CHE 331: Petroleum Refinery Engineering

Timing Tuesday, Thursday: 10:00 AM - 10:55 AM

Wednesday: 01:30 PM - 02:25 PM
No. of classes 3-0-0

Mode Online (MS Teams)

Grading policy Mid-Sem Exam (assignment-based): 25%

End-Sem Exam (assignment-based): 25%
End-Sem Exam (real time): 10%
Quizzes (03): 30%
Online viva (one-to-one): 10%
Books Gary, Handwerk, and Kaiser; Petroleum
Refining: Technology and Economics
Fahim, Alsahhaf and Elkilani; Fundamentals
of Petroleum Refining
My notes
Published papers etc.
Instructor Dr. JP Chakraborty
Department of Chemical Engg & Tech
IIT (BHU)
jpc.che@iitbhu.ac.in
Participants Vth semester ChE &
VIIth semester non-ChE

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 Some units

1 bbl = 42 US gallons

1 US gallon = 3.78541 L

1 bbl = 158.98722 L

1 MMT = 1 million metric ton

The first real petroleum refinery was that of William Barnsdall and William A. Abbott, built at
Titusville, Pennsylvania, in 1860. In India, the first well was started in Digboi in 1889 and
completed in 1890 (202 m depth). Digboi refinery started in 1901. It was also the first refinery in
Asia. Its highest production was 7000 BPD (Barrels per day). It is now a part of IOCL. Its
capacity is 0.65 MMTPA (million metric tons per day). It is the world’s oldest oil refinery still in
operation.

Current scenario in India

India’s refining capacity

Year MMTPA
1998 62.0
2014 215.066
2019 249.366

Total 22 refineries

17 PSU (IOCL, BPCL, HPCL): ~142 MMTPA

3 Private sectors (RIL, ESSAR etc.): ~88 MMTPA

2 JV (BORL, HPCL Mittal Energy): ~19 MMTPA

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Export

In 2011-12, India has exported 60.5 MMT of petroleum products worth USD 58.2 billion. India
is the largest exporter of petroleum products in Asia since August, 2009.

Demand for petroleum products

FY MMTPA
2006-07 80
2010-onwards 155
2018 201.9

India meets ~30% of its total energy requirements through import

India’s self-reliance on crude

Year Production Consumption %

2001 642.4 2183.73 29.4
2011 782.34 3426.00 22.8
Crude production is not keeping pace with consumption; hence, self-reliance is decreasing

Energy consumption mix in India (2007-8), from Planning Commission

Resource %
Coal 53
Oil 33
Natural gas 10
Nuclear, hydro, wind etc. ~3

Energy consumption mix in India (2018)

Resource %
Coal 44
Oil 25

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 Natural gas 5
Nuclear 1
Renewable (including hydro) 10
Other (including biomass) 15

Composition of crude oil

Colour: golden brown to black (light to thick)

It is a complex mixture of hydrocarbons

Component %
Carbon 84 - 86
Hydrogen 11 - 14
Nitrogen 0.1 – 2.0
Oxygen 0.1 - 1.5
Sulfur 0.5 – 6.0
Trace metals Iron (Fe), nickel (Ni), vanadium (V), arsenic
(As) etc. present as organometallic compound

Oxygen in crude

Oxygen is present as naphthenic acid (mixture of several cyclopentyl and cyclohexyl carboxylic
acids): R-C(O)OH; C10H18O2 etc.

Crude oil with high oxygen/naphthenic acid content has high TAN (total acid number).

Nitrogen in crude

Nitrogen is most often found in naphthene-base oils

Present in the form of basic compounds similar to alkyl quinolines

Crude oil having N content more than 0.25 wt% requires special processing

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Pyridine (C5H5N); pure quinoline (C9H7N)

Quinoline (C9H7N)

Sulfur in crude

Sulfur is present as dissolved free sulfur; H2S; or as organic compounds such as thiophenes,
sulfonic acids, mercaptans, alkyl sulfates and alkyl sulfides.

Thiophene (C4H4S)
Benzothiophene (C8H6S)
Dibenzothiophene
Sulfur in crude creates corrosion, odor problems; it is also responsible for poor explosion
characteristics of gasoline fuels.

Corrosive sulfur compounds can be removed by treatment with alkalies, a process known as
“sweetening”.

Mercaptan (R-S-H)

Example: if R is ethyl radical, then the corresponding molecule will be ethyl mercaptan; benzyl
mercaptan (C6H5-CH2-SH)

Sulfides (R-S-R): dimethyl sulfide (CH3-S-CH3)

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Sulfur compounds are foul smelling and some are corrosive

Sweet crude Sour crude

Sulfur content < 0.5 wt% Sulfur content > 0.5 wt%

Some organometallic compounds (having Fe, Ni, V, As) are poisonous to some catalysts

Hydrocarbon series present in crude

CnH2n+2, CnH2n, CnH2n-2, CnH2n-4,…, CnH2n-20, etc.

There may be 3000-4000 compounds present in crude

Example of hydrocarbon series

Paraffin (CnH2n+2): n-hexane or n-C6H14

Olefin (CnH2n): n-hexene or n-C6H12

Naphthene (CnH2n): cyclohexane, C6H12, cyclic but not aromatic:

Aromatic (CnH2n-6): benzene or C6H6:

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Diolefin (CnH2n-2): 1,5-hexadiene (C6H10)

Acetylene (C2H2):

Olefins are not present in crude

Paraffin wax consists of high-boiling straight or branched chain paraffin molecules/hydrocarbons

Similarity and difference between olefinic and naphthenic hydrocarbons

Olefin naphthene
CnH2n CnH2n
Both are hydrocarbon Both are hydrocarbon
Unsaturated Saturated
Straight-chain Cyclic compound

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 C 2 H4 C6H12
Reactive; can react by direct combination with Not so reactive; can react only by displacement
other materials of hydrogen by another material

Resins and asphaltenes

Resins Asphaltenes
Large molecule (primarily H and C) Do not dissolve in crude oil
There are 1 to 3 S, O, N etc. atoms per Dispersed as colloids
molecule
Ring structure (mostly aromatic) Solid, dry, black powder (non volatile)
3-10 rings per molecule Insoluble in n-heptane
Readily dissolve in crude Soluble in toluene
Heavy liquid or sticky solid C, H, O, N, S and trace of V and Ni

Routine Laboratory Tests

API gravity

sp. gr. measured at 60oF/15.6oC

it is useful in many correlations:

API gravity for asphalt is 10 (sp. gr. = 1.0)

API gravity for gas like material is 65 (sp. gr. = 0.72)

API gravity for crude ~20-45 (sp. gr. 0.80-0.93)

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Light crude has high API gravity and low sp. gr.

Heavy crude has low API gravity and high sp. gr.

Sulfur content and API gravity have greatest influence on the value of crude oil

API gravity is measured by means of hydrometers (D287), pycnometers (D941 & D1217)

Oil with oAPI < 10 is called extra heavy or bitumen [bitumen from oil sands, Alberta, Canada
has API = 8]

Reid vapor pressure (RVP)

Used for volatile nonviscous product such as gasoline (ASTM D323)

For LPG, a modified equipment and procedure is used

It is an indication of the pressure that a material will develop within a closed container

Important for very low boiling material

Safety in transport, vapor lock in gasoline feed systems etc.

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The apparatus is shaken and then put into a bath kept at 100oF (37.8oC)

Air expands and the vapor pressure is read

For gasoline, RVP~10-15 psig

RVP is an indication of the ease of starting and vapor-lock tendency of a motor gasoline as well
as explosion and evaporation hazards

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High RVP helps to improve economics and engine starting characteristics (but there will be
vapor lock tendency)

Low RVP prevents vapor lock and reduces evaporation losses (but engine start problem)

Varies between 7.2 psi (49.6 kPa) in the summer and 13.5 psi (93.1 kPa) in the winter.

Example problem

RVP is not an additive property, hence, RVP Blending Indices are used

BIRVPi = (RVPi)1.25 (developed by Chevron, USA)

xvi = vol fraction of component i;

Component Quantity (BPD) RVP (psi)

LSR gasoline 5000 11.1
HSR gasoline 4000 1.0
Reformate 94 RON 6000 2.8
FCC gasoline 7000 13.9
1.25
Ex. For LSR gasoline, BIRVPi = (11.1) =20.26

Component Quantity (BPD) xvi BIRVPi xvi*BIRVPi

LSR gasoline 5000 0.23 20.26 4.66
HSR gasoline 4000 0.18 1.0 0.18
Reformate 94 6000 0.27 3.62 0.98
RON
FCC gasoline 7000 0.32 26.84 8.59
Sum 22000 1.0 - 14.41
So, BIRVP,Blend = 14.41; hence, RVPBlend = (14.41)(1/1.25) = 8.45 psi

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Flash and fire points

Flash point (ASTM D93)

The flash point of an oil is the temperature at which the vapor above the oil will momentarily
flash or explode.

Accessories: closed cup containing the oil, heating and stirring equipment and a special
adjustable flame

Pensky Martens (PM) apparatus used for middle distillate and fuel oils

Abel apparatus used for kerosene (45-50oC; for IOCL, FP > 35oC) and lighter distillates

Empirical method

Flash point (oF) = 0.77 *(ASTM 5% oF - 150oF)

N.B. the ASTM 5% oF will be available from ASTM distillation curve

Fire point (ASTM D93)

The fire point of some oil is the temperature at which the vapor above the oil are evolved rapidly
enough to burn continuously.

Fire point = Flash point + (5 – 10oC)

Cloud point and pour point

Indicates behavior of oil at low temperature

Viscosity index is important for lubricating oil

Cloud point (ASTM D2500)

The temperature of initial precipitation of wax or other solid material

The temperature at which wax or other solid material begins to separate from solution

For paraffinic oils, this is the starting temperature of crystallization of paraffin waxes

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It is typical specification of middle distillate fuels

Pour point (ASTM D99)

The temperature at which the wax content of an oil crystallizes to form a gel structure

Rough indicator of the paraffin content

Lower the pour point, lower is the paraffin content and higher is the aromatic content

Critical specification of middle distillate products used in cold climates

Octane number

Applicable for gasoline

Measure of the antiknock characteristics of a fuel (usually gasoline)

Knocking is the resistance to self-ignition

It is the percentage by volume of isooctane that must be mixed with n-heptane in order to match
the knock intensity of the fuel undergoing testing (isooctane is C8H18 or 2,2,4-trimethylpentane)

Two methods

Research Octane Number (RON) (ASTM D2722)

Method F1

600 rpm

Inlet air temperature 125oF (~52oC)

Represents city driving conditions

Motor Octane Number (MON) (ASTM D2723)

Method F2

900 rpm

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Inlet air temperature 300oF (~150oC)

Represents highway driving conditions

By definition: pure n-heptane has ON = 0; pure isooctane has ON = 100

n-paraffins have the lowest ON; aromatics and branched paraffins have highest ON

2,2-dimethyl butane, C6H14 (RON) = 92; n-hexane, n-C6H14 (RON) = 25

Aniline point (AP)

Aniline = phenylamine = aminobenzene (C6H5NH2)

Minimum temperature for complete miscibility of equal volume of aniline and the test sample

Rough indicator of the aromaticity of the sample

Increases rapidly with increasing paraffin content or decreases rapidly with increasing aromatic
content

It is also used as a classification of the ignition quality of diesel fuels

More aromatic, less is AP; and more is the damage to rubber parts; hence, AP ≥ 65 oC (150oF) is
recommended in order to minimize damage to rubber parts in a mud circulating system

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Diesel index (DI) = [AP (in oF)*(oAPI)]/100

A DI in between 45-55 is good.

