Oil refinery Process

Goal of Refining
• Produce fuel for transportation, power generation and
heating

• Production of specialties such as solvent and lube oil

• Production of intermediate for chemical industries

2
Overview of Oil Refinery

3
 Different Process in Oil refinery
Physical Process Chemical Process
Thermal Catalytic
Desalting/ Dehydrati Vis breaking Hydrotreating
on
Distillation/ Delayed coking Catalytic reforming
Vacuum distillation
Propane deasphalting Flexicoking Catalytic cracking
Solvent extraction Hydrocracking
Solvent Dewaxing Catalytic Dewaxing
Blending Alkylation
Polymerization
Isomerization

4
 Desalting and Dehydration
• Crude oil contains inorganic salts, suspended solid and water dissolved
metals
• Common inorganic salts are chlorides of Ca, Mg and Na
• If the salt content of the crude is greater than 10 lb/1000 bbl (expressed as
NaCl), the crude requires desalting to minimize fouling and corrosion
caused by salt deposition on heat transfer surfaces and acids formed by
decomposition of chloride salts.(<1000 lb/bbl). How salt can cause
corrosion?
• Salt deposit and scaling lower the performance of heat exchanger
• Presence of sodium and arsenic and other metals can cause catalyst
poisoning

5
• Removal of suspended solids is important but why?
• Two methods: Chemical desalting and Electrical
desalting
• Chemical desalting; Hot water is mixed along with
surfactant and allowed to settle in gravity tank
• Electrical desalting is the application of high-voltage
electrostatic charges to concentrate suspended water
globules in the bottom of the settling tank
• Surfactant is added when concentration of suspended
solid is high
• Oil is heated from 150-350oF. But why? And how much
can the temperature be increased?
• Ammonia is used to reduce corrosion
• After desalting, crude oil is pumped to distillation units 6
 Atmospheric distillation
• Central separation process in oil refinery is distillation.
• How different product are separated using distillation?
• Atmospheric distillation and vacuum distillation
• Atmospheric distillation cannot give fine product
• More refined (cleaner) products like high octane gasoline,
high centane diesel and aromatics and alkenes and less low-
value fuel oil
• Can we heat crude oil to maximum to get high quality product
using atmospheric distillation?
• We cannot heat the crude oil beyond 630K ? Why..
• Do we need some other form of process ?
• Typical column is 4m in diameter and 20-30 m in height
• 15-30 number of trays
7
Simple atmospheric crude distillation. 8
9
 Vacuum distillation
• Vacuum distillation is used for fractionation of atmospheric column residue
• Typical pressure is < 0.1 bar.
• Vacuum distillation required substantial amount of heat. How to get that heat?
• Steam stripping is used for light oil fraction size to increase the recovery
• Kerosene is not steam striped. It is heated with bottom product form atmospheric
column. Why not steam stripping here
• Heavy fraction is sent to mild vaccum column
• Stream from mild vacuum column is further used in high-vaccum column
• Vacuum column has much larger diameter compared to atmospheric column .
Why?

10
 Propane deasphalting
• Heavy distillation products have higher coke formation tendency
• Coke formation tendency of larger aromatic is higher.
• Where large aromatic compound could be in atmospheric and vacuum distillation
• Coke formation tendency can be removed by extracting large aromatic compound using
propane
• Heavy feed, usually vacuum reside, is feed into deasphalting unit counter currently
against propane
• Alkanes are dissolved in propane
• Propane is recovered via depressurization and recycled back
• Residual oil is purged with steam to remove residual propane
• Asphalt reside is send to thermal process such as visbreaking, delayed cooking and
Flexicoking

11
 Titbit
• What is wet and dry natural gas?
• Sour and Sweet natural gas?
• Associated and non associated gas?
• Why there is a flare on oil exploration rig?
• Linear alkanes and Branched alkanes?
• Which one is the most in Gasoline and diesel?

12
 Thermal Process
• Vis breaking
• Delay Coking
• Flexicoking
• What is the purpose of thermal process?
• Heating a hydrocarbon to a sufficient high temprature,thermal cracking
happens
• Thermal process are flexible but they have advantage of producing large
amount of low value products

13
 visbreaking
• Visbreaking mean reduction in viscosity or breaking
• It’s a mild thermal cracking process used for viscosity
reduction of vacuum residue
• Its operate under temperature range of 710-760K for 1-8 min
• Usually less than 10% of gasoline and lighter products are
produced
• More then 80% is the cracked residue with viscosity lower
then vacuum residue

14
 Delayed coking
• A thermal cracking process with long residence time
• Much more serve then visbreaking as a result coke is formed
• Coke formed is similar to highly order coal used as fuel in power plant
• Original goal of delayed coking was to reduce the high molecular weight
substance and reduced the quantity of residue oil
• Coke produced I being used for electrode materials, largest non fuel use of
coal
• Heated feed is injected into the coke drum which usually remain for
operation for about 16-24 hrs.
• Coke from drum is removed using high pressure water jet

