NAME: Mammadli Javid

INTERNSHIP PLACE: H. Aliyev Baku Oil Refinery

INTERNSHIP DURATION: 1st June, 2017 - 30th June , 2017

DATE OF SUBMISSION: 6th July, 2017

INSTRUCTOR: Sevda Zargarova

Contents
Synopsis .............................................................................................................................................................. 3
Introduction........................................................................................................................................................ 3
Overall Information ...................................................................................................................... 3
Safety and Health Procedures ....................................................................................................... 3
Catalytic Reforming ............................................................................................................................................ 4
Overall Information ...................................................................................................................... 4
Section 1( Hydrotreatment) .......................................................................................................... 4
Section 2( Platforming) ................................................................................................................. 6
Section 3(Regeneration) ............................................................................................................... 7
Delayed Coking ................................................................................................................................................... 8
Overall Information ...................................................................................................................... 8
Catalytic Cracking ............................................................................................................................................... 9
Overall Information ...................................................................................................................... 9
Initial Refinery .................................................................................................................................................... 9
Overall Information .....................................................................................................................11
Conclusion ........................................................................................................................................................ 14
Glossary ............................................................................................................................................................ 14
References ........................................................................................................................................................ 15

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 Synopsis

Summer internship report comprises of general data about the major areas of and the primary
processes taking place in H. Aliyev Baku Oil Refinery visited by Baku Higher Oil School 2nd year students. These
data include brief information about the plant itself, applications of oil refinery products, safety precautions
in the plant, detailed or short general information about each one of the 4 major sites (Initial refinery,
Catalytic Reforming, Delayed Coking, Catalytic Cracking), material balance of a part of one unit, reactions
taking place during different manufacturing processes as well as the conditions required for them, physical
properties of the main feed, some additional discussions between engineers and students and the
distinguished glossary used throughout the report.

Introduction

Overall information
Baku Oil Refinery being located in the capital city of Azerbaijan and established in 1953 , is considered
to be the most principal refinery of the area. The plant is operated in order to refine the oil and produce
considerably important commodities which have a huge range of usage in our daily lifes and industry. From
24 types of oil produced in Azerbaijan, 21 of them are refined in this grand plant, manufacturing 15 various
products(of which nearly 45% are exported)[1]. Currently , the plant meets euro-3 standard which will
presumably be converted to euro-5 . In more industrialized countries with modern refineries this standard is
euro-7, however for now the capacity of Baku Oil Refinery allows it to be transferred to euro -5 only. For this
conversion, strict modernization processes by SOCAR are currently being accomplished. Experts from all over
the world are involved in this process which is anticipated to be fulfilled until 2020. Furthermore, the refinery
is awarded for specifying requirements of ISO 9001 (quality), ISO 14001 (environmental management
system) and ISO 8001 (health and safety). In order to assure high quality products before processing,a sample
of feed is analyzed in highly equipped laboratories of SOCAR. The production rate of the refinery is 6 million
tonnes per year with miscellaneous products, a small part of which is as following. Gasoline and diesel- as a
fuel for cars, mazut- as a fuel for ships, coke – used in electrodes or as a fuel , kerosene – used in planes as a
jet fuel, tar- for bitumen(asphalt) production, hydrogen- mostly internally used in the plant (in
hydrotreatment , cracking and etc.), propane , butane- are liquefied and sold as a heating fuel for domestic
consumption and etc.

Safety and Health Procedures

Stringent safety measures are taken in the plant. Some points are indicated below[2]:
 The processes which can be potentially dangerous are not regulated manually.
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  In order to reduce long exhaustive working hours , resting times are also arranged.
 While setting new units, fire cases should be carefully taken into consideration. The area should be
supplied with fire extinguishers (water and foam).No open fire is allowed on the area.
 Hot units should be isolated and potentially volatile places to explosion should be ventilated properly.
Light, sound and other types of alarms for emergency should normally work.
 The whole staff must be trained professionally. Staff has to wear special safety outfit which includes,
hard hat, glasses, resistant boots and the uniform.

