1.

INTRODUCTION

Benzene was isolated for the first time in 1825 by Michael Faraday as a
product of whale oil pyrolysis. Benzene is a natural component of crude oil and is
one of the most elementary petrochemicals. Benzene is a cyclic hydrocarbon with a
molecular formula of C6H6 and its structure has alternating double bonds with
hexagon shape.

The molecule of benzene is formed when 6 carbon atoms is joined in a ring

with 1 hydrogen atom attached to each carbon. Benzene is a colourless gas,
odourless, highly flammable, volatile and has a pleasant, sweet smell. It is widely
used in producing chemical products such as detergent, gasoline, kerosene,
pesticide, and plastic. Benzene is produced in large quantities from petroleum
sources and is used for the chemical synthesis of ethyl benzene, phenol,
cyclohexane and other substituted aromatic hydrocarbons. Benzene is also widely
used as a solvent in chemical industry and production of numerous chemical.

There are few processes that can be used to produce benzene. One of the
processes is catalytic reforming 1. Catalytic reforming is the reforming of naphtha with
the help of a catalyst which produces petrol with a high octane rating. This process
involves dehydrogenation process which the benzene is used to separate from the
other aromatic chemical substance by distillation. Also, this process uses platinum
chloride as a catalyst and it requires the pressure ranging from 8-50 atm and
temperature from 500-525⁰ C.

Next, toluene hydrodealkylation2 is also one of the major processes used to

produce benzene. Basically, the aim of this process is to turn toluene into benzene
and it is a hydrogen intensive process where toluene is mixed with hydrogen by
using a catalyst such as platinum or chromium oxide. Sometimes, the catalyst is
being neglected when high temperature is used.

Steam cracking3 is among one of the most common processes used to

produce benzene. This process produced ethylene and other alkenes from aliphatic
hydrocarbons. Pyrolysis gasoline is the by-product of steam cracking of petroleum by
products like paraffin gases, naphtha and gas oils.

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 Toluene disproportionation4 is also one of the processes to produce benzene.
This process has a reaction in which a substance reacts simultaneously to be
oxidized and reduced which will produce two different products. Benzene and xylene
are described as a demanding product and it can be produce by toluene
disproportionation as an alternative to toluene hydrodealkylation. The catalyst used
in this process is zeolites.

Lastly, benzene can be produced by the production from coal tar5 .This
process improved methods of recovery and purification that coke-oven benzene has
been able to withstand the competition of petroleum-derived benzene as well as it
has. Production of benzene from coal tar involves recovering benzene from coal tar.

All of these processes will then be discussed in detail in the process

background section. This section will focus on how the benzene is produced and
description of its process mechanism and how it reacts with the other chemical
substances in a block flow diagram.

Physical and Chemical Properties of Benzene

Description Colourless liquid

Molecular formula C6H6
Molecular weigh t 78.1 g/mol
Density o.879g/cm3 @ 25℃
Boiling point 80.1℃
Vapor pressure 100 torr @ 26.1 ℃
Solubillity Soluble in ethanol, chloroform, ether, carbon desulfide, acetone,
oils and glacial acetic acid, slightly soluble in water
Conversion factor 1 ppm – 3.2 mg/m3 @ 25℃

Benzene molecule

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2.0 BACKGROUND OF TOLUENE HYDRODEALKYLATION

Toluene hydrodealkylation is a process to convert toluene to benzene. The

process is known as hydrogen intensive process and it uses chromium or platinum
oxide as a catalyst under a certain condition. When the reaction temperature is too
high, the catalyst is usually neglected. Toluene and hydrogen reacts in the reactor
with the help of platinum oxide as a catalyst to produce benzene and methane.

C 6 H 5 C H 3 + H 2 → C6 H 6 +C H 4

Process condition:

Catalyst Chromium or platinum oxide

Temperature 500-660⁰C

Pressure 20-60 atm

3.0 PROCESS AND INSTRUMENT DIAGRAM

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4
process and instrument diagram for hydrodealkylation of toluene to produce benzene

4.0 PROCESS FLOW

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 Process details:

1. Hydrogen is heated in a reactor in a presence of catalyst and it will produce benzene

and methane.
2. Toluene is pumped to combine with the stream of mixed hydrogen and fresh
hydrogen gas.
3. Mixture of toluene and hydrogen is pre-heated before it is introduced to the furnace
and then it will be sent to the reactor.
4. The catalytic process occurs at low temperature and offer higher selectivity.
5. Then, the product will be cooled and next it will proceed to be separated from the
unreacted hydrogen in a separator.
6. Unreacted hydrogen is compressed and it will be recycled back to the feed and
reactor.
7. The product that left the separator are heated before it is being sent to the
distillation column which the toluene is separated from the stream and recycled back
to the feed.
8. Further fractionation will separate methane and toluene from benzene product.

