ChE 460

Oil and Natural Gas Upgrading

Formal Report
Crude Distillation
Leslie Squire
Sakeena Akhtar
Jeffrey Toppings
Fahd Hussain
Hee-Tae Kwag
Date Due: January 29, 2015

Department of Chemical and Biological Engineering

University of Saskatchewan

ABSTRACT
The refining of oil is of economic importance around the world, and the distillation of crude oil
is the first major step in this important process. An analysis of the book Petroleum Refining:
Technology and Economics by Gary, Handwerk, and Kaiser gives us the four major steps in the
crude distillation process. Crude oil goes through a process that washes corrosive salts out of the
crude. The desalted oil then travels through a series of heat exchangers and a furnace, which
increase the temperature of the oil. Hot oil then enters a distillation column at atmospheric
pressure, which is able to separate the crude oil into streams, each containing compounds with
similar boiling points. Lastly, the streams that boil at the highest temperatures enter a second
distillation column, which is under vacuum conditions. The lack of pressure allows the highboiling components to be separated into more specific streams. The input fluid into this process
is crude oil, and the products are a variety of gases, waxes, and oils, which then proceed to
further processing so that they can become useful end products.

TABLE OF CONTENTS

Introduction .................................................................................................................................................. 1
Process Overview ......................................................................................................................................... 2
Desalting ................................................................................................................................................... 2
Heat Exchanger Network .......................................................................................................................... 6
Separation Scheme ................................................................................................................................... 7
Atmospheric Distillation ....................................................................................................................... 7
Vacuum Distillation ............................................................................................................................... 8
Products ...................................................................................................................................................... 10
Safety Concerns .......................................................................................................................................... 10
Environmental Concerns ............................................................................................................................ 11
Carbon Footprint ..................................................................................................................................... 12
Conclusion .................................................................................................................................................. 13
References .................................................................................................................................................. 14
Appendix A: Desalting Process .................................................................................................................. 15
Appendix B: Desalting Process Conditions ................................................................................................ 16
Appendix C: Atmospheric and Vacuum Distillation .................................................................................. 17
Appendix D: HYSYS Simulation .................................................................................................................. 18

1
INTRODUCTION
The purpose of this report is to survey the crude oil distillation process of an oil refinery. The
information presented in this report is important because the oil and gas industry has a significant
impact on Canadas economy.
This report will go into detail on the crude distillation process, which consists of four main parts:
desalting, heat exchange, atmospheric distillation, and vacuum distillation. Also, the products of
the distillation towers will be discussed in relation to where they go for further processing in the
oil refinery. Safety and environmental concerns will also be discussed in detail relating to the
crude oil distillation process.
The textbook written by Gary, Handwerk, and Kaiser, Petroleum Refining: Technology and
Economics, was the main resource used to provide an overview of the crude distillation process.
Also, several journal articles and websites were consulted to provide information on the newer
technologies available as well as the environmental and safety concerns that go along with the
crude distillation process.

2
PROCESS OVERVIEW
The crude oil distillation process was simulated in HYSYS and is attached in Appendix D.
DESALTING
Crude oil, as it gets extracted and sent to processing, contains numerous contaminants including
the following:
1. Salts, usually NaCl, MgCl2, SO42-, CaCl, are in the forms of dissolved or suspended salt
crystals in water emulsified with crude oil (Gary et al 2007).
2. Suspended solids such as sand, clay, and soil particles.
3. Metallic compounds such as vanadium, nickel, cobalt, and iron compounds from
pipelines, tanks and tankers.
Crude oil usually contains about 2 to 15 wt% salts but often the crude oil can have a range of
approximately 0 to 30 wt%. All of these contaminants can disrupt crude oil processing and cause
millions of dollars in damage. Salt can cake out the inside of the equipment causing plugging as
well as poor heat transfer rate in exchangers. The major concern for the salts in the crude is the
decomposition of the chlorides can cause equipment corrosion. Metallic compounds in the crude
oil can also cause catalyst poisoning which is very expensive. Crude oil containing more than 10
pounds of salt (NaCl) per thousand barrels is usually treated with one desalter and crude oil
containing more than 20 pounds of salt (NaCl) per thousand barrels must go through two
desalters to lower the salt content. The final result of the desalter should have less than 1 PTB
where 1 PTB is as follows:
PTB = ((1000) (% Sediment & water)/ (100 - % S&W)) *(350SG_brine) (ppmw/10^6)
(Manning 1995).
Historically, crude oil used to have a very small salt content but the amounts of contaminants are
getting higher which is driving up the reason to desalt the crude oil. Even though the need for

