Mini DP Chlorobenzene

Table of Content

No.

Title

Page

1.

Introduction to Chlorobenzene

2.

Process Description & Process Analysis

3.

Plant Location & Site Selection

4.

Process Flow Diagram (PFD)

5.

Workbook

6.

Material & Energy Balance

7.

Pinch Calculation

8.

Major Equipment Design

Piping & Instrumentation Diagram (P&ID)

9.

Plant Layout

10. Capital & Manufacturing Cost

11. Hazard Analysis (Environmental

Considerations)

12. References

13. Appendices

Introduction to Chlorobenzene

Chlorobenzene is an aromatic organic compound with the chemical formula C6H5Cl. It is made from chlorine and benzene trough chlorination process. It is a colorless volatile flammable liquid with an almond odor and used as a solvent and in the production of phenol and DDT and other organic compounds.

As a group, chlorobenzenes are much less reactive than the corresponding chlorinated derivatives of alkyl compounds and are similar in reactivity to the vinyl halides. They are very stable to nucleophilic attack due to resonance in the molecule resulting in a shortening of the carbon-chlorine bond distance and an increase in bond strength.

Chlorobenzenes are not attacked by air, moisture, or light. at room temperature and pressure. Chlorobenzenes also are not affected by steam, prolonged boiling with aqueous or alcoholic ammonia, other alkalis, hydrochloric acid, or dilute sulfuric acid. To form phenols, hydrolysis takes place at elevated temperatures in the presence of a catalyst.

Hot concentrated sulfuric acid attack chlorobenzenes to form chlorobenzene-p-sulfonic acid. Nitric acid will react with chlorobenzenes at the meta- and parapositions on the ring to form chloronitrobenzenes at -30°C to 0°C (-22°C to 32°F). At higher temperatures, the nitration will either proceed further to form a dinitrochloro-compound, chloronitrophenol, or a nitrophenol.1 Chlorobenzenes are attacked by electrophilic agents. Para- is predominantly substitution for

monochlorobenzene with some ortho-substitution. Electrophilic substitution might be resisted by the higher chlorinated benzenes but can be substituted under extreme conditions.

Some free radical reactions undergo on Chlorobenzenes. Formation of organometallic compounds (grignards, aryl-lithium compounds) provides a useful route to many organic intermediates. Photochemical transformations occur on irradiation of chlorinated benzenes, which are much less stable to radiation than benzene. When subjected to ultraviolet irradiation or pulse hydrolysis in solution, chlorobenzenes may polymerize to biphenyls, chloronaphthalenes, or more complex products. The ability of chlorobenzenes to undergo wide varieties of chemical reactions makes chlorinated benzenes useful as reactants in numerous commercial processes to produce varied products. All chlorinated derivatives of benzene are soluble in lipids. Partition coefficient data for chlorobenzenes show an increase in partition coefficient with an increase in the degree of chlorination. In general, a positive correlation exists between partition coefficient and degree of bioaccumulation.

Identification

Chlorobenzene identification in the commercial industry is listed as below in Table 1.2:

Chemical Name Chlorobenzene

Molecular Structure

Synonyms Monochlorobenzene, Chlorobenzol, Phenyl

chloride, Benzene chloride

IUPAC Name Chlorobenzene

Classification Aryl halides

UN Identification Number UN1134

Hazardous Waste ID No. D001, U037, D021

Formula C6H5Cl

The physical and chemical properties of chlorobenzene can be concluded in the Table 1.1.

Properties Value

Molecular Weight 112.56G

Normal Freezing Point -45.58 °C

Vapor Pressure 1.17 kPa

Normal Boiling Point, 131.69 °C

Liquid Density 1.11 g/cm3

Reference temperature for liquid Density

20 °C

Uses

Chlorobenzene is usually used as a solvent for pesticide formulations, diisocyanate manufacture, and degreasing automobile parts and for the production of nitrochlorobenzene. Furthermore, chlorobenzene can be used as intermediate in the phenol and dichlorodiphenyltrichloroethane (DDT) production.

Health

The United States Environmental Protection Agency (EPA) stated that the exposure of the chlorobenzene to human being appears to be primarily occupational. EPA has listed some information on the health hazard information of chlorobenzene.