Block flow diagram

Mixed gas
Heat
Exchanger

Toluene
Benzene
(10 000kg/h)

Feed Mixer Reactor Separator

Hydrogen
(820kg/h)

Mixed
Liquid Distillation
Column

Toluene

Figure shown Block flow diagram of the toluene dehydroalkylation of benzene

PROCESS FLOW DIAGRAM

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 Figure 3: Simulation Process Flow Diagram

Hydrodealkytion of Toluene

SP 2 C1

S 14 Recycle Hydrogen
S 12

S 13

S 20
S 22
S 15 S 11
M5
M6
Fuel Gas
S 16
SP1 S 25
S 17
M2 S7
Hydrogen
M4
S9
S 18
R1
S6
S8

M3 S4
S3 S C2
S 28
S5

E2
E1 E5 F1 S 26
S2 S 23
S1 S 10
M1 S 27
Toluene P1

F2
Benzene
E4

S 19

S 21
E3

SC1

S 24

Toluene Recycle

Figure shown the simulation PFD for the toluene hydrodealkylation process.

The hydrodealkylation of toluene 1 (HDA) is a process used to produce benzene. The

main reaction in the process is:

Toluene + H2  Benzene + CH4

Toluene and hydrogen are converted in a reactor packed with catalyst to produce
benzene and methane. Typically the reaction reaches a conversion of 90%. The reaction is
highly exothermic and the typical operating conditions are 500 C to 660 C, and 20 to 60 bar.
Figure 1 shows the block diagram of the HDA process.

The HDA process begins with mixing fresh toluene with a stream of recycle
unreacted toluene, the mixing is achieved in a storage tank. The toluene is then pumped to
combine it with a stream of mixed hydrogen and fresh hydrogen gas. The mixture of
hydrogen and toluene is preheated before it is introduced to the heater or furnace. In the
furnace the stream is heated to 600 C, the reaction temperature, then introduced into the
reactor. The reactor is where the main reaction happens:

C7H8 + H2 = C6H6 + CH4

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 This reaction is irreversible, and it requires catalyst. The catalyst consists of
chromium or molybdenum oxides, platinum or platinum oxides, on silica or alumina. Another
minor reversible side reaction2 is often observed:

2 Benzene = Diphenyl + H2

The catalytic process occurs at lower temperatures and offers higher selectivity but
requires frequent regeneration of the catalyst. The products are then cooled and introduced
into a pair of separators that separate the unreacted hydrogen. Portion of the unreacted
hydrogen is compressed and recycle back to the feed and the reactor. The products leaving
the separators are then heated before being introduced into a distillation column, where
toluene is separated from the stream and recycle to the feed. This allow for greater
conversion. Then further fractionation separates methane and toluene from the benzene
product. The heating requirements are achieved with low, high and medium pressure steam.
The cooling requirements are achieve by cooling water at temperature of 30 C and pressure
of 1 bar.

The process begins with the first phase of a process: the reactor feed preparation.
This begins with combining 108.7 kmol/hr of a fresh stream of toluene at 25oC, and 1.9 bar,
with a recycle stream of unreacted toluene in a storage tank TK-1 at 112oC and 2.43 bar.
Toluene is then pumped through pump P-1, the discharge pressure of the pump must be
25.5 bar, this is pumped to a second storage tank TK-2 where toluene is combined with a
combined stream of fresh and recycle of hydrogen. The new two-phase stream is preheated
in E-1 to 163.9oC, high pressure steam at 45 barg is used for this purpose. The stream exists
the pre-heater as a one-phase stream because the toluene was vaporized. The stream is
then introduced into the heater, H-1, this fired heater is a type of furnace which uses air to
combust fuel gas to produce enough heat to raise the temperature of the stream to 600oC.
The reactor feed preparation has now been completed. The stream is at the desired
pressure, 24.81 bar, and temperature, 600oC, necessary for the reaction to occur.

