CB426: Petroleum Refinery &

Petrochemicals
LTPC 3-0-0-6
 Reference Books
• W.L. Nelson, Petroleum Refinery Engineering, McGraw Hill, New York, 1961

• K. H. Altgelt, M. M. Boduszynski, Composition and analysis of heavy petroleum fractions, Dekker,

1994

• J. H. Gary and G. E. Handwork, Petroleum refining technology and economics, 4th Ed., Dekker,
2001
 What is Petroleum?
• The petroleum, also called crude oil, is a fossil fuel.

• Like coal and natural gas, petroleum was formed from the remains of ancient marine
organisms, such as plants, algae, and bacteria. Over millions of years of intense heat and
pressure, these organic remains (fossils) transformed into carbon-rich compounds.

• It is thick flammable, brown to black mixture of solid, liquid and gaseous hydrocarbons that
occurs naturally beneath the earth’s crust.

• We rely on as raw materials for fuel and a wide variety of products.

 What is Petrochemicals?
• Petrochemicals are the chemical products obtained from petroleum by refining.

• Petrochemicals are used to manufacture thousands of different products that people use in
daily life.
 Adhesives

 Cosmetics

 Fertilizers

 Paints

 Rubber

 Fabrics

 Plastics
 Crude oil is black Gold!
• The world economy runs on the transactions of oil barrels done by the countries

• Its availability or shortage decides the situation of economy in a country

• Various other industries are related to petroleum industry

 Classification of Crude oil
• Petroleum is a mixture of hydrocarbons and the non-hydrocarbon elements (small quantities of oxygen, sulphur, nitrogen, vanadium,
nickel, and chromium)
• Hydrocarbon present in crude petroleum are classified into 4 general types:
(a) Paraffins, (b) Naphthenes, (c) Aromatics, (d) Olefins
Paraffins Naphthenes Olefins Aromatics
• Paraffin series of hydrocarbons is • Naphthenes (Cycloparaffins): • Olefins do not naturally occur in • Aromatic series of hydrocarbons is
crude oils but formed during chemically and physically very
characterized by the rule that the Hydrocarbons in which all of the processing. Similar to Paraffins but different from the paraffins and
carbon atoms are connected by a available bonds of the carbon atoms at least two of the carbon atoms Cycloparaffins (Naphthenes)
are joined by double bonds. • Aromatic hydrocarbons contain a
single bond and the other bonds are saturated with hydrogen are • General formula is CnH2n benzene ring which is unsaturated
are saturated with hydrogen called Naphthenes. There are many • Olefins are generally undesirable but very stable and behaves
in finished products as the double similar to saturated compound.
atoms. types of Naphthenes present in bonds are reactive and the • Examples: Benzene, Toluene,
• General formula for paraffins is crude oil. compound are more easily Ethylbenzene, Ortho-Xylene,
oxidised. Meta-Xylene, Para-Xylene,
CnH2n+2 • They are classified according to • Some olefins are desirable as have Naphthalene)
• Simplest paraffin: Methane (CH4) boiling range and their properties higher octane number than • Diolefins are also present with 2
paraffin compounds with the hydrogen atoms missing or 2
followed by ethane; propane; determined with help of correlation same number of carbon atoms. double bonds present in each
normal and iso-butane; normal, factors. molecule. Are extremely active
due to double bonds present react
iso and neo-pentane • Cyclopentane, Cyclohexane, with other unsaturated molecules
Decahydronaphthene forming HMW gum like solids
 Crude assay analysis
• True boiling point distillation analysis

• °API gravity

• Correlation Index (CI)

• Watson characterization factor (KW)

• Viscosity gravity constant (VGC)

• Pour point
 True boiling point (TBP) analysis
(American Society of Testing and Materials, ASTM 2892)
• It is widely used batch distillation process for characterization of crude oils traditionally for
marketing and refining purposes
• TBP distillation curve is obtained by plotting the cumulative mass or volume distillation
fraction with increasing temperature and such a curve give a “footprint” of the composition
of crude oils.
• The shape of these curves is dependent on the volatility of components in a given crude oil
• Gives information regarding the volatile behaviour of hydrocarbon mixtures
• It is a method to isolate the specified fraction from a crude oil for testing
• This method cannot be used for fractions with initial boiling points (IBP) greater than 400°C
 True boiling point (TBP) analysis
(ASTM 2892)
• Distillation is carried out at atmospheric pressure from IBP to about 210°C vapour
temperature and at reduced pressure beyond this temperature
• Distillation under a partial vacuum avoids cracking of the more complex components
• Vapor temperatures measured at reduced pressure are translated to “Atmospheric
Equivalent Temperature (AET)*”
• Samples of distillate are collected at specified temperature cut points
• Mass and density of each fraction are measured and distillation yield by mass is calculated
• TBP curves in cumulative mass fraction distilled vs. boiling temperature expressed in AET
• TBP curve describes a given crude oil in terms of its chemical make-up

*Maxwell, J. B., and L. S. Bonnell. "Derivation and precision of a new vapor pressure correlation for petroleum hydrocarbons." Industrial &
Engineering Chemistry 49, no. 7 (1957): 1187-1196.
 True boiling point (TBP) analysis
(ASTM 2892)
*Fig.2 TBP curve

+Fig.1 TBP Set-up

*Behrenbruch, Peter, and Thivanka Dedigama. "Classification and characterisation of crude oils based on distillation properties." Journal of Petroleum Science and
Engineering 57, no. 1-2 (2007): 166-180.
+https://www.scribd.com/document/371674304/Tbp-Apparatus
 True boiling point (TBP) analysis
(ASTM 2892)
• Idealized method to achieve the best possible separation in distillation column
 Large number of theoretical plates for liquid-vapour contact
 An extremely high reflux ratio
• For number of theoretical plates more than 100 and a high reflux ratio of 100, the distillation
curve will be as shown below:

P+R Tb

Temperature (°C)
P
R

Ta

50% 70% 100%

Heat % volume distillate
 ASTM distillation
• ASTM distillation is also a batch distillation operation
• It operates without the presence of a contact plate and a reflux ratio of zero

Cooling water

RR=0 Tb

Temperature (°C)
# Plates=0

% volume
distilled
Ta

Heater 50% 70% 100%

% volume distillate
 Equilibrium Flash Vaporization distillation
Vapor

Tb TBP

Temperature (°C)
ASTM
EFV

Flash Drum
Feed
Heater

Ta

Liquid
50% 70% 100%
% volume distillate
 Important terms
• IBP: Initial boiling point
Temperature at which 1st drop of distillate appears
• FBP: Final boiling point
Temperature at which highest boiling compound evaporates
SL.
Boiling point Abbreviation Formula
No.
3
𝑁
1. Cubic average boiling point CABP 𝐶𝐴𝐵𝑃 = 𝑥𝑣𝑜𝑙,𝑖 (𝑇𝑖)1/3
𝑖=1
𝑁
2. Volume average boiling point VABP 𝑉𝐴𝐵𝑃 = 𝑥𝑣𝑜𝑙,𝑖 𝑇𝑖
𝑖=1
𝑁
3. Weight average boiling point WABP 𝑊𝐴𝐵𝑃 = 𝑥𝑤,𝑖 𝑇𝑖
𝑖=1
𝑁
4. Molar average boiling point MABP 𝑀𝐴𝐵𝑃 = 𝑖=1 𝑥𝑚𝑜𝑙,𝑖 𝑇𝑖

(𝑀𝐴𝐵𝑃 + 𝐶𝐴𝐵𝑃)
5. Mean average boiling point MeABP 𝑀𝑒𝐴𝐵𝑃 =
2
 Problem
Gasoline consists of a mixture of iso-pentane, 3-Methylpentane, iso-octane, meta-xylene, and hexyl
cyclohexane. Calculate MABP, WABP, VABP, CABP, MeABP.

Compound Mol. Density Boiling point V (mL) Weight (g)

Wt. @15°C (g/mL) (°C)
(g/moL)
Iso-pentane 72.2 0.62 28 0.1 0.062
3-Methylpentane 86.2 0.66 63 0.2 0.132
Iso-octane 114.2 0.69 99 0.3 0.207
Meta-Xylene 106.2 0.86 139 0.2 0.172
Hexyl cyclohexane 168.3 0.808 225 0.2 0.162

MABP=109.3°C, WABP=123.6°C, VABP=117.9°C, CABP=106.5°C, MeABP=107.9°C

 Average boiling point: ASTM (D86) Distillation Curve
ASTM distillation curve
190

175
𝑇10% + 𝑇30% + 𝑇50% + 𝑇70% + 𝑇90%
Boiling point, °C

160 𝑉𝐴𝐵𝑃 =
5
145

130

115

100
0 10 20 30 40 50 60 70 80 90 100
Recovered fractions, volume %
Average boiling point: ASTM (D86) Distillation Curve

Drawbacks of ASTM (D86) Distillation Curve

Automation Long measurement time ~ 60 mins
Precision Large sample volume required: 100 mL
Reproducibility Fire extinguisher
Fire Hazard Manual filling-Operation bias
Limited sample range Errors in volume measurement
Manual cleaning required
Expensive consumables: Glass flask
 Average boiling point: ASTM (D2887) Gas
Chromatographic method curve