Catalytic Reforming

Table 1. Identity of feed[2]

SOME PROPERTIES AND (85-180OC GASOLİNE FRACTION)
CHARACTERISTIC OF FEED
TEMPERATURE Around 40oC
DENSITY No more than 0.7555 g/cm3 (20oC)
COLOUR Colourless
COMPOSITION OF No more than 0.03 % mass Sulphur, 0.02 % mass water, 2 ppm mass
MIXTURE nitrogen, 2 ppm mass chlorine, 5 ppb mass arsenic, 25 ppb mass lead (Pb)
Overall information
In general , the main target of catalytic reforming is to convert low octane gasoline fraction into the
higher one. In the refinery it is achieved by different sophisticated processes happening within 3 sections.
The first procedure is called the hydrotreatment procedure after which platforming section and regeneration
of catalyst take place.

Section 1: Hydrotreatment process

This process is aimed to partially free feed from certain impurities, such as sulphur, nitrogen,halides,
metals (mainly poisonous Arsenic), oxygen compounds and to saturate olefins by means of hydrogenation
reactions in the presence of catalysts (Cobalt and Molybdenum on alumina). The following steps are
undertaken in the refinery for hydrotreating of naphtha:

 4 tanks (№ 2111, 2112, 2113, 2114) hold the feed which is then pumped to the heat exchangers (
there are 5 consecutive heat exchangers ET-111/5,4,3,2,1) in order to be heated from 40 0C up to
3040C.
 Later on it is further heated from 304 degrees up to 374 degrees centigrade in the furnace (BH-111)
which has 4 inlets (through 2 processes: convection* and radiation) .
 It is then sent to the reactors(DR 111) in which hydrotreatment occurs mainly by exothermic reactions
in the presence of Co and Mo catalyst on alumina and then product leaves with the outlet
temperature of 371oC
 Unstable hydrogenate leaving the reactor is condensed while being passed through heat exchangers
and coolers (which cool it down to the vicinity of the feed temperature of 38 oC)
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  Hydrogenate reaches the separator in which it is decomposed into 3 streams: Light hydrocarbons
(upper), main product (which is still unstable hydrogenate) and wastewater. Hydrogen containing gas
is compressed and then mixed with hydrotreatment raw material
 As hydrogenate leaves the separator it again goes through heat exchangers in order to be heated up
to 172oC (which is liquid) and then enters from the top inlet (6 th plate) of evaporation column
(stabilization unit- DT 121) (top and bottom temperature in turn-1470C and 2340C, top and bottom
pressure in turn- 10.2 and 10.5 kgg/cm2 )
 A portion of leaving 234 0C stable hydrogenate goes to platforming stage while remaining portion
goes to furnace for further heating (up to 2420C ) and entering the column again as reflux.

Main reactions of hydrotreatment in reactor

( conditions: inlet pressure of no more than 33,0 kgg/sm2 , outlet pressure of 32,3 kgg/sm2 catalysts –Co
and Mo on alumina)
a) Saturation of olefins (both cyclic and non-cyclic):
Example: hydrogenation of non-cyclic 2-hexene
CH3- CH2- CH2-CH=CH- CH3 + H2 => CH3- CH2- CH2-CH2-CH2- CH3 (and isomers of it)
As the reaction is strongly exothermic it should be carefully conducted.
b)Desulphuration (conditions: 315-3400C, if it were conducted at higher temperatures Sulphur can react
with olefins producing sulfides)
Below given one of the examples of typical desulphuration reaction :
CH3-CH2-CH2-S-CH2-CH2-CH3+ 2H2 => 2CH3-CH2-CH3 + H2S
c)Nitrogen removal
Pyridine is the example of cyclic nitrogenous compound in naphtha

Pyridine + 5H2  CH3 – CH2 – CH2 – CH2 – CH3 + NH3

d)Separation of oxygen
Below given the example of hydrogenation of aromatic oxygen compounds to aromatic carbohydrogenes:
Phenol-R +H2 => phenyl-R + H20
e)Separation of halides
Below given the example of hydrogenation of butylchloride-1 to butane:

CH3 – CH2 – CH2 – CH2 – Cl + H2  CH3 – CH2 – CH2– CH3 + HCl

f)Removal of metals

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If the process takes place at more than 315oC metal composition of gasoline (Ca, Mg, Fe, As, Rb etc.)
precipitates on the surface of catalyst thus are removed.
Possible undesirable reaction
NH3 + HCl => NH4Cl (this compound can precipitate and block some units)
Some of the products (the ones indicated in in bold letters) are then utilized for the treatment of sour
water.