Acute Effects:

Acute exposure to chlorobenzene may cause redness and inflammation of the eyes and eyelids, runny nose, sore throat, redness and irritation of the skin, headache, dizziness, drowsiness, incoherence, ataxia, and loss of consciousness. Furthermore, it also may cause twitching of the extremities, deep and rapid respiration, and irregular heartbeat. Respiratory arrest may follow.

1. A child who ingested chlorobenzene became unconscious and cyanotic and had muscle spasms but recovered completely.

2. Acute inhalation exposure of animals to chlorobenzene produced narcosis, restlessness, tremors, and muscle spasms.

3. Acute animal tests in rats, mice, rabbits, and guinea pigs have demonstrated chlorobenzene to have low acute toxicity by inhalation and moderate acute toxicity from oral exposure.

Chronic Effects (Non-cancer):

Long term exposure to chlorobenzene may cause chronic central nervous system (CNS) depressions which are headache, dizziness, and somnolence. Based on effects seen in animals, chronic exposure may cause elevated liver enzymes, enlarged and tender liver, and blood, pus, or protein in the urine. Prolonged or repeated skin contact may cause skin burns.

1. Chronic exposure of humans to chlorobenzene affects the CNS. Signs of neurotoxicity include numbness, cyanosis, hyperesthesia (increased sensation), and muscle spasms. 2. Headaches and irritation of the mucosa of the upper respiratory tract and eyes have also

been reported in humans chronically exposed via inhalation.

3. The CNS, liver, and kidneys have been affected in animals chronically exposed to chlorobenzene by inhalation.

4. Chronic ingestion of chlorobenzene has resulted in damage to the kidneys and liver in animals.

5. EPA has calculated a provisional Reference Concentration (RfC) of 0.02 milligrams per cubic meter (mg/m3) for chlorobenzene based on kidney and liver effects in rats. The RfC is an estimate (with uncertainty spanning perhaps an order of magnitude) of a continuous inhalation exposure to the human population (including sensitive subgroups), that is likely to be without appreciable risk of deleterious noncancer effects during a lifetime. It is not a direct esimator of risk but rather a reference point to gauge the potential effects. At exposures increasingly greater than the RfC, the potential for adverse health effects increases. Lifetime exposure above the RfC does not imply that an adverse health effect would necessarily occur. The provisional RfC is a value that has had some form of Agency review, but it does not appear on IRIS.

6. The Reference Dose (RfD) for chlorobenzene is 0.02 milligrams per kilogram body weight per day (mg/kg/d) based on histopathologic changes in the liver in dogs.

7. EPA has medium confidence in the study on which the RfD was based because it provided both a no-observed-adverse-effect level (NOAEL) and a lowest-observed-adverse-effect level (LOAEL) and incorporated several biochemical and biological endpoints; medium confidence in the database because several subchronic, chronic, developmental, and reproductive toxicity studies provide supportive data, but they did not give a complete assessment of toxicity; and, consequently, medium confidence in the RfD.

Reproductive/Developmental Effects:

1. No information is available on the reproductive or developmental effects of chlorobenzene in humans.

2. Chronic inhalation exposure of rats to chlorobenzene did not adversely affect reproductive performance or fertility. However, a slight increase in the incidence of degenerative testicular changes was observed.

3. Chlorobenzene does not appear to be a developmental toxicant and did not produce structural malformations in rats and rabbits acutely exposed via inhalation.

Cancer Risk:

1. No information is available on the carcinogenic effects of chlorobenzene in humans. 2. In a National Toxicology Program (NTP) study of rats and mice exposed to

chlorobenzene via gavage (experimentally placing the chemical in the stomach), an increased incidence of neoplastic nodules of the liver in high dose male rats was observed, but not in female rats or male or female mice.

3. EPA has classified chlorobenzene as a Group D, not classifiable as to human carcinogenicity.

Handling

A worker who handles chlorobenzene should wear protective clothing such as gloves, boots, aprons, and gauntlets to prevent skin contact with chlorobenzene. Eyewash fountains and emergency showers should be available within the immediate work area whenever the potential exists for eye or skin contact with chlorobenzene. Contact lenses should not be worn if the potential exists for chlorobenzene exposure.