Viscosity

Resistance to flow

Measured using capillary viscometer or U-tube viscometer

Another type is Ubbelohde viscometer (U-shaped glass tube held vertically in a controlled
temperature bath)

Cannon-Fenske (glass capillary used)

Size 200; range 20 - 100 cSt.

1 cP (centipoise) = 10-2 poise (g/cm.s)

Kinematic viscosity (μ/ρ)

1 poise = 1 g/cm.s = 10-1 Pa.s

Kinematic viscosity of water (at 20oC) = 1.0038 cSt

1 St = 1 cm2/s = 100 mm2/s = 100 cSt

Hagen-Poiseulli equation used for laminar flow of Newtonian fluids

Good for gasoline, naphtha, kerosene

Other type of viscometers:

Redwood (UK), Engler (Germany), Saybolt (USA)

Saybolt Universal Second (SUS), (D88): used for lubricants (60 cc oil used)

Time (in sec) taken by 60 cc oil to flow through a calibrated tube at 100oF.

100 cSt (at 100oF) = 100*4.632 = 463.2 SUS

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100 cSt (at 210oF) = 100*4.664 = 466.4 SUS

ASTM D2983 method is used to measure viscosity of crude oil

Saybolt Furol Second (SFS), (D88): used for fuel oil

Degree Engler: (efflux time of the oil in sec)/(efflux time of water in sec)

Correlations available to convert SUS, Engler/Redwood viscosities to kinematic viscosity:

ASTM D567 gives the data; ASTM D567-53 (1955) withdrawn, replaced by D2270

Viscosity index (V.I., ASTM D2270)

Indicates the rate of change of viscosity with temperature

Usually ranges from 0 to 100; but VI <0 or VI>100 also possible

Generally a specification for lubricating oils; high VI is desirable for lube oils

High viscosity index means the oil does not become viscous at low temperature and does not
become too thin at high temperature

VI = 0 (Naphthenic lube oil); VI = 100 (paraffinic lube oil)

VI Classification
<35 Low
35-80 Medium
80-110 High
>110 Very high
VI = [100*(L-U)]/(L-H)

U: kinematic viscosity at 40oC (102oF)

L & H: parameters based on kinematic viscosity at 100oC (212oF)

Engine oil from BPCL has VI = 96, 98 etc.

Gear oil, VI = 98

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4 stroke engine oil (for 2 wheeler/motor cycle/scooters etc.)

VI = 123

SERVO 4T Synthetic 10W-30/IOCL: VI = 150 (minimum)

Laboratory Distillation

3 different types of laboratory distillation in common use

(a) True Boiling Point (TBP) Distillation

(b) ASTM Distillation
(c) Equilibrium Flash Vaporization (EFV)

TBP Distillation (can be performed on a crude or a fraction)

Large amount of reflux and large no. of trays

Also known as US Bureau of Mines Hempel Distillation

A laboratory batch distillation performed in a 15 theoretical plate fractionating column with 5:1
reflux ratio

A good fractionation results in accurate boiling temperature

ASTM D2892 used for TBP

1st phase

527oF (275oC) end point at 1 atm pr.

2nd phase

572oF (300oC) end point at 40 mm Hg pr.; then back to 760 mm Hg; the temperature becomes
790oF (421oC)

The portion of the distillation at reduced pressure is necessary to prevent excessive pot
temperature, which may cause cracking of crude oil

The data obtained at 40 mm Hg and 572oF should be converted to 760 mm Hg using charts

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The corresponding temperature is 790oF (421oC) @760 mm Hg

ASTM D86 (AD) for low-boiling; ASTM D1160 (VD) used for high-boiling fractions

AD: atmospheric distillation; VD: vacuum distillation

A simulated distillation method (ASTM D2887) may also be used to obtain TBP data for crude
oil

Binary mixture (A & B)

A: 70 vol% BP = Ta

B: 30 vol% BP = Tb

Perfect separation of components A and B

ASTM Distillation

Some reflux will be there

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One equilibrium stage

ASTM distillation is used as a specification for petroleum products

IBP of ASTM distillation is higher than that for TBP

FBP of ASTM distillation is lower than that for TBP

Ex. Kerosene; TBP Range 135-300oC; ASTM range 160-275oC

Equilibrium Flash Vaporization (EFV)

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Comparison between TBP, ASTM, and EFV

Carbon Residue

Measure of the coking or carbon forming tendency

Roughly related to the asphalt content of the crude

Lower the carbon residue, more valuable the crude

Ramsbottom Carbon Residue (RCR) – D524; OR

Conradson Carbon Residue (CCR) – D189

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Determined by destructive distillation of the sample in the absence of air, to a coke residue

CCR (ASTM D189)

To determine the amount of carbon residue left after evaporation and pyrolysis of an oil under
specified conditions

RCR (ASTM D524)

Determined by a standard laboratory test procedure which subjects the sample to severe thermal
cracking conditions

Expressed in wt% of the original sample

Recommended to replace CCR

Water and sediment content of crude

Removed or separated by the method of centrifuge

Asphalt

Used for road repair

Ductility, penetration are important properties

Ductility: measure of its capacity to elongate or stretch (rupture)

Penetration: measure of its consistency

Refinery products

About 3000-4000 types of petroleum product available in the market

LPG, naphtha, petrol (or gasoline), diesel, kerosene, jet fuel, gas oil, lubricating oil, greases and
waxes, fuel oil, coke, asphalt etc.

Different types of lubricating oils, fuel oils etc. available

Example: 209 types of asphalts are there in the market

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Desalting

Step 1

ADU (Atmospheric Distillation Unit)

VDU (Vacuum Distillation Unit)

Schematic diagram of the Atmospheric Distillation Unit (ADU is also called a Fractionator)

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Another option for ADU may be:

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Light distillate (300-500oF)

Different boiling range from different refineries

300 - 600oF; OR 375 - 600oF; OR 375 - 550oF

Low boiling products (C1 to C4)

Sl. No. Component Application

1 Methane Refinery fuel
2 Ethane Refinery fuel; can also be used
during pyrolysis to give
ethylene, propylene etc.
3 Propane Refinery fuel; LPG
manufacture
4 n-butane LPG, refinery processes,
gasoline blending etc.
5 iso-butane Alkylation (to get high octane
number gasoline)
Boiling point of important paraffins/alkanes

Sl. No. Component Boiling point (oC)

1 CH4 (methane) -161.50
2 C2H6 (ethane) -89.00
3 n-C3H8 (n-propane) -43.70
4 n-C4H10 (n-butane) -1.00
5 n-C5H12 (n-pentane) 36.10
6 n-C6H14 (n-hexane) 68.73
7 n-C7H16 (n-heptane) 98.42
8 n-C8H18 (n-octane) 125.60
9 n-C9H20 (n-nonane) 151.00
10 n-C10H22 (n-decane) 171.00-174.00
11 n-C11H24 (n-undecane) 193.00-197.00

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 12 n-C12H26 (n-dodecane) 216±3.00
13 n-C13H28 (n-tridecane) 235.50
14 n-C14H30 (n-tetradecane) 253.9±3.00
15 n-C15H32 (n-pentadecane) 270.6±3.00
16 n-C16H34 (n-hexadecane) 286.90
17 n-C17H36 (n-heptadecane) 301.90
18 n-C18H38 (n-octadecane) 317.00
19 n-C19H40 (n-nonadecane) 330.00
20 n-C20H42 (eicosane) 343.10

Naphtha

Light naphtha is a component of gasoline

Heavy naphtha is used as a feedstock for catalytic reforming

Also blended with LGO to make jet fuel

Used as solvent

Used as a petrochemical feedstock (undergoes pyrolysis to form methane, ethylene, propylene,

benzene etc.; ex. Naphtha cracker)

Distribution of products in Guwahati refinery of IOCL

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LN: feed for Hydrogen Unit; RN: goes to Gasoline pool; HN: fed to Hydrotreater Unit

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Hydrotreater Unit: used for improving the quality of HSD by removal of sulfur and boosting
the Cetane No of HSD.

Cetane No.(CN)

The percentage of pure cetane (or n-hexadecane, CN=100; n-C16H34) in a blend of cetane and α –
methyl naphthalene* (CN = 0) which matches the ignition quality of a diesel fuel sample

ASTM D613 for CFR engine (Cooperative Fuel Research engine); CN~40-60

Specified for middle distillate fuels

Ex: CN of high speed diesel (HSD) from IOCL is ≥45.

Synonymous with the octane number of gasoline

*α-methyl naphthalene

Cetane index (CI)

A number calculated from the average boiling point and gravity of a petroleum fraction in the
diesel fuel boiling range, which estimates the cetane no. of the fraction.

An indication of carbon to hydrogen ratio

An example of an additive used to improve cetane number is 2-ethylhexyl nitrate (C8H17NO3)

Calculation of cetane index (CI)

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All in oC.

D = Density at 15oC (kg/m3);

Assignment: Calculate the CI of some diesel fuel which has the following parameters:

Density = 950 kg/m3; T10 = 224oC; T50 = 282oC; T90 = 347oC;

Ans: CI = 22.56;

Steps to calculate the CI

1 Get initial estimate of CN from 50% (v/v) distillation recovery temperature and density at
15oC (may be obtained from the Swedish Standards Institute)
2 From 90% (v/v) distillation recovery temperature and density, get one correction factor
3 Use 10% (v/v) and 90% (v/v) distillation recovery temperature to determine a second
correction factor
4 Add these two correction factors to the initial estimate, to obtain a correct CI.

Gasoline

Boiling range: 40-200oC

RVP at 40oC: 35-80 kPa

It is a blend of LSR gasoline, catalytic reformate, catalytically cracked gasoline, polymer

gasoline, alkylate, n-butane

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Additives

A. gum forming inhibitors (isobutyl-p-aminophenol)

B. Metal deactivators: copper and other metals can act as oxidation catalysts
C. Anti-freeze agents:
Used to lower freezing point
Various alcohols
Methanol was used earlier; but now ethylene glycol or propylene glycol is used
D. Corrosion inhibitor: ammonium sulfonate
E. Antiknock or octane booster: TEL (tetra ethyl lead) used earlier; now MTBE (methyl
tertiary butyl ether) is used

Properties of interest

Ease of startup, warm up rate, tendency to vapor lock, evaporation losses, losses to the
crankcase oil-governed by the proportion of various boiling range materials in the gasoline.