Section 2: Platforming section

Table 2. Identity of feed

SOME PROPERTIES AND (85-180OC HEAVY GASOLİNE FRACTION)

CHARACTERISTIC OF FEED
TEMPERATURE Around 121oC
END BOILING POINT No more than 190oC
HEAVINESS Should be heavy gasoline fraction
COMPOSITION OF 6-11 carbon aromatics, naften, paraffin
MIXTURE

Platforming is the part of catalytic reforming process in which Platinium catalyst is involved and this
process is used to increase the resistance of detonation* of gasoline and ligroin, and to obtain aromatics ,
such as benzene , toluene and xylene (further improvement of gasoline to higher octane rating). Hydrogen
consisting gas is also obtained through this process which is then used in hydrotreatment process (an example
of recycle). Following steps are vital in platforming process:

 After leaving the evaporation column (DT-121) , in the first section, hydrogenate enters the heat
exchangers ET-121/1,2 and is cooled down to 1210C
 Then it is mixed with hydrogen containing gas and is sent to the heat exchangers so as to be heated
up to 4680C
 Next, it goes to the oven for further heating (with radiation part up to 543 0C) and being ready for to
be sent to the reactors
 In reactors (under 8.4-10.6 kgg/cm2 pressure, 5430C), endothermic reactions take place. After first
reactor ( DR-211) , it goes to the oven with 4600C (a further proof of endothermic reactions) to be
reheated up to 5430C and is sent to the second reactor- DR 212 and leaving at 5060C and being
reheated up to 5430C it goes to the next- third reactor (DR-213) and leaves at 5190C. Then the mixture
enters again at 5430C to DR-214 and finally exits from 4th reactor at 5270C and 8.4 kgg/cm2 for being
forwarded to heat exchangers of ET-211/1,2 . There it is cooled down to 1180C
 For further cooling process it is transferred to air coolers for being cooled down to 43 0C. Then by the
help of cold water its temperature decreases to 380C
 Finally hydrogen composing gas is removed from the mixture and unstable platformate is forwarded
to the separator and following the stabilization unit. Hydrogen containing gas , on the other hand, is
recycled back for being used in hydrotreatment.

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 Main reactions of platforming in reactor
(conditions: 530-544 degrees centigrade, Platinium catalyst)
a)Conversion of naftens (dehydrogenation, isomerization, hydrogenation and hydrocracking ):
An example showing conversion of metyl-cyclohexane to toluene (dehydrogenation)
C7H14 =>> C7H8 + 3H2
b)Conversion of parafins (isomerization, decyclation and hydrocracking ):
Example of hydrocracking
C6H14 + H2 =>> C5H12 + CH4
c)Conversion of aromatics (isomerization and dealkylation ):
Example of dealkylation
m-xylene =>> toluene

Me Me
=>>
+ CH4
Me

As a result of all of those aforementioned procedures (overall platforming) we finally obtain

aromatic rich reformate.

Section 3: Regeneration of catalyst section

During the reactions in the reactor, the activity of a catalyst is decreased by the coke precipitation on
the surface of it , and for boosting the catalyst regeneration process is indispensable. The process takes place
in a regenerator column and the following steps are attempted to achieve the boosted catalyst:

 In the upper part, combustion of coke is conducted at high temperature with a low concentration of
oxygen
 In the middle part, oxidation process of a catalyst (high oxygen concentration) and managing chloride
balance (with the help of dichloroethane) is achieved.
 Drying process of a catalyst is accomplished at the lower part of the regenerator column and the final
step is to reduce the catalyst which takes place in the upper part of the reactor

Main reactions of a regeneration process

a)Combustion of coke:
(-CH-)2n + 5n/2 (O2) =>> 2nCO2 + nH2O
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 For eliminating the production of CO during combustion process chlorine is added.
b)Oxydation of platinium catalyst:
2Pt + O2 =>> 2PtO
c)Reduction of platinium catalyst:
PtO + H2 =>> Pt + H2O
After final process of reduction, regeneration process finishes and the catalyst is given to the reactors [2].