Use of respirator also should be considered for handling the chlorobenzene. Good industrial hygiene practice requires that engineering controls be used to reduce workplace concentrations of hazardous materials to the prescribed exposure limit. Respirators must be worn if the ambient concentration of chlorobenzene exceeds prescribed exposure limits.

Spill and leaks

In the event of spill or leak involving chlorobenzene, persons not wearing protective equipment and clothing should be restricted from contaminated areas until cleanup is complete. The following steps should be undertaken following a spill or leak:

1. Do not touch the spilled material. 2. Notify safety personnel.

3. Remove all sources of heat and ignition. 4. Ventilate potentially explosive atmospheres.

5. Water spray may be used to reduce vapors, but the spray may not prevent ignition in closed places.

6. For small dry spills, use a clean non-sparking shovel and gently place the material into a clean, dry container, cover and remove the container from the spill area.

7. For small liquid spills, absorb with sand or other non-combustible absorbent material and place into closed container for later disposal.

8. For large liquid spills, build dikes far ahead of the spill to contain the chlorobenzene for later reclamation or disposal.

Storage

Chlorobenzene should be stored in a cool, dry, well-ventilated area in tightly sealed containers that are labeled in accordance with OSHA’s hazard communication standard (29 CFR 1910.1200). Outside or detached storage is preferred. Inside storage should be in a standard flammable liquid storage room. Containers of chlorobenzene should be protected from physical damage and should be stored separately from oxidizers, dimethyl sulfoxide, silver perchlorate, other incompatible material, heat, sparks, and open flame. Only non-sparking tools may be used to handle chlrobenzene. To prevent static sparks, containers should be grounded and bonded for transfers. Because containers that formerly contained chlorobenzene may still hold product residues, they should be handled appropriately.

Market Analysis of Chlorobenzene

Demand and consumption pattern

Only three of many possible products resulting from the chlorination of benzene continue to have any large-volume applications—monochlorobenzene, o-dichlorobenzene and p-dichlorobenzene—and they are the major focus of this report. These three products combined account for as much as 92–96% of the total chlorobenzenes market. Other chlorobenzenes that have commercial applications but are not produced on a large scale include m-dichlorobenzene, trichlorobenzenes, tetrachlorobenzenes and hexachlorobenzene. Market information on these products is included in the report where available.

Monochlorobenzene accounts for nearly 73% of total chlorobenzene consumption. China is the world's largest manufacturer and consumer, accounting for nearly 82% of total consumption in the four major regions shown below. Monochlorobenzene represents about 70% of chlorobenzene consumption in Western Europe, and 52% of consumption in the United States, but only 10% in Japan, where p-dichlorobenzene is a larger factor than in the other regions. Nitrochlorobenzene is the most significant end use for monochlorobenzene. Nitrochlorobenzenes are consumed as intermediates in the manufacture of dyes and pigments, rubber-processing chemicals, pesticides (e.g., parathion and carbofuran), pharmaceuticals (e.g., acetaminophen) and other organic chemicals. Monochlorobenzene has been used for the synthesis of diphenyl ether (also known as diphenyl oxide or DPO) and is increasing in demand for sulfone polymers.

o-Dichlorobenzene is a chemical intermediate consumed mostly for 3,4-dichloroaniline in the United States, South America and Western Europe and as an herbicide intermediate in Japan. Worldwide, p-dichlorobenzene is used primarily as a raw material for polyphenylene sulfide (PPS) resins, for deodorant blocks for indoor air, and for moth control. Polyphenylene sulfide is a growing high-performance polymer that is produced only in the United States, Japan and China. PPS resin production has increased rapidly both in the United States and Japan over the past five years and has become significant in China since 2010. PPS production is projected to continue to grow over the next five years, with additional capacity planned in China and the Republic of Korea. There are no producers of PPS resins in Western Europe.

The gradual shift in global demand away from industrialized regions and further into developing countries has resulted in a buildup of new chlorobenzene capacity in Asia. China is the world's most diverse market and home to four of the world's five largest producers. It also accounts for an estimated 68–75% of global capacity.

