Refinery Processes

SANA AHMAD MINHAS

Desalter
Salts present in the crude oil are predominantly in chloride form:
(NaCl 70-80 wt % .MgCl2 20-10 wt % ,CaCl2 10 wt % )
Problems with the salt content
1. It will cause deposits
2. corrosion
3. catalyst poisoning in catalytic processes.
The efficiency of a two stage desalter is better.
The desalted srude oil salt content shall be very low (<1ppm)
 Distillation and fractionation
•Distillation: The essence of distillation is to heat a given liquid
until it became vapour and then condensing the vapours the
material is converted to liquid again. Since there is no chemical
alteration in the material structure, only phase transition, the
distillation is a physical process.
• Batch distillation and continuous distillation
• Fractionation: Fractionation also called as rectification provides
sharper separation. The essence is that between the contacted
materials (one in liquid, one in vapour phase), which are not in
equilibrium, there is a two way material and heat transfer.
Main equipment types of a distillation column
• Shell
•Column internals
•Reboiler
•Condenser
•Reflux drum

•Rectification and
stripping section
•Evaporation section
Operation of a column
Column internals (trays)
Packing

to support the packing layer

to support the packing layer

Atmospheric and vacuum distillation
• Aim: crude oil separation to main fractions
• Feedstock: desalted crude oil
• Process parameters: Atmospheric: 1 bar, 320°C, Vacuum:
40mbar, 410 °C
• Heat balance: neutral
• Products: 10 products
Amine Wash
Aim: Removal of sulphur impurities
Solvent: Amines
Heat balance: neutral
Product: Desulphurised fuel gas
LPG desulphurisation
•Aim: Impurities removal from LPG: H2O, H2S, CH3SH, COS, CO2
•Feedstock: LPG from distillation origin
•Process parameters:
Adsorption: 20 bar, 25°C
Regeneration: 2 bar, 300°C
•Heat balance: neutral
•Adsorbent: 5A or 13X zeolit molecular sieve
•Products: desulphurised LPG, sour fuel gas
Hydrotreating
•Aim: desulphurisation of gasoline-vacuum distillate fractions
•Feedstock: LN, HN, petroleum, gasoil, vacuum distillate,
hydrogen
•Process parameters: 30-80 bar, 350-420 °C
•Heat balance: exothermic
•Catalyst: NiMo, CoMo, NiW
•Products: desulphurised LN, HN, petroleum, gasoil, vacuum
distillate
Isomerization
• Aim: nC5-6 transformation to iC5-6
• Feedstock: light naphtha
• Process parameters: 150-250°C, 20-30 bar
• Heat balance: exothermic
• Catalyst: Pt/Al2O3
• Products: iC5, iC6
Blending
Blending is the physical mixture of a number of different liquid
hydrocarbons to produce a finished product with certain desired
characteristics.
Products can be blended in-line through a manifold systems, or
batch blended in tanks and vessels.
Additives including octane enhancers, anti-oxidants, anti-knock
agents, gum and rust inhibitors, detergents, etc. are added during
and/or after blending to provide specific properties not inherent in
hydrocarbons.
CCR Reforming
• Aim: Production of high octane gasoline blending component
•Octane number and cetane number
•Feedstock: heavy naphtha
•Process parameters: 500°C, 8 bar
•Heat balance: endothermic
•Catalyst: Pt-Re/Al2O3
•Products: reformate, hydrogen, benzene rich fraction
Aromatic Extraction
Aim: production of individual aromatics (BTX)
•Feedstock: reformate, benzene rich fraction, pyrolisis C6-7 fraction
•Process parameters: 8 bar, 130°C
•Heat balance: neutral
•Solvent: selective to aromatic molecules
•Products: benzene, toluene, xylenes
Catalytic Processes
Catalytic conversion processes may be classified as
Change the carbon number (Catalytic cracking and hydrocracking)
Change the carbon/hydrogen ratio (Hydrogenation and dehydrogenation)
Change the shape of molecule (Isomerization)
Catalytic Cracking
Aim: to increase gasoline and lighter components production.
Process : Cracking is catalyzed which promote the rupture of C-C bonds.
The formation of coke and deactivation the catalyst.
Removal of coke
Fluid Catalytic Cracking
• Aim: Valuable white products production via catalytic cracking
•Feedstock: (desulphurised) vacuum distillate
•Process parameters: 540°C, 2-3 bar
•Heat balance: endothermic
•Catalyst: zeolite in Al2O3 matrix
•Products: gasoline (50%), olefinic LPG, gasoil, residue (MCB)
Process: Oil is cracked in the presence of a finely divided catalyst,
which is maintained in an aerated or fluidized state by the oil vapours.
Catalyst section and a fractionating section
(operate together as an integrated
processing unit).
The catalyst section contains the reactor and
regenerator, which, with the standpipe and
riser, form the catalyst circulation unit. The
fluid catalyst is continuously circulated
between the reactor and the regenerator
using air, oil vapors, and steam as the
conveying media.
Spent catalyst is regenerated to get rid of
coke that collects on the catalyst during the
process.
Spent catalyst flows through the catalyst
stripper to the regenerator, where most of
the coke deposits burn off at the bottom
where preheated air and spent catalyst are
mixed.
Fresh catalyst is added and worn-out catalyst
removed to optimize the cracking process.
Hydrocracking
For higher molecular weight fractions such as atmospheric residues and vacuum gas oils ,
cracking in the presence of hydrogen is required to get light products. In this case a dual function
catalyst is used.
Hydrocracking is a two-stage process combining catalytic cracking and hydrogenation, wherein
heavier feedstock is cracked in the presence of hydrogen to produce more desirable products.
The process employs high pressure, high temperature, a catalyst, and hydrogen
Hydrocraking
Aim: valuable white products production via hydrocracking
•Feedstock: (desulphurised) vacuum distillate, hydrogen
•Process parameters: 100-180 bar, 350-420 °C
•Heat balance: exothermic
•Catalyst: NiW, NiMo ,zeolite
•Products: gasoil, gasoline, LPG
Preheated feedstock is mixed with recycled hydrogen and sent to the first-stage reactor, where catalysts convert sulfur
and nitrogen compounds to H2S and NH3.
After the hydrocarbon leaves the
first stage, it is cooled and
liquefied and run through a
separator. The hydrogen is
recycled to the feedstock.
The liquid is charged to a
fractionator.