ASTM D2887: Gas Chromatographic Method

250

200 𝑇10% + 𝑇30% + 𝑇50% + 𝑇70% + 𝑇90%

Boiling point, °C

𝑊𝐴𝐵𝑃 =
150 5
100

50

0
0 10 20 30 40 50 60 70 80 90 100
Recovered fractions, weight %

https://www.agilent.com/cs/library/applications/application-distillation-astm-d2887-8890-gc-5994-0548en-agilent.pdf
 Average boiling point: ASTM (D2887) Gas
Chromatographic method curve
Benefits of ASTM (D2887) Gas Analysis setup
Chromatographic Distillation Curve • Standard sample: Mix of C5 to C100 n-alkanes
• Crude oil sample
Fully automated
High precision No. of C-atoms B.P. Range (°C) Uses
Repeatable 1-4 0-30°C Natural Gas

Reliable 5-10 30-180°C Gasoline

Safer 10-16 180-260°C Fuel for home, Jet fuel

Small sample volumes 16-60 260-350°C Diesel fuel

>60 350-575°C Motor Oil

>70 >490°C Fuel oil for ships

>80 >580°C Roofing tar, Road tar

 Average boiling point: ASTM (D2887) Gas
Chromatographic method curve
Analysis setup
• Standard sample: Mix of C5 to C44 n-alkanes
• Crude oil sample

No. of C-atoms B.P. Range (°C) RT (mins)

C5 T5 R5 mins

C6 T6 R6 mins

C7 T7 R7 mins

Up to C44 T44 R44 mins

 Average boiling point: ASTM (D2887) Gas
Chromatographic method curve
Boiling point yield curve

Crude Oil sample

https://www.agilent.com/cs/library/applications/application-distillation-astm-d2887-8890-gc-5994-0548en-agilent.pdf
 °API Gravity
• °API gravity express the gravity or density of crude oil and liquid petroleum products.
• °API is devised jointly by API-American Petroleum Institute and the NIST-National Institute of
Standards and Technology.

141.5
API Gravity can be calculated as: °𝐴𝑃𝐼 = 𝑆𝐺
− 131.5

Where °API=Degrees API Gravity

SG=Specific Gravity at 60°F, 15.5°C

• Density is a temperature dependent property.

• °API gravity increases with increasing temperature as specific gravity decreases with increasing
temperature.
 °API Gravity

°API
https://www.engineeringtoolbox.com/api-gravity-d_1212.html
 Correlation Index, CI
• Characterization of crude oil fractions: Useful in evaluation of individual fractions from crude oil

87.552
𝐶𝐼 = + 473.7𝑆𝐺 − 456.8
𝑇𝑏

Where 𝑇𝑏 = Mean average boiling point (degree Rankine)

𝑆𝐺= Specific gravity @ 15.6°C (or 60°F)

Crude oil composition CI

Straight-chain Paraffins < 29.8
Naphthenic < 57
Aromatic > 75
 Watson characterization factor, KW
• Classification of crude oil with respect to hydrocarbon types
1
(𝑇𝑏 )3
𝐾𝑊 =
𝑆𝐺

Where 𝑇𝑏 = Volume or Mean average boiling point (degree Rankine)

𝑆𝐺= Specific gravity @ 15.6°C (or 60°F)

Crude oil composition Kw

Straight-chain Paraffins 11-12.9
Naphthenic 10-11
Aromatic < 10
 Viscosity gravity constant, VGC
• VGC is a useful function for the approximate characterization of the viscous fractions of
petroleum
10𝑆𝐺 − 1.0752 ∗ log(𝑉 100°𝐹 − 38)
𝑉𝐶𝐺 =
10 − log((𝑉 100°𝐹 − 38)

Where 𝑉 100°𝐹 = Viscosity in Saybolt Universal Seconds (SUS)

𝑆𝐺= Specific gravity @ 15.6°C (or 60°F)

Fractions VGC
Straight-chain Paraffins 0.74-0.75
Naphthenic 0.89-0.94
Aromatic hydrocarbon 0.95- 1.13
 Pour point
• It is the lowest temperature at which oil will pour or flow under gravity when it is cooled
• Petroleum products cannot be stored or transferred through a pipeline when temperature is less
than its pour point
• Standard test procedures for measuring pour points of crude oil or petroleum fractions are
described in the ASTM D97 and ASTM D5985 method
• Pour point of crude oils relates to their paraffin content; the higher the paraffin content, the higher
the pour point.
• Pour point of crude oil varies from -60°C to 30°C
 Refining processes
• Distillation & Solvent extraction: Physical separation process
• Cracking, visbreaking, coking: Breakdown processes
• Reforming, alkylation, isomerisation, and polymerization: Rebuilding processes

Cracking Visbreaking Coking Reforming Alkylation Isomerization Polymerization

Is a process in Is a mild Is a process of Is a process to Is a process in Is similar to Is the process of
which large thermal upgrading convert low- which light reforming, the converting light
complex operation bottoms from octane gaseous hydrocarbon olefin gases into
hydrocarbons with/without fractionating naphthas into hydrocarbons molecules are hydrocarbons of
broken down blending with column into high-octane are combined to rearranged higher molecular
into smaller lighter heating higher-value gasoline produce high- converting weight and high
lighter oils to reduce products i.e. blending octane normal octane number
components viscosity of petroleum components components of paraffins to that can be used
for bottom coke gasoline iso-paraffins. as gasoline
commercial residue to fuel blending stocks
use oil
 Simple Refinery Flow
1
2 1. LPG: Propane + Butane
9 2. Light straight run
7 Naphtha: Pentane + Slightly
3 heavier Naphtha range
8 material
5
3. Kerosene + gas oil
6 4. Vacuum distillation residue
10 5. Heavy gas oil
9
4 6. VDR
7. Light or heavy gas oil
Dewaxing 8. By-product from CC unit
9. Heavy Naphthas
Lubricating 10. VDR
oil + Wax

Separation Finishing Conversion

 Cracking process
• Heavier fractions are converted into lighter fractions by application of heat with/without catalyst

Thermal cracking Catalytic cracking

Carried out without catalyst Carried out with catalyst
Accomplished by heating feed: 450° to 750°C at Accomplished by heating feed: 480 to 550°C at
1-70 atms 0.7 to 1.4 atms
Catalysts: Synthetic composites of alumina/silica
Acid treated natural clays
Zeolites
Ease of cracking depends upon the boiling range Accelerates the reactions
and chemical nature of feed Modify yield and nature of product
• Important reactions: Decomposition; Dehydrogenation; Isomerization; Polymerisation
Production of gasoline from gas oil Gasoline obtained is superior in quality
 Cracking process
CH3(CH2)8CH3 ------- CH3(CH2)4CH3 + CH3-CH2-CH=CH2
n- Decane n- Hexane 1-Butene

CH3 CH3

2CH3-CH2-CH=CH2 ↔ CH3-CH2-C-C=CH3

CH3
1-Butene iso-Octene
 Visbreaking process
• Visbreaking is a thermal cracking process carried at 470° to 520°C and 4-20 atms
• Residues from vacuum distillation units with/without blended with gas oils subjected to thermal
treatment to produce heavy furnace oil (fuel oil)
• Meet the requirement of viscosity and pour point
• Visbreaking depends upon the temperature and time

Thermal severity index (TSI) is a measure of “Thermal severity” under reaction conditions
𝑇𝑆𝐼 = 𝑓 𝑇, 𝑡

𝐸
𝑑𝐶𝐴 − 𝑎
- 𝑑𝑡 = 𝑘𝐶𝐴 −−−−−−→ 𝑘 = 𝐴𝑒𝑥𝑝 𝑅𝑇
𝐸
− 𝑎
TSI=t ∗ 𝑒𝑥𝑝 𝑅𝑇
 Coking process
• Residues from refinery is the feed for coking
• It is the severe thermal (480-590°C) cracking of vacuum residue
• Due to high severity of thermal cracking during coking, the residue feed is completely converted to
gas, light (naphthas) and medium (gas oils) distillates, and petroleum coke
• Coke used as a fuel or as a filler for manufacturing anodes for the electrolysis of alumina
 Reforming process
Light Naphtha to • Reforming is a process of preparing
Gasoline pool
high-octane gasoline
Naphtha • Can be performed with/without a
Naphtha splitter
H2 catalyst
Catalytic
Crude oil • Upgrading by rearrangement or
Heavy Reformer
Naphtha reforming of molecules without
affecting the molecular weight
• Catalysts used: Chromia-alumina;
High Octane
Distillation Gasoline Platinum on a silica-
alumina/alumina base
 Reforming process
CH2
CH3
H2C CH CH3

H2C CH2
+ 3H2

CH2

Methyl cyclohexane Toluene

CH3
CH3

H2C CH2 CH3 + 4H2

H2C CH2
CH2 Toluene
n-heptane
 Crude oil desalting process
Atmospheric
Wash water pump

Desalted crude
distillation
Process
water Emulsion
breaking
chemicals
Crude charge water
Electrostatic De-salter
Crude oil (electrically powdered)
Mixing valve
Static mixer Effluent
water to VOC
stripper
Deoiler
hydrocyclone
Atmospheric and Vacuum Distillation Units
Gas
Cooling water
To Light End Unit (LEU) 43°C LPG
Atmospheric distillation unit

Pump arounds Water

(several) tray 32
Naphtha

Steam
Kerosene Stabilized
Naphtha
Vacuum distillation unit
Steam
Desalter Furnace exit Light gas 0.004 atm
120-150°C 400°C max oil Lubricating oil
Steam
Wash tray 1 Heavy gas oil
1 atm
Stripping Fuel oil
Atmospheric residue
steam 0.04 atm
Furnace Vacuum distillate residue (VDR)
380°C To deasphalting and coking
 Topping refinery
Important units in the topping refinery operation