With the exception of high-performance polymers, the markets for chlorobenzenes are mature. Demand for chlorobenzenes in more industrialized regions has been on a decline for the past few decades as a result of the substitution of alternative chemistry in the production of such products as phenol, rubber chemicals and moth control agents. Growing environmental concern over usage in herbicides and solvents has additionally contributed to the slow decline. However,

strong growth in China and growing global demand for p-dichlorobenzene have since stabilized this trend, resulting in a moderate, average growth rate of 4% per year for the forecast period. Future Demand for Chlorobenzene

The capacity of chlorobenzene in China reached 320 000 t/a at the end of 2003, accounting for 50% of the world total. The output of chlorobenzene in China was around 260 000 tons in 2003. Chlorobenzene is mainly used to produce o- and pnitrochlorobenzene, 2,4-dinitrochlorobenzene and diphenyl ether. It is also used in the synthesis of solvents, pesticides and dyestuffs. The consumption composition of chlorobenzene in 2003 was 73.8% for o- and p-nitrochlorobenzene, 10% for 2,4-dinitrochlorobenzene, 1.7% for diphenyl ether and 14.5% for others. The import and export amounts of chlorobenzene in China are fairly small. The export amount was estimated to be 3 000 tons in 2003. The competition in chlorobenzene and major downstream products is mainly between domestic producers rather than from foreign products. Furthermore, the consumption of chlorobenzene in other sectors is also relatively stable, mainly determined by o - a n d p – nitrochlorobenzene production. With the rapid capacity expansion, the production cost of o- and p-nitrochlorobenzene in China has consistently fallen. Foreign countries have slowed down the development of o- and p-nitrochlorobenzene production and mainly depended on the import of downstream fine chemicals derived from o- and p-nitrochlorobenzene such as dyestuffs, pigments, pharmaceuticals and pesticides from China. The export of o- and p-nitrochlorobenzene has therefore been promoted. Chlorobenzene will still experience brisk production and sales in China in 2004 and there will be a supply shortage in some areas. If there are no drastic fluctuations in raw material supply, however, the price of chlorobenzene will be kept stable.

Process Description & Process Analysis

Continuous process Batch process Raschig process

1. Direct chlorination (Continuous process)

C6H6 + Cl2 C6H5Cl + HCl

C6H6 + Cl2 C6H5Cl + HCl

The process begins with a series of small, externally cooled cast iron or steel vessels containing the catalyst (which may consist of Rashig ring of iron or iron wire). The catalyst used is usually Ferric chloride. This can be added as solution in benzene. Chlorine is supplied into each vessel through suitably positioned inlets to maintain a large benzene-to-chorine reaction at all points along the reaction stream. The temperature is maintained about 20 to 40 for this reaction in order to minimize the production of dichlorobezene which occur at higher temperature. Besides, this range of temperature is the best temperature for production of large amount of monochlorobenzene. This process will produce large amount of monochlorobenzene and small amount of dichlorobenzene. The feed, which are liquid benzene and gaseous chlorine are at temperature 25 and atmospheric pressure then fed to the reactor which operates at 2.4 bars.

The reaction is exothermic process. Cooling process is required to maintain the temperature at 40 90% of the HCl formed is first cooled to condense impurities (benzene and chlorinated product) and then it is scrubbed in a scrubber using refrigerated chlorobenzene. The crude chlorobenzene stream leaving reactor is washed with NaOH solution (20wt%) in order to maintained slightly alkaline to protect downstream equipment from corrosion) in a pre-neutralizer. The product stream is free from HCl. Then, the product is fed to a Benzene Recovery Column (distillation column). Here, the bottom is almost slightly 100% pure chlorobenzene. The

top contain 98% by weight of benzene and 2% chlorobenzene. All the benzene is recycled to the benzene storage via a purifier. From purifier the monochlorobenzene is sent to the refrigeration system. The bottom contains monochlorobenzene and dichlorobenzene. This bottom product is fed to the chlorobenzene column that may be contain 12-25 trays which operated at 3-7 lb/in2 abs. The temperature may be 100 -200 . The distillate has purity of 99% monochlorobenzene while bottom has purity of 97% dichlorobenzene.

This reaction will produce HCI as the side product. All the desired product and undesired product are then fed to the Benzene Recovery Column (distillation column). The advantages of continuous process are, it produce higher amount of monochlorobenzene which is 95% conversion and the process also operate at lower temperature.