Vapor locking tendency is related to RVP

To control vapor, RVP should not exceed the limit:

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 Ambient temp, oF Max allowable RVP, psia
60 12.7
90 8.0

Optimum light ends

% boiling below 158oF (70oC)

~20% in summer

~25% in winter

S content

IOCL specification: 50 mg/kg, max (0.005 wt%)

Aromatics (like benzene) increase octane no., but they are carcinogenic

Benzene content 5 vol% (max) for existing refineries by 2000;

In 2014, it is 1 vol% (max) in motor gasoline (Mogas) of IOCL.

Aviation gasoline (Avgas)

Used in spark-ignition IC engine to propel aircraft

Narrower boiling range and a lower vapor pressure (so it remains in liquid form at reduced
pressure at high altitude, thus preventing vapor lock)

Mainly aromatics and highly branched paraffins

Some Avgas still use TEL (pollutant and toxic) to prevent engine knocking

But turbine and diesel engines are designed to use kerosene-based jet fuel

Light Distillate

ASTM end points: 270 - 300oC (boiling range)

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Example: kerosene, jet fuel, diesel, heating oil etc.

Kerosene

Boiling range: 175 - 270oC

API gravity: 41.5 - 43

Flash point: ~50oC

Aromatic is undesirable in kerosene

If aromatic is high, it creates smoke (aromatics are primarily responsible for smoke)

Sometimes naphtha is added to lower flash point or IBP

Smoke point

Measures the burning quality of jet fuels, kerosene and illuminating oil

Defined as the height of the flame in mm beyond which smoking takes place

Measured using ASTM D-1322

In IOCL, the smoke point of SKO (Superior Kerosene Oil/Kero) is minimum 18 mm.

Jet fuel

Naphtha jet fuel (military application)

A fuel in the heavy naphtha boiling range having an average gravity of 52.8 degrees API, 20
to 90% distillation temperatures of 290 – 470oF (143 – 243oC), and meeting Military
Specification MIL-T-5624L (Grade JP-4). It is used primarily for military turbojet and
turboprop aircraft engines because it has a lower freeze point than other aviation fuels and
meets engine requirements at high altitudes and speeds.

Kerosene jet fuel (commercial application)

Naphtha jet fuel: ASTM boiling range: 65 - 250oC

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Kerosene jet fuel: ASTM boiling range: 175 - 290oC

Both are produced by blending suitable stocks of naphtha and light distillate (N & LD)

Freezing point: -40 to -50oC (max)

Flash point: 45 to 65oC

Aromatic content: 20 vol% max (for clean burning)

Diesel

Blend of light distillate and heavy distillate

Two types of diesel (No. 1 and No. 2)

No. 1 diesel or HSD

Boiling range: 180-300oC

Cetane no: >50

Used in high speed engines in automobiles, trucks and buses

For some HSD, API gravity is 35 and Aniline point is 65oC.

Diesel index (DI) = (35*149)/100 = 52.15

No. 2 diesel or LSD

Boiling range: 190-340oC

Flash point: 50oC or 52oC

Sulfur content: <0.2 wt%

Cetane number: 40

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 the higher the H/C ratio, the better is the burning characteristics (i.e., the higher the

smoke point and the higher the cetane index)

Heavy distillate

ASTM end point: 340-370oC

Atmospheric Gas Oil (AGO)

ASTM end point ~ 425oC

Combined with VGO to form the feed to catalytic cracking

Vacuum Gas Oil (VGO)

ASTM boiling range: 425-600oC

Feed to catalytic cracking

Source of lube oil stocks

Lubricating oils

Important properties (pour point, viscosity, VI, flash point (175-230oC))

High boiling, high viscosity fraction of the crude with undesirable materials removed

Residue

Heavy liquid fuel and solids (fuel oil, coke, asphalt, carbon black)

Coke

Used as fuel

Used in electrode manufacture

Used in calcium carbide production (CaC2, which is used to manufacture C2H2 etc.)

Asphalt

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Colloids of resins and asphaltenes in oil

Classification and evaluation of crudes

G/H: pp 16-29

Crude oils are classified as paraffin base, naphthene base, asphalt base, or mixed base

There are some crude with up to 80% aromatic content and called aromatic base

US Bureau of Mines

Uses specific gravities of two key fractions

Fraction No. 1: 250 - 275oC at 1 atm. pr.

Fraction No. 2: 275 - 300oC at 40 mm Hg

Key fraction
No. 1 No. 2
Paraffin ≥40 ≥30
Paraffin, intermediate ≥40 20-30
Intermediate, paraffin 33-40 ≥30
Intermediate 33-40 20-30
Intermediate, naphthene 33-40 ≤20
Naphthene, intermediate ≤33 20-30
Naphthene ≤33 ≤20

Characterization factors

Several correlations between yield and aromaticity/paraffinicity of crude oil exist, but the
two most widely used are the UOP or Watson “characterization factor” k W and the US
Bureau of Mines “correlation index” (C.I.).

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TB = mean avg. boiling point, oR

G = sp. gr. at 60oF

kW varies between 10-15;

kW ~ 10 for highly aromatic material

kW ~ 15 for highly paraffinic compounds

(10.5, highly naphthenic base) < [kW (crude)] < (12.9, paraffin base)

Viscosity, aniline point, mol. wt., critical temperature etc., are correlated with kW.

CI scale is based upon straight-chain paraffins having a CI value of 0 & benzene having a CI
value of 100

Lower the CI, higher is the concentration of paraffin

Higher the CI, higher is the concentration of naphthene and aromatics

Mean avg. boiling point (MeABP) = (MABP+CABP)/2

MABP = molal avg. boiling point = or =

Xi is the mol fr.; xi is the wt. fr.; Tbi is the normal boiling point of the ith fraction/component

CABP = cubic average boiling point =

Xvi = vol. fr. of component i

VABP = volume average boiling point

35
 or

Desalting crude oil

The crude requires desalting if the salt content is greater than 10 lb/1000 bbl (expressed as
NaCl)

Desalting is carried out to minimize fouling and corrosion caused by salt deposition on heat
transfer surfaces and

Acids formed by decomposition of the chloride salts

In addition, some metals in inorganic compounds are dissolved in water, which is emulsified
with crude, can cause catalyst deactivation

Irrespective of the criterion, many companies desalt all crude oils

Advantage/benefits:

1 Reduced equipment fouling

2 Reduced corrosion
3 Longer catalyst life

Two-stage desalting is used if salt content is > 20 lb/1000 bbl of crude

Basic principle is to wash the salt (dissolved or suspended as crystals) from crude using
water

Separation ease and efficiency depend on pH, gravity and viscosity of crude as well as the
volume of wash water used per volume of crude

A secondary function of desalting is removal of suspended solid from crude

36
Suspended solid represents very fine sand, clay, soil particles, iron oxide and iron sulfide
particles from pipelines, tanks, or tankers etc.

Total suspended solid removal should be ≥ 60% and 80% removal of particles greater than
0.8 micron in size

Desalting is carried out by mixing crude oil with water (3 to 10 vol%) at temperature from
200 to 300oF (90 to 150oC)

o
API Water wash, vol% Temperature, oF (oC)
>40 3-4 240-260 (115-125)
30-40 4-7 260-280 (125-140)
<30 7-10 280-300 (140-150)

Oil and water phases are separated in a settling vessel by adding chemicals to assist in
breaking of emulsion (demulsifier)

OR by developing a high-potential electric field to coalesce the droplets of salty water

rapidly

AC OR DC can be used (12,000 to 35,000 volt)

Single stage desalting unit, efficiency 90-95%

Two-stage desalting unit, efficiency ≥99%

Single-stage electrostatic desalting system

37
Heavy naphthenic crudes form more stable emulsions than other crudes; hence operate at
lower efficiency

For very heavy crude oils (<15oAPI), addition of gas oil as a diluent to the second stage is
recommended to provide better separation efficiency

Analytical method to determine the salt content of crude oil:

1 HACH titration with mercuric nitrate after water extraction of the salt
2 Potentiometric titration after water extraction
3 Conductivity measurement, etc.

[BPCD: barrels per calendar day; BPSD: barrels per stream day]

38
Atmospheric Topping Unit

After desalting, crude oil is pumped through a series of heat exchangers to the atmospheric
topping unit

Temperature is raised to about 550oF (288oC) by heat exchange with product and reflux
stream

It is then further heated to about 750oF (399oC) in a furnace (direct-fired heater or “pipe-
still”) and charged to the flash zone of atmospheric tower

The furnace discharge temperature is sufficiently high (~750oF) to cause vaporization of all
products withdrawn above the flash zone

Reflux is provided by condensing the tower overhead vapors and returning a portion of the
liquid to the top of the tower, and by pump-around and pumpback streams lower in the tower

Crude towers do not normally use reboilers, but several trays incorporated below the flash
zone and steam is introduced below the bottom tray to strip any remaining gas oil from the
liquid in the flash zone and to produce a high-flash-point bottoms

Steam reduces the partial pressure of the hydrocarbons and thus lowers the required
vaporization temperature

Atmospheric tower normally contains 30 to 50 trays

5 to 8 trays are needed for each sidestream product and same no. above and below the feed
plate; so, if 4 liquid sidestream drawoff is there, it requires about 30-48 trays

39
 Schematic diagram of the atmospheric topping unit

The overhead condenser condenses C5 and heavier fraction of the vapors

This is light gasoline portion of the overhead, containing some propane and butane and
remaining high-boiling components

Some of this condensate is returned as reflux, and remainder is sent to the stabilization
section of the refinery gas plant where butanes and propanes are separated from C5-180oF (C5
– 82oC) LSR gasoline

Vacuum Distillation

Heavier fractions of crude oil will undergo thermal cracking if distilled at atmospheric
pressure (because temperature will be very high)

40
Consequences

(i) Loss of valuable product

(ii) Equipment fouling

Hence, they are distilled under vacuum (because boiling point decreases with decreasing
pressure)

25 to 40 mm Hg pressure maintained in vacuum tower

To improve vaporization, pressure sometimes lowered to 10 mm Hg, by the addition of steam

(in furnace inlet)

Steam increases furnace tube velocity and minimizes coke formation and decreases
hydrocarbon partial pressure

Stripping steam required is function of boiling range of feed and fraction vaporized, and
generally ranges from 10 to 50 lb/bbl feed

Furnace outlet temperature~730 to 850oF (388-455oC)

Highest outlet temperature, “dry” operation, i.g., no steam is added either to furnace inlet or
to vacuum tower

Lowest outlet temperature, “wet” operation, i.g., steam added to both the furnace inlet and
vacuum tower

Intermediate temperature used for “damp” operation, i.e., steam is added to furnace inlet only

For most crude oils, furnaces can be operated from 3 to 5 years between turnarounds

Low pressure increases the volume of vapor per barrel vaporized significantly; hence larger
diameter of vacuum tower is required (can be up to 40 ft diameter)

41
 Schematic diagram of the vacuum tower

Auxiliary Equipment

Flash drum

Sometimes a flash drum is installed between feed-preheat heat exchangers and atmospheric
pipe-still furnace

Lower boiling fractions which vaporize in heat exchangers, are separated in the flash drum
and flow directly to the flash zone of the fractionators (ADU)

The liquid is pumped through the furnace to the ADU flash zone

This results in a smaller and lower-cost furnace and lower furnace outlet temperature for the
same quantity of overhead streams produced

