CHAPTER 1

INTRODUCTION

1.1 OVERVIEW OF RAW MATERIAL

1.1.1 Benzene

Benzene is an organic compound with a chemical formula of C 6H6 and is classified as

a hydrocarbon. Benzene is a clear, colourless, volatile and highly flammable, liquid aromatic

hydrocarbon that has a gasoline-like odour. This compound can be found in crude oils, by

product of coal distillation and as a by-product of oil-refining processes. In industry benzene

is used as a solvent for fats, resins, waxes, oils, inks, paints, plastics, and rubber, and is

used in the synthesis of numerous chemicals. It is also a constituent in motor fuel, aid in

the extraction of oils from seeds and nuts as well as in photogravure printing. Benzene is

also used as a chemical intermediate and in the manufacture of detergents, explosives,

pharmaceuticals, and dyestuffs.

Figure 1.1: Structure of Benzene (Qalm, 2017)

Benzene is produced from the process of hydrodemethylation of toluene under either

catalytic or thermal conditions. In catalytic toluene hydrodealkylation, toluene is first mixed

with a hydrogen stream which is then passed through a vessel that is packed with a catalyst

of supported chromium or molybdenum oxides, platinum or platinum oxides, on silica or

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alumina. The operating temperatures has a range from 500 to 595 C and pressures are

between 4-6 MPa (40-60 atm). This reaction is highly exothermic and injection of quench

hydrogen is placed at several places along the reaction to control the temperature.

Conversions per pass usually reach 90% and selectivity to benzene is often more than 95%.

This process occurs at lower temperatures and offers wide selectivity but requires

continuous regeneration of the catalyst. Products leaving the reactor pass through a

separator to remove unreacted hydrogen which is recycled to the feed. Further fractionation

is done to separate methane from the benzene product.

Table 1.1: Physical properties of Benzene (PubChem, 2017)

Property Value
Molecular Weight 78.114 g/mol
Boiling Point 80C
Melting Point 5.5C
Flash Point -11C
Density at 20 C 0.88
Vapor Density 2.77
Heat of Vaporisation at 25 C 33.83kJ/mol

1.1.2 Propylene

Propylene is an unsaturated organic compound with a single double bond having a

chemical formula of C3H6. It is a colourless gas at room temperature with a naturally

pungent smell. Although similar to propane, it has a double bond which gives it a

combustion advantage and is extremely flammable and non-toxic. Propylene is an

alternative to propane for heating and cutting due to its combustion advantage and is

widely used as a fuel gas for high-velocity oxygen fuel (HVOF) processes. Moreover, the

chemical and plastics industries depend on propylene as a fuel gas. Other applications

include organic synthesis to produce materials such as phenol and acetone. Propylene can

be polymerised to form polypropylene plastic and be employed as a refrigerant, or in

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calibration mixtures. In addition, it can be used to test the efficiency of gas burners and

engines. (The Linde Group, 2017)

Figure 1.2: Structure of Propylene (CIEC, 2014)

Propylene can be obtained during the refining of gasoline and it can also be produced

by splitting, cracking and reforming hydrocarbon mixtures. According to ICIS (2007), there

are two sources of propylene which are as a byproduct from the steam cracking of liquid

feedstocks such as naphtha as well as LPGs, and from refineries using off-gases produced in

fluid catalytic cracking (FCC) units. The remainder of propylene is produced using on-

purpose technologies. For example, propane dehydrogenation (PDH) and metathesis.

Table 1.2: Physical Properties of Propylene (PubChem, 2017)

Property Value
Molecular Weight 42.08 g/mol
Boiling Point -48C
Melting Point -185C
Flash Point -108C
Specific gravity at 20 C 0.514
Heat of Vaporisation at boiling point 104.62 cal/g

1.1.3 Availability of Raw Material

It is vital that the raw materials which are benzene and propylene needed for the

production of cumene, can be obtained locally from Malaysia. This is because if there is less

production of raw materials in Malaysia, then it would be necessary to import the raw

materials which contributes to a higher cost. Therefore, it is important to study the

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availability of raw materials and their production capacity that are available locally. Table

1.3 below shows the following companies that manufactures the raw materials which are

benzene and propylene. From the table, it can be seen that only Titan Petchem (M) Sdn Bhd

that is located in Pasir Gudang, Johor produces both benzene and propylene.