3
desalting is dependent on the salt content, now many companies desalt all crude oils. Reduced
equipment fouling and corrosion and longer catalyst life provide justification for this additional
treatment (Gary, Handwerk and Kaiser 2007, 71).
There are several ways to measure the salt content of crude oils including the following:
1. HACH titration
HACH titration uses a digital titration apparatus sold by HACH Company which can
measure the molarity of salts and also other reagents.
2. Potentiometric titration
Potentiometric titration is done by measuring the potential between two electrodes as a
function of volume. It is used to measure the pH as a function of the volume added. The
pH will be higher when more salt is present.
3. Mohr titration
Mohr titration calculates the chloride ion concentration of a solution by titrating with
silver nitrate. As more silver nitrate is added, silver chloride precipitation is formed. Like
other titrations, it measures the pH of the solution against the volume of titrant.
4. Conductivity
Salt water is very conductive due to ions forming when salts are dissolved in water.
When the salts dissolve, electrolytes are formed which makes the crude oils conductivity
higher. Although the conductivity method is the one most widely used for process
control, it is probably the least accurate of these methods. Whenever used, it should be
standardized for each type of crude oil processed (Gary, Handwerk, and Kaiser 2007,
79).

4
The principal way of desalting is to wash the inflow of crude with water. Figure 1 in Appendix
A shows the desalting process. The basic process for desalting is as follows:
+ + () +
Desalting is carried out by adding 3 to 10 vol% of water to the crude oil at temperature ranging
from 200 to 300 F usually reached by heat exchangers. Keeping the pH of the solution between
6 and 8 will allow optimal dehydration. The pH can be adjusted by adding additional water,
caustic soda or acid. Ammonia can be added to prevent the corrosion of equipment before
desalting. The density, pH, viscosity, and crude compositions some factors that affect operating
conditions; for example, heavier oil needs more water and needs to be processed at a higher
temperature. Operation conditions for different crude oil densities are listed in Table 1 of
Appendix B.
The salt gets washed out by water by mixing the water and the crude vigorously in a
mixer. After the water has taken the salt out of the crude oil, the oil needs to be separated from
the water before being sent to the distillation columns. When it comes to demulsification, the oil
producers want fast separation, low amount of residual water in the crude oil, and low amount of
oil in the disposed water. The demulsification process follows two steps, with the first step being
flocculation. The flocculation occurs when the droplets clump together, forming aggregates
(PetroWiki). After flocculation, coalescence follows. The coalescence step is when water
droplets fuse or coalesce tougher to form a larger drop (PetroWiki).
Demulsification can be completed in a variety of ways, usually being done by chemical
addition, electrostatic treating, or settling time. Chemicals used to demulsify are made up of
solvents, such as benzene, toluene, and surface-active ingredients, which displace the polar
materials around the water. These chemicals can also change physical properties. A desalter can

5
also act as a surge drum, giving time for the suspended particles to settle and be taken out of the
crude oil.
Electrostatic treating is done by applying a high-potential electrical field across the
settling vessel to coalesce the droplets of salty water (Gary, Handwerk, and Kaiser 2007, 76).
Electrostatic treating utilizes both AC and/or DC producing anywhere from 12000V to 35000V.
Electrostatic treating is quite effective since for single-stage desalting units, 90 95%
efficiencies are obtained and two-stage processes achieve 99% or better efficiency (Gary,
Handwerk, and Kaiser 2007, 76). Figure 2 in Appendix B shows the single stage and two stage
electrostatic desalting processes. Electrostatic treatment is effective due to variety of reasons as
follows:
1. When the electrical current is applied, the water droplets become polarized and the
poles of the droplets are brought adjacent to each other [which promotes] coalesce
(PetroWiki).
2. Due to the electrical charge, the water droplets become attracted to the electrodes
which also help with coalesce.
3. When alternative current is applied, the film of emulsifier around the water droplets
weakens and breaks, making it easier for the water droplets to mix.
The best results are achieved when DC and AC fields are used; however, it also increases the
operational complexity which will increase the operating cost.
While chemical and electrostatic combination is the technology most often used for desalting,
other ways to desalt are constantly being developed and one of these new technologies is to use a
hydro cyclone structure. This relatively new process uses the different densities of the crude and
water to separate the crude and wastewater. The crude oil is mixed with 5-8 vol% water and goes