15
 Flexicoking
• Process developed by Exxon company
• Vacuum residue oil is contacted with hot fluidized coke
• Thermal cracking produced gas, liquids and more coke
• Coke is about 30% of cracking process
• Coke particles are transported into heater which is also a fluidized bed
• Primary purpose is the transfer heat from gasifier to reactor
• Part of coke is recalculated back to reactor while part of it is send to gasifier where
coke is gasified with steam and oxygen
• Gas produced is used to fluidized the reactor as well
• After steam generation gas is passed through cyclone. Why?
• Venturi scrubber is used to remove

16
 Tidbit
• What is API gravity?
• Light, medium and heavy crude oil?
• How crude oil prices are related with API
gravity?
• Syn gas and why its name like this?

17
Barrel of crude oil

18
 Catalytic Process
• Catalytic Process is pillar of oil processing
• Most important process in oil refining is fluid
catalytic cracking
(FCC),Hydrotreating ,hydrocracking, catalytic
reforming and alkylation

19
Octane no. of various hydrocarbon and main refinery
gasoline stream

20
 Octane no. of gasoline base stock

• Octane no. is the measure of gasoline quality

• RON: Reasearch Octane No

• MON: Motor Octane No.

21
 Diesel
• Cetane no. are higher for linear alkanes
• Naphthalene ,mostly aromatic compound , has lower centane
no.
• Its opposite for octane no.

22
 Catalytic cracking
• Originally thermal cracking was used bur now catalytic cracking is used
• Feed stock for catalytic cracking are vacuum gas oil
• Vacuum Gas Oil or VGO is part of the petroleum hydrocarbon heavy distillate
family. Vacuum Gas Oil also known as cat feed, which is feedstock for fluid
catalytic crackers used to make gasoline, gasoil and many other by-products
• Catalyst is solid acid catalyst
• C-C bond is rupture resulting into positively charged hydrocarbon ions
• Besides C-C cleavage, various side reaction such as;
– Isomerization, Protonation and deprotonation,alkylation, polymerization, cyclization and
condensation
• Catalytic cracking is a complex network of reaction
• Formation of coke is an essential feature of cracking process
– Advantages and disadvantages of coke formation
• Catalytic cracking was first large scale application of fluidized bed.so comes the
name FCC

23
Difference between thermal and catalytic cracking
for n-hexadecane

24
 Catalyst for catalytic Cracking
• Initial catalyst for catalyst cracking was AlCl3 solution
• Resulted into corrosion and waste, Later solid catalyst was developed
• Later, acid treated clay were used
• Amorphous silica minerals were used due to higher thermal stability and
higher activity due to high acidity and low tendency for coke formation.
• Discovery of zeolites was a breakthrough because it was more active and
stable
• Zeolites are mixed with silica-alumina
• Gasoline yield with current catalyst is 40-50wt %
• Product distribution was improved with time

25
 Catalytic process
• Originally fix bed and moving bed reactor were used for catalytic process. Now a days, fluid catalytic cracking (FCC)is used
• First FCC was made of 2 fluidized beds
• Now its replaced by modern FCC unit
• Disadvantage of fluidized bed reactor
– Difference in residence time of hydrocarbon resulting into below optimal production
– Causing an age distribution in catalyst
• Modern cracking unit has riser but old don't have it? why

26
 Modern FCC process

After 30 days, approximately 5% of catalyst is added

27
 Environment issue with FCC
• SOx and NOx generation during burning of coke
• NOx is reduced by elective catalytic reduction
process
• SOx can be reduced by either eliminating from
feed and post FCC capture
• Sulfur in feed can be reduced by Hydrotreating
• From flue gases, flue gas desulphurization is
done

28
• Difference between petrol and diesel engine?

29
 Feed stock for petrochemicals
• Lower alkenes C3-C4 are in high demand due to its use in
petrochemical industry

• ZSM-5 catalyst is mixed with conventional y-zeolite

• ZMS-5 has narrow pores and thus accessible to only linear

or slightly branched alkanes and alkenes and not to more
branched ones and aromatic compound

• Theoretically, in FCC branched alkanes are cracked. Is it

not contradictory with above statement
30
Processing of heavier feed stock in FCC units
• Processing of heavy residue in FCC units become possible due
to improvement in reactor and striper, improved feed injection
etc.
• Cracking of vacuum residue will generate much coke or
conventional feed stock in FCC units and what would be the
consequence on heat generation during catalyst regeneration?
• High metal content such as Ni and Vanadium can destroy the
catalyst.
• How to remove these metals?
• High content of sulfur in vacuum reside will increase the
amount of Sulfur in product and off gases