Table 1.3: Availability of Raw Materials in Malaysia (IHS Markit, 2016)

Petrochemical Capacity Company Location

Products (mtpa)
Titan Petchem (M) Sdn Pasir Gudang,

Bhd Johor
MTBE (M) Sdn Bhd Kuantan, Pahang
Benzene 775 thousand

Optimal Olefins (M) Sdn Kuala Lumpur

Bhd
Titan Petchem (M) Sdn Pasir Gudang,

Propylene 854 thousand Bhd Johor

Aromatics Malaysia Sdn KLCC, Kuala

Bhd Lumpur

1.2 Overview of Product

Cumene is the common name for isopropylbenzene, an organic compound that is an

aromatic hydrocarbon. It has a chemical formula of C 9H12. It is a constituent of crude oil

and refined fuels. Almost all cumene are produced as a pure compound on an industrial

scale is then converted to cumene hydroperoxide, which is used as an intermediate in the

synthesis of other industrially important chemicals such as phenol and acetone. Cumene is

produced from benzene and propylene in Friedel-Craft Alkylation of benzene by propylene

(PubChem, 2017).

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 Figure 1.3: Structure of Cumene (Royal Society of Chemistry, 2015)

Cumene is a clear, colourless, flammable liquid with an aromatic odor. Cumene is

less dense than water and the vapors heavier than air. It may be toxic by inhalation,

ingestion and skin absorption (PubChem, 2017).

Table 1.3: Physical Properties of Cumene (PubChem, 2017)

Property Value
Molecular Weight 120.195 g/mol
Boiling Point 152C
Melting Point -96C
Flash Point 31C
Specific gravity at 20 C 0.862
Solubility at 25 C in water 61.3mg/L
Vapor Density relative to air 1:4.2
Vapor Pressure at 25 C 4.55 mmHg
Stability Volatile
Auto-Ignition Temperature 420C
Viscosity at 25C 0.737mPa.sec
Heat of Vaporisation at 25C 45.13kJ/mol

1.2.1 APPLICATION OF CUMENE

Cumene is produced mainly for phenol and acetone production. It is a vital

intermediate for the production of phenol which is used for the manufacturing of epoxy

resins for paints coatings and mouldings, as well as polycarbonate plastics such as CDs and

domestic electrical appliances. Furthermore phenol can be used as a feedstock caprolactam,

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an intermediate in the production of nylon-6 which is used in the manufacture of nylon and

polyamide plastics for a variety of products, including carpets, clothing, and moulded

components and packaging. Besides, alkylphenol is used in the manufacture of surfactants,

detergents and emulsifiers, as well as insecticide and plastics production. (Greener

Industry, 2017)

Cumene is also an intermediate for the production of acetone which is used as a

primary ingredient in nail polish removers as it has the property to easily mix with water

and evaporates quickly in the air. Moreover, acetone is used in a wide range in the textile

industry for degreasing wool and degumming silk. Acetone is regurlarly incorporated in

solvent systems used in the formulation of lacquers for automotive and furniture finishes as

well as able to reduce the viscosity of lacquer solutions. (ChemicalSafetyFacts, 2017)

However, cumene can also be used as a blending component in gasoline pool, as a

method to avoid benzene restrictions in gasoline. It can be said that the use of cumene as a

blending component will rise when its price falls below its alternate octane value (IHS

Markit, 2016). According to Cumene-Industrial, 2010, asmall quantity of cumene is also

used as a coating in paints and inks and in laboratory settings which include material

transfer and equipment cleaning. It can be used also as starting material in the production

of acetophenone, methyl styrene, diisopropyl benzene and dicumyl peroxide. It is also

deemed to be a good solvent for fats and resins and such cumene has been suggested as a

replacement for benzene in many of its industrial applications. (academia)

1.3 OVERVIEW OF POTENTIAL ROUTES

There are several potential routes to produce cumene from the Friedel-Crafts

reaction between benzene and propylene where each routes utilises different acid

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catalysts such as aluminum chloride (AlCl3), solid phosphoric acid (SPA) and acidic

zeolites that have been utilised in commercial operations. The production of cumene is

from the reaction between benzene and propylene occurs based on Friedel-Crafts alkylation.

(Nexant, 2013).

Example of Friedel-Crafts reaction is where cumene is formed as major product

when benzene is treated with propyl bromide at 80 oCwith addition of anhydrous aluminium

chloride. During the reaction, the propyl carbocation is rearranged to more stable isopropyl

carbocation by hydrogen ion shift. Thus, the major product obtain is cumene rather than

propyl benzene. (Adichemistry, 2017)

Figure 1.4: Reaction of Friedel-Crafts Alkylation of Benzene with Propylene

(Adichemistry, 2017)

There are two reactions take place in Friedel-Crafts alkylation of benzene with

propylene. The main reaction is electrophilic aromatic substitution of benzene and

propylene to synthesis cumene as shown in Equation 3.1. At the same time, side reaction

between propylene and cumene produced a side product which is diisopropyl benzene

C
( 12 H 18 ) , DIPB as shown in Equation 3.2. (Engineers Guide, 2017)

Main Reaction: C3H6 + C6H6 C6H5-C3H7 (3.1)

Propylene Benzene Cumene

By-Product Reaction: C3H6 + C6H5-C3H7 C12H18 (3.2)

Propylene Cumene Diisopropylbenzene (DIPB)

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 Transalkylation of benzene with the side product which is DIPB can also produce

two moles of cumene as shown in Equation 3.3. Therefore, transalkylation reactor is

installed in most of the production processes in order to optimize the production of cumene.