42
Stabilizer

Sometimes a stabilizer is incorporated in crude distillation section instead of the refinery gas
plant section

Liquid condensed from overhead vapor stream contains propane and butanes which make
vapor pressure much higher (than the vapor pressure required for gasoline blending)

So, the condensed liquid in excess of reflux requirements is charged to a stabilizing tower
where vapor pressure is adjusted by removing C3 and C4 from LSR gasoline stream

Later, n-butane is added to the gasoline stream to provide the desired RVP

CDU products

Fuel gas

CH4 and C2H6

Sometimes C3 in excess of LPG requirements is also included in the fuel gas stream

Wet gas

Contains C3 and C4; as well as C1 and C2

C3 and C4 are separated to be used for LPG

C4 is used for gasoline blending and alkylation unit feed

LSR naphtha

Stabilized LSR naphtha (or LSR gasoline) stream is desulfurized and used in gasoline
blending or processed in an isomerization unit to improve octane before blending into
gasoline

HSR naphtha or HSR gasoline

Feed to catalytic reformer to produce high-octane reformate for gasoline blending and
aromatics

43
Gas oils

Light, atmospheric and vacuum gas oils are processed in a hydrocracker or catalytic cracker
to produce gasoline, jet and diesel fuels. HVGO can be used as feedstock for lubricating oil
processing unit

Residuum

Vacuum still bottoms can be processed in a visbreaker, coker or deasphalting unit to produce
heavy fuel oil or cracking and/or lube oil base stock (LOBS)

For asphalt crude, the residuum can be processed further to produce road and/or roofing
asphalt

Ch5: Coking and Thermal Processes

Coking can be considered as a severe thermal cracking process in which one of the end
products is carbon (i.e., coke), [very low H/C ratio]

Coke contains some volatile matter

To eliminate all volatile matter from petroleum coke, it must be calcined at approximately
1095 to 1260oC (2000 to 2300oF)

Vacuum residuum → Coking → Coker gas oil → Catalytic cracker

Coking of vacuum residue decreased coke formation on the cracker catalyst and allowed
increased cracker throughput

44
Types, properties and uses of petroleum coke

All cokes produced from the coker are called “green” cokes and contain some high-
molecular weight hydrocarbons called volatile matter

Fuel grade cokes are sold as green coke

But, coke used to make anodes for aluminum production or electrodes for steel production
must be calcined at temperature from 1800 to 2400oF (980 to 1315oC) to reduce volatile
matter to a very low level

Sponge coke

Delayed coker coke is produced as hard, porous, irregular-shaped lumps ranging in size from
fine dust to 20 inch

They are called sponge coke (looks like black sponge)

Needle coke

Microscopic elongated crystalline structure

45
Produced from highly aromatic feedstock (FCC cycle oil etc.) when a coking unit is operated
at high pressure (100 psig) and high recycle ratio (1:1)

Preferred over sponge coke for use in electrode manufacture because of its lower electrical
resistivity and lower coefficient of thermal expansion

Shot coke (undesirable)

Called shot coke because of clusters of shot-sized pellets

Got produced during operational upset or while processing very heavy residual crude

Shot clusters can grow large enough to plug the coke drum outlet (>12 inch)

Also produced from some high sulfur residual

Main use of pet coke

i Fuel
ii Manufacture of anode
iii Direct use as carbon source for manufacture of elemental phosphorus, calcium
carbide and silicon carbide
iv Manufacture of electrode
v Manufacture of graphite

Sulfur content

Sulfur content in petroleum coke varies with the sulfur content of coker feedstock

Varies from 0.3 to 1.5 wt% (occasionally may be as high as 8 wt%)

Delayed Coking

This was developed to minimize refinery yields of residual fuel oil by severe thermal
cracking of stocks such as vacuum residuals, aromatic gas oil etc.

46
Coke deposition in the heaters reduced by achieving high velocity (minimum retention time)
in the heaters

Installed insulated surge drum on the heater effluent

So the feed got sufficient time for coking hence “delayed coking”

Delayed coking unit

Furnace outlet temperature ranges from 900-930oF (482-500oC) and pressure ~60 psig (4 bar)

Higher the outlet temperature, greater the tendency to form shot coke and more frequent is
decoking requirement

Usually decoking is done after every three to five months

Coke removal

47
When one drum is full (or filled up to a safe margin), the heater effluent is switched to the
empty coke drum and full drum is isolated, steamed to remove hydrocarbon vapors, cooled
by filling with water, opened, drained and the coke removed

Most plants use a hydraulic system (by using a no. of high pressure water jets (2000 to 4500
psig))

Operation

Coke drums are filled and emptied on a time cycle, however, the fractionator is operated
continuously

Operation Hours
Fill drum with coke 24
Switch and steam out 3
Cool 3
Drain 2
Unhead and decoke 5
Head up and test 2
Heat up 7
Spare time 2
Total 48

Gas composition for delayed coking (sulfur-free basis)

Component Mol%
C1 51.4
C2 15.9
C2 = 1.5
C3 = -
C3 8.2
C4 = -

48
 i-C4 -
n-C4 -
H2 13.7
CO2 0.2

Typical split of Coker naphtha

o
Component Vol% API
Light naphtha 35.1 65
Heavy naphtha 64.9 50

Sulfur and nitrogen distribution for delayed coking

(basis: sulfur and nitrogen in feed to coker)

Component Sulfur (wt%) Nitrogen (wt%)

Gas 30.0 -
Light naphtha 1.7 -
Heavy naphtha 3.3 1
LCGO 15.4 2
HCGO 19.6 22
Coke 30.0 75

Flexicoking

49
 Schematic diagram of a flexicoker

Feed can be vacuum resid, coal tar, shale oil, tar sand bitumen etc.

Feed preheated to about 600 to 700oF and sprayed into the reactor where it contacts a hot
fluidized bed of coke

This hot coke is recycled from coke heater

Reactor temperature ~950 to 1000oF

Recycled coke provides sensible heat and heat of vaporization for the feed and the
endothermic heat for the cracking reaction

The cracked vapor product passes through cyclone separator (to separate coke particles up to
7 micron and above) and then are quenched in the scrubber vessel by wash oil

50
Some of high-boiling (925+oF) product condense and are recycled to the reactor

The balance of cracked vapor flow to the coker fractionator where various cuts are separated

Wash oil circulated in scrubber provides quench cooling and reduces amount of entrained
fine coke particles

Coke produced by cracking gets deposited as thin film on surface of existing coke particles

Then coke is stripped with steam so that no other product leaves along with coke

Coke reheated to about 1100oF in the heater

Heater is also fluidized bed and its primary function is to transfer heat from gasifier to reactor

Then coke from the heater flows to a gasifier (fluidized bed)

Coke + air + steam → CO + H2 + CO2 + N2

Sulfur in coke is converted to H2S (high quantity) and COS (small quantity)

Nitrogen in coke converted to NH3 and N2

This product gas from top of gasifier enters heater from the bottom and helps in fluidization
and provide the heat needed in the reactor

About 60 to 97% of coke can be gasified

Coke gas from heater is cooled in a waste heat steam generator and then passes through
external cyclones and a venture-type wet scrubber

Coke fine collected from this scrubber and purge coke (collected from heater bottom)
represent the net coke yield and contain essentially all of the metal and ash components of
the reactor feedstock

After removal of coke fine, the coke gas is treated to remove H2S and then used as refinery
fuel

51
This fuel gas has much less heating value (100 to 130 Btu/scf) than natural gas (900 to 1000
Btu/scf)

Fluid Coking

Simplified version of flexicoking

Only two fluid beds are used in a fluid coker: a reactor and a burner (in place of the heater)

Only 20 to 25% of the coke produced in the reactor is burned to satisfy the heat requirements
of the reactor and the feed preheat

Comparison of coking yields

Feed: Arabian medium 1050+oF vacuum resid

Gravity, oAPI 4.9

Sulfur, wt% 5.4
Nitrogen, wt% 0.26
Conradson carbon, wt% 23.3
Nickel, wt ppm 32
Vanadium, wt ppm 86
Iron, wt ppm 30
Yields

Parameter Delayed coking Fluid coking Flexicoking

Recycle cut point, oF 900 975 975
Yields on fresh feed, wt%
Gas 9.3 11.8 11.8
Light naphtha 2.0 1.9 1.9
Heavy naphtha 8.0 7.8 7.8
Gas oil 46.7 50.4 50.4
Gross coke* 34.0 28.1 28.1**
Net coke 34.0 22.4 2.3**

52
C5+ liquid 56.7 60.1 60.1**
*after this, we make total which is 100; after total, net coke and C5+ liquid appear

Gas + (C5+ liquid) + net coke = 100%

**balance not matching as gasifier output is not accounted for

The coke which is gasified in a Flexicoker produces coke gas of the following approx.
composition (after H2S removal):

Component Mol%
H2 15
CO 20
CH4 2
CO2 10
N2 53
Total 100

Visbreaking

Relatively mild thermal cracking

It is used to reduce viscosity and pour point of vacuum tower bottom (VR)

Refinery production of heavy fuel oil can be reduced by 20-35% by visbreaking

Gas oil produced by visbreaking is also used to increase catalytic cracker feedstock and
gasoline yield

Long paraffinic side chains attached to aromatic rings are the primary cause of high pour
point and viscosity for paraffinic base residue

Visbreaking is carried out to optimize the breaking of these long side chains and their
subsequent cracking to shorter molecules with lower viscosity and pour point

53
The principal reactions during visbreaking

(i) Cracking of the side chains attached to cycloparaffin and aromatic rings at or close to
the ring so the chains are either removed or shortened to methyl or ethyl groups
(ii) Cracking of resins to light hydrocarbons (primarily olefins) and compounds which
convert to asphaltenes
(iii) Above 900oF, some cracking of naphthene rings

Visbreaking may be classified as (i) coil or furnace cracking, and (ii) soaker cracking

Visbreaking time-temperature relationship

Time, min Temperature

o o
C F
1 485 905
2 470 878
4 455 850
8 440 825

Coil cracking uses higher furnace outlet temperature (885-930oF) and shorter reaction time,
1-3 min

Soaker cracking uses lower furnace outlet temperature (800-830oF) and longer reaction time;
so it has the advantage of lower energy consumption

Run time (before shutting down to remove coke)

Coil visbreaker: 3 to 6 months

Soaker visbreaker: 6 to 18 months

54
 Schematic diagram of coil visbreaker

In coil cracking process, the feed is heated to cracking temperature [885-930oF (474-500oC)]
and upon exit, is quenched with gas oil or tower bottoms to stop cracking reaction

55
 Schematic diagram of soaker visbreaker

In the soaker cracking operation, the feed leaves the furnace between 800 to 820oF (427-
438oC) and passes through a soaking drum, which provides the additional reaction time,
before it is quenched

Pressure can be ~750 psig (high) for liquid-phase visbreaking and ~100-300 (low) psig for
20-40% vaporization at the furnace outlet

In coil/furnace cracking, fuel consumption ~80% of operating cost; in soaker cracking it is

30-35% lower

Visbreaking results, Kuwait long Resid

Feed Product
Yield, wt%

56
 Butane and lighter 2.5
C5-330oF naphtha 5.9
Gas oil, 660oF EP 13.5
Tar 78.1
Product properties
Naphtha (oAPI) 65.0
Naphtha (Sulfur, wt%) 1.0
Gas oil (oAPI) 32.0
Gas oil (Sulfur, wt%) 2.5
Tar or feed Feed Tar (product)
% on crude -
o
API 14.4 11.0
Sulfur, wt% 4.1 4.3
Viscosity, cSt, 50oC 720 250
A few questions:

Q1 Why is thermal cracking not a common process in the US refinery?