31
 Catalytic reforming
• Key process for production of gasoline component with high
octane number
• Production of aromatics for chemical industry
• Feed stocks are usually straight-run naphtha and gasoline range
compound like C6-C11
• Change in molecular weight is small but mainly internal
rearrangement of hydrocarbon

32
 THERMODYNAIC S OF CATALYTIC REFORMING

• Most of catalytic reforming reaction are moderately to highly endothermic

especially dehydrogenation of naphthenes that is a prominent reaction in
catalytic reforming
• Light naphtha is the fraction boiling between 30 °C and 90 °C and consists
of molecules with 5–6 carbon atoms.
• Heavy naphtha boils between 90 °C and 200 °C and consists of molecules
with 6–12 carbons.
• Dehydrogenation and aromatization are carried out using metal catalyst
• Isomerization and cracking proceed via carbonium ion pathway, so its
involved acidic catalyst
• Catalytic reforming is also called as platforming due to use of platinum
catalyst
• Feed is pretreated using Hydrotreating process to remove metals such as
ammonia, sulfur, organic nitrogen and hydrogen sulfide
33
 Process for catalytic reforming
• Performance of catalytic reformer is a compromise
between optimal octane no. and product yield,
Optimal catalyst stability and minimum coke
formation
• Two main types of reforming process
– Semi Regenerative Reformer(SRR)
– Fully rege
– Continuous Regenerative reformer (CRR)

34
 Semi Regenerative Reformer(SRR)
• Consist of 3-4 adiabatic fixed bed reactor in series with intermediate heating
• Earlier SRR units has operating pressure of 25-35 bar, but recent units operates at 15-20 bar as
a result of improved catalyst performance
• Kinetically faster reaction occurred in first reactor like dehydrogenation of naphthenes to
aromatics
• To keep high reaction rate, off gases are reheated before being send to second reactor and so
on.
• Catalyst is regenerated over the period of 0.5-1.5 year
• Why temperature on reactor inlet is increasing compared to previous one?
• Why temperature difference is getting smaller over the reactors?
• What do you think about size of reactor?

35
 Fully regenerative reforming
• How to further reduce the operating pressure and increase the
yield and octane no?
• Catalyst improvement and what else? Operational innovation?
• Presence of a swing reactor in fully regenerative reforming
• On reaction was offloaded, catalyst rengenerated and then put
back into operation.
• No shut down in reforming unit
• But how pressure is reduced?

36
 Continuous regenerative reforming
• Use of moving bed reactor that help for continuous catalyst regeneration reducing operating
pressure to 3-4 bar.
• Flow of catalyst is crucial in this system. In practice spherical particles are used
• Catalytic reforming is mainly used for improving octane no.
• It can b used for aromatic production, but operating condition will be much severe .

37
 Alkylation
• Alkylation is the reaction of isobutane with alkanes to form higher branched
alkanes
• Purpose is to produced high octane gasoline from low molecular weight alkenes
( propene,butene and pentenes) and isobutane
• Advantage is the elimination of gas phase molecules and only liquid fraction with
high octane no. 87 up to 98
• Sulfuric acid alkylation unit (SAAU) or Hydrofluoric acid alkylation unit (HASU)
• Acid catalyst are also used

38
 Hydrotreating
• Limited to hydrogenation and hydrogenolysis reaction (S,N,O) for
removal of heteroatoms
• Hydrogenation of aromatic compound and double bond
• Difference b/w hydrogenation and hydrogenolysis
• Hydrotreating is sometimes called as hydro purification
• Major objective of Hydrotreating is to protect catalyst from hetero
compounds
• Improvement of gasoline like odor, color and stability
• Hydrotreating is also classified as
– Hydrodesulphurization (HDS), hydrodenitrogenation (HDN),
Hydrodeoxygenation (HDO), hydrodemetallization (HDM)
• Hydrotreating is an essential step for catalytic reforming of naphtha
• Sulfur content to reformer should not be more than 1ppm

39
40
Operating conditions of Hydrotreating

• Hydrotreating is getting importance for diesel

• Production of Ultra low sulfur diesel (ULSD)
• Maximum sulfur level is 10-15ppm
41
42
 Hydrocracking
• Heavy gas oil and vacuum gas oil are converted into lighter
products like naphtha, kerosene and diesel fuel
• Heavy oil market is declining, so we have to make its better
use
• Hydrocracking convert large molecules to lighter molecules
• Hydrocracking is combination of hydrogeneation and catalytic
cracking
• Hydrogenation is exothermic while catalytic cracking is
endothermic
• What is difference b/w hydrocracking and FCC
• What is difference b/w Hydrotreating and hydrocracking

Easily cracked alkane rich atmospheric and vacuum gas oil

Hydrocracking mainly used aromatic feed
43
• Hydrogenation, dehydrogenation and heteroatom
removal required hydrogenation catalyst
cracking required acidic catalyst
44