C12 H 18+C 6 H 6 2C 6 H 5 C3 H 7 (3. 3)

There are few process of cumene production that are analysed, in order to choose the

best route that has both high yield and high quality according to the standard. The

processes are Monsanto-Lummus Crest process, UOP Cumene process and UOP Q-MAX TM

process.

1.3.1 Monsanto- Lummus Crest Cumene Process

The main feature of this process is low benzene recycle ratio. This process is able to

yield cumene overall at about 99 wt% based on benzene and 98wt% based on propylene

(Othmer.K, 2015). According to Kirk-Othmer, in Monsanto-Lummus process, dry benzene,

fresh and recycle, and propylene are mixed in the alkylation reactor with AlCl 3-HCl

catalyst. In this process, aluminium chloride catalyst is used and since this catalyst is has

strong acidity, it is separated from the organic phase by washing the reactor effluent with

water and caustic. Meanwhile, the distillation system is designed to recover high purity

cumene product. Any unconverted benzene are recycled to the reaction system.

1.3.2 UOP Cumene Process

Universal Oil Products Platforming Process (UOP) developed a fixed bed, Kieselguhr

supported phosphoric acid catalyst system. In this process, the solid phosphoric acid

catalyst is used where it provides an almost complete conversion of propylene on a one-pass

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basis. The difference of this process from others is that, yield of cumene is achieved without

transalkylation of diisopropylbenzene due to the catalyst used. Based on research, the

overall yields of cumene for this type of process are at about 97-98 Wt. % with

transalkylation and 94-96 Wt % without transalkylation.

1.3.3 UOP Q-MAXTM Process

According to UOP LLC, Q-Max process is a new cumene technology in which highly

selective, robust and stable zeolitic catalyst is used for the cumene production process. The

Q-Max process provides excellent cumene product quality of 99.97 wt-% purity and cumene

yield around 99.7wt-%. There are two types of catalysts used in Q-MAX Process which are

QZ-2000 and QZ-2001.

The QZ-2000 is a zeolitic catalyst which operates with low benzene circulation while

QZ-2001 is an enhanced stability version of QZ-2000 catalyst that has twice the stability as

per compared to QZ-2000 in alkylation reactor. The advantage of this process is that the

DIPB stream is recycled to increase the conversion to the transalkylation reactor where

both recycled DIPB and benzene are converted to more cumene. (UOP LLC, 2006).

Based on each process characteristics, advantages and disadvantages, UOP Q-

MAXTM process is selected for this project. Justifications of selecting this process are further

discussed and explained with detailed comparison and information of all of the potential

routes to produce cumene in Chapter 3.

1.4 OVERVIEW OF PLANT AREA AND LOCATION

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 There are two potential areas for the plant of cumene production which are Kawasan

Perindustrian SILC and Senai Industrial Park where both are located in the state of Johor.

There are several factors that needed to be considered to choose the best location such as

the availability of raw materials, transport facility, distance from supplier and availability

of utilities.

In the case of Kawasan Perindustrian SILC, it is located in Gelang Patah, Johor and

can be accessed from the main city Johor Bahru which is 15 minutes away and 30 minutes

from Singapore Central Bussiness District (CBD). A total of 1300 acres of land size

available (Nusajaya Development, 2012). The land value is about RM 40 per square ft. The

nearest raw material supplier of both benzene and propylene is Lotte Chemical Titan Sdn

Bhd located in Pasir Gudang, Johor where the distance is around 45km.

In the case of Senai Industrial Park, it is located in Senai, Johor and is 10 minutes

away from the North- South highway. A total of 200 acres of land size available and it cost

around RM 33 per square ft (iProperty, 2017). The nearest raw material supplier of both

benzene and propylene is Lotte Chemical Titan Sdn Bhd located in Pasir Gudang, Johor

where the distance is around 36 km.

Based on details of these location, the best location chosen for the plant is Senai

Industrial Park because it is located nearer to the raw material supplier and thus the

transportation cost is lesser compared to Kawasan Perindustrian SILC. Moreover, the cost

of land of the Senai Industrial Park is much cheaper than the SILC at RM 33 per square ft.