6
through a spiral hydro cyclone structure with the wastewater flowing out the bottom of the
structure and desalted crude flowing out the top. The process is reminiscent of a distillation
tower with one inlet and multiple outlet products. Hydrocyclones used for desalting can be quite
efficient with the efficiency ranging from 86% to 99% (Bai et al 2007).
HEAT EXCHANGER NETWORK
After desalting, crude oil is pumped through a series of heat exchangers to raise the temperature
of the feed to 550F (288C) (Gary, Handwerk, and Kaiser 2007, 80). The heat for these heat
exchangers is provided by product and reflux streams which are subsequently cooled. After
being pumped through the heat exchangers, the stream is heated further in a furnace/fired heater
to 750F (399C) and then flows to the distillation units (Gary, Handwerk, and Kaiser 2007, 80).
The furnace discharge temperature can range from 650-750F (343-399C) (Gary, Handwerk,
and Kaiser 2007, 80).
Often a flash drum is placed between the heat exchangers and the furnace so that the lower
boiling fractions that get vaporized in the heat exchangers can be separated in the flash drum and
flow directly to the flash zone of the atmospheric distillation column. Liquid will still get
pumped through the furnace to the flash zone in the atmospheric distillation column. According
to Gary, Handwerk, and Kaiser, a flash drum being placed between the heat exchangers and the
furnace will result in a smaller furnace and therefore lower the cost of running and purchasing
the furnace (Gary, Handwerk, and Kaiser 2007, 86).
Also, a furnace is often placed between the atmospheric distillation tower and the vacuum
distillation tower which heats the topped crude oil steam before flowing into the vacuum
distillation column. This furnace will heat the topped crude oil steam to 730-850F (Gary,
Handwerk, and Kaiser 2007, 87).

7
SEPARATION SCHEME
Two steps are used in crude oil separation. First, distillation at atmospheric pressure is
completed and then the high-boiling bottoms are fed to a high vacuum distillation unit. By
separating crude oil in two steps, high efficiencies and lower costs are achieved. Figure 3 and
Figure 4 in Appendix C show the atmospheric and vacuum distillation process, respectively.
ATMOSPHERIC DISTILLATION
Atmospheric distillation occurs after the crude oil has passed through the desalting unit and has
been heated up by heat exchangers and a furnace. According to Gary, Handwerk, and Kaiser, the
furnace discharge temperature is high enough to vaporize all products above the flash zone and
10-20% of the bottoms. Vaporizing 10-20% of the bottoms allows for internal reflux which
causes fractionation on the trays just above the flash zone (Gary, Handwerk, and Kaiser 2007,
80). The atmospheric distillation columns usually have 30-50 trays and 5-8 trays are needed for
each side stream product (Gary, Handwerk, and Kaiser 2007, 82).
Reflux is the technique of removing vapors from the top of the tower, condensing them and
returning them back to the column. Reflux is used to get better fractionation and to help control
column temperature. Pump-around reflux takes off a liquid stream, cools the stream and returns
it 1-3 trays above the original tray. Pump around reflux occurs at lower points of the tower and
allows for less required reflux at the top of the tower which increases the energy efficiency of the
distillation operation and also results in a smaller column size. Since temperature is higher near
the bottom of the column, pump-around reflux allows for greater recovery of heat energy
through heat exchangers.
Along with reflux condensers, distillation columns usually contain a reboiler at the bottom which
vaporizes some of the liquid stream and returns the vapors back into the column. According to