2. Batch process

In the batch process, benzene is contained in a deep, iron or mild steel vessel lined with lead cooling coils. The catalyst that usually used for this process is FeCl3, is added in a benzene solution. Chlorine is fed to into bottom of the chlorinator through a lead covered at temperature 45 in order to minimize the formation of dichlorobenzene. Then the crude chlorobenzene stream and HCl stream are collected and treated in the purification and recovery process.

For another type of batch process is describe by Faith, Keyes, and Clark’s Industrial Chemicals. The chlorine is bubbled into a cast iron or steel tank containing dry benzene with on percent of its own weight of iron filings. The temperature is maintained at 40°C to 60°C (104°F to 140°F) until density studies indicate that all benzene is chlorinated. Then, the temperature is raised to between 55°C and 60°C (131°F to 140°F) for six hours until the density raises to 1.280g/cm3 (79.91 lb/ft3). The same methods of chlorobenzene purification and HCl recovery in batch form are then employed. At 100% chlorination, the products are 80% of monochlorobenzene, 15 % of p-dichlorobenzene, and 5% of o-dichlorobenzene.

3. Hooker/ Raschiq Process

C6H6 + HCl + ½ O2 (AIR) C6H5Cl + H2O

C6H5Cl + H2O C6H5OH + HCl

This process is conducted at elevated temperature which is in the range of 230 to 270 . This process involve the reaction between benzene and mixture of hydrochloric acid gas and air in the presence of an oxychlorination catalyst. This catalyst consists of copper and iron chlorides on an inert support. Once-through conversion for this process is limited (10 – 15 percent ) to prevent the excessive formation of polychlorobenzene. The catalyst is put in the beds to prevent damage since this process is exothermic process. In order to control the overall temperature, the benzene is injected at lower temperature. This process is then followed by purification of monochlorobenzene which can be done by fed the product from the reactor into the distillation column which is known as brick-lined column.

The top stream of this column contain water/benzene azeotrope while at the bottom are 1/1 mixture of benzene and chlorobenzenes. The top product which is benzene and water is recycled back into the reactor while the bottom products which are benzene and chlorobenzene is neutralized with caustic soda, washed with water and distillate in two columns to separate the dichlorobenzene, monochlorobenzene and benzene. Then the process is followed by hydrolysis of the monochlorobenzene by steam in the presence of tricalcium phosphate or silica gel base catalyst which can be reactivated periodically to reduce carbon deposited. The formation of dichlorobenzene in the oxychlorination reaction and the polyphenols in the hydrolysis process reduce the yield.

The process contains a few disadvantages. The high temperature in the process favours high combustion rates of benzene which cause the reaction uncontrollable. Compare to the other process, this process produce high cost of vapour phase chlorination process which make it become uneconomical process for the production of monochlorobenzene. This process also can only produce small amount of chlorobenzene since this once-through conversion is limited.

Comparison between the three process

PROCESS RASCHIQ PROCESS CONTINUOUS

Raw Material  Benzene

 Hydrochloric acid

 Oxygen (air)

 Benzene

 Chlorine Reaction Conditions Temperature at range 220 -

260 and in gas-phase Temperature at range 20 -

40 and in liquid -phase

Reactor Fixed-Bed Reactor Continuous Stirrer Tank

Reactor

Catalyst Copper and iron chloride Ferric chloride

Advantages  Large economic

advantages because HCl produce in the hydrolysis of

chlorobenzene can be used for the

oxychlorination of benzene.

 Economy in steam and cooling required for evaporating and condensing the benzene.  Less purification operations.  Lower operating labor  Simple operation  liquid phase  High conversion of benzene (95%)  High production of monochlorobenzene  Produce less by products  only small amount of dichlorobenzene.

Disadvantages  Produce many

by-products 

 High cost of equipments

dichlorobenzene, trichlorobenzene, tetrachlorobenzene and others.  The benzene conversion is limited,10-15%.  The reaction is uncontrollable because of the high temperature.

 High cost of vapour phase chlorination process.

 Has large investment for corrosion-resistants  hydrochloric acid is highly corrosive  Required special material of

construction for very low temperature.

PROCESS BATCH

Raw Material  Benzene

 Chlorine

Reaction Conditions Temperature at range of 40 - 60 and in

liquid-phase

Reactor Batch Reactor

Catalyst Ferric chloride

Advantages  High production of

monochlorobenzene compare raschiq process.