Coke Production Area

Overall information
Petroleum coke or in other words petcoke is one of the last products in oil refinery and is obtained
when residual oils are treated catalytically.[3] The product coke is utilized in electrodes and is not the only
product of the process. Along with it dry gas, light and heavy gasoil are manufactured as well. Coking process
is mainly composed of reactions which undergo via radical mechanism and could be also regarded as deep
thermocracking process. Initial reactions are polymerization of unsaturated carbohydrogens, condensation
of aromatics with unsaturated carbohydrogens.
Table 3. Identity of feed

SOME PROPERTIES AND
CHARACTERISTIC OF MAIN
FEED
DENSITY
SULPHUR COMPOSITION
FREEZING POINT
(TAR AND HEAVY PHLEGM FROM №55 CRACKİNG UNİT RESPECTIVELY)
No more than 950 kg/m3 (Tar) and 980-1000 (phlegm) kg/m3 (20oC)
No more than 1% (Tar) and 0.8% (phlegm) on a mass basis
250C (for heavy phlegm)

Following general steps are constantly being taken in refinery so as to obtain coke and other products:

 3 tanks provide the feed (tar) to the heat exchangers (ID 330) by pumps in which it is heated by the
help of light gas-oil. It is then pumped to next heat exchangers (ID 331) in which it is heated by the
help of heavy gas-oil.
 Stream, being 170-190oC at temperature, then enters the furnace with two parallel streams. If
pressure is less than 0.01 kgg/cm2 in the furnace it is turned off. After being heated (280-3600C) it
enters the K-301 rectification column from the first and the seventh plate.
 Sending some parts of feed to the first plate is done in order to balance the recycle ratio. Rectification
column is a type of separator and in this column feed meets gas coking products from reactors thus
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 is heated to the certain temperature. Feed is then pumped to furnace S-301/1 and S-301/2 in which
it is heated up to 505oC and from these ovens it goes to one of the R-301/1,2 and R-301/3,4 cameras
respectively.
 In order to get high quality coke its temperature is regulated by the help of heavy phlegm of catalytic
cracking or coking.
 Coking process takes place in reactors in which heavy and light phlegms are also utilized in order to
assist the process. Camera is filled with coke and it is then separated from the feed. 4t/hour water is
blown to the filled camera so that the coke can be cooled and the volatile carbohydrogens could be
removed. After blowing process, cooling water is pumped to cameras for 6 hours. After being cooled,
water is removed and eventually the cutting procedure initiates by the help of telescope(for 5-6
hours)[4].

Catalytic Cracking Area

Overall information
Catalytic cracking process takes place in the 5th section of refinery and is aimed to increase the octane
number of gasoline (alike to reforming , however with a different feed). In general, cracking is the breakage
proccess of large molecules into smaller ones. The feed to the unit comes from various sites, such as light
phlegm from coking unit, hydrogen composing gas from reforming and vacuum distillate from initial refinery
site. Main feed (vacuum distillate) should have the lower boiling point more than 2900C, no more than 0.2%
water,0.9% sulphur composition. The catalystys utilized in the process are composed of silicates(mainly
Zircon –ZrSiO4), aluminium oxide , sodium oxide and some promoters.

Main Sections
The feed goes through 5 several main procedures:

 100th section- hydrotreatment of diesel distillate: relatively pure distillate coming from the initial
refinery goes through cleansening process in 100th section . In this procedure it is cleaned of
unneccessary composition and transferred to the 200th section.
 200th section- catalytic cracking and rectification: cracking process takes place in this area with the
help of units as reactor, air compressors and the rectification block. Within the cracking process feed
firstly is externally diffused on the catalyst(adsorbtion) . Next, cracking products and not reacted
materials are desorbed from the surface of catalyst and finally cracking products are isolated from the
reaction zone in order to be rectified later. Mainly, alkanes undergo cracking reactions and one
example is shown below:

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 C16H34 =>> C8H18 + C8H16

However cycloalkanes and aromatics can also undergo cracking reactions former one giving less coke
but has more yield of gasoline , while the latter one with less yield of gasoline but more of coke.
Temperature in the reactors range from 520 to 545 degrees centigrade. At the end we still have a
nonstabile gasoline to be delivered to the section 300.
 300th section- absorption* and gas fractioning: This area is intended to stabilize , absorb and
fractioning of nonstabile gasoline and oil gas. Due to the differences in partial pressures absorbent
selectively absorbs the different phases of the mixture leaving the gas mixture. In the absorber unit
the pressure is regulated at 12 kg/cm2 for both absorption and desorption processes. Certain gases
(C3, C4 series carbohydrogens) are provided for sales from that section and some (methane , ethane)
are sent to Sumqayit for other production purposes
 400th section - utilization of heat: This section is targeted for the reutilization of energy resources.
For doing so , the heat of smoke gases from regenerator and from furnaces is used to circulate water
vapour throughout the certain units in order to meet their technological demands .
 500th section- electrofiltration: In this section smoke gases (which are utilized in 400th section) are
cleaned from catalyst particles. This is done in order to prevent the blocking of water sprayers.

As a result of the whole procedure we obtain high octane gasoline and diesel for automobile engine,
propane-propylene, butane- butylene fraction, dry carbohydrogen gases , pot fuel, some coke and
heavy/light phlegm[5].

Initial refinery of crude oil area

Overall information
The units of this area are harnessed in order to obtain vehicle gasoline (85oC-180 oC fraction), kerosene
(140 oC-240 oC fraction), diesel fuel (240 oC-360 oC), vacuum gasoil (360 oC-520 oC) ,tar(or mazut -more than
520 oC) and some carbohydrogen gases.

Main Sections
For obtaining high quality of those aforementioned materials, process is divided into several parts:
Electrodialisys desalination*:

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 The crude oil still has its water content along with certain salts (chlorides of sodium, magnesium and
calcium) ,minerals and other mixtures held within itself in suspension. With the purpose of removing
aforementioned materials and some other mixtures, such as certain organic compounds (metallic) and
arsenic containing compounds ,as well as getting the feed ready for the process of initial refinery electro
desalination block is utilized. The question is - why do we need to remove those materials? The answer is
crystal clear- This process is fulfilled so as to prevent hydrochloric acid corrosion of the unit and to avoid
hindrance in the snake-shaped pipes of oven and heat exchangers (because of certain salts and some other
mechanical mixtures).By doing so less damage to the units and surely less usage of energy are achieved
throughout the process.

Atmosphere block:
Consecutively, this block receives already desalinated oil from desalter and seperates oil (by means
of rectification) yielding mainly following products: carbohydrogen gases, huge range gasoline fraction,
aviakerosene distillate, diesel fuel and mazut (important residual fraction of oil which is further treated in
vacuum block for coke formation and some gasoline). The conditions for the upper part of separation column
are as follows: Pressure and temperature should be up to 15 atm and 1650C respectively. Just a part of the
main unit’s scheme (C-2 column with plates) and material balance of the process are indicated in table 4.
and picture 1:
Table 4. Mass (IN) Mass % Mass (OUT) Mass %
Mass Balance (tonnes/day) (IN) (tonnes/day) (OUT)
M1(Oil) 17640 100 0 0
M2(Carbohydrogen 0 0 88.20 0.50
Gas)
M3(<620C fr) 0 0 151.70 0.86
M4 (620C-1050C fr) 0 0 594.47 3.37
M5(1050C-1800C fr) 0 0 1797.52 10.19
M6(1800C-2500C fr) 0 0 1693.44 9.60
M7(2500C-3200C fr) 0 0 1658.16 9.40
M8(3200C-3500C fr) 0 0 786.74 4.46
M9(3500C-5000C fr) 0 0 4007.81 22.72
M10(TAR>5000C fr) 0 0 6676.74 37.85
LOSSES 0 0 185.22 1.05
Total: 17640 100.00 17640 100.00

Picture 1.

According to conservation of mass law: M1=M2+M3 + M4 + M5 + M6 +M7 + M8 +M9 + M10 + losses

17640t/day =(88.2+151.7+594.47+1797.52+1693.44+1658.16+786.74+4007.81+6676.74+185.22)t/day
Stabilization and seperation of gasoline block:
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 In this section , gasoline is stabilized and separated into following fractions: <85 oC, 85-180 oC and
<180oC gasoline fractions.
Vacuum block:
This block is utilized for processing the residue of oil from atmosphere block (mazut) to manufacture
two primary products: vacuum gasoil (which is a feed to catalytic cracking unit) and tar (feed for the delayed
coking or pot fuel).