8
Gary, Handwerk, and Kaiser, crude distillation units usually use steam injection instead of
reboilers. Several trays are added below the flash point and steam is injected from the bottom.
The steam strips remaining gas oil from the liquid and produces high-flash-point bottoms. Steam
injection also reduces the partial pressures of the feed and lowers the vaporization temperature.
Further purification of liquid side streams is done in separate stripping towers which contain four
to ten trays with steam injection at the bottom. The vapor phase is sent back to the vapor zone of
the atmospheric distillation column (Gary, Handwerk, and Kaiser 2007, 82).
The overhead condenser condenses the light gasoline components which contain propane, butane
and higher-boiling components. Some of the condensate is returned as reflux and the rest is sent
to be further refined in the stabilization section of the refinery gas plant where the butanes and
propanes are separated from C5-180F (C5-82C) LSR gasoline (Gary, Handwerk, and Kaiser
2007, 84).
VACUUM DISTILLATION
At atmospheric pressure the temperature required to distill the heavier fractions is high enough to
cause thermal cracking. To prevent this, the heavy fractions are sent to a second distillation unit
that distills under vacuum conditions. According to Gary, Handwerk, and Kaiser, the absolute
pressure ranges from 25 to 40mmHg and can be further reduced by steam injection to 10mmHg
or less (Gary, Handwerk, and Kaiser 2007, 84). The lower pressure allows for distillation at a
lower temperature.
Gary, Handwerk, and Kaiser state that steam injection in the vacuum distillation column
minimizes coke formation, increases the furnace tube velocity, and decreases the partial
pressures of the hydrocarbons. The amount of steam added is a function of the feeds boiling

9
range and the fraction vaporized, usually ranging between 10 and 50 lb/bbl (Gary, Handwerk,
and Kaiser 2007, 85).
According to Gary, Handwerk, and Kaiser, vacuum distillation columns can be operated in three
different ways including the following: dry, wet, and damp operating conditions. Dry operating
conditions use the highest furnace outlet temperatures and no steam is added to the column. Wet
operating conditions use the lowest furnace outlet temperatures and steam is added at the furnace
inlet and the bottom of the vacuum tower. Damp operating conditions use intermediate
temperatures and steam is only added to the furnace inlet (Gary, Handwerk, and Kaiser 2007,
85).
The fraction of feed vaporized is based on the effective pressure (which is the absolute pressure
minus the partial pressure). It is essential to design the tower to have as little pressure drop as
possible in order save operating costs.
Vacuum distillation columns have a much larger diameter then atmospheric columns because the
low operating pressures result in a large increase in volume of the vapor. Gary, Handwerk, and
Kaiser state that vacuum towers can have diameters up to 12.5m (Gary, Handwerk, and Kaiser
2007, 86).
According to Gary, Handwerk, and Kaiser, the desired operating pressure is maintained by the
use of steam injectors and barometric condensers or vacuum pumps and surface condensers
(Gary, Handwerk, and Kaiser 2007, 86). The amount of ejectors required is based on the vacuum
needed and the vapor quality.

10
PRODUCTS
According to Gary, Handwerk, and Kaiser, the main products of atmospheric and vacuum
distillation from lowest boiling point to highest boiling point are fuel gas, wet gas, LSR
naphtha/LSR gas, HSR naphtha/HSR gas, gas oils, and residuum.
Fuel gas contains both methane and ethane and is often referred to as dry gas. Wet gas contains
propane and butanes used for liquefied petroleum gases as well as methane and ethane. LSR
naphtha/LSR gas is used for gasoline blending later on in the oil refinery process. HSR
naphtha/HSR gas is used to produce high octane reformate for gas blending and aromatics. Gas
oils can be classified into three types: light gas oils, atmospheric gas oils, and vacuum gas oils.
Gas oils are used to produce gasoline fuels, jet fuels, and diesel fuels. Heavier vacuum gas oils
are used to produce lubricating oil. Residuum is the product from the vacuum distillation
column bottoms and is used to produce heavy fuel oils, cracking base stocks, and lube base
stocks (Gary, Handwerk, and Kaiser 2007, 86-88).
SAFETY CONCERNS
The feedstock and products of crude oil distillation contain highly flammable compounds
including alkanes such as methane, ethane, propane, butane, and pentane. When mixed with air,
these substances can pose extremely dangerous fire and explosion hazards. Accidents can be
avoided by careful monitoring of temperature and concentration in process vessels (Airgas USA,
4). Vacuum distillation poses an extra concern, as air leakage into the vessel may not be
monitored, as gas alarms often only exist outside process vessels. It is important that air leaks
into the column are noticed and dealt with before the alkane-air mixture becomes explosive
(Ulrich and Vasudevan 2004, 499).