Equipment Function
Furnace Preheating of crude oil
Heat exchangers Exchange heat between fractions and crude oil
Condensers To condense the outlet stream and send back
Fractionating towers: ADU and VDU Separation of spectrum of products based on relative volatility
Steam-stripping columns Secondary column for further rectification
Pumps and connecting pipes Connecting equipment/units
Storage and accumulation tanks For storage
 Operational data for ADU and VDU
Parameters ADU Parameters VDU
Tower diameter (in meters) 2.5-12 Tower diameter (in meters) Up to 14
No. of trays 25-40 Pressure at tower top 0.02 atm
∆Pmax / tray 0.015 atm Tower top temperature 225-250°C
∆P b/w flash zone to tower top 0.5 atm Steam per barrel of crude processed 0.3 to 5 kg
∆P b/w furnace outlet to flash zone 0.4 atm
Pressure at tower top 1.5 atm
Tower top temperature 100-110°C
Reflux drum pressure 1.5 atm
Steam per barrel of crude processed 5 kg
 Crude Oil CH4, C2H6
Fuel or Synthesis gas H2SO4 NaOH
Light Gas

Sulfonated/ Sulfated detergents

C3-C4 Saturates
Recovery LPG Fuel or Synthesis gas
Pre-treatment n-C4 i-C4

Butane
Light Polymer: C6-C9

Un-saturates
Desalting Polymerization
Isomerization Detergent
Propylene tetramer: C12 Manufacturer
Propylene
Butylene i-Octane
Atmospheric distillation
H2O+Salts Alkylation
Benzene
Petrol Sulphur Catalytic H2

NH3
(Low grade) removal Reforming Ammonia
Gasoline (High Octane) Manufacturer
H2S to H2SO4
Naphtha Heavy Naphtha N2
Naphtha
splitter
Gasoline pool
Kerosene
Kerosene Diesel Fuels
Gas Oil Catalytic
cracking
Diesel/Jet Fuel
Domestic heating oil
Fuel oil
Visbreaking
distillation
Vvacuum

Treated oil Lube oil Treating Blending Lubricating Oils

Deasphalted oil Phenol solvent MEK solvent Additives
extraction Dewaxing Wax
Deasphalting Acid Treating Paraffin Wax
Asphalt
Coking Petroleum coke
 Refinery processes
Refinery processes

Unit Operations Unit Processes

Physical processes Chemical processes

• Cracking
• Distillation
• Reforming
• Absorption
• Polymerization
• Extraction
• Alkylation
• Adsorption
• Isomerization
• Crystallization
• Hydrodealkylation
• Hydrogenation
 Chemistry of Cracking Processes
• Cracking involves the thermochemical conversion of hydrocarbons by heating at high temperatures

of 400-700°C in the absence of oxygen

• Purpose is to crack larger hydrocarbons to smaller hydrocarbon molecules

• Both non-catalytic and catalytic cracking is applicable in petroleum refinery

• Use of catalyst in cracking reduces the severity of operating conditions and increases the selectivity

of product formation with less side reactions

• Fixed bed catalytic cracking was applied in 1936

• Moving and fluidized bed catalytic cracking was applied in 1945

 Chemistry of Cracking Processes
• Thermal cracking mechansims
 Free radicals are formed by the cleavage of C-C or C-H bonds with each fragment retaining one of the pair of
shared electrons that make up the bond
 These free radicals are highly reactive species
. . Thermal polymerization:
Free radical chain reaction

C4H10 -----C4H9 + H Initiation Polymerization of olefins forms

.
C4H9 ----- C3H6 + CH3
. Propagation
larger HCs than present in the
feedstock
.
CH3 + RH ----- CH4 + R
. Propagation C1 and C2 gaseous hydrocarbons
are major products from thermal
.
R ----- Olefin + R1
. Propagation cracking
.
2R1 ----- Olefin + Alkane Termination

 Thermal coking: Free carbon is formed on complete degradation of HCs. RH -----→ xC + yH

 Catalytic Cracking Mechanisms
 Catalytic cracking produces no C1 and C2 gaseous HCs
 Secondary and Tertiary HCs isomers are formed

CH3 CH3
Iso-Octane
CH3-C-CH2-CH-CH3

CH3

 Relatively less coke (free carbon) is formed.

 In case feedstock containing aromatics: Aromatic rings are stable but long alkyl chain attached to the rings
are subjected to cracking
 Cracking process conditions
 Process parameters to be optimized: (i) Optimum time, (ii) Temperature, (iii) Pressure, (iv) Catalyst-to-feed ratio
and these process specifications depend on feed, reactivity, desired product, and coking tendency
Feed Process Time (seconds) Temperature (°C) Pressure (atm)
Thermal cracking
CH4 HC≡CH production 0.1 1350 1
C2H6 H2C=CH2 production 1 800 12
Gas oil Thermal cracking 60 600 21
Residual crude Coking ---- 500 2-3
Catalytic cracking
Gas oil High yield of petrol fraction ---- 480 1.7-2
Space velocity: 0.5-3/hr
Catalyst-oil wt. ratio: 5-20
 Houdry catalytic cracking reactor
 Houdry introduced continuous
catalytic cracking process in 1936 Gas

 Reactor type: Fixed bed reactor

Combustion gases
Gasoline
packed with natural alumina-silica
catalyst pellets
 10 min make-clean cycle
Light gas oil
 Expensive tubular reactor and shell

Strip w/steam ~ 5mins

side molten salt circulated
 Expensive alloy for reactor

Hot air
construction to withstand
oxidation/reduction
Heavy gas oil
Gas oil Furnace
800°C
Alumina-silica catalyst
 Moving/fluidized bed catalytic cracking
reactor
 In moving /fluidized bed, the catalyst is moved from cracking to regenerating section control
 Catalyst selection: Composition, form, regenerative properties, poisoning, aging etc.

a) Acid-treated silica-alumina
Synthetic oxide: 13-15% Al2O3
87-85% SiO2
3-4 mm pellets for moving bed
Catalyst composition
b) Natural clays of bentonite and kaolin
20-80 mesh micro-spherical synthetic
catalyst for fluidized bed
c) synthetic alumina/silica + zeolites
(introduced in 1965)
Fine powder with an average particle
size of 60–75 μm ( particle size
distribution ranging from 20 to 120 μm)

 Catalyst is poisoned by metals: Fe, Ni, V, Cu

 Catalyst should have high tolerance to Sulphur
 Once through reactor the yield is up to 50%; recycle leads to yield above 50% is standard to give highest petrol yield
 Moving/fluidized bed catalytic cracking
reactor
 Balance b/w cracking and coking rates to decide optimum temperature ~500°C best average
 Increasing pressure reduces unsaturation and octane number, increases coke production but
increases reactor throughput
Note: Light olefin gases such as ethylene, propylene, butylene are polymerized to HMWs HCs increasing
the ON that can be used as gasoline blending stocks.

1.4 -2 atm best range

 5-20 wt. ratio used with 0.3-0.6% coke levels in reactor
 Balancing of mechanical loss of catalyst is essential and additions dropping to 10-25% of initial value
 Deliberate additional discard is practiced where cracking capacity is tight
Advantage of catalytic over thermal cracking
 Produces high quality (80-90 ON) petrol from any crude
 Selective cracking and less light ends
 More Isomerization
 Greater portion of aromatics
 Less polymerization
 Relatively little coke
 Greater ability to tolerate high “Sulphur” feedstocks
 Uniformity of temperature and pressure control
 Flue gas to stack

Gas
Cyclones
Reflux drum

Distillation column
Regenerator
Petrol
Fluidized bed CC
Gas oil unit
Cracked
Product
Spent
catalyst Slurry

Regenerated

Recycle
catalyst

Steam Air Lift

Feed
 Moving bed CC unit

500°C

(700-750°C)
(150°C)

https://www.e-education.psu.edu/fsc432/content/fluid-catalytic-cracking-fcc
 Thermal coking
 Coking processes are implemented to refine heavy end of crudes Typical yields from a complete coking
 Coking is the most severe thermal process to treat VDR operation
 On thermal cracking during coking, VDR is completely converted to gas, Light ends 5 wt. %
light and medium distillates, and coke Petrol 20 wt. %
 3 different coking processes are used in refinery: (i) Delayed coking, (ii) Gas oil 60-65 wt. %
Fluid coking, and (iii) Flexi-coking Coke 10-15 wt. %
 Common objective of coking is to maximize the distillate product yield
by rejecting large quantities of carbon residue known as petroleum coke
 Petroleum coke find applications as fuel or as filler manufacturing
anodes
 Petroleum coke is characterized by its sulphur and metal contents
 Out of 3 coking process, delayed coking is the preferred approach
 Process conditions for coking

 Higher temperatures result in higher yields of gas, petrol, and coke

 Gases obtained from thermal coking are more olefinic

 Petrol (~20 wt. %) is not stable hence hydrogenation treatment required to improve its stability

 Higher pressures are not desirable yielding more gaseous products and coke

 Optimum temperature and pressure condition for coking: ~500°C and 2-4.5 atms
 Delayed coking process
Hot vapours & steam

 Steam is added to prevent coking in the heater

 Necessary heat for coking is provided in the heater
whereas coking takes place in coke drum hence the
process is called “delayed coking”
 Hot vapours from the top of the coke drums are
quenched by incoming VDR feed in fractionator to

500°C prevent coking in fractionator

 The heat from the hot vapours provide the sensible
2-4.5atms
heat to feed to strip the light fractions of VDR

https://www.e-education.psu.edu/fsc432/content/delayed-coking
Fluidized coking process

Coker Unit

https://www.e-education.psu.edu/fsc432/content/fluid-and-flexi-coking
 Flexi-coking process

Coker Unit
Fuel gas of
Synthesis gas:
H2, CO, CO2, CH4

https://www.e-education.psu.edu/fsc432/content/fluid-and-flexi-coking
Catalytic Reforming

