, cresols,

naphthenic acids, sulphonates, sulphates, and sulfoxides
1.4.8 Nitrogen
 Nitrogen is present in two forms: Basic and non basic
 Basic nitrogen is characterized by its titratability with perchloric acids
 Non-basic nitrogen is not titratable hence no possibility of extraction
 Nitrogen exist in the form of indoles, pyridines, quinolines, and
amines, usually well below 2%
1.4.8 Nitrogen
 Nitrogen compounds annoy problems in processing and stability of
products1
 Catalyst deactivation or poisoning2, gum formation3 are some of the
offshoots of nitrogen
 Most of the nitrogen pigments impart color4 to crude and fractions
 The most interesting compounds of nitrogen are porphyrins
 These are obtained from living organisms and preserved in petroleum
 Since anerobic conditions were prevailing during petroleum formation;
otherwise oxidation would have destroyed them.
 The proper understanding of this pigments may augment the knowledge of
origin and formation of petroleum
 Chlorophill is also a complex porphyrin, where central atom is magnesium
instead of nickel or vanadium or iron
 Iron porphyrins are also known as heme; the constituents of red cell in the
blood
 Porphyrin pigments are usually associated in complex form with metals like
copper, iron, vanadium and nickel.
1.4.9 Asphalts, Resins and Bitumens
 Asphalts are
 high molecular weight complex molecules
 black in colour
 soluble preferably in aromatic solvents and carbon di sulphide
 Resins are mostly compounds of highly condensed ring structure

containing oxygen, sulphur and nitrogen, some times inorganics too
 bitumen is a manufactured product it is essentially made up of three

components, asphalts, resins, and mineral oil
 These three components comprise a colloidal system

 Asphalts are suspended in oil and
 Resins contribute to the stability of the system
1.4.10 Less inorganics
 The other elements present are nickel, vanadium, iron, silica, sodium,
magnesium and halogens, etc.
 Even though the analysis is not desirable as these metals hardly

exceed 0.01%, yet may be analyzed for sensitive purposes
 The ash formation is mainly due to these metals and inorganics1
 Some times organometallic compounds are available in colloidal form
 Inroganics always leave a marked influence on fractions2

 Ex: halides may give off halogens during hydrolysis or thermal decomposition
 Corrosion, pollution, ash, etc. are mainly contributed by inorganics3
 Quality of crude had fractions are always violated by these small

amounts4
2.1 EVALUATION OF PETROLEUM
 A. Crude is classified on the basis of residuum (a heaviest product or

a material left behind after distillation of fractions)
 Accordingly:
 Residue containing more than 5% paraffins is paraffinic crude
 Residue containing less than 2% paraffins is naphthenic based
 Residue containing 2% to 5% paraffins is considered as mixed based
 Key fraction no.-1 and key fraction no.-2 are defined as
 Key fraction no.-1 (Kerosen range) has a boiling range of 250 OC-275 OC at
normal pressure
 Key fraction no.-2 (Lube range) has a boiling range of 389 OC-422 OC at
760mm pressure i.e. 275 OC-300 OC at a pressure of 40mm hg mercury
 API (American Petroleum Institute) gravity is defined as
where, ρ=sp. gravity of fraction at 15.6 OC/15.6 OC

 Key fraction no.-1 and key fraction no.-2 are defined as
 Key fraction no.-1 (Kerosen range) has a boiling range of 250 OC-275 OC at
normal pressure
 Key fraction no.-2 (Lube range) has a boiling range of 389 OC-422 OC at
760mm pressure i.e. 275 OC-300 OC at a pressure of 40mm hg mercury
 B. Classification of crude is defined with chosen Key fraction and

API gravity of the chosen fractions
 These are then characterized as:
o When key fraction No.1 has API gravity
 40 or more it is paraffinic,
 Less than 33 it is naphthenic, and
 In the range of 33-40 it is mixed base
o When key fraction No.2 has API Gravity