11
In their gaseous form, these alkanes can cause suffocation when inhaled, as well as mild to
severe anesthesia. Most of these gases are odorless, which increases the likelihood of inhalation.
Exposure can be limited by alarms that recognize gas leaks and by wearing personal protective
equipment (Fisher Scientific).
The high-boiling products of distillation, including kerosene, paraffin waxes, bitumen, and
petroleum coke pose somewhat less of a hazard than the low-boiling gaseous products as they
are more easily contained and monitored. High-boiling products are also flammable when
exposed to an ignition source. Kerosene poses a toxicity hazard to humans and when inhaled or
ingested in significant enough quantities can be fatal (Irving Oil Refining 2012, 1). At ambient
temperatures, waxes, bitumen, and petroleum coke are solids and can be left in the open for
storage, although they are still a fire hazard.
ENVIRONMENTAL CONCERNS
The main area for environmental and safety concerns in oil refineries relate to the severe
temperature and pressure conditions as valve leaking can cause fires and oil spills (Metso 2011,
2). Crude distillation contributes to air pollution, wastewater concerns, industrial accidents such
as fires and explosions, and noise pollution. Restrictions are often placed on contaminants that
are released into the air by refineries. Oil refineries are usually located far away from urban
areas as an environmental and safety precaution.
The article Environmental Impacts of the Oil Industry details some of the environmental
problems of an oil refinery and ways to mitigate the problems. Water contamination can be dealt
with by treating the water with aeration, flocculation, carbon adsorption, and ion exchange as
examples depending on the type of contaminant. Oil spills can be reduced by making sure the
storage areas for raw materials and products are waterproofed and have a drainage system to the

12
wastewater treatment section of the plant. Particulate emissions into the atmosphere can be
reduced by treating the streams using cyclones, electrostatic precipitators, and scrubbers. Gas
emissions such as sulfur oxides, nitrogen oxides, ammonia, acid mist and fluorine compounds
can be controlled by using wet scrubbers and carbon adsorption. The release of hazardous
solvents, acid materials, and alkaline materials can be prevented by maintaining equipment to
prevent leaks and by putting catch basins around streams containing dangerous or hazardous
materials. The flow of traffic around the refinery can be impacted by many large vehicles
carrying dangerous goods. To minimize the effect on public safety, the best routes should be
selected during feasibility studies to reduce the risk of accidents. To mitigate the noise pollution
from equipment, buildings that contain equipment which operate at loud noise levels should be
soundproofed. Also, emergency response plans should be in place to reduce the environmental
impact from a large oil spill/leak, fires, and explosions (Mariano and Revere).
CARBON FOOTPRINT
Oil refineries have a significant carbon footprint on the environment. As stated by Costa et al,
It can be estimated that, for a typical 200,000 bpd refinery, the crude preheat train fouling
would be responsible for about US$ 6 millions/year of extra energy costs and 62500 metric
tons/year of CO2 emissions (Costa et al 2011, 49). Also, these additional emissions would
correspond to 3.9% of the total carbon footprint of the refinery (Costa et al 2011, 49). Perhaps
in the future, newer and more environmentally friendly technology will be developed for the
crude oil distillation process.

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CONCLUSION
The distillation of crude oil is an important process in the Canadian and international economy.
The four largest steps in the process are desalting, heating, atmospheric distillation, and vacuum
distillation. The process is important because it separates the crude oil into many specific
products and only then does the crude oil become useful. Crude oil distillation can be hazardous
because the compounds used are flammable and pose health risks. The process can have a
negative impact on the environment because it contributes to air, water, and noise pollution.
Regulations are set to control this pollution and new technologies are being developed to
minimize the environmental impact of the refining process.