The fractionator bottoms are

again mixed with a hydrogen
stream and charged to the
second stage. Since this material
has already been subjected to
some hydrogenation, cracking,
and reforming in the first stage,
the operations of the second
stage are more severe (higher
temperatures and pressures).
Again, the second stage product is separated from the hydrogen and charged to the fractionator.
LPG Merox and Fractionation
It is a catalytic chemical process used in oil refineries and natural gas processing plants to
remove mercaptans from LPG.
It includes the removal of hydrogen sulfide, carbonyl sulfide and alkaline mercaptans
Aim: production of LPG with a minimum content of total sulfur (less than 10 ppm).
Etherification
Etherification is the well-known dehydration of an alcohol to form ethers. This is commonly
practiced with both aliphatic and aromatic alcohols (phenols). In the case of a simple aliphatic
alcohol acid catalysis is sufficient to produce the ether.
Aim: production of high octane (bio) oxygenate
•Feedstock: olefinic C4 fraction (isobutylene), (m)ethanol
•Process parameters: 50°C, 20 bar
•Heat balance: highly exothermic
•Catalyst: highly acidic ion exchange resin
•Products: MTBE/ETBE, C4 raffinate
Alkylation
Alkylation combines low-molecular-weight olefins (primarily a mixture of propylene and
butylene) with isobutane in the presence of a catalyst, either sulfuric acid or hydrofluoric acid
(HF) to produce a gasoline range alkylate.
The product is called alkylate and is composed of a mixture of high-octane, branched-chain
paraffinic hydrocarbons.
Two types of alkylation
• Sulphuric acid alkylation
•Hyfroflouric acid alkylation
HF Alkylation
Aim: production of aromatic free gasoline blending component
•Feedstock: olefinic C4 fraction, olefinic C3 fraction, i-butane
•Process parameters: 30°C, 2-5 bar
•Heat balance: exothermic
•Catalyst: HF acid
•Products: alkylate, n-butane, propane
Thermal Cracking
Thermal cracking is an extraction process in which hydrocarbons such as crude oil are heated to
a high temperature to break the molecular bonds. Thermal cracking is a refining process in
which heat and pressure are used to break down, rearrange, or combine hydrocarbon molecules

Thermal processes used in refineries are:

Visbreaking
Steam Cracking
Coking
Visbreaking
Viscosity breaking aims to thermally crack long-chain feed molecules to shorter ones, thus
reducing the viscosity and the pour point of the product.
In this process, the feed is usually a high viscosity, high pour point fuel oil that cannot be used or
transported, especially in cold climates
Two types
Coil Visbreaking
Soak Visbreaking
Coking Processes
Coking is a severe method of thermal cracking used to upgrade heavy residuals into lighter
products or distillates.
Coking produces straight-run gasoline and various middle-distillate fractions used as catalytic
cracking feedstock.
The process completely reduces hydrogen so that the residue is a form of carbon called "coke."
The two most common processes are delayed coking and continuous (fluid and flexi)
coking.
Delayed Coking
This process is based on the thermal cracking of vacuum residue forming coke and lighter
products such as gases, gasoline and gas oils.
The vacuum residue is heated in a furnace and flashed into large drums where coke is deposited
on the walls of these drums, and the rest of the products are separated by distillation.
Long residence time needed to allow the cracking reactions to proceed to completion.
The feed is first preheated in furnace where the desired coking temperature is achieved and fed
to the coking drums normally installed in pairs where the cracking reaction takes place and the
coke is deposited in the bottom of the reactor. The coke drums overhead vapors flows to the
fractionating column where they are separated into overhead streams containing wet gas LPG
and naphtha and two side gas oil streams.
Delayed coking
Delayed Coking
Aim: valuable white products production via thermal cracking
•Feedstock: vacuum residue
•Process parameters: 3-5 bar, 500 °C
•Products: olefinic LPG, gasoline, gasoil, distillate, coke
Fluid and Flexi Coking
Fluid coking is non- catalytic fluid bed process where residue is coked by
spraying into a fluidized bed. Higher temperature with shorter contact time
than delayed coking results in increased light and medium hydrocarbons with
less coke generation. Shorter residence time can yield higher quantities of
liquid less coke.

It is continuous process involves thermal cracking in a bed fluidized coke and

gasification of the coke produced at 870 oC. This process contains an additional
step of gasification. The gases leaving the gasifier are low calorific value fuel
gases and are burned in the furnace or power plants. It can be applied to wide
variety of feed stocks.
There is much more to learn !