 Low cost of factory equipment because of the simple design of batch reactor.

 Reaction it easy to control due to low temperature.

Disadvantages  Lower conversion compare to

continuous (80%).

 Produce higher amount of by-products  dichlorobenzene

 Only can produce small scale production.

 Require strict scheduling and control.

 Higher operating labor costs due to equipment cleaning and preparation time.

 Many people need to operate the process.

PROCESS SELECTION

Based on the review and screening, the most suitable process for the production of the monochlorobenzene is by continuous process. The process was selected because it is more beneficial compare to batch process and Raschig process. The selection is based on a few important criteria that need to be considering in this process. One of the criteria is continuous process can give higher conversion of monochlorobenzene which is 95% conversion. Besides, the temperature used for this process is only between 20 - 40 . At this low temperature, the operating cost can be reduced because it does not required heating process. Furthermore it is easy to handle the reaction at low temperature and this range of the temperature is the best temperature to produce high amount of the monochlorobenzene. Furthermore, the continuous process also produce high amount of monochlorobenzene and small amount of dichlorobenzene compared to the other two processes that produce dichlorobenzene, tri-chlorobenzene, penta-chlorobenzene and also tetra-penta-chlorobenzene. Another criteria is, for this process the benzene that been used is in liquid phase which is cheaper compared if we used benzene in vapor phase. Therefore, it indirectly can reduce the operating cost. Other than that, the continuous process only need a bit of workforce. So, only a few workers need to be hired and it indirectly also can reduce the labor cost.

Review of the process production of monochlorobenzene from benzene and chlorine (from question)

Liquid benzene (which must contain less than 30 ppm by weight of water) is fed into a reactor system consisting of two continuous stirred tanks operating in series at 2.4 bar. Gaseous chlorine is fed in parallel to both tanks. Ferric chloride acts as an catalyst produce in situ by the action of the hydrogen chloride on mild steel. Cooling is required to maintain the operating temperature at 328K. The hydrogen chloride gas leaving the reactor is first cooled to condense most of the organic impurities. It then passes to an activated carbon adsorber where the final traces of the impurity are removed before it leaves the plant for use elsewhere.

The crude liquid chlorobenzenes stream leaving the second reactor is washed with water and caustic soda solution to remove all the dissolved hydrogen chloride. The product recovery system consists of two distillation columns in series. In the first column (the ―benzene column‖) unreacted benzene is recovered as top product and recycled. In the second (the ―chlorobenzene column‖) the mono- and dichloro-benzenes are separated. The recovered benzene from the first column is mixed with the raw benzene feed, and this combined stream is fed to a distillation column (the ―drying column‖) where water is removed as overhead. The benzene stream from the bottom of the drying column is fed to the reaction system.

Plant Location & Site Selection

It is important to have a proper selection of the location of the plant. The geographical location of the plant could give a very strong influence to the success of the plant/industry itself. During the selection of the site of the plant, it is crucial to always keep in mind the objectives of the company. This will lead to a very careful considerations on the various factors that could make the plant to give a big contributions towards its working environment and thus, making it into an economically viable unit.

Any mistakes in selecting the plant location could lead to undesired situations or problems to occur, such as; a higher cost and investment, the difficulties in both marketing and transporting of the products, dissatisfaction of the employees and customers, as well as interruptions in the production process and an excessive wastage. Therefore, a complete survey of both the advantages and disadvantages of the various areas should be made prior to selecting the final site/location of the plant. The following are the list of the factors that should be taken into considerations during the selection of the site of the plant:

1. Location, with respect to the marketing area 2. Raw material supply

3. Transport facilities 4. Availability of labour 5. Availability of utilities 6. Availability of suitable land

7. Environmental impact (including the waste/effluent disposal) 8. Local community considerations

9. Climate

10. Political and strategic considerations

Other than those listed above, the room for expansion and safe living conditions of the operating plant are also important in the site selection. The following are the details on how the above factors affect the site selection of the plant.

1. Location with Respect to Marketing Area

The cost of an industrial land depends on few factors such as the physical characteristic of the land, market economic conditions and most of all its location, with respect to the marketing area. The price of the land site should be as economical as possible to reduce the total investment and construction cost of the plant. It is important to choose the lowest reasonable land price, with good storage and handling infrastructures. The price of the land can be referred to the real estate agency. For materials that are produced in large or bulk quantities, it is important that the proposed plant site should be located as close to the primary market so that the cost of transportation can be maximized. Other considerations include the demand of the product within the area and the availability of the raw materials suppliers should also be taken.