Q2 Why does thermal cracking produce a gasoline that has a relatively low octane
number?
Q3 What makes thermal cracking an attractive process for producing ethylene?
Q4 Why is the delayed coking process called “delayed”?
Q5 What makes flexicoking process flexible?
Thermal severity index (TSI)

TSI = f(T,t); T = temperature; t = time

Arrhenius equation: ; TSI = ( )

57
#Problem:

A coil visbreaker operates at 500oC for 1 min. How long will it take to achieve the same
thermal severity at 450oC in a soaker visbreaker process? An apparent Arrhenius activation
energy for thermal cracking is given as 50 kcal/mol.

Ch6: Catalytic Cracking

Most important and widely used refinery process for converting heavy oils into more
valuable gasoline and lighter product

Almost completely replaced thermal cracking (TC) because more gasoline having a higher
octane number can be produced

Light gases produced by catalytic cracking (CC) contain more olefins than those produced by
thermal cracking

TC vs CC yields on similar topped crude feed

Component TC CC
Wt% Vol% Wt% Vol%
Fresh feed 100.0 100.0 100.0 100.0
Gas 6.6 - 4.5 -
Propane 2.1 3.7 1.3 2.2
Propylene 1.0 1.8 2.0 3.4
i-C4 0.8 1.3 2.6 4.0
n-C4 1.9 2.9 0.9 1.4
Butylenes 1.8 2.6 2.6 3.8
C5+ gasoline 26.9 32.1 40.2 46.7
Light cycle oil 1.9 1.9 33.2 32.0
Residual oil 57.0 50.0 - -
Coke 0 5.0
Coke produced remains on the catalyst particle and rapidly lowers its activity

So regeneration of catalyst is necessary

58
Regeneration is done by burning off the coke with air

Average riser reactor temperature: 900 to 1000oF (480 – 540oC)

Oil feed temperature: 500 to 800oF (260 – 425oC)

Catalyst exit temperature from regenerator: 1200 to 1500oF (650-815oC)

Catalytic cracker
Moving-bed Fluidized-bed
Example: Example:
Thermafor catalytic cracker (TCC) Fluid catalytic cracker (FCC)
-very few TCC in operation -mostly FCC in the world

FCC
Bed cracking unit Riser (transfer line) cracking unit

59
 Process flow (catalytic cracking)

Hot oil feed is contacted with catalyst in either feed riser line or reactor

As reaction progresses, catalyst is gradually deactivated by deposition of coke on the surface

of the catalyst

Catalyst and hydrocarbon vapors separated mechanically and feed remaining on the catalyst
is removed by steam-stripping before the catalyst enters the regenerator

Product vapor are taken (from top) to a fractionators

Spent catalyst enters regenerator and is reactivated by burning off the coke deposits with air

Treg carefully controlled to prevent catalyst deactivation by overheating and this is done by
controlling flow rate of air (to obtain a desired CO2/CO ratio in exit flue gas)

Flue gas and catalyst separated by cyclone separator and electrostatic precipitators

FCC

Catalyst particle size ~70 micron (avg)

60
61
62
63
In the regenerator, the heat of combustion raises the catalyst temperature to 1150 to 1550oF
(620-845oC) and most of this heat is transferred by the catalyst to the oil feed in the riser

Regenerated catalyst contains ~0.01 to 0.4 wt% coke

Zeolite catalysts have much higher cracking activity than amorphous catalysts

They also need shorter residence time to prevent overcracking of gasoline to gas and coke

Atmospheric and vacuum tower bottoms are blended into the FCC feed

Residual feedstocks have much higher metal content (Ni and Vanadium) and greater coke
forming potential (Ramsbottom and Conradson carbon residue) than distillate feeds

These contaminants

(i) Reduce catalyst activity

64
(ii) Promote coke and H2 formation
(iii) Decrease gasoline yield

Catalyst activity loss is primarily due to V (vanadium)

Increased coke and H2 formation is primarily due to Ni

Problems of high coke formation

(i) Increased coke burning requirement

(ii) Increased air/oxygen demand
(iii) Higher regenerator temperature
(iv) Greater heat removal

If feed contains up to 15 ppm (Ni+V), then Ni catalyst activity can be passivated by addition
of organic antimony compounds to the feed and reduction in coke and hydrogen yield up to
15% and 45%, respectively;

If feed contains >15 ppm metals and has Conradson carbon >3%, hydroprocessing of FCC
feed may be required to remove metals, reduce carbon forming potential and increase yield
of gasoline and middle distillates by increasing the hydrogen content of the feed

Please study Fig 6.7 and Fig 6.8

Mechanism of cracking reactions

Catalytic cracking → (primary and secondary reactions) → products

Primary reaction (C-C bond scission and immediate neutralization of carbonium ion)

Paraffin → paraffin + olefin (n-heptane)

Alkyl naphthene → naphthene + olefin (methyl cyclohexane)

Alkyl aromatic → aromatic + olefin (ethyl/propyl benzene)

65
66
 Catalytic cracking of paraffins

Characterized by high production of C3 and C4 hydrocarbons in the cracked gases

Reaction rate and products determined by size and structure of paraffins

Isomerization to branched structures and aromatic hydrocarbons formation resulting from

secondary reaction involving olefins

Catalytic cracking of olefins

Cracking rates of olefins much higher than rates of paraffins

Main reactions

(i) C-C bond scission

(ii) Isomerization

67
(iii) Polymerization
(iv) Saturation, aromatization and carbon formation (coke formation)

Isomerization followed by saturation and aromatization are responsible for high octane no. of
catalytically cracked gasoline

Cracking of naphthenic hydrocarbons

The most important reaction in presence of silica-alumina is dehydration to aromatics

(<1000oF or 540oC)

There is also C-C bond scission in both the ring and attached side chain

Cracking of aromatic hydrocarbons

Aromatic hydrocarbons with alkyl group containing less than 3 carbon atoms are not very
reactive

For long side chain attached to aromatic ring, the main reaction is splitting off of side chains
without breaking the ring

Ex.

Ethyl benzene → benzene + reaction product from attached alkyl radical

[This is an important reaction for benzene recovery]

Cracking catalysts

Commercial catalysts

(i) Acid-treated natural aluminosilicates

(ii) Amorphous synthetic silica-alumina combinations
(iii) Crystalline synthetic silica-alumina catalysts called zeolites or molecular sieves

Commercially used catalysts are type 3 or combination of type 2 and 3

68
Comparison of amorphous and zeolite catalysts [Table 6.2]

Amorphous Zeolite
Coke, wt% 4 4
Conversion 55 65
C5+ gasoline, vol% 38 51
C3- gas, wt% 7 6
C4’s, vol% 17 16

Please go through Table 6.3 also

Advantage of zeolite catalyst over natural and synthetic amorphous catalyst

I Higher activity
II Higher gasoline yield at a given conversion
III Gasoline produced contains large % of paraffinic and aromatic hydrocarbons
IV Lower coke yield (hence larger throughput at a given conversion level)
V Increased isobutane production
VI Ability to go to higher conversion per pass without overcracking

Ch 7: Catalytic Hydrocracking (CH)

This process started in refinery because:

I Demand for gasoline and jet fuel increased rapidly as compared to diesel and home
heating oil
II Large amount of inexpensive hydrogen available as a byproduct from catalytic
reforming unit
III Strict environmental norms for low sulfur and aromatics content in motor fuel
First commercial operation of distillate hydrocracker started by Chevron in 1958

Low pressure operation is possible due to improved catalyst

69
(i) Increased demand for high-octane unleaded gasoline and kerosene-type jet fuel
(ii) Decreased demand for distillate fuel oil

These two important factors have promoted the conversion of higher-boiling petroleum
materials to gasoline and jet fuel

Advantages of hydrocracking

I Better balance of gasoline and distillate production

II Greater gasoline yield
III Improved gasoline pool octane quality and sensitivity
IV Production of relatively high amount of isobutene
V Supplementing FCC to upgrade heavy cracking stocks, aromatics, cycle oils, and
coker oils to gasoline, jet fuels and light fuel oils
In a modern refinery, FCC and CH work as a team

Typical feed for FCC: AGO, VGO etc. (that are paraffinic and easily cracked)

Typical feed for CH: cycle oil (vacuum and coker gas oils are also used as hydrocracker
feed); coker distillate (more aromatic)

These are very refractory (which retains its strength at high temperature) and resist catalytic
cracking

High pressure and hydrogen atmosphere make them relatively easy to hydrocrack

Hydrocracking is broken into two general types of processes

Hydrocracking Process which operates on distilled feed

Hydroprocessing Process which operates on residual material [Ch 8]

70
Table 7.1: Typical Hydrocracker feedstocks

Feed Product
Kerosene Naphtha
Straight-run diesel Naphtha and/or jet fuel
AGO Naphtha, jet fuel, and/or diesel
VGO Naphtha, jet fuel, diesel, lube oil
FCC LCO Naphtha
FCC HCO Naphtha and/or distillates
Coker LCGO Naphtha and/or distillates
Coker HCGO Naphtha and/or distillates

Hydrocracking reaction

It is believed that the mechanism of hydrocracking is catalytic cracking with hydrogenation

superimposed

Catalytic cracking is scission of a C-C single bond, &

Hydrogenation is addition of hydrogen to a carbon-carbon double bond

Cracking and hydrogenation are complementary; cracking provides olefins for hydrogenation
and hydrogenation in turn provides heat for cracking

Overall reaction provides excess of heat (exothermic)

71
72
This excess heat increases the reactor temperature and accelerates the reaction rate

Rate of reaction and/or Treactor controlled by injecting cold hydrogen as quench into the
reactors to absorb the excess heat of reaction

Another important reaction is initial hydrogenation of a condensed aromatic compound to a

cycloparaffin

This allows subsequent cracking and thus converts a low-value component of catalytic cycle
oils to a useful product

Another important reaction is isomerization

The olefinic product formed are rapidly hydrogenated, thus maintaining a high concentration
of high octane isoparaffins and prevents the reverse reaction back to straight-chain molecules

73
As compared to normal cracking operation, hydrocracking yields less amount of C3 and
lighter gases

The volumetric yield of liquid product is very high

CH reaction temperature 550-750oF (290 to 400oC)

Reactor pressure 1200-2000 psig (82-136 atm)

Circulation of large quantities of hydrogen with feedstock prevents excessive catalyst fouling
and permits long runs without catalyst regeneration

It is necessary to remove catalyst poison to give long catalyst life

Frequently the feedstock is hydrotreated to remove sulfur and nitrogen compounds as well as
metals

Feed preparation

Hydrocracking catalyst is easily poisoned by metallic salts, oxygen, organic nitrogen

compounds and sulfur in the feedstock

Feedstock is hydrotreated to saturate olefins and remove sulfur, nitrogen and oxygen
compounds

Molecules having metals are cracked and metals are retained on the catalyst

Nitrogen → ammonia

Sulfur → hydrogen sulfide

For some hydrocracking catalyst, presence of H2S in low concentration acts as a catalyst to
inhibit the saturation of aromatic rings which results in high octane gasoline

In the hydrotreater many hydrogenation reactions take place like olefin saturation, aromatic
ring saturation…etc. (cracking is insignificant at the operating conditions)

Exothermic heats of desulfurization and denitrogenation reaction are high (2400 to 2800
kJ/std m3 of H2)

74
Water content should be brought down to <25 ppm

As in hydrocracking, steam causes the crystalline structure of catalyst to collapse and

dispersed rare-earth atoms to agglomerate

To remove water, the stream is passed through silica gel or molecular sieve dryer

Table 7.2 Hydrocracking Processes available for license

Process Company
Isomax Chevron and UOP, LLC
Unicracking UOP
GOFining ExxonMobil Research and Engineering Co
Ultracracking BP Amoco

75
All hydrocracking and hydroprocessing operations in use today are fixed-bed catalytic
processes with liquid downflow

The GOFining process (ExxonMobil Research and Engg Co.)