 Catalytic reforming is used to convert HCs to aromatics

 Aromatics like Toluene have high ON of 104

 Aromatics used as a raw material for petrochemical
industries

 Catalytic reforming feedstock are HCs fractions:

 Naphtha grades
 Naphtha is a generic name given to light HCs boiling
in the gasoline range (60-200°C)
 Light Naphthas < 100°C
 Intermediate Naphthas
 Heavy Naphthas > 150°C
Common reactions in Catalytic reforming of Naphthas
 Dehydrogenation (Endothermic reactions)

CH3 CH3

↔ + 3H2

Methyl cyclohexane Toluene

CH3 CH3
 Cyclization
CH3

CH3-CH2-CH2-CH2-CH2-CH2-CH3 ↔ ↔
-H2
n-heptane Dimethyl cyclopentane Methyl cyclohexane
Common reactions in Catalytic reforming of Naphthas
 Isomerization

CH3

↔ ↔-3H2
Ethyl cyclopentane Methyl cyclohexane

 Hydrocracking (not desirable)

CH3-CH2-CH2-CH2-CH2-CH2-CH3 + H2 → C3H8 + C4H10

n-heptane Propane Butane

ON is less than aromatics

 Catalytic Reforming Catalysts
 Catalytic reforming, dehydrogenation catalyst are required

 Catalysts coupled to “Alumina” or “Silica-alumina” base matrix:

 Platinum
 Molybdenum oxide
 Chromium oxide
 Cobalt
 “Pt” though molybdate
expensive is best option in terms of selectivity and lack of
hydrocracking

 In catalytic reforming, whatever carbon depositing takes place on catalyst surface

can be removed by steam or air oxidation

 Reforming is done under high H2 pressure so that many catalyst poisons (S and N)
are hydrogenated and easily removed from the catalyst surface

 High H2 pressure suppress coking of catalyst to larger extent

 Heavy metals such as “Pb” and “As” permanently damage “Pt” catalyst
 Catalytic Reforming Catalysts
 Thermodynamically, it is predicted that dehydrogenation is feasible at low pressures and high temperature
 High temperature also favours hydrocracking and carbon deposition
 Carbon deposition can be suppressed by high hydrogen pressures with use of product hydrogen recycle
 A comprise is made b/w catalyst activity and yield of reformate of a given ON with process conditions
 Catalyst Platinum
 Pressure 15-30 atm
 Temperature 470-525°C
 Space velocity 1.5 kg/hr of feed per kg catalyst
 Catalytic reforming: Dehydrogenation
Methyl cyclohexane Toluene
(Reactant) (Product)
 Catalytic reformates make excellent blending stocks since they

% mole yield aromatics (Toluene)

100
contain no olefins
80
 Reformates are also oxidation resistant (stable)
 Reformates have high octane no. (≥80) 60 500°C
 Reformate are low in sulphur and gum 40 300°C
 Broader boiling range making good cold weather petrol
20
 Produced reformates form basis for the aromatic petrochemical
industry
10 20 30 40 50
Pressure (atm)
 Catalytic reforming: Dehydrogenation
Light ends
*Fixed bed reactor
“Pt” catalyst size 1.5-3 mm

Distillation column
Excess H2 gas
Crude oil
Furnace
stock
low grade
Gasoline
stock/
Naphtha

Reformate

Heavy ends H2 Recycle gas

#1 *Reactor #2 Reactor
#3 Reactor

Hydrogenation Purifier Primary

Heater #2 Heater #3 Heater
(To remove S and N)
 Catalytic Alkylation
 Alkylation is addition of any alkyl functional group to a compound
 Alkylation processes are similar to those of polymerization but olefins reacts specifically with iso-paraffins
 Alkylate produced is a higher quality product for petrol blending:
 High ON ~ 85-95
 Stable & saturated branched paraffins
 Alkylation units are more expensive to build and operate but the demand of these units is high due to high
ON products

 A refinery has economic justification for both alkylation and polymerization units, selective olefin feed
preparation is used to maximize capacity

 2-butene which polymerizes least rapidly, is separated from catalytic cracking distillate for alkylation
feedstock

 Iso-paraffins are produced in isomerization units

 Catalytic Alkylation Reactions
Olefins + Iso-paraffin Alkylates
C3-C4: Propene and Butene HMWs iso-paraffins
(a) Carbonium ion formation

C-C=C-C + H2SO4
+ -
C-C-C-C + HSO4 Initiation
Butene Acid catalyst Carbonium ion
(Olefin)
C C
+ Propagation
C-C-C-C + C-C-C C-C-C-C + C-C +
Carbonium ion H n-Butane C
(n-paraffin) Reactive iso-paraffin carbonium ion
Iso-butane
C (Iso-paraffin)
C
+
C-C + + C-C=C-C C-C-C-C-C Addition
C Butene
iso-paraffin carbonium ion (Olefin) C C
Carbonium ion intermediate
 Catalytic Alkylation Reactions
C C
+
C-C + + C-C=C-C C-C-C-C-C Addition
C C C
iso-paraffin carbonium ion Olefin Carbonium ion intermediate

C C C C
+ + C-C + Regeneration
C-C-C-C-C + C-C-C C-C-C-C-C
C C H C C C
Carbonium ion intermediate Iso-paraffin 2,2,3 Tri-methyl pentane iso-paraffin carbonium ion
 Catalytic Alkylation Reactions
Olefins + Iso-paraffin Alkylates
C3-C4: Propene and iso-butene HMWs iso-paraffins
(a) Carbonium ion formation

C=C-C + H2SO4
+ -
C-C-C + HSO4
Initiation
Propene Acid catalyst Carbonium ion
(Olefin)
C C
+ Propagation
C-C-C + C-C C-C-C + C-C+
Carbonium ion C C
Propane
Iso-butane (n-paraffin) Reactive iso-butyl (iso-paraffin)
carbonium ion
C (Iso-paraffin)
C
C-C + + C=C-C +
C-C-C-C Addition
Propene
C (Olefin) C C
iso-paraffin carbonium ion Carbonium ion intermediate
 Catalytic Alkylation Reactions
C C
C-C + + C=C-C +
C-C-C-C Addition
C Propene
iso-paraffin carbonium ion
(Olefin) CC
Carbonium ion intermediate

C C C C
+ C-C C-C-C-C + C-C + Regeneration
C-C-C-C +
C C C C C C
Carbonium ion intermediate Iso-butane 2,2,3 Tri-methyl butane iso-paraffin carbonium ion
(Iso-paraffin) (Alkylate) (Regeneration of carbonium ion)
 Catalytic Alkylation: Catalysts
Sulfuric acid (H2SO4)
85% acidity, circulated @ 4-10°C in emulsion
from containing 50% acid
Acid consumption: 0.05-0.2 ton acid per ton
feed requiring H2SO4 plant near refinery and
spent acid disposal for economical operation
Hydrofluoric (HF)
Competitive with H2SO4 but consumes only
1/10th the weight of H2SO4 used
 HF requires extreme safety in handling
 Produces lower grade alkylate
 Operates @ 37°C level, requiring no
refrigeration
 HF distilled and recycled as compared to
H2SO4 spent acid disposal
Catalytic Alkylation: Reaction conditions
Reactions are exothermic
Parameter Conditions
Temperature Sulfuric acid (H2SO4)
Best yield: Low T
H2SO4 catalyst more T sensitive
 0°C lower limit because of viscosity effect
 21°C upper limit because of sulfation reaction
Hydrofluoric (HF)
No effect of T on HF in the T range of -20°C to 60°C
Standard temperature: 37°C
Pressure Just above bubble point pressure of mixture of HCs
 No real effect of increasing pressure
Feed  Iso-butane/olefin ratio: to avoid polymerization, a large excess of iso-butane is used
ranging from 5:1 to 15:1
Reaction time  Contact time: 5-50 min depending upon the type of liquid-liquid contact
 Catalytic Alkylation: H2SO4 process
Recycle of Iso-butane
H2SO4 process

4-10°C

Removal of mercaptans
Removal of residual acid
 Catalytic Alkylation: HF process Recycle of Iso-butane

HF Recycle of Iso-butane
Make (to supress polymerization) i-C4
HF C3
HF Process Drier H2O

Depropanizer
Olefin feed + Caustic Settler

HF Stripper
C4 Feed wash

Deisobutanizer
Impeller
reactor

(Caustic wash or adsorption

Spent caustic

HF Rerun Column
Fresh caustic

by bauxite adsorbent)
Removal of mercaptans

Defluorinator
n-Butane
Acid oils +
Alkylate
 Isomerization
 Catalytic isomerization of n-paraffins (less ON) to isomers for alkylation feedstock is a necessary refinery operation
 Reaction: Reaction is mildly exothermic
 Catalysts:
 AlCl3-HCl promoted adsorbed on porous carriers or used as a liquid
 Both vapour & liquid phase catalytic isomerization reactions are in commercial practice

Mol % of iso-paraffin
 Catalyst: 0.3-1.5 tons of isomer per kg of catalyst
100
i-C5
 Reaction conditions: T, P, space velocity, feed purification
 Temperature: Balance b/w equilibrium which is favoured @ low T and rates 50 i-C4
 100-150°C used with 40-50% conversion and recycle to achieve 98% yield
50 100 150
 Pressure: No effect on reaction, 17-27 atm, used as an economic balance b/w throughput and reactor vessel
costs
 Space velocity: 0.5-2.5 m3/hr feed per m3 of catalyst
 Feed purification: Must remove water, S & mercaptans compounds which can react with AlCl3
 Isomerization
HCl Isomerized product
HCl make-up
Vapour fraction: Light Ends
to HCl absorber
n-Paraffin