The stream is then introduced into the reactor R-1, this reactor is a vertical vessel
packed with catalyst. This is the main part of the process where the main reaction, which
produces benzene, happens:

C7H8 + H2 = C6H6 + CH4

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 Toluene + Hydrogen = Benzene + Methane

This is a catalytic exothermic reaction, and the temperature is controlled by injecting

hydrogen into the reactor. Hydrogen is injected at 40.4 kmol/hr 44.96 oC and 25.5 bar. The
exiting stream exits at 24.81 bar and 671 oC, it contains methane, benzene, toluene, and
hydrogen. The one pass conversion is typically around 75%. The process then continues to
the separator feed preparation phase. This process phase begins with introducing the
stream into a cooling water heat exchanger E-2. This heat exchanger cools the product
stream to 38oC, which condenses most of the toluene and benzene in the stream.

The stream then proceeds to the final phase of the process: the separation. In this
phase, the desired product is separated from the by products and the unreacted
components. That is, benzene is separated from unreacted toluene, unreacted hydrogen
and the by-product methane. This is achieved by introducing the two-phase stream
containing benzene, methane, hydrogen and toluene into a high-pressure phase separator,
F-1. In this flash drum the vapor and liquid are separated. In the overhead mainly hydrogen
and methane exits, and in the bottom some hydrogen, methane, and mainly all the toluene
and benzene exit. The overhead stream is split into two streams; one stream is compressed
to 25.5 bar in compressor C-1 and is recycle back to the feed and to the reactor, the other
stream is a portion of the fuel gas stream. The separation happens at a temperature of 38 oC
and 23.9 bar.

The partially separated stream is then introduced in a second separator, F-2, where
mainly all the methane and hydrogen is separated in the overhead stream. This separator is
a low-pressure separator. The liquid exiting the low-pressure flash drum consist of mainly
toluene and benzene and traces of dissolved hydrogen and methane. The separation is then
completed by heating the stream in heat exchanger E-3, and then introducing it to a
distillation column, T-1. The stream is heated to a temperature of 90 oC in E-3, low pressure
steam is used for this purpose. The distillation column is used to purify the benzene product
by separating all the unreacted components and the by products. This tower consists of 42
sieve trays, a reboiler E-6, a condenser E-5, a reflux drum F-3, and a reflux pump P-2.
Toluene exits as a liquid in the bottom at a temperature of 112 oC and 2.43 bar. The
overhead containing benzene, traces of hydrogen and methane, is condensed in E-5 at a
temperature of 112oC and a pressure 2.5 bar. Cooling water is used to condense the vapor
exiting the column. A remaining hydrogen and methane are then separated in the reflux
drum F-3; this vapor stream is combined with the other gases streams: the overhead of the
first separator F-1, and the overhead of the second separator F-2, which are combined to
form the fuel gas. The liquid stream exiting in the bottoms of the reflux drum is pumped to a
discharge pressure of 3.3 bar. The pumped stream is separated in two streams. One stream
is feed to tray one of the column and the other stream is cooled down to 38 oC in heat
exchanger E-4. The cooled product stream is then sent to storage.

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 In the benzene distillation process, a feed stream consists of benzene,
toluene, hydrogen and methane is fed into the distillation column. The feed stream
consists of 74.8% benzene, 24.6% toluene while the rest are made up of methane
and hydrogen. When the feed stream enters into the column, it will move to the flash
zone which is the incoming feeds will be separate into vapour and liquids. Those
molecules which have a low temperature of boiling point will change to vapour state
and move upwards to the top of distillation column. Meanwhile, the heavier
molecules which have a high temperature of boiling point will remain at the liquid
state and settle to the bottom of the column. The movement of liquid is occurring
along the weir meanwhile the vapour move through the holes at the trays.

The distillates stream flows through an insulated pipe to a condenser (E-104)

in order to reduce the temperature of the distillates stream before allowing it to flow
into the reflux drum (V-104). The cooling water is passed through the condenser
through an insulated pipe for cooling down the temperature of the distillates stream.
The temperature and flow rate of the cooling water stream are being controlled by a
temperature control valve and a flow rate control valve respectively. Waste product
from the distillates stream is withdrawn by using chemical sewer which connected to
the condenser through a gate valve. The middle section of the condenser passes
through a right angled pressure relief valve to the vent to the flare while the top
section of the condenser passes through to another right angled pressure relief valve
in order to vent to the atmosphere. These valves act as safety valves which maintain
the operating pressure of the condenser by releasing excessive pressure build up in
the condenser.

The condensed stream then flows through an insulated pipe into a reflux drum
(V-104) to separate the fuel gas and benzene extract. The reflux drum consists of a
Temperature Indicator (TI) and Pressure Indicator (PI). It is also being connected
with a sample port which is being used to examine the composition of the sample.
Simultaneously, the waste product is being removed through the chemical sewer.
The overhead product is being passes through a pressure controlling system and the
reading of the pressure is being converted into pneumatic signals before being sent
to the pressure control valve. A hand operated valve is being installed at the line
which is acting as a safety valve if there is an emergency. The overhead product
flows to the feed drum or storage as a fuel gas.