Fixed-bed regenerative process

Employs a molecular-sieve catalyst impregnated with a rare-earth metal (15 lanthanides,

scandium and yttrium; i.g., lanthanum, cerium etc.)

Single-stage or two-stage

Operating condition 660 - 785oF (350 - 420oC); 1000 – 2000 psig (68-136 atm)

T and P vary with the age of catalyst, product desired and properties of feedstock

If one-stage is used; then heavier material from the bottom of the fractioner is recycled back
to the reactor

For process, please read pp. 165-167

If the feed is not hydrotreated, there is a guard reactor before the first reactor

The guard reactor has cobalt-molybdenum on silica-alumina to convert organic sulfur and
nitrogen compounds to H2S, NH3 and hydrocarbons to protect the precious metal catalyst in
the following reactor

Hydrocracking Catalyst

Most CH catalysts consist of a crystalline mixture of silica-alumina with a small uniformly

distributed amount of rare earths (rare-earth metal like platinum, palladium, tungsten and
nickel used as hydrogenation base) contained within the crystalline lattice

Silica-alumina provides cracking activity

Rare-earth metals promote hydrogenation

Catalyst activity decreases with time and reactor temperature increased to increase reaction
rate and maintain conversion

76
Regeneration required after 2-4 years

Decoking done to remove coke particle

Catalyst can undergo several regeneration cycles

Mostly, silica-alumina is used as cracking base and rare-earth metal is used as hydrogenation
base

Ch8: Hydroprocessing and Resid Processing

Resid (bottom of the barrel):

Atmospheric Reduced Crude (ARC): IBP 650oF (343oC), OR

Vacuum Reduced Crude (VRC): IBP 1050oF (566oC)

Resid contains higher concentration of sulfur, nitrogen, metal etc.

ratio in the molecules are much smaller

Density and sulfur content of crude increasing day by day; hence amount of VRC is also
increasing (1050+oF)

Earlier this resid has been sold as asphalt or as heavy fuel oil

Due to stricter environmental regulations, nowadays it is impossible to sell them as fuel oil;
they must be processed and converted so that they can be blended into transportation fuel

Low H/C ratio in the molecule causes rapid catalyst deactivation

Ni and V in the resid act as catalyst for reaction creating carbon and light gaseous
hydrocarbons

As a result, catalytic processes usually use ARC as their feedstock and VRC feedstocks are
generally processed by noncatalytic processes

ARC processed using

Reduced crude catalytic cracking units

77
Hydroprocessing units

VRC processed using

Delayed coking

Flexicoking

Solvent extraction…etc

Study Composition of vacuum tower bottoms and Fig 8.1

Read pp. 181-182

Asphaltene fraction

Liquid propane (C3H8) used to extract the oil fraction from VRC

Liquid n-pentane, n-hexane or n-heptane is then used to extract the resin fraction from the
residue from the propane extraction

The material insoluble in either propane or higher hydrocarbon is termed as asphaltene

fraction

Asphaltene fraction has very low H/C ratio

Mol wt. ~5000 to 10000 (mixture of highly condensed ring compounds)

80 to 90% of metal in the crude (Ni and V) is contained in asphaltene

Contains higher content of sulfur, nitrogen and carbon forming compound than VRC

VRC obtained from crude was solvent extracted (n-hptane) by Hensley (Amoco Research)
and it contained ~2 to 15wt% asphaltenes

Rossi et al. (Chevron) extracted VRC obtained from similar crude, using n-pentane and
found asphaltene content up to 25wt%

Resin fraction

78
Contains condensed-ring aromatics

Has a substantial amount of paraffinic structures

Used as solvent for asphaltenes

Av. Mol. wt. ~ 600 to 5000

Sulfur concentration about the same as in the VRC

Contains ~10 to 20 wt% metals in the crude; so the oil fraction is almost free of metal
contamination

Oil fraction is highly paraffinic and contains no metals, has lower sulfur and nitrogen content
than VRC

Processing options
Catalytic Noncatalytic
 Uses ARC  Uses VRC
 Fixed-bed hydroprocessing  Solvent extraction
 Ebullated-bed or expanded-bed  Delayed coking
hydroprocessing  Flexicoking
 Moving-bed hydroprocessing
 Reduced crude FCC

Hydroprocessing

(i) used to reduce boiling range of feedstock, &

(ii) removes substantial amounts of metals, sulfur, nitrogen and carbon forming compounds

Fixed-bed processes

Residfining, ARDS, VRDS, RESID HDS

Ebullated-bed or expanded-bed process

79
H-Oil, LCfining

Feed conversion of 25 to 65% can be attained

Other names of the same process

Hydroconversion, hydrorefining, resid HDS, etc.

Typical fixed-bed process (EXXON RESIDfining hydroprocessing unit)

Operating pressure is above 2000 psig

Low space velocity

Charge rates ~ 30,000 to 40,000 BPSD (4760-6360 m3/SD) per train of reactors

Each train will have a guard reactor (to reduce metal content and carbon forming potential of
the feed) followed by 3 to 4 hydroprocessing reactors in series

Catalyst of the guard reactor has large pore size (150 – 200 Ao) silica-alumina catalyst with
low loading of cobalt and molybdenum

Fixed-bed process

Desalted crude goes to atmospheric tower

80
Atmospheric resids are filtered before being fed to the hydroprocessing unit to remove solids
> 25 Ao in size, mixed with recycle hydrogen, heated to reaction temperature and charged
into the top of the guard reactor

Suspended solid will be deposited on top of the guard reactor and metal deposited on catalyst

There is substantial reduction in Conradson and Ramsbottom carbon residue

Feed to the following reactors is low in metal and carbon forming precursors

3 to 4 reactors (after the guard reactor) operated to remove sulfur and nitrogen and crack
1050+oF (566+oC) material to lower boiling compounds

Table 8.1: Results from Hydroprocessing heavy Venezuelan crude oil (Jobo)

Feed Product
Gravity, oAPI 8.5 22.7
Sulfur, wt% 4.0 0.8
Nickel, ppm 440 19
Residue, wt% 13.8 2.8

Self-study

(i) Expanded-bed hydrocracking process

(ii) Moving-bed hydrocracking process

(iii) Solvent extraction

Ch9 (G/H): Hydrotreating (HT)

Relatively mild operation

Primary purpose is to saturate olefins, reduce sulfur, nitrogen, etc. and not to change the
boiling range of the feed

Catalytically stabilizes petroleum product

81
Olefin → paraffin

Gum-forming unstable diolefin → paraffin

And removes objectionable elements (sulfur, nitrogen, oxygen, halides, and trace metals)
from feedstocks by reaction with hydrogen

HT feed: naphtha to reduced crude

When specifically sulfur is removed, it is called HDS (Hydrodesulfurization)

About 30 HT processes available for license

(feed + H2-rich gas) → preheater → reactor

Reaction temperature ≤ 800oF (427oC), to minimize cracking

Feed heated to ~ 500 – 800oF

Fixed-bed reactor used

Metal-oxide catalyst used

Product: H2S, NH3, saturated hydrocarbon; free metals (remain on catalyst)

Other products leave with stream

Product stream cooled and then H2 is separated in a stripper (to strip H2S and light ends)

82
 Hydrotreating catalysts

Cobalt and molybdenum oxides on alumina, nickel oxide, nickel thiomolybdate, tungsten and
nickel sulfides, and vanadium oxide

Nowadays, the mostly used catalysts are cobalt and molybdenum oxides on alumina

They are highly selective, easy to regenerate and resistant to poisons

They should be activated by converting the hydrogenation metals from the oxide to sulfide
form

If nitrogen removal is the primary consideration, nickel-cobalt-molyddenum or nickel-

molybdenum compound supported on alumina are more efficient

If sulfur reduction is the primary objective, then cobalt-molybdenum catalyst is better

Catalyst consumption varies from 0.001 to 0.007 lb/bbl (0.003 to 0.02 kg/m3) feed

It depends on severity of operation, gravity and metals content of the feed

Aromatics reduction

H2 partial pressure is the most important parameter

Reaction temperature ~ 700 to 750oF

83
Exothermic reaction and equilibrium yields are favored at low temperature

Hydrotreating the feed to FCC unit reduces sulfur content but increases aromatic content
(mono-aromatic content is increased)

Reactions

Desulfurization is the main reaction

Sl. No. Reaction Expression

1. Desulfurization Mercaptans RSH + H2 → RH + H2S

Sulfides R2S + 2H2 → 2RH + H2S

Disulfides (RS)2 + 3H2 → 2RH + 2H2S

Thiophenes C4H4S + 4H2 → C4H10 + H2S

2. Denitrogenation Pyrrole C4H4NH + 4H2 → C4H10 + NH3

Pyridine C5H5N + 5H2 → C5H12 + NH3

3. Deoxidation Phenol C6H5OH + H2 → C6H6 + H2O

Peroxides C7H13OOH + 3H2 → C7H16 + 2H2O

4. Dehalogenation Chlorides RCl + H2 → RH + HCl

5. Hydrogenation Pentene C5H10 + H2 → C5H12

6. Hydrocracking Decene C10H22 + H2 → C4H10 + C6H14

Ease of Desulfurization

Depends upon type of compound

Low-boiling compounds are desulfurized easily

Difficulty increases in the order:

84
Paraffins (least difficult) > naphthenes > aromatics (most difficult)

Ease of Denitrogenation

Nitrogen removal requires more severe operating condition

For middle distillate fraction (from ADU), which contains high concentration of nitrogen
compounds, more efficient nitrogen reduction is achieved by using catalyst [90% nickel-
molybdenum and 10% nickel-tungsten]