Fractionator
Flash drum

HCl Stripper
Drier

feed

*AlCl3
Reactor
Recovery
Caustic Wash

AlCl3 make up
Fresh caustic Spent Caustic
(Removal of HCl traces)
n-Paraffin Recycle

* AlCl3 is volatile at reaction condition and soluble in liquid HCs

 Hydrodealkylation
 Combined hydrogenation and de-alkylation process is employed
 Petroleum refinery is a source of aromatics
 Development of catalytic reforming processes
 Development of improved separation processes for isolating high purity aromatics
 Reforming produces about equal yields of benzene, toluene, and xylene; market for benzene is high
 Dominant benzene is obtained from hydrogenation and de-alkylation process

Hydrodealkylation of Toluene Hydrodealkylation of Xylene Hydrodealkylation of Ethylbenzene

C6H5CH3 + H2 →C6H6+ CH4 o,m,p-C6H4(CH3)2 + H2 →C6H5CH3 + CH4 C6H5C2H5 + H2 →C6H6+ C2H6

2C6H6 + H2 →C12H10+ H2 C6H5CH3 + H2 →C6H6+ CH4

 Hydrodealkylation
 Reaction conditions:
 Temperature: 500-600°C
C6H5CH3 + H2 →C6H6+ CH4
600°C/20-60 bars  Pressure: 20-60 bar
 Addition of CH4 is a strategic decision
that enhances safety, temperature
control, reactivity control, and
economic efficiency
 Catalyst offers lower temperatures and
higher selectivity
 Catalyst: Platinum supported on silica-
alumina, chromium oxide

Unreacted Toluene + Biphenyl

side reaction product
Rani, J., Thakur, P. and Majumder, S., 2023. Energy integration of hydrodealkylation (HDA) of toluene. Materials Today: Proceedings.
 Polymerization
 Olefinic feed polymerizes to form dimer and trimer of C3 and C4 olefins from catalytic cracking converted to a liquid
blending component for gasoline pool with improved ON
 Reactions are highly exothermic i.e. 11-16 kcal of heat per gmol of olefinic feed
 Catalyst: Acid catalysts are required. Solid catalysts are favoured.
 65% H2SO4 at 20-36°C (cold process) or at 93°C (hot process)
 Liquid H3PO4 acid, phosphoric acid on inert carrier such as silica or Kieselgurh
 Cu2P2O7 (Copper pyrophosphate) catalyst supported on charcoal
 Reaction conditions: T, P, t and reaction rate
 Temperature: (a) Sufficiently high for acceptable rate but too high T i.e. 400-500°C gives tar deposition
(b) 150-220°C acceptable range for solid catalysts
 Pressure: (a) High P increases conversion at lower T and reduces HMWs polymer formation;
(b) 25-100 atm. better range
 Reaction time: (a) Balance for satisfactory conversion to petrol without excessive high HMW polymer formation
(b) Space velocity of 0.7-3 kg/hr feed per kg of catalyst
(c) Reaction rates vary with type of crude oil
 Polymerization: Reaction
(a) Carbonium ion formation:

C C
C-C + H+ (acid catalyst) C-C+
C C
Olefin Carbonium ion

(b) Addition reaction:

C C
+
C-C+ + C=C-C-C C-C-C-C-C
C Olefin
C C
Carbonium ion Intermediate Carbonium ion
 Polymerization: Reaction
(c) Regeneration:

C C
+
C-C-C-C-C C-C-C=C-C + H+
C C C C
Intermediate Carbonium ion 2,2,4 Tri-methyl pentene

(d) Isomerization reaction:

C
+
C-C-C-C ↔ C-C+
Carbonium ion C
Carbonium ion
 Polymerization: Block diagram
Propane
Water wash Butanes to

Propane
(Remove traces of alkali) isomerization
Mixer Mixer
C3-C4
Olefin Feed

Depropanizer

Debutanizer
Waste water
Fresh Caustic Spent Caustic
Tubular reactor
(5-15cm dia tubes)

Stabilizer
H2
(Removal of mercaptans) Cooling water

H2
 Highly exothermic reaction; requires proper control
of temperature to avoid HMWs formation
 Polymer gasoline is stable after mild hydrogenation Polymer Gasoline
Treatment of petroleum products/fractions
Physical Chemical
impurities impurities

Sand/mud/moisture
/catalyst Sulphur/Nitrogen/
dust/solvent Oxygen
droplets

Gas treatment:
Washed with water
& dried
Major impurity
H2S, Mercaptans,CS2
Liquid-settling or by
using dehydrating
agent
 Removal of sulphur compounds
 Removal of S: Sweeting processes
 Mercaptans (Methyl mercaptan: CH3SH) are oxidised to disulphide
 Physical extraction process-H2S is extracted using ethanolamine
 In situ destruction of S compounds-treatment of Mercaptans with 93% H2SO4
 Catalytic desulphurization-Hydrogenation and hydrolysis of CS2 in presence of a catalyst

Methyl mercaptan (CH3SH): S containing Oxidation of these mercaptans to disulfides by contacting

volatile organic pollutant (SVOC) the rich caustic stream with a solid catalyst in the presence of
• highly toxic oxygen followed by separation of the disulfides from the
• strong volatility treated caustic.
• belongs to malodorous gas Doctor solution: Sodium plumbite (a solution of lead oxide
posing a threat to human life and health in caustic soda)

H2S disgusting rotten egg odour

H2S in high concentration can rapidly paralyze H2S adsorption by liquid reagents (basic aqueous solution
human’s nerve, which means it is hard to notice the or ethanolamine) is a widely accepted strategy to collect
danger because H2S will immediately kill people H2S gas in industry
 Removal of sulphur compounds

Catalytic desulphurization
Destruction of S compounds by H2SO4 acid
In catalytic desulphurization reactions:
 Reacted with concentrated H2SO4
 Molecule bearing S is not removed (as seen in extraction or
RSH + H2SO4 ----RSHSO4 + H2O
acid treatment) but only S atoms are picked up.
RSH + RSHSO4 --- (RS)2 SO2 + H2O
 Material loss is negligible with possible recovery of S.
(RS)2 SO2 -------- R2S2 + SO2
 Cu-Cr-Al catalyst
 Acid sludge is disposed
 Cu- Cr-Va catalyst
 Co- Mo oxide catalyst (widely used catalyst)
 Lead doctoring process
 Removal of S: Sweeting processes
 Mercaptans (Methyl mercaptan: CH3SH) are oxidised to disulphide

 Lead doctoring process

Reaction:

 Na2PbO2 + 2RSH ->(RS)2Pb + 2NaOH

 (RS)2Pb +S -> R2S2 + PbS

Catalyst regeneration

 PbS + 2NaOH + ½ O2-> Na2PbO2 + S + H2O

 Merox process
 Removal of S: Sweeting processes
 Mercaptans (Methyl mercaptan: CH3SH) are oxidised to disulphide
 Merox process: Catalyst contains cobalt phthalocyanine deslofenamide, tetrasolfonamide,
tetrasulfonate dissolved in fresh NaOH
Extraction Reaction: General equation:

 NaOH + RSH ---->NaSR + H2O Merox-catalyst

2RSH + 1/2 O2 ------- H2O + R2S2
Redox step

 NaSR +H2O + 1/2 O2----> 2NaOH + R2S2

 Lead doctoring process: Sodium plumbite
Reactor-1: Na2PbO2 + 2RSH ->(RS)2Pb + 2NaOH
Reactor-2: (RS)2Pb +S -> R2S2 + PbS
S
Settler-1 Settler-2 (Black suspension)
Sour gasoline
Sweet product

5-15 mins

Air

Drain

Regenerator
Recycle Na2PbO2
T=100°C Discharge
Fresh caustic- Sodium plumbite soln P= 1-5 Atms solution
Air
PbS + 2NaOH + ½ O2-> Na2PbO2 + S + H2O
 Ratio of doctor soln: Gasoline is 1:5
 Time of contact: 0.5-1 min Discharge soln
 Merox process
Treated Gasoline stream + H2O + NaOH + Co salt + NaSR Sweet product
NaSR +H2O + 1/2 O2 ----> 2NaOH + R2S2
*Co-salt Air
NaOH + RSH ---->NaSR + H2O

Merox Separator
Towers (2)
Towers (1)
Extractor

Sour
Gasoline
Disulphides
Air

Separator Air
Compressor

Merox

Merox
Recycled Merox

*Proprietary Liquid catalyst: Co-salt complex Pump

http://www.hitekengineers.com/liquid-liquid-extraction-column.html
 Catalytic desulfurization

Vaporized Gasoline
400°C 400°C
H2 gas
Catalytic
Heater reactors
Sour
gasoline

Furnace
 Cu-Cr-Al catalyst
H2S  Cu- Cr-Va catalyst
 Co- Mo oxide catalyst

Separator
Cooler
Sweet Product
 Treatment of lube oil fraction
 Treatment is done to improve the quality of lube oil (lubricating oil)
 Fluidity of oil
 Oil viscosity
 Colour and stability
 Viscosity index (VI) is an important characteristic of lube oil.

 Desirable is “viscosity remain constant across a wide temperature range”

 Lubricant with higher VI is more desirable as it provides more stable lubricating film
over a wider temperature range

 Treatment methods for lube oil

 Clay treatment
 Solvent treatment
 Dewaxing
 Treatment of lube oil fraction
Viscosity index is calculated from:

𝐿−𝑈
𝑉𝐼 = × 100
𝐿−𝐻

Where 𝐿 is viscosity at 40°C of an oil with VI = 0

𝐻 is viscosity at 40°C with a VI = 100
𝑈 is viscosity of the tested oil at 40°C.

