Petroleum Refining
Crude oil is recovered from the reservoirs by three processes followed sequentially
Primary: oil along with gas flows out of drilled wells because of inherent pressure inside the
reservoir. Over time this pressure falls and eventually production ceases by this process.
Secondary: wells are drilled in strategic locations. Water is pumped through some of them
called injector wells and oil is produced from some of them called producer wells. During
the initial stages only oil is recovered from producer wells. Slowly and gradually, injected
water finds its way to producer well. Eventually the wells produce only water.
Tertiary: when secondary process does not produce oil any more, tertiary processes are
adopted. Injection of CO2, steam, surfactants lowers surface tension between oil and water
phases, dissolve more oil, and thus produce oil.
I believe today many reservoirs use secondary process and few use tertiary process.
The oil produced has tiny brine droplets, which should be removed to protect equipment from
corrosion due to salts. Water washing followed by coalescence of fine droplets by
application of electricity removes brine below acceptable limits.
Now the crude oil is ready for fractionation and further processing.
The approximate elemental composition of crude oil is as follows:
C: 83-87 wt%, H: 10-14 wt%, O: 0.05-1.5 wt%, N: 0.2-3 wt%, S: 0.05-6 wt% and
metals < 0.1 wt%.
Some of the organic compounds present in crude oil are:
Alkanes normal CH3-CH2-R
CH3
Branched CH3-CH2-CH-R
Cyclo alkanes:
Aromatics:
Phenanthrene
and others in this class – polycyclic compounds.
Sulphur compounds in crude oil
H2S, R-SH, R-S-R,R-S-, S-R,
Would you expect the crude oil to contain alkenes and alkynes?
Flow sheet in the next page shows different processes that happen in a refinery and the
products of the refinery.
A crude oil could have following true boiling point (TBP) – vol % data
Volume % TBP (oC)
05 40
10 85
30 215
50 340
70 495
How do you interpret this data?
In addition, the following products and their end boiling points are known
End point (oC)
1 Off gas 10
2 Light St. run naphtha 70
3 Naphtha 180
4 Kerosene 240
5 Light diesel 290
6 Heavy diesel 340
7 Atm. Gas oil 370
8 Residue >550
When crude oil is distilled in a tower, side products can be drawn. Their characteristics are
determined by their boiling points. For example if a stream is drawn between 180-240 oC, it
will have kerosene in it. Note it could contain some amount of compounds, which boil <
180 and some > 240 oC.
Crude oil distillation
Petroleum refining begins with a crude oil distillation unit. This unit (or column) operates at
pressures slightly above atmospheric pressure. This column typically is 4m in diameter and
20-30 m in height with 15-30 trays.
Gases
Crude oil
Water
Reflux Naphtha
Slops
Vacuum
Circulating reflux
Circulating reflux Steam Intermediate
Vacuum gas oil
Furnace
Vacuum
residue
Heavy gas oil
Furnace
Kerosene
Light gas oil
Steam Mild vacuum Driers
column
Main Strippers
Fractionator
A major limitation of atmospheric distillation is that the crude cannot be heated to high
temperatures because the hydrocarbons decompose at T > 630 K to produce carbonaceous
material, also called coke. This production happens by thermal cracking or pyrolysis. Coke
deposits on walls of vessels, leads to loss in yield of useful products from crude oil.
Flow sheet in previous page shows a typical modern two column distillation. One operates at
atmospheric pressure and the other under vacuum (< 0.1 bar). The crude oil passes through
several heat exchangers before it is heated in furnace to ~620 K to feed the atmospheric
distillation unit.
Can you guess why crude oil is not heated with vapor stream leaving the top of crude
distillation unit?
What’s the implication of circulating reflux on distillation performance?
Why is steam added at the bottom of atmospheric distillation unit?
Side streams are drawn at various locations, depending on requirements; these are also steam
stripped to produce liquids that are taken for final product blending. The vapors from the
strippers are input to the columns few trays above the side draws.
The residue from the atmospheric crude distillation unit is heated further and distilled in
vacuum distillation unit. This unit recovers higher boiling compounds from the crude oil.
This unit is much bigger than atmospheric unit because it has to handle large volumetric
flows at reduced pressures.
Packed columns offer larger gas-liquid contact than tray columns, which one is more
preferable for vacuum distillation column, a structured packing or random packing? Why?
Propane deasphalting process
The vacuum residue (bottom stream of vacuum distillation unit) still contains significant
quantities of high molecular weight hydrocarbons, which can eventually be converted to
useful products. The ‘lighter’ the hydrocarbon the better is the quality of deasphalted oil.
How can these hydrocarbons be removed?
A. Heating the residue
B. Distilling under vacuum
C. Extracting with a solvent such as propane or butane. (Why propane/butane?)
What is the minimum pressure at deasphalting temperatures of 310-330 K?
Vacuum residue is fed at the top of extraction tower. Propane flows into the tower in
counter-current direction to the residue. When the two liquids mix, alkanes in the residue
dissolve in the propane and asphaltenic materials do not dissolve. Deasphalting process is a
liquid-liquid extraction. The extracts separated from propane are called deasphalted oil.
What needs to be done downstream of the extraction tower?
Study the recovery of propane and separation of deasphalted oil in the flow sheet shown in
next page.
Schematic of propane deasphlating process
Condensers
Propane recycle
Steam
Condenser
Steam
Cond.
Water
Propane
Vacuum
evaporator
residue
310-330 K Deasphalting Steam
35-40 bar tower
Propane
Storage Deasphalted
oil
Make-up
propane Steam
Liquid propane
Flash Asphalt
drum Strippers
What’s the function of heat exchanger?
Strippers:
Flash drum:
How about replacing propane with butane? Butane is available in large quantities in
refineries. Comment on yield and quality of de-asphalted oil extracted with butane.
The deasphalted oil is sent to fluidized catalytic cracking (FCC) unit.
The asphalt is subjected to one of the three thermal processes: visbreaking, delayed coking
and flexi coking.
Visbreaking: the residue (asphalt) is heated to 710-760 K in a furnace and passed through a
reactor where enough residence time is provided to crack the residue into gasoline, gas oil.
These are separated in distillation columns. The cracked residue is a fuel oil, which is used
by several chemical industries to make steam. Gasoline goes to blending pool; heavy gas oil
is further processed to convert it into gasoline and other products.
Schematic of visbreaking process
Gasoline
R
e Heavy
Vacuum a gas oil
residue c
730 K t
Fract
20 bar o Vacuum
Furnace iona
r fractionator
tor
Flash
Cracked
residue
Light gas oil
Delayed coking: the goal of this process is to convert the vacuum or asphalt into gases, liquid
and coke.
Study the flow sheet in the next page. A coke drum (4 m diameter, 25 m height) fills in about
16-24 h during which another drum is made ready. The drums fill with coke. The mixture of
gas and liquid emerging from the top is separated in distillation columns.
Explain Visbreaking:
Delayed coking:
Gas
Na
Gas oil
stripper
Gas oil
Coke Furnace
Vacuum
residue
Schematic of delayed coking process