Though the land size is smaller than of SILC, it is assumed that 20 acres is enough for the

plant to produce 100000mt of cumene.

FACTORS LOCATION

Kawasan Perindustrian Kawasan Perindustrian

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 SILC Senai

Availabilty of raw material Both benzene and propylene Both benzene and propylene

available from Lotte available from Lotte

Chemical Titan Sdn BhD Chemical Titan Sdn BhD

Distance from raw material 45 36

source (Km)

Land Availabilty 1300 acres 20 acres

Cost per square ft RM 40 RM 33

Transportation facility 15 minutes away from main 10 minutes away from the

city and 30 minutes from North- South highway

Singapore Central

Bussiness District (CBD)

1.5 PROBLEM STATEMENT

Cumene is an intermediate that is used in the production of phenol and acetone and

is used widely in the industries mainly industries related to the production of plastic. Due

to the increase in demand for phenol production as plastic related objects are produced

more into the years. This causes the demands of cumene to be increasing and are expected

to grow throughout until 2020 as the demand for phenol in the industry is increasing.

However, the production of cumene is expected to get tighter as one of the major producers

of cumene is expected to shutdown which is the Sunocos company (ICIS 2017).

In Malaysia, there are limited numbers to none cumene suppliers although there are

numbers of major companies that can supply the raw material which is benzene and

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propylene. This is a major problem where with the availability of raw materials, cumene is

not produced in large scale but is needed to import cumene in order to process phenol and

acetone. This brings in a great amount of import cost to the companies processing phenol

whih may reduce their production rate. Therefore, this project brings the opportunity to

create a win-win situation to the Malaysian companies that process phenol and acetone or

any other that needs cumene as purchasing cumene from our plant will lessen their cost for

import and the transport fee. Along with this the production of the cumene can be a good

opportunity for anyone to tackle as it can serve as a good business opportunity and

approach in Malaysia and even globally.

1.6 PROJECT SCOPE

The project scope is to design and execute the most feasible process of production

cumene from the reaction of benzene and propylene in Malaysia. The main requirement of

the project, as indicated by the supervisors, is to build a process plant with a business

capital of RM500 millions. The estimated payback period, which is the length of time

required to recover the cost of an investment, should be less than 5 years. Moreover, the raw

materials can be sourced locally or abroad. Taking into consideration practicality wise, the

location of the plant will be limited within the boundaries of Malaysia where the preferable

location to operate the plant is Frontier Industrial Park, Johor. Therefore, the plant is to be

safely operated environmentally at the suitable production rate and desired purity of

product while ensuring the product reaches the demand.

1.7 AIM AND OBJECTIVES

The long-term aim of this project is to design a plant for the production of cumene in

Malaysia that are environmentally friendly to achieve and sustain profitable investment.

The objectives of the design project are as listed below:

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 i. To design a process with the capacity to produce cumene from the reaction of benzene

and propylene with a conversion rate at or more than 80%.

ii. To analyse the process and design whether it is economically competitive and feasible.
iii. To identify the most appropriate process and catalyst for the production of cumene.
iv. To analyse the availability of raw materials and the global market trend of cumene.
v. To analyse and select the best route in producing the cumene based on the study of

reaction kinetics of the process.

vi. To calculate Material and Energy Balance of the process using Excel spreadsheet.
vii. To develop several Process Flow Diagram (PFD) and choose the most feasible design for

the project.
viii. To stimulate the design using stimulation software such as ASPEN HYSYS and

SuperPro Designer.
ix. To develop Piping and Instrumentation Diagram (P&ID) in order to select the most

feasible design for the project.

x. To design the unit operations for the large scale production of cumene.
xi. To investigate the utility requirement for the cumene plant.
xii. To develop a better P&ID from the pinch analysis and process optimisation.

1.8 SUMMARY

Cumene is the intermediate for the production of phenol and acetone. Due to the

high demand of phenol, the demand for cumene has a steady increase. Due to the demand

and the lack of cumene plant in Malaysia, this project was conducted in order to supply

cumene to the local industries.

The production of cumene is from the Friedel-Crafts reaction of benzene and

propylene. Of all the potential routes of the production of cumene, the UOP Q-Max TM

process is the best where it is able to produce cumene of purity at 99.97% and percentage

yield of cumene at 99.7% as well as being environmentally friendly. This process uses the

catalyst QZ-2000 and QZ-2001 which are regenerable catalyst. The plant will be located in

Frontier Industrial Park, Johor due to the availability of raw materials and distance

between raw material supplier and plant location.

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