The values of L and H for a specific viscosity of oil is available in ASTM D2270*

*ASTM International, “Standard Practice for Calculating viscosity index from Kinematic Viscosity
at 40 °C and 100 °C,” ASTM International, Conshohocken, PA, 2016.
 Solvent extraction method
 Solvent treatment focuses on improvement of certain characteristics of lube oil

 Lube oil is used to maintain fluidity, viscosity at operational conditions

 Solvent treatment is carried out to improve VI by removal of: (a) Heavy Aromatics and heavy naphthenes,
(b) Asphalt, and (c) Wax

 Solvent extraction method: (a) Phenol solvent, (b) Furfural solvent, (c) N-methyl pyrrolidone (NMP)

 These solvents remove aromatic compounds responsible for increase in the viscosity

C5H9NO
 Solvent extraction method
Phenol solvent extraction
 T range: 60-100°C
 Solvent: Feed ratio: 1.5-2.5
 Lube fraction: Paraffinic/Naphthenic
 Raffinate yield: 50-90% depending upon the
amt. of solvent used.
 Higher solvent amt. provides better quality of
Raffinate but less yield
 Phenol treated lubes posses good oxidation
stability with less sludge formation and carbon
deposition
Furfural solvent extraction
 T range: 75-125°C
 Solvent: Feed ratio: 1-2
 Used for: Lube oil, Gasoline, Diesel
 Widely used solvent
 Raffinate does not possess much
solvent
 Has tendency to react with O2 forming
HMWs and losing its solvent properties,
hence require N2 inert atmosphere
 Problem 2
Calculate: Weight average boiling point (WABP) and plot: Percentage yield (%)
vs. BP (°C) for the given data set form ADU

Compound Con. (g/L) BP (°C) V (L)

Iso-pentane 72.2 28 0.1
3-methylpentane 86.2 63 0.2
Iso-octane 114.2 99 0.3
Meta-xylene 106.2 139 0.2
Hexylcyclohexane 168.3 225 0.2
 Viscosity Index of Hydrocarbons
Viscosity index of Hydrocarbons
Type of Hydrocarbon Viscosity index
 n-Paraffins  175
 i-Paraffins  155
 Mono-cyclic naphthenes  142
 Bi-cyclic naphthenes  70
 Aromatics  50
 Lube oil extraction process: Furfural
Furfural rich fraction
Inert gas to
Recycle
Lube oil rich raffinate

Raffinate Stripper
Furfural
Furnace accumulator
Inert gas
Extraction Tower

 60-90°C
 10-14 atms Raffinate (Lube oil) to
Furfural stream Dewax Process
Furfural

Oil feed

Furfural rich extract Extract stripper Inert gas

Furnace Extract
 Lube oil extraction process: Furfural
 Inert N2 gas is used as a stripping medium as furfural solvent is prone to polymerization on exposure to steam
and air

 Furfural extraction process is designed to produce lube oil having desirable lube oil qualities
 High viscosity index (VI): Removal of heavy aromatics and naphthenes
 Stability
 Colour

 Critical operating variables for furfural extraction unit:

 Furfural-to-oil ratio: It has greatest effect on the quality and yield of the raffinate
 Extraction temperature: T is selected as a function of lube oil viscosity and miscibility
 Extract recycle ratio: Extent of separation b/w the lube oil and aromatics
 Lube oil extraction process: NMP
NMP rich flash

Steam Stripper
Lube oil rich raffinate

Raffinate Stripper
NMP
Furnace accumulator
Steam
Extraction Tower

Raffinate (Lube oil) to

NMP stream Dewax Process

NMP flash

Oil feed

Steam Stripper
Extract stripper
NMP rich extract Steam
Furnace Extract
 Lube oil extraction process: NMP
 This process was developed as a replacement for phenol extraction because of the safety, health, and
environmental problems associated with the use of phenol
 NMP possess 69% lower viscosity than phenol at 50°C
 Complete miscibility of NMP with water, no azeotrope formation of NMP with water
 Recovery of NMP is better than that for phenol, and NMP losses are only 25 to 50% those of phenol
 The lower viscosity of NMP gives greater throughput for a given size tower
 For a given solvent-to-oil ratio for NMP and phenol extraction, the quality of product obtained is same but
raffinate oil yields average 3 to 5% higher for the NMP extraction.
 Dewaxing of Lube oil
 Lube oil heavy fraction contains high amt. of wax which causes viscosity to increase
 High wax content affects viscosity and flow property of oil
 Pour point is also affected due to wax presence
 Lube oil stocks must be dewaxed or will not flow properly at ambient temperature
 Dewaxing is done in order to regulate oil flow property and pour point
 Dewaxing is one of the most important and most difficult processes in lubricating oil manufacturing
 Dewaxing by the application of refrigeration to crystallize the wax and solvent to dilute the oil portion
sufficiently to permit rapid filtration to separate the wax from the oil
 Dewaxing of Lube oil: Solvent dewaxing
 2 principal solvents used in solvent dewaxing processes:
 Propane
 Ketones
 Solvent act as a diluent for the high molecular-weight oil fractions to reduce the oil viscosity and provide
sufficient liquid volume to permit pumping & filtering
 Difference in both methods lies in the equipment used for refrigeration and solvent recovery portion of the
process
 About 85% of dewaxing units based on ketone solvent
 Dewaxing method
Propane dewaxing method
 Readily available, less expensive, and easier to
recover
 Large differences b/w filtration temperatures and
pour point of finished oils (5-25°C)
 Direct chilling can be accomplished
 High filtration rates can be obtained because of its
low viscosity at very low temperatures
Ketone dewaxing method
 Small difference b/w filtration temperature & pour
point of dewaxed oil (5-10°C)
 Lower pour point capability
 Lower refrigeration requirements
 Fast chilling rate; Shock chilling can be used to
improve process operation
 Good filtration rates but lower than for propane
 Ketone dewaxing method

Oil stripper
Inert
MEK makeup
Cooler
MEK

Stripped Solvent
Accumulator
Filterate
Inert Gas

Vapours
Steam Dewaxed Oil
to storage
Rotary filters

Wax strippers
Steam
Wax

Lube oil Inert Gas

feed
Chiller unit Wax Rundown
Wax to
storage
 Composition of lube oil
 Lube oil is composed of 80-90% of petroleum hydrocarbon distillates:

Property Paraffinic oil Naphthenic oil

Chemical structure Long carbon chains Multiple carbon rings
Resistance to oxidation High Medium
Pour point High Low
Viscosity High Low
Volatility Low High
Specific gravity Low High
 Propane deasphalting process
 Deasphalting is removal of the asphaltene portion of the feedstock for catalytic conversion units
 Catalyst performance is greatly impaired by heavy metals and carbon presence of feedstock for CCU
 Asphaltene HMW aromatic compounds contains most metals which make up most of the asphalt portion of
the residue
 Asphaltenes are composed mainly of polyaromatic carbon ring units with o
 Oxygen
 Nitrogen
 Sulfur heteroatoms,
combined with trace amounts of heavy metals: vanadium and nickel
and aliphatic side chains of various lengths

Molecular structure of Asphaltene

 Propane deasphalting process
 Asphaltene portion in the lube oil results in the following
 High pour points
 Large viscosity changes with temperature (low VI)
 Poor oxygen stability, poor colour, high cloud points
 high carbon- and sludge forming tendencies.

 Solubility of Lube oil HC in propane decreases with an increase in temperature

 In 40-60°C T range, propane has solvent properties: Lube oil HC are propane soluble
 Propane at critical T of 96.8°C: Lube oil HC are insoluble
 In 40-96.8°C T range: HMW asphaltenes are insoluble in propane
 Separation by distillation is generally by molecular weight of the components and solvent extraction is by type
of molecule
 Propane deasphalting falls in between these categories because separation is a function of both molecular
weight and type of molecular structure
 Propane deasphalting process
Propane vapours
154°C

LP Oil stripper
0.3 atm
HP oil vaporizer

Steam
157°C
15 atm

Oil feed 60°C CW

33 atm
Extraction Tower

Propane
compressor
De-asphalted Oil
Steam Propane
accumulator Cooler
Propane vapours
H2O Propane vapours

HP Asphalt flash

LP Asphalt stripper
274°C
Propane

tower
15 atm
40°C

Steam

Asphalt heater Asphalt rich phase Asphalt

 Natural Gas Sweeting
 For commercial applications such as CNG, Power generation etc. Natural gas should meet specific
requirements for quality
 Should not contain higher levels of CO2 , NOx , and H2S
 To regulate emissions and release of toxic gases, authorities mandate natural gas producers to minimize S
content in their products.
 Sour gas must be sweetened before it is sent out from the refinery or gas processing plant
 Natural gas is termed as ‘sweet gas’, if it contains only trace quantities of H 2S and CO2
 Sweet gas is pure natural gas and is non-corrosive, requires little refining, and we can transport and market it
safely
 Natural Gas Sweeting
Reasons for gas sweetening process: Removal of the contaminants from gas is required for the reason of:

 Corrosion control
 Toxicity
 Gas/Liquid product specifications
 To prevent poisoning of catalyst in downstream facilities
 Control of the overall heating value of the natural gas
 To meet environmental requirements: CO2, H2S are very common contaminants in Natural gas