 30 or more API gravity it is paraffinic,
 less than 20 API gravity it is naphthenic, and
 between 20-30 API gravity it is mixed base
 In the case of mixed base crudes, the nearness to extremities is
mentioned for avoiding any doubtful
 Example
 If a key fractions No.1 of a crude is having
 39 API, it is mixed base but more oriented towards paraffinicity rather than
naphthenicity
 API of 33.3 is not only mixed base but titled towards naphthenic nature rather than
paraffinic nature
 In such cases it is judicious to use (for the above fractions as) mixed base (paraffin),
mixed base(naphthene) respectively
 In case of key fraction No.2, if the pour point is

 Less than 3OC, for this fraction then the base is ‘wax free’
 Greater than 3OC then the base is ‘waxy’
 Petroleum is classified into mainly three types as:
1. Paraffin based
2. Mixed Based/Intermediate and
3. Naphthenic based
 Petroleum is classified into mainly three types as:
1. Paraffin based
2. Mixed Based/Intermediate and
3. Naphthenic based
 1. Classification based on the location of crude was habitual

 Example: Pensylvania crudes classified as paraffinic base and Gulf coast crudes
as napthenics.
 2.Some crudes rich in aromatic series were also classified as aromatic
crudes or benzenoid base crudes
 As all naphthenic crudes give plentiful aromatics such formal classifications
need not be attended.
 These ideas of classification (1 & 2) need not be any more
entertained, as location or formation can never give the idea of crude
 Irrespective of the base of the crude all the hydrocarbon series
(aliphatic, aromatic and naphthenic) are present in all crudes but to
different extent
 Knowledge of base or type of a crude is very essential as

 It depicts the usual properties enmass and
 Adequately inform the difficulties in processing in refinery
API Gravity
 Sp. gravity of close boiling cuts usually lies very close to each other
and therefore difficult to differentiate each other
 Therefore magnification is essential
 API gravity magnifies the sp. gravity of fractions

 For a blend, the API gravity is given as
 Thus API gravity of a mixture is equal to the sum of the individual API gravity
of a component multiplied by corresponding weight fraction in the mixture
2.1.1 U.O.P Characteristics Factor (K)
 Characterization factor is of immense utility in refinery calculations
 It predicts the qualities of crude,
 It give almost all necessary information and valuable data about the fraction
(right from physical properties to tendency of cracking with API gravity and
molecular weight as other parameters)
 Original K factor was formulated on OR and ρ at (60OF)
 The relation is given by
Where R=average boiling point OK or OT or OR
ρ=sp.gravity at 15.6O/15.6OC
 If the characterization factor (K)
 Is 12.5 and above, the crude is classified as paraffin base,
 Less than 10, the crude is classified as napthenic base, and
 Intermediate values are regarded as mixed base crudes
 If the characterization factor (K)
 Is 12.5 and above, the crude is classified as paraffin base,
 Less than 10, the crude is classified as napthenic base, and
 Intermediate values are regarded as mixed base crudes
 K-value of a mixture is the sum of the components ‘K’ value
multiplied by their weight fractions in mixture.
W1,W2,W3 are weight fractions of different components

K1,K2,K3 are respective characterization factors
2.1.2 Correlation Index
 Correlation index is also related to boiling point and specific gravity
 Similar to characterization factor
TB=boiling point (molal) OK

ρ=sp. Gravity at 15.6OC/15.6OC
 Correlation index for

 Paraffins is taken as zero, and
 Aromatics is taken as 100
 The value is not quantitative hence a relative indication of the groups