H2 consumption

70 scf/bbl of feed per wt% sulfur

320 scf/bbl of feed per wt% nitrogen

180 scf/bbl of feed per wt% oxygen removal

All reactions are exothermic; temperature rise of ~ 5 to 20oF (3 – 11oC) is usually observed

Ch10: Catalytic Reforming and Isomerization

Demand for unleaded high-octane gasoline

Catalytic reformate meets about 30-40% of US gasoline requirement

Change in boiling range is small; minor amount of cracking takes place

Catalytic reforming primarily increases the octane no. of motor gasoline but not its yield

Feedstock

HSR naphtha [180-375oF (82-190oC)], &

Heavy hydrocracker naphtha

Both consist of PONA (paraffins, olefins, naphthenes and aromatics)

85
PONA Analysis of feedstock and product

Component Feed Product

Paraffins 30-70 30-50
Olefins 0-2 0-2
Naphthenes 20-60 0-3
Aromatics 7-20 45-60
(paraffins + naphthenes) → cyclization → isomerization

Ease and probability of these reactions increase with carbon number

So, naphthas containing 7 or more carbon no. are used as reformer feed

LSR naphtha [C5-180oF (C5-82oC)] largely composed of pentanes and hexanes

C5 cannot make an aromatic ring

C6 can be converted to benzene (carcinogenic); besides, benzene content in gasoline is

limited by EPA/CPCB

So, the hexane content of the reformer feed is minimized

Moreover, hydrocarbons boiling above 400oF (204oC) are easily hydrocracked and cause an
excessive carbon deposition on the catalyst

Reactions

Desirable reactions

i Paraffins are isomerized and converted (partially) to naphthenes;

naphthenes are subsequently converted to aromatics
ii Olefins are saturated to form paraffins and paraffins then react like step (i)
iii Naphthenes are converted to aromatics
iv Aromatics are left essentially unchanged

86
Reactions leading to formation of undesirable product

i Dealkylation of side chains on naphthenes and aromatics to form butanes and lighter
paraffins
ii Cracking of paraffins and naphthenes to form butane and lighter paraffins

Four major reactions take place

1 Dehydrogenation of naphthenes to aromatics

2 Dehydrocyclization of paraffins to aromatics
3 Isomerization
4 Hydrocracking

Self-study: Table 10.1

Dehydrogenation reaction

Highly endothermic, hence causes a decrease in temperature

These reaction rates are very high as compared to other reforming reactions; so, there is a
need to have interheaters between catalyst beds so that a high temperature (and acceptable
reaction rate) is maintained

Major reactions

Sl. No. Reaction Details

1 Dehydrogenation of alkylcyclohexanes to Methyl cyclohexane →
aromatics toluene + 3H2
2 Dehydroisomerization of alkylcyclopentanes to Methyl cyclopentane →
aromatics cyclohexane →
benzene + 3H2
3 Dehydrocyclization of paraffins to aromatics n-heptane → toluene + 4H2

87
Reaction 1 is much faster than reaction 2 or 3

Conversion to aromatics increases the gasoline end point (because boiling point of aromatics
is higher than boiling point of paraffin or naphthenes of the same carbon number)

Yield of aromatics increased by

1 High temperature
2 Low pressure
3 Low space velocity
4 Low H2/HC mole ratio [but sufficient H2 partial pressure must be maintained to
avoid excessive coke formation]

88
Isomerization reactions

Rapid reaction with small heat effects

Sl. No. Reaction Description

1 Isomerization of normal paraffins to n-C5H12 → iso-pentane
isoparaffins
2 Isomerization of alkyl cyclopentanes Methyl cyclopentane (91 RON) →
to cyclohexanes, plus subsequent cyclohexane (83 RON) →
conversion to benzene benzene + 3H2 (>100 RON)

Isomerization yield increased by

1 High temperature (increase in reaction rate)

2 Low space velocity (increase in reaction time)
3 Low pressure

High H2/HC mole ratio (e.g., low HC partial pressure) favors formation of isomers

Hydrocracking reaction (HC)

Exothermic

Lighter liquid and gas are produced

Relatively slow

Involves cracking and saturation of paraffins

n-decane + H2 → isohexane + n-butane

extent of HC reaction is determined by concentration of paraffins

89
HC yield increased by

1 High temperature (increase in reaction rate)

2 Low space velocity (increase in reaction time)
3 High pressure

It is necessary to control the rates of HC and aromatization reaction (reactor temperature is

monitored carefully)

Low-pressure reforming generally used for aromatics production

TBP range of feedstock ~ 155-345oF (68-175oC)

Feed Product
Methyl cyclopentane Benzene
Cyclohexane Benzene
Dimethyl cyclopentane Toluene
Dimethyl cyclohexane Xylene
Cycloheptane Toluene
Methyl cycloheptane Xylene

Aromatic production from paraffin

1 mole of paraffin Aromatic

P6 0.05 mole A6
P7 0.10 mole A7
P8 0.25 mole A8
P9 0.45 mole A9
P10 0.45 mole A10

90
Feed preparation

The active material in most catalytic reforming catalysts is platinum. Certain metals,
hydrogen sulfide, ammonia, and organic nitrogen and sulfur compounds will deactivate the
precious catalyst. Feed pretreating, in the form of hydrotreating, is usually employed to
remove these materials. The hydrotreater employs a cobalt–molybdenum catalyst to convert
organic sulfur and nitrogen compounds to hydrogen sulfide and ammonia, respectively,
which are then removed from the system with the unreacted hydrogen. The metals in the feed
are retained by the hydrotreater catalyst. Hydrogen needed for the hydrotreater is obtained
from the catalytic reformer. If the boiling range of the charge stock must be changed, the feed
is redistilled before being charged to the catalytic reformer.

Catalytic Reforming Processes

There are several major reforming processes in use today. These include the Platforming
process licensed by UOP LLC (Photo 4, Appendix E), Powerforming (Exxon) (Photo 5,
Appendix E), Ultraforming (Amoco), Catalytic Reforming (Engelhard), Magnaforming
(ARCO), Reforming (Institut Francais du Petrole [IFP]), and Rheniforming (Chevron). There
are several other processes in use at some refineries but these are limited to a few
installations and are not of general interest. Reforming processes are classified as
continuous, cyclic, or semiregenerative depending upon the frequency of catalyst
regeneration. The equipment for the continuous process is designed to permit the removal
and replacement of catalyst during normal operation. As a result, the catalyst can be
regenerated continuously and maintained at a high activity. As increased coke laydown and
thermodynamic equilibrium yields of reformate are both favored by low pressure operation,
the ability to maintain high catalyst activities and selectivities by continuous catalyst
regeneration is the major advantage of the continuous type of unit. This advantage has to be
evaluated with respect to the higher capital costs and possible lower operating costs due to
lower hydrogen recycle rates and pressures needed to keep coke laydown at an acceptable
level. The semiregenerative unit is at the other end of the spectrum and has the advantage of
minimum capital costs. Regeneration requires the unit to be taken off-stream. Depending
upon severity of operation, regeneration is required at intervals of 3 to 24 months. High
hydrogen recycle rates and operating pressures are utilized to minimize coke laydown and

91
consequent loss of catalyst activity. The cyclic process is a compromise between these
extremes and is characterized by having a swing reactor in addition to those on-stream in
which the catalyst can be regenerated without shutting the unit down. When the activity of
the catalyst in one of the on-stream reactors drops below the desired level, this reactor is
isolated from the system and replaced by the swing reactor. The catalyst in the replaced
reactor is then regenerated by admitting hot air into the reactor to burn the carbon off the
catalyst. After regeneration it is used to replace the next reactor needing regeneration. The
reforming process can be obtained as a continuous or semiregenerative operation and other
processes as either continuous, cyclic, or semiregenerative. The semiregenerative reforming
process is typical of fixed-bed reactor reforming operations and will be described here. The
semiregenerative process is shown in the simplified process flow diagram given in Figure
10.1. The pretreated feed and recycle hydrogen are heated to 925 to 975°F (498–524°C)
before entering the first reactor. In the first reactor, the major reaction is the dehydrogenation
of naphthenes to aromatics and, as this is strongly endothermic, a large drop in temperature
occurs. To maintain the reaction rate, the gases are reheated before being passed over the
catalyst in the second reactor. As the charge proceeds through the reactors, the reaction rates
decrease and the reactors become larger, and the reheat needed becomes less. Usually three
or four reactors are sufficient to provide the desired degree of reaction and heaters are needed
before each reactor to bring the mixture up to reaction temperature. In practice, either
separate heaters can be used or one heater can contain several separate coils. A typical gas
composition leaving each of the reactors in a four reactor system, with a HSR naphtha feed
of 180–380°F; severity, 99 RON; and pressure, 163 psi (1124 kPa) is as follows:

Feed 1 2 3
P 60 59 50 29
N 29 8 6 5
A 11 33 45 87
Total 100 100 96* 87*
Note: reactor outlet, mol/100 mol feed.; *summation not 100

92
The reaction mixture from the last reactor is cooled and the liquid products condensed. The
hydrogen-rich gases are separated from the liquid phase in a drum separator, and the liquid
from the separator is sent to a fractionator to be debutanized. The hydrogen-rich gas stream is
split into a hydrogen recycle stream and a net hydrogen by-product which is used in
hydrotreating or hydrocracking operations or as fuel. The reformer operating pressure and the
hydrogen/feed ratio are compromises among obtaining maximum yields, long operating
times between regeneration, and stable operation. It is usually necessary to operate at
pressures from 50 to 350 psig (345–2415 kPa) and at hydrogen charge ratios of 3–8 mol
H2/mol feed (2800–7600 scf/bbl). Liquid hourly space velocities in the area of 1 to 3 are in
general use. The original reforming process is classified as a semiregenerative type because
catalyst regeneration is infrequent and runs of 6 to 24 months between regeneration are
common. In the cyclic processes, regeneration is typically performed on a 24- or 48-hour
cycle, and a spare reactor is provided so that regeneration can be accomplished while the unit
is still on-stream. Because of these extra facilities, the cyclic processes are more expensive
but offer the advantages of low pressure operation and higher yields of reformate at the same
severity.

Alkylation

The addition of an alkyl group to any compound is an alkylation reaction but in petroleum
refining terminology the term alkylation is used for the reaction of low molecular weight
olefins (butylenes etc., C4=) with an isoparaffin (isobutane etc.) to form higher molecular
weight isoparaffins or alkylates. Although this reaction is simply the reverse of cracking, the
belief that paraffin hydrocarbons are chemically inert delayed its discovery until about 1935.
The need for high-octane aviation fuels during World War II acted as a stimulus to the
development of the alkylation process for production of isoparaffinic gasolines of high
octane number. Although alkylation can take place at high temperatures and pressures
without catalysts, the only processes of commercial importance involve low temperature
alkylation conducted in the presence of either sulfuric or hydrofluoric acid. The reactions
occurring in both processes are complex and the product has a rather wide boiling range. The
hydrocarbon and acid react in liquid phase. Isobutane and olefins are collected mainly from
FCC and delayed coker. Decreased demand for methyl tertiary butyl ether (MTBE) has

93
resulted in increased attention on alkylation process. By proper choice of operating
conditions, most of the product can be made to fall within the gasoline boiling range with
motor octane numbers from 88 to 94 and research octane numbers from 94 to 99.