 Reason for CO2 removal for gas sweetening
 When combined with water forms carbonic acid
(H2CO3) which is corrosive
 CO2 reduces the BTU value of the gas
 If present in 2-3% gas is not saleable
 Reason for H2S removal for gas sweetening
 Extremely toxic gas
 Highly corrosive
 Reason for Mercaptans (R-SH): Removal for gas
sweetening
 It has smell
 If comes in contact with bacteria (inside the
final product storage) then released H2S
 2R-SH Bacteria → R-SSR + H2S
 Natural Gas Sweeting
Tail gas Off gas to
Gas Treating initiator
well
Temp Unreacted H2S/ SOx/ Molecular Sieves
CS2 etc.
Pressure Activated carbon
Metal S Sulphur Unit Claus Process

Raw Gas Dehydration Mercury Removal

Acid gases (H2S, CO2) (Removal of H2O (Adsorption on activated Carbon
in Glycol unit) /other sorbents )

Condensate (Oil) & Acid gas Cryogenic Process

water removal
N2 Rich Gas N2 Rejection
Removal Adsorption Process

Waste H2O Absorption Process

Condensate to an
Oil refinery NGL Recovery Turbo-expander &
Demethanizer
Absorption

To sales gas
pipeline
 Types of gas sweetening techniques
 Chemical reaction process for gas sweetening: Amine process
 MEA (Mono ethanol amine: HOCH₂CH ₂NH ₂)

 DEA (Diethanol amine: HN(CH₂CH₂OH)₂)

 DGA (Diglycolamine: C4H11NO2)

 DIPA (Di-iso Propanol Amine: C6H15NO2)

 MDEA (Methyl Dethanol Amine: CH3N(C2H4OH)2)

Natural Gas Composition and Specifications
 Natural gas as recovered at the wellhead consists of mostly methane (CH4), ethane (C2H6), propane (C3H8),
butane (C4H10), and pentane (C5H12)
 Impurities found in natural gas
 Water: Most gas produced contains water, which must be removed. Concentrations range from
trace amounts to saturation

 S species: If the H2S concentration is greater than 2 to 3%, carbonyl sulphide (COS), carbon
disulphide (CS2), elemental S and Mercaptans may be present

 Mercury: Trace quantities of mercury may be present in some gases; level reported vary from 0.01
to 180μg/m3. Typically, the mercury level in pipeline gas should be reduced to 0.01 μg/m3

 Diluents: The gases CO2, H2S, NOx

 Oxygen: A significant amt. of corrosion in gas processing is related to O2 contamination
Specifications for Pipeline Quality Gas

https://www.e-education.psu.edu/fsc432/content/natural -gas-composition-and-specifications
Amine Process

𝐻2 𝑆 + 𝑅2𝑁𝐻 ↔ 𝑅2𝑁𝐻2+ + 𝐻𝑆 −

𝐶𝑂2 + 2𝑅2𝑁𝐻 ↔ 𝑅2𝑁𝐶𝑂𝑂 − + 𝑅2𝑁𝐻2+

𝐶𝑂2 + 𝐻2𝑂 + 𝑅2𝑁𝐻 ↔ 𝑅2𝑁𝐻2+

 Claus Process
 Claus process is the most significant elemental ‘S’ recovery process from gaseous H2S
 Gases with >25% H2S content is suitable for recovery of ‘S’ from the Claus process
 H2S produced in desulphurization of recovery products is converted to ‘S’ in Claus plant

Thermal stage Catalytic stage

• H2S is oxidised @ temperatures above 850°C
and precipitates to elemental ‘S’
2𝐻2 𝑆 + 𝑂2 → 2𝑆 + 2𝐻2𝑂 ∆H=-187 KJ/mol
• Air: Acid gas ratio is controlled in such a way
that all of the H2S is converted to SO2
• H2S is oxidised @ temperatures above 850°C
and precipitates to elemental ‘S’
• A small portion of the process gas (containing 20-
30% of sulphur content in the feed stream) goes
to the catalytic stage.

• Main portion of the hot gas in the combustion • In presence of activated alumina or titanium
is cooled down leading to condensation of dioxide the following reaction takes place:
elemental ‘S’ formed. 2𝐻2𝑆 + 𝑆𝑂2 → 3𝑆 + 2𝐻2𝑂 ∆H=-41.8 KJ/mol
 Claus Process
• Heating is necessary to prevent ‘S’ condensation in the
catalyst bed
• Catalytic conversion is maximized @lower T but should
be above the dew point of ‘S’ i.e. 115°C

(S+ H2S + SO2)

H2S + SO2
Al2 O3 Al2 O3 Al2 O3
Elemental ‘S’

Elemental ‘S’
(H2S + CO) TiO2 TiO2 TiO2

𝟐𝑯𝟐 𝑺 + 𝑶𝟐 → 𝟐𝑺 + 𝟐𝑯𝟐 𝑶 ∆H=-187 KJ/mol

𝟐𝑯𝟐𝑺 + 𝑺𝑶𝟐 → 𝟑𝑺 + 𝟐𝑯𝟐𝑶 ∆H=-41.8 KJ/mol
𝟐𝑯𝟐 𝑺 + 𝟑𝑶𝟐 → 𝟐𝑺𝑶𝟐 + 𝟐𝑯𝟐 𝑶 ∆H=-518 KJ/mol
 Claus Process
 If acid gas feed to the combustion chamber contains COS and CS2, they are
hydrolyzed in the catalytic reactor:

𝐶𝑂𝑆 + 𝐻2𝑂 ↔ 𝐻2𝑆 + 𝐶𝑂2

𝐶𝑆2 + 2𝐻2𝑂 ↔ 2𝐻2 𝑆 + 𝐶𝑂2

 Tail gas from Claus process still containing combustible components and Sulphur
compounds (H2S, H2, and CO) burned in incineration unit
 Dehydration process
 Glycol dehydration is a liquid desiccant system for the removal of water from natural gas and natural gas liquid

 Most common and economical means of H2O removal from natural gas stream

 Glycols typically seen in industry include:

 Triethylene glycol (TEG): HOCH2CH2OCH2CH2OCH2CH2OH
 Diethylene glycol (DEG): (HOCH2CH2)2O
 Ethylene glycol (MEG): CH2OHCH2OH
 Tetraethylene glycol (TREG): HOCH2CH2OCH2CH2OCH2CH2OCH2CH2OH

 Issues with presence of H2O in natural gas:

 @ low ‘T’ H2O can freeze in piping
 @ high ‘T’ forms hydrate with CO2 and CH4 plugging equipment & piping
 Free water phase containing portions of acid gas and can cause corrosion

 Pipeline quality specification for gas that the H2O content < 100 mg/mL
Dehydration process

Elevated pressure for absorption

HC vapours

HC liquids

The reboiler temperature is limited to 204°C

to prevent thermal degradation of glycol

https://en.wikipedia.org/wiki/Glycol_dehydration
 Mercury removal from Natural gas
 ‘Hg’ presence in Natural gas: concn <10 ppb to >1 ppm

 ‘Hg’ removal is critical

 It is toxic
 Poisons catalysts used in downstream processing units
 Can damage downstream equipment through liquid-metal embrittlement
 Corrosion leading to crack initiation and propagation in equipment constructed of aluminium
 Damage to equipment results in numerous equipment failures, unscheduled shutdowns

 ‘Hg’ in natural gas and its condensate mainly originate from source rocks that undergo thermal conversion
to become hydrocarbons

 Presence of Hg compounds
 Monomethyl mercury
 HgS, Hg2Cl2
 Dialkyl mercury
 Elemental Hg

Wang, Jiaxin, Ying Liu, Tao Wang, Mohamed A. Serageldin, and Wei-Ping Pan. "A review on mercury in natural gas and its condensate: Accurate characterization and efficient control tech nologies for total and speciated
mercury." Fuel 355 (2024): 129526.
Mercury removal process
 Provide consistent gas
quality for Hg content
typically < 10ng/m3

 Purpose of having
liquid/gas coalesce is to
remove liquid H2O & HC
that shorten adsorbent life

 Purpose of having gas

particle filters is to remove
protect metering,
downstream processes and
other instrumentation from
abrasive adsorbent fines

http://www.pall.com
 Feedstock of Petrochemical
 These are the chemicals that are made from petroleum and natural gas
 About 5% of the oil and gas consumed each year is needed to make all the petrochemical products
 Petrochemicals play an important role on our food, clothing, shelter and leisure
 Typical feedstocks to petrochemical processes include:
 C1 compound: Methane & Synthesis gas
 C2 compound: Ethylene & Acetylene
 C3 compound: Propylene
 C4 compound: Butanes and Butenes
 Aromatic compound: Benzene
 C1 compound: Methane & Synthesis gas
Air
Partial combustion Nitric acid
Carbon black NH3
N2 from Air
Pyrolysis Ammonia
Hydrogen
nitrate

Synthesis
Methane Steam (catalyst)
gas H2 and Urea
/ O2
Steam
(H2 and CO) CO2
Air
Hydrogen cyanide
O2 CO2
Acetylene Catalyst Air (Catalyst)
Acrylonitrile Methanol Formaldehyde
HCl
Dimer Methyl chloride
Chlorine
HCl HCl/Acetic acid alkali Methylene dichloride
Chloromethanes
Chloroprene Vinyl Chloroethylenes Chloroform
Chloride/acetate Chlorine
Carbon tetrachloride
 Methanol Industry

Coal Coal Natural gas Natural gas Natural gas

Feedstock China USA China USA Middle East
Feedstock cost 50 $/MT* 70 $/MT 12 $/mmBTU+ 4 $/mmBTU 1 $/mmBTU
Total capital investment, $
1,240 1,500 930 1,160 1,260
Million
Operating cost, $/MT
Raw material 61.41 99.78 469 160 43
Utilities 73.97 51.53 9 5 5
Fixed cost 38.09 41.93 26 30 33
Cash cost of production 173.47 193.24 504 195 79
Depreciation 60.61 74.4 43 58 63
Return on capital 74.36 89.76 56 70 76
Total cost of production 308.44 357.4 603 323 219

Cost of methanol production for a unit producing 5,000 metric tonnes per day methanol based on 2012
coal prices in China and USA and 2012 natural gas prices in China, Middle East, and USA.