is only possible hence its use is marginal
Furthermore:
Visit the following links
1. For overall refinery understanding
https://www.youtube.com/watch?v=jk0WrtA8_T8
2. Individual operations/processes
http://www.refiningnz.com/visitors--learning/classroom--learning-
resources/learning-centre/how-it-works---the-refining-
process/hydrocracker.aspx
 The most interesting compounds of nitrogen are porphyrins
 These are obtained from living organisms and preserved in petroleum
 Since anerobic conditions were prevailing during petroleum formation;
otherwise oxidation would have destroyed them.
 Chlorophill is also a complex porphyrin, where central atom is magnesium
instead of nickel or vanadium or iron
 Iron porphyrins are also known as heme; the constituents of red cell in the
blood
 Porphyrin pigments are usually associated in complex form with metals like
copper, iron, vanadium and nickel. The proper understanding of this pigments
may augment the knowledge of origin and formation of petroleum
 The following is an example of nitrogen complex
Gravity API - 38.8
Sulfur wt.% - 0.2-0.0%
Vanadium ppm. - 0.5-2.5%
Nickel ppm. - 1.0-170
Vanadyl porphyrin ppm. - 0.7-1130
Nicke; porphyrin ppm. - 1.0-390

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Petroleum Refining Processes

(NITW; CH353; 4-Credits)

Gregory Stephanopoulos, Professor, MIT

Gregory Stephanopoulos, Professor, MIT

“I became a chemical engineer because of the elegant way in which the

Karthish Manthiram, Professor, MIT

1. To explain the concepts of origin and formation of crude oil

1. To explain the concepts of origin and formation of crude oil

2. To explain the properties, testing methods of the raw crude and

1. To explain the concepts of origin and formation of crude oil

2. To explain the properties, testing methods of the raw crude and

3. To explain various treatment techniques of the raw crude and

1. To explain the concepts of origin and formation of crude oil

2. To explain the properties, testing methods of the raw crude and

3. To explain various treatment techniques of the raw crude and

4. To explain processes involved in converting the crude into various

CO1: Characterize the petroleum and petroleum products

CO1: Characterize the petroleum and petroleum products

CO2: Identify the methods involved in crude preprocessing

CO1: Characterize the petroleum and petroleum products

CO2: Identify the methods involved in crude preprocessing

CO3: Design the fractionating column for crude

CO1: Characterize the petroleum and petroleum products

CO2: Identify the methods involved in crude preprocessing

CO3: Design the fractionating column for crude

CO4: Differentiate the treatment techniques involved in post processing

CO1: Characterize the petroleum and petroleum products

CO2: Identify the methods involved in crude preprocessing

CO3: Design the fractionating column for crude

CO4: Differentiate the treatment techniques involved in post processing

Petroleum processing data-

Petroleum processing data-

Thermal and catalytic processes-

Origin, formation and composition of petroleum-Petroleum processing

2. J.G.Speight, and B. Ozum, Petroleum Refining Processes, Marcel Dekker,

3. Mohamed A. Fahim, Taher A. Al-Sahhaf, Amal Elkilani,

4. R. A. Meyers, Hand Book of Petroleum Refining Processes, McGraw

2. J.G.Speight, and B. Ozum, Petroleum Refining Processes, Marcel Dekker,

3. Mohamed A. Fahim, Taher A. Al-Sahhaf, Amal Elkilani,

4. R. A. Meyers, Hand Book of Petroleum Refining Processes, McGraw

Surprise tests/Minor tests --- 20 Marks

Mid-Semester Examination --- 30 Marks

End Semester Examination --- 50 Marks

Total --- 100 Marks

• Most of the time mode of teaching will be on ppt

• Course is purely theory

• Understand and revise many times for exam point of few

•After you go through basic courses of chemical engineering, when you

• CR make sure projector is on and every thing is set

14 weeks course

14 weeks course

 Most of the countries are importers of energy.

 Most of the countries are importers of energy.

 Most of the countries are importers of energy.

 Most of the countries are importers of energy.

 Thus its competence to serve mankind is unquestionable

 The controversies may be serious by understanding the formation of

 The controversies may be serious by understanding the formation of

 Perhaps resources may not be the problem, but availability may be

 The controversies may be serious by understanding the formation of

 Perhaps resources may not be the problem, but availability may be

 Efforts are in progress