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 The extracted benzene stream is separated into two insulated pipes with a
gate valve installed at each. Next, the benzene extract flows into two pumps (P-102A
& P-102B) respectively. The waste product from the benzene extract is being
removed by using chemical sewer meanwhile a high purity of benzene is being
pumped into the distillates stream. A level control valve is being installed just before
the distillates storage tank and it is being controlled by an electrical system.

The distillates stream is then being splits into reflux stream and product
stream. The reflux stream is being fed back to the distillation column. A hand
operating gate valve is in the opened position in order to ensure the reflux stream
returns to the upper part of the distillation column. Before it enters the distillation
column, the flow rate of the reflux stream is being monitored by the flow rate control
system which being used to control the desire or suitable flow rate that entering the
distillation column. The product stream flows to the feed drum or storage as a
benzene.

At the bottom of the distillation column, there is a mixture of Benzene and

Toluene which is being flows into to reboiler through an insulated pipe. Basically, the
main purpose of using the reboiler is to generate a flux of benzene vapour which
being used as a feed to the distillation tower. The top stream of the reboiler recycles
the mixture back to the bottom part of the distillation column for being used in the
further distillation. The benzene reboiler uses a steam control strategy to control the
heat transfer rate of inlet steam using a temperature control system. The steam that
flows can be adjusted by a hand operated gate valve. Besides that, the latent heat of
the stream is used to heat up the Benzene Toluene mixture in the reboiler and then it
will flow out of the reboiler as a condensate. The reboiler is connected to two vents
which are to vent out the non-condensable gases in order to improve the heat
transfer efficiency. The bottom part of the distillation column is connected to a
chemical sewer with a valve which being used to control the flow rate.

The composition of the residue at the bottom of fractional column is rich in

toluene therefore it will be discharge through an insulated pipe. The column base

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level is controlled by a level controlling system which being connected to a
combination of three gate valve and a control valve. Lastly, the stream is being
recycled to the toluene feed drum for further distillation process.

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 5.0 APPLICATION OF PRODUCT

1) Benzene product

Gasoline product, plastic bottle, glue and etc.

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2) Toluene product

Nail polish stains & ink remover, tnt and etc.

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 6.0 EQUIPMENT USED

1) Pump

2) Mixer

3) Flash Vessel

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4) Compressor Vessel

5) Reactor

6) Seperator Vessel

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 7.0 FUNCTION OF EQUIPMENT

1) Pump
 Used to move fluid under pressure from one location to another.

2) Mixer
 Mixing other gases to increase their characteristic.

3) Flash Vessel
 Flash (or partial) evaporation is the partial vapor that occurs when a saturated
liquid stream undergoes a reduction in pressure by passing through
a throttling valve or other throttling device.

4) Compressor Vessel
 Air Compressor produces pressurized air by decreasing the volume of air and
in turn increasing its pressure.

5) Seperator Vessel
 Separators are used for mechanical separation and clarification of mixtures
comprising solids and liquids.

6) Reactor
 Reactor can be used to change molecule or structure of fluid.


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 8.0 DETAIL DRAWING & MODEL DESIGN

1) Mixer detail drawing and model.

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2) Pump detail drawing and model.

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 9.0 CONCLUSION

As the conclusion, petroleum refineries are very large industrial complexes that
involve many different processing units and auxiliary facilities such as utility units and
storage tanks. Each refinery has its own unique arrangement and combination of
refining processes largely determined by the refinery location, desired products and
economic considerations. Oil can be used in a variety of ways because it contains
hydrocarbons of varying molecular masses, forms and lengths. The differences in
the structure of these molecules account for their varying physical and chemical
properties and this variety makes the crude oil are useful in a broad range of several
applications. We also had known that piping also has many other industrial
applications which are crucial for moving raw and semi-processed fluids for refining
into more useful products. Piping systems are documented in piping flow diagram &
instrumentation. Process and instrument diagram (P&ID) is one of the type in piping
flow diagram & instrumentation. P&ID is a detailed diagram in the process industry
which shows the piping and vessels in the process flow, together with the
instrumentation and control devices. It contains the pipe line numbers, direction of
flow, pipe line sizes, pipe specification, all equipment, all valves and all
instrumentation with control device.

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