*MT: Metric ton; +mmBTU: Metric million British Thermal Unit

W.H. Calkins, Chemicals from methanol. Catal. Rev. Sci. Eng. 26(3 and 4), 347–358 (1984)
 Methanol formation from Synthesis gas
Properties and uses Synthesis gas
 CH3OH is a colourless liquid that boils @ 65°C
 High P and moderate T conditions

∆H ≈ -ve
It solidifies @ -94°C
 It forms explosive mixture with air and burn 𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻
with a non-luminous flame Mixed catalyst: Oxides of Zn, Cr, Mn, Al
 It is completely miscible in water Methanol
 It is used as rocket fuel, solvents, and antifreeze

Side reactions: 𝐶𝑂 + 3𝐻2 → 𝐶𝐻4 + 𝐶𝑂2

2𝐶𝑂 + 2𝐻2 → 𝐶𝐻4 + 𝐶𝑂2
a𝐶𝑂 + 𝑏𝐻2 → 𝐴𝑙𝑐𝑜ℎ𝑜𝑙𝑠 + 𝐻𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠

C2H5OH; CH3CH2CH2OH (CH3)2O

 Methanol formation from Synthesis gasPurge gas
Recycle: H2 & CO

Steam Methanol
Ether

Vapours
Reactor:
200-350 atms
300-375°C

CH3OH Tower
Ether Tower
CO + H2

drum
Flash
(1:2.25)
Synthesis gas Heavy
Fuel gas
Alcohols
Let down to 14 atms

Settler
KMnO4 Water
Crude
 Thick walled reactor needs to be designed
Methanol  Undesired alcohols formation reduces the yield of product
 KMnO4 removes the HCs such ketones & aldehydes formed
as side products
 Formaldehyde production
1
Reactions: a) Oxidation: 𝐶𝐻3𝑂𝐻 + 2 𝑂2 → 𝐻𝐶𝐻𝑂 + 𝐻2𝑂
b) Pyrolysis: 𝐶𝐻3𝑂𝐻 → 𝐻𝐶𝐻𝑂 + 𝐻2
Silver or Zinc oxide catalyst on wire gauge
Atmospheric pressure & 500-600°C
1
Undesired Reactions: 𝐶𝐻3𝑂𝐻 + 𝑂 → 𝐶𝑂2 + 2𝐻2 𝑂
2 2
Zn-Ag oxide catalysts SEM image
(Nanoparticles)
Uses of HCHO
 Formaldehyde is stable in only water and there, 37% HCHO soln with 3-15% methanol (stabilizer) is
produced as formalin
 Formalin is used as a preservative
 Resins used in the manufacture of composite wood products
 Building material and insulation

Movahedi, F., Masrouri, H. and Kassaee, M.Z., 2014. Immobilized silver on surface-modified ZnO nanoparticles: As an efficient catalyst for synthesis of propargylamines in water. Journal of Molecular Catalysis A:
Chemical, 395, pp.52-57.
 Air
Pyrolysis reaction:

Methanol
CH3OH evaporator

Heated Air
Oxidation reaction:

Catalytic
Reactor
Water

Scrubber

Light Ends Stripper

(H2, CO2)
Vent gases
Formaldehyde production

Alcohol Stripper
Recycle CH3OH
vapor
37% soln
Aqueous HCHO
 C2 Petrochemicals
Catalyst
Polyethylene Ethanol amines
Polyglycols
Oxygen/acetic acid
Ammonia
Refinery catalyst Vinyl acetate Water
Oxygen /Catalyst
cracked gas Ethylene oxide Ethylene glycol
Hypochlorous acid Alkali
Ethylene HCN Dehydrogenation
chlorohydrin Di and Triethylene glycols
Ethylene Chlorine
Ethylene Acrylonitrile
HCL Alcohols/alkyl
dichloride phenol Glycol ether &
Vinyl chloride polyglycol (ether)
Ethylene
dibromide
Cracking of HCl Ethyl
ethane, propane chloride
Water (catalyst) Ethyl Acetic
Acetaldehyde
alcohol Acid
Water
H2SO4
Sulfuric esters
Benzene
Ethyl benzene Styrene
 Ethylene dichloride production
Reactions: 𝐶2𝐻4 + 𝐶𝑙2 → 𝐶2𝐻4𝐶𝑙2

Undesired product: HCl & C2H6 is also formed

 Reaction occurs in a liquid phase reactor with ethylene dichloride serving as the liquid medium
 Catalyst: FeCl3 or ethylene dibromide; T=50°C and P=1.5-2 atm
 Reaction is exothermic
 Crude product is washed with NaOH so as to remove HCl
Uses of ethylene dichloride
 It is used in production of vinyl chloride
 Used as an intermediate in the production of tetrachloroethylene
 Used as an solvent in textile, metal cleaning and adhesive industries
 Ethylene dichloride production
6-8% NaOH soln
Off gases
H2/CH4/C2H4/C2H6

HCl scrubber
Refrig Caustic Wash
Vapours: 𝐶2 𝐻4 𝐶𝑙2
Water
Removal of HCl

Liquid:
Gaslift reactors

Wash 6-8% NaOH soln

Heterogeneous reaction 40-60°C Wash
Reaction medium: 𝐶2𝐻4 𝐶𝑙2 1.5-2 atm
Chlorine

Settler
Reactor

Fractionator
Heat control loop Ethylene
Dichloride
Ethylene Crude
Catalyst: C2H4Cl2
Liquid: 𝐶2 𝐻4 𝐶𝑙2
FeCl3/C2H2Br2

https://en.wikipedia.org/wiki/Iron(III)_chloride
Heavy Ends
 Vinyl chloride production
Reaction in gaseous form: 𝐶2𝐻4𝐶𝑙2 ↔ 𝐶𝐻2𝐶𝐻𝐶𝑙 + 𝐻𝐶𝑙

 Catalyst: Charcoal is used as the catalyst

 The reaction is a reversible gas phase reaction
 The product is stabilized using a stabilizer as vinyl chloride is highly reactive without stabilizer
 Quenching is done in order to inhibit the reverse reaction

Uses of Vinyl chloride

 It is a monomer in formation of PVC which is used in making of
pipes, wire coatings, packaging material
 Industrially used as an extraction solvent for sensitive products
 It is used as aerosol propellant
 It is used in making of Chloroacetaldehyde

Source: Google images

 Vinyl chloride production
Tubular Pyrolysis Furnace Cold Liquid EDC Quench
4 atms/ 500°C
Removal of HCl Stabilizer
moisture

Vinyl chloride
Liquid C2H4Cl2

Fractionator
Vinyl chloride

Fractionator
Vapor C2H4Cl2

EDC Quencher
Vapor C2H4Cl2

EDC
C2H4Cl2 Flue gas
storage
Dryer
Steam

Polyvinyl
chloride
C2H4Cl2 Vapor recylce
 Ethylene Oxide production
1
Reactions: 𝐶2𝐻4 + 𝑂2 ↔ (𝐶𝐻2)2𝑂 ∆𝐻 = −ve
2

 Ethylene to air ratio: 3-10% (Air is used in excess)

 Side reaction products: CO2 and H2O
 Catalyst: Silver oxide on alumina
 Operating T and P: T=250-300°C and 8-120 atm
 Supressing agent for side reaction: EDC

Uses of Ethylene Oxide

 It is used in manufacturing of following petrochemicals:

 Ethanol amines
 Mono ethylene glycol
 Diethylene glycol
 Non ionic surfactants
 Glycol ethers
 It is used as a permanent antifreeze for automobile radiators
 In making of non-ionic detergents
 Ethylene Oxide production
Fixed bed CO2/N2/ Steam Light ends + H2O

Steam tubular reactor:

250-300°C
Recycle Ethylene

H2O absorber
H2O oxide

/CO2/N 2/ Steam
Ethylene oxide

Desorber

Stripper

Stripper
Dowtherm
H2O
Ethylene oxide
+ Light ends +Heavy
Ethylene ends + H2O
Recycle
H2O
Air
Purge Ethylene oxide
Steam in H2O Heavy ends
(Side reactions: Glycols
due to presence of H2O)
 Styrene from Ethyl benzene
Reactions: 𝐶2 𝐻4 + 𝐶6 𝐻6 ↔ 𝐶6𝐻5𝐶𝐻 = 𝐶𝐻2 ∆𝐻 = −ve
 Step1: Alkylation of Benzene
 Step2: Dehydrogenation of ethylbenzene
 Catalyst used: AlCl 3 granules
 Operating T and P: T=95°C and 1 atm
Uses of Styrene

 Styrene is mainly used for making plastics toys and model kits. Moreover, housing for machines
as well as refrigerator door and air conditioner cases are made of styrene

Important points:

 Steam is used for quenching instead of water to avoid additional reactions.

 Styrene, benzene, toluene, and ethylbenzene are closely boiling systems hence vacuum
distillation
 Styrene from Ethyl benzene Ethyl benzene
Superheated steam
Steam
Vent
C6H6

Quench Tower
C6H5-CH3 to

Benzene
column
recovery
Dehydro unit
Catalytic
800°C

H2O
Ethyl Benzene
column

Finishing
90°C

column
Styrene
Tar