Alkylation reactions

In alkylation processes using hydrofluoric or sulfuric acids as catalysts, only isoparaffins

with tertiary carbon atoms, such as isobutane or isopentane, react with the olefins. In
practice only isobutane is used because isopentane has a sufficiently high octane number and
low vapor pressure to allow it to be effectively blended directly into finished gasolines. The
process using sulfuric acid as a catalyst is much more sensitive to temperature than the
hydrofluoric acid process. With sulfuric acid it is necessary to carry out the reactions at 40 to
70°F (5 to 21°C) or lower, to minimize oxidation or reduction reactions which result in the
formation of tars and the evolution of SO2. When anhydrous hydrofluoric acid is the catalyst,
the temperature is usually limited to 100°F (38°C) or below. In both processes, the volume of
acid employed is about equal to that of the liquid hydrocarbon charge and sufficient pressure
is maintained on the system to keep the hydrocarbons and acid in the liquid state. High
isoparaffin/olefin ratios (4:1 to 15:1) are used to minimize polymerization and to increase
product octane. Efficient agitation to promote contact between the acid and hydrocarbon
phases is essential to obtain high product quality and yields. Contact times from 10 to 40
minutes are in general use. The yield, volatility, and octane number of the product is
regulated by adjusting the temperature, acid/hydrocarbon ratio, and isoparaffin/olefin ratio.
At the same operating conditions, the products from the hydrofluoric and sulfuric acid
alkylation process are quite similar. In practice, however, the plants are operated at different
conditions and the products are somewhat different. The effects of variables will be discussed
for each process later, but for both processes the more important variables are:

1. Reaction temperature

2. Acid strength

3. Isobutane concentration

4. Olefin space velocity

94
The principal reactions which occur in alkylation are the combinations of olefins with
isoparaffins as follows:

Isobutylene + isobutane → 2,2,4-trimethylpentane (isooctane)

Propylene + isobutane → 2,2,-dimethylpentane (isoheptane)

Another significant reaction in propylene alkylation is the combination of propylene with

isobutane to form propane plus isobutylene. The isobutylene then reacts with more isobutane
to form 2,2,4-trimethylpentane (isooctane). The first step involving the formation of propane
is referred to as a hydrogen transfer reaction.

Please see Fig 11.1 (G&H) for more details

Process variables

The most important process variables are reaction temperature, acid strength, isobutane
concentration, and olefin space velocity. Changes in these variables affect both product
quality and yield. Reaction temperature has a greater effect in sulfuric acid processes than in
those using hydrofluoric acid. Low temperatures mean higher quality and the effect of
changing sulfuric acid reactor temperature from 25 to 55°F (-4 to 13°C) is to decrease
product octane from one to three numbers depending upon the efficiency of mixing in the
reactor. In hydrofluoric acid alkylation, increasing the reactor temperature from 60 to 125°F
(16 to 52°C) degrades the alkylate quality about three octane numbers. In sulfuric acid
alkylation, low temperatures cause the acid viscosity to become so great that good mixing of
the reactants and subsequent separation of the emulsion is difficult. At temperatures above
70°F (21°C), polymerization of the olefins becomes significant and yields are decreased. For
these reasons the normal sulfuric acid reactor temperature is from 40 to 50°F (5 to 10°C)
with a maximum of 70°F (21°C) and a minimum of 30°F (-1°C). For hydrofluoric acid
alkylation, temperature is less significant and reactor temperatures are usually in the range of
70 to 100°F (21 to 38°C). Acid strength has varying effects on alkylate quality depending on
the effectiveness of reactor mixing and the water content of the acid. In sulfuric acid
alkylation, the best quality and highest yields are obtained with acid strengths of 93 to 95%
by weight of acid, 1 to 2% water, and the remainder hydrocarbon diluents. The water

95
concentration in the acid lowers its catalytic activity about 3 to 5 times as much as
hydrocarbon diluents, thus an 88% acid containing 5% water is a much less effective catalyst
than the same strength acid containing 2% water. The poorer the mixing in a reactor, the
higher the acid strength necessary to keep acid dilution down. Increasing acid strength from
89 to 93% by weight increases alkylate quality by one to two octane numbers. In
hydrofluoric acid alkylation the highest octane number alkylate is attained in the 86 to 90%
by weight acidity range. Commercial operations usually have acid concentrations between 83
and 92% hydrofluoric acid and contain less than 1% water. Isobutane concentration is
generally expressed in terms of isobutane/olefin ratio. High isobutane/olefin ratios increase
octane number and yield, and reduce side reactions and acid consumption. In industrial
practice the isobutane/olefin ratio on reactor charge varies from 5:1 to 15: 1. In reactors
employing internal circulation to augment the reactor feed ratio, internal ratios from 100:1 to
1000:1 are realized. Olefin space velocity is defined as the volume of olefin charged per
hour divided by the volume of acid in the reactor. Lowering the olefin space velocity
reduces the amount of high-boiling hydrocarbons produced, increases the product octane, and
lowers acid consumption. Olefin space velocity is one way of expressing reaction time;
another is by using contact time. Contact time is defined as the residence time of the fresh
feed and externally recycled isobutane in the reactor. Contact time for hydrofluoric acid
alkylation ranges from 5 to 25 minutes and for sulfuric acid alkylation from 5 to 40 minutes.
Although the relationship is only approximate, Mrstik, Smith, and Pinkerton developed a
correlating factor, F, which is useful in predicting trends in alkylate quality where operating
variables are changed.

where

IE = isobutane in reactor effluent, liquid volume %

(I/O)F = volumetric isobutane/olefin ratio in feed

(SV)o = olefin space velocity, v/hr/v

96
 The higher the value of F, the better the alkylate quality. Normal values of F range from 10 to
40.

Alkylation feedstocks

Olefins and isobutane are used as alkylation unit feedstocks. The chief sources of olefins are
catalytic cracking and coking operations. Butenes and propene are the most common olefins
used, but pentenes (amylenes) are included in some cases. Some refineries include pentenes
in alkylation unit feed to lower the FCC gasoline vapor pressure and reduce the bromine
number* in the final gasoline blend. Alkylation of pentenes is also considered as a way to
reduce the C5 olefin content of final gasoline blends and reduce its effects on ozone reduction
and visual pollution in the atmosphere. Olefins can be produced by dehydrogenation of
paraffins, and isobutane is cracked commercially to provide alkylation unit feed.
Hydrocrackers and catalytic crackers produce a great deal of the isobutane used in alkylation
but it is also obtained from catalytic reformers, crude distillation, and natural gas processing.
In some cases, normal butane is isomerized to produce additional isobutane for alkylation
unit feed.

Unit Isobutane (liquid vol%) Olefins (liquid vol%)

Hydrocracker 3 -
FCC 6 15
Coker 1 15
Hydrotreater 1 -
Reformer 2 -
Isomerization 1 -
Crude unit 0.5 -

*Bromine number is the amount of bromine in grams absorbed by 100 grams (3.5 oz) of a
sample. The number indicates the degree of unsaturation. The Bromine Number is useful as a
measure of aliphatic unsaturation in gasoline samples.

97
 Role of alkylation and polymerization units in the refinery

Refinery gases produced from different units are collected and sent to the gas plant. Olefins
and isobutanes are separated and used as a feed to the alkylation plant. Sources of these two
components from different refinery units are shown in the Table. Olefins are sent to the
polymerization unit as shown in Figure. Both alkylation and polymerization units produce
gasoline which can be sent to the gasoline pool.

Figure: Schematic diagram of alkylate production

Alkylation products

The product streams leaving an alkylation unit are:

1 LPG grade propane liquid

2 Normal butane liquid
3 C5+ alkylate
4 Tar

98
Range of operating variables in alkylation

HF H2SO4
Isobutane concentrations
vol% in reaction zone 30-80 40-80
External ratio to olefins 3-12 3-12
Internal ratio to olefins - 50-1000
Olefin concentration
Total HC contact time, min 8-20 20-30
Olefin space velocity, v/hr/v - 0.1-0.6
Reactor temperature
o
F 60-115 35-60
o
C 16-46 2-16
Reactor acid concentration, wt% 80-95 88-95
Acid in emulsion, vol% 25-80 40-60

Theoretical yields and isobutene requirements based on olefin reacting

Alkylate, vol% Isobutane, vol%

Ethylene 188 139
Propene 181 128
Butenes (mixed) 172 112
Pentenes (mixed) 165 96

Catalysts

Concentrated sulfuric and hydrofluoric acids are the only catalysts used commercially today for
the production of high octane alkylate gasoline but other catalysts are used to produce
ethylbenzene, cumene, and long-chain (C12 to C16) alkylated benzenes. As discussed in previous
section, the desirable reactions are the formation of C8 carbonium ions and the subsequent
formation of alkylate. The main undesirable reaction is polymerization of olefins. Only strong

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acids can catalyze the alkylation reaction but weaker acids can cause polymerization to take
place. Therefore, the acid strengths must be kept above 88% by weight H2SO4 or HF in order to
prevent excessive polymerization. Sulfuric acid containing free SO3 also causes undesired side
reactions and concentrations greater than 99.3% H2SO4 are not generally used. Isobutane is
soluble in the acid phase only to the extent of about 0.1% by weight in sulfuric acid and about
3% in hydrofluoric acid. Olefins are more soluble in the acid phase and a slight amount of
polymerization of the olefins is desirable as the polymerization products dissolve in the acid and
increase the solubility of isobutane in the acid phase. If the concentration of the acid becomes
less than 88%, some of the acid must be removed and replaced with stronger acid. In
hydrofluoric acid units, theacid removed is redistilled and the polymerization products removed
as a thick, dark ‘‘acid soluble oil’’ (ASO). The concentrated HF is recycled in the unit and the
net consumption is about 0.3 lb per barrel of alkylate produced. Unit inventory of hydrofluoric
acid is about 25–40 lb acid per BPD of feed. The sulfuric acid removed usually is regenerated in
a sulfuric acid plant which is generally not a part of the alkylation unit. The acid consumption
typically ranges from 13 to 30 lb per barrel of alkylate produced. Makeup acid is usually 98.5 to
99.3 wt% H2SO4.

*************************Questions from Students***************************

Q1. Sir you have told us that from different process we obtain different types of
gasoline having different octane number, like gasoline obtained from catalytic
hydrocracking and FCC have high octane number than when it is obtained from
thermal cracking. So is this high octane number gasoline is used for blending only?
Now second thing is that how can be make more profit either by blending good quality
gasoline with poor one or by directly selling high octane no gasoline? Sir in India is only
one type of gasoline is sold in the market or we also have different ranges of gasoline
like USA? If only one type then why?

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Q2. In comparison of TC and CC you have told that in TC coke is 0% while in all the
coking operation we use TC. Why?

Q3. In your journal on cracking of n-heptane you have mentioned that CS2(carbon
disulfide) is used to suppress coke formation on the wall of reactor so can it be used in
catalytic cracking process too?

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