Treatment of fuels with alkaline block:

This block is designated with the intention of obtaining vehicle gasoline, kerosene and diesel fuel. For
obtaining aforementioned commodities <85 oC fraction of gasoline, 140-240 oC and 240-360 oC kerosene and
diesel fuel fractions respectively are treated with aqueous solution of sodium hydroxide by technology of
Merichem company of the USA. After each treatment with alkaline, treatment with water, salt and soil is also
applied. Following reactions take place during the treatment:
a)Treatment of gasoline:
2Nа0H + H2S =>> Na2S + 2H20
b)Treatment of kerosene (the same for diesel fuel treatment):
2Nа0H + H2S =>> Na2S + 2H20
R-C00H + Na0H=>>R-C00Na + H20
Utilization of heat of smoke gases and water vapor production unit:
In this block the heat of smoke gases from furnace is reused as well as water vapor with the pressure
of 13.0 kgg/cm2 is produced.
As a result of the whole process different precious fractions of oil are produced and some components
of it are sent to different sections of the plant ( catalytic cracking, reforming, coking) for further processing[6].

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 Conclusion

As already discussed , Baku Oil Refinery is relatively large and sophisticated plant controlling four
major processes. To regulate this grand plant, safety measures ranging from the security of the units to the
health of the staff are approached seriously. In general, each section among four has its own operation units
and special staff who have the considerable knowledge of units and processes. Catalytic Reforming (3 rd
section) is the process which is targeted to increase the octane rating of the gasoline, which is really crucial
as the gasoline is the main fuel component. The process itself is further divided into hydrotreatment
(removing impurities), platforming (for stabilizing) and regeneration process of catalyst. The 4 th section in the
plant is Coking area , which intends to produce petroleum coke that is applied in electrodes and used as a
fuel. Next comes the Catalytic Cracking section , which has the similar aim with the 3 rd section – increasing
the octane rate. Many of the reactions take place in the presence of a catalyst. The 2nd area is the initial
refinery which is the first place crude oil enters. In this section , oil is initially treated and feeds to the
aforementioned sections are obtained through several processes. Moreover, maintaining recycle ratio higher
and avoiding too much waste are one of the targets of the plant as well(utilizing hydrogen gas from
platforming in hydrotreatment section or reuse of the product gases and phlegms in the furnace and the heat
exchangers are prime examples).
Overall, the reason for those elaborate processes taking place in the plant is quite obvious. To obtain
pure products in organic chemistry is roughly impossible. Otherwise, gasoline could be obtained directly and
the whole process would be very basic. Nevertheless, products from each section needs further treating
which is the reason plant is that sophisticated. Furthermore, the losses (both heat and material) throughout
the processes are inevitable , on the grounds that some units are not working properly (since they are very
old) as well as the refinery is considered for only heavy oil (Siberian ) and the weather is relatively hot making
the situation difficult. Hopefully, those problems will not count after the ongoing modernization procedures.

References

[1] http://www.socar.az/socar/en/activities/refining/heydar-aliyev-baku-oil-refinery, Heydar Aliyev Baku Oil

Refinery
[2] Catalytic Reforming process technological regulations by Baku Oil Reinery named after H.Aliyev
[3] Petroleum coke on the website of the IUPAC Compendium of Chemical Terminology
[4] Delayed Coking process technological regulations by Baku Oil Reinery named after H.Aliyev
[5] Catalytic Cracking process technological regulations by Baku Oil Reinery named after H.Aliyev

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[6] Initial Refinery process technological regulations by Baku Oil Reinery named after H.Aliyev
[7] Incropera, Frank P.; DeWitt, David P. (1990). Fundamentals of Heat and Mass Transfer
[8] Fickett; Davis (1979). Detonation. Univ. California Press
[9] http://www.ivt.ntnu.no/ept/fag/fordypn/tep03/innhold/TEP03_part4_absorption.pdf Norvegian
University of Science and Technology, “Absorption” by professor Olav Bolland
[10] http://www.lenntech.com/electrodialysis.htm, Membrane Technology

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