14
References
Airgas USA Material Safety Data Sheet: n-Butane Accessed January 24 2015,
https://www.airgas.com/msds/001007.pdf
Air Products and Chemicals, Inc. Material Safety Data Sheet: Methane Accessed January 24,
2015. http://avogadro.chem.iastate.edu/MSDS/methane.pdf
Bai, Z. S., and H. L. Wang. 2007. "Crude Oil Desalting Using Hydrocyclones." Chemical
Engineering Research & Design: Transactions Of The Institution Of Chemical Engineers
Part A 85, no. 12: 1586-1590. Academic Search Complete, EBSCOhost (accessed
January 24, 2015)
Consumers' Co-operative Refineries Limited Material Safety Data Sheet: Propane Accessed
January 24, 2015.
https://www.rrcoop.com/product_pdfs/MSDS/0127_PROPANE_LIQUEFIED_PETROL
EUM_GAS.pdf
Costa, A. L. H., V. B. G. Taveres, E. M. Queiroz, F. L. P. Pessoa, F. S. Liporace, S. G. Oliveira,
and J. L. Borges. 2011. Analysis of the Environmental and Economic Impact of Fouling
in Crude Preheat Trains for Petroleum Distillation. Heat Exchanger Fouling and
Cleaning IX 2011 Conference 47-49. Accessed January 24, 2015 from
http://www.heatexchangerfouling.com/papers/papers2011/7_Costa_Environmental%20and%20Economic%20Impa
ct%20of%20Fouling_F.pdf
Fisher Scientific Material Safety Data Sheet: n-Pentane Accessed January 24, 2015.
http://avogadro.chem.iastate.edu/MSDS/pentane.htm
Gary, James H., Glenn E. Handwerk, and Mark J. Kaiser. 2007. Petroleum Refining: Technology
and Economics. 5th edition. Boca Raton, Florida: CRC Press
Irving Oil Refining. 2012. Material Safety Data Sheet: Kerosene Accessed January 27, 2015.
https://irvingoil.com/files/03500_Kerosene_-_English.pdf
Manning, Francis S, Thompson, Richard E., Manning, William P, Buthod, Paul, and Sublette,
Kerry L. 1995. Oilfield Processing. Volume 2, Crude Oil. Tulsa, Oklahoma: PennWell
Books
Mariano, Jacqueline B. and Emilio L. L. Rovere. Environmental Impacts of the Oil Industry
Accessed January 24, 2015. http://www.eolss.net/Sample-Chapters/C08/E6-185-18.pdf
Metso. 2011. Crude Distillation Accessed January 24, 2015.
http://valveproducts.metso.com/neles/ApplicationReports/2721_Refinery/2721_01_02en.
pdf
PetroWiki. "Oil Demulsification." Accessed January 24, 2015.
http://petrowiki.org/Oil_demulsification.
Praxair Inc. Material Safety Data Sheet: Ethane Accessed January 24, 2015.
http://www.praxair.com/~/media/North%20America/US/Documents/SDS/Ethane%20C2
H6%20Safety%20Data%20Sheet%20SDS%20P4592.ashx
Ulrich, G.D. and Vasudevan, P.T. 2004. Chemical Engineering Process Design and Economics:
A Practical Guide. 2nd edition. Durham, New Hampshire: Process Publishing.

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Appendix A: Desalting Process

Figure 1: Desalting Process

(Manning et al 1995)

Figure 2: Single and Two Stage Electrostatic Desalting Treatment Systems

(Gary, Handwerk, and Kaiser 2007, 80)

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Appendix B: Desalting Process Conditions
API

Water wash, vol%

Temp. F (C)

> 40

3-4

240-260 (115-125)

30-40

4-7

260-280 (125-140)

<30

7-10

280-330 (140-150)

Table 1: Desalting Process Operating Conditions

(Gary, Handwerk, and Kaiser 2007, 79)

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Appendix C: Atmospheric and Vacuum Distillation

Figure 3: Atmospheric Distillation

(Gary, Handwerk, and Kaiser 2007, 83)

Figure 4: Vacuum Distillation

(Gary, Handwerk, and Kaiser 2007, 87)