2. Raw Material Supply

This is one of the most important factors taken into consideration whenever a selection of plant location/site is made. The nearness of the source of the raw materials for the production of Chlorobenzene (which are benzene and chlorine) has to be considered since this will influence both the transportation and storage charges of the raw materials. This is very important especially if large volumes of raw materials are needed for the Chlorobenzene production process. The nearer the source of the raw materials could reduce the transportation and storage charges. Attention should also be given to the price as well as the purity of the raw materials themselves.

3. Transport Facilities

They are three forms of major transport facilities, which are the road network (land-port), seaport and airport. A plant site should be close to at least two of this major form of transport in order to boost the import-export activities. Land-port can be connected via road or railway. Road transport using lorry, etc. is suitable for local distribution from a central warehouse while rail transport using the train is used for long-distance transport of bulk chemical because is cheaper. Good road linkage will aid in the selling of product to local customer. Seaport facilities is connected via waterway such as canal, river and sea; using tankers that is usually practiced if involving import and exportation of product and raw materials with other country. Meanwhile, air transport using the airplane, helicopter, etc. is convenient and efficient for the movement of

personnel and essential equipment and supplies. Transportation factor also important in case of emergency such as an accident at the plant site for example fire at the workplace. Good road linkage from the site to the nearest fire station can prevent further property damage if this kind of accident happens.

4. Availability of Labour

This factor has been in the top 10 list (ranked by the Area Development Corporate Survey) of the important factors in site selection. The location of the plant should have sufficient available labors to be employed. Labors are needed for the construction as well as for running the plant. The availability of both the skilled and semi-skilled labors will lead to the efficiency of the operating plant itself. For example, when a large amount of money is invested by a plant, the needs of the skilled labors become very important in order to ensure the operations in the plant could run smoothly. Also, skilled labors such as the electricians and pipe fitters are important in the maintenance of the plant. Unskilled labors however are important as well for training in operating the plant.

5. Availability of Services such as Utilities, Water, Fuel, Power

Water, electricity and fuel are very important factors in site selection to ensure the plant can be operated smoothly. Nearness to the available power facility will reduce the plant operation cost. Most chemical processes required a large quantity of water for cooling process and general use. Thus, the plant needs to be located near to the source of water of suitable quality which is usually near to coastal (sea) area or lake. Other source for this process water may come from a river, deep wells, and reservoirs or even purchased from a local authority. Electrical power is a must at all sites, without electrical power, the plant might be shut down. Therefore the availability of power plants near to the plant site is very important. Stable and uninterrupted power of required magnitude, without fluctuations in voltage and frequency is important for the successful operation of the plant. Other than that, a reasonably competitive priced fuel is important for steam and power generation.

6. Availability of Suitable Land

It is important to first examine carefully the characteristics of the proposed plant site. This means that the topography of the tract of land and the structure of the soil has to be considered and examined very well. It should be noted that either the land or the soil of the proposed site could affect the cost of the construction. The characteristic of the land that is considered as the most suitable for the construction of a new plant is for it to be flat, well drained and having suitable load-bearing characteristics. Even though there is no immediate expansion is, it is best for a new plant to be constructed at a location with an additional space (for future changes).

7. Environmental Impact, Including Effluent Disposal

A plant site needs a smooth operation to maximize the production but in the same time release the minimum amount of waste or effluent so that cause less impact to the environment. For example, constructing a site next to sea coastal may be convenient for cooling water supply but it will cause harm to the local aquatic ecosystem in the water through excessive withdrawals or thermal pollution (from discharges of hot cooling water). All industrial processes will produce waste products. The site selected must have efficient disposal system such as drainage and dumping site. Disposal of toxic and harmful effluent need to follow the local regulations, and during the site survey, appropriate authorities need to be consulted to determine the standards that must be met.

8. Local Community Considerations

The proposed plant site should also consider the opinions of the community nearby the location of the plant. The proposed site should be accepted by the local community. It must be ensured that the plant that is going to be constructed at the proposed site will not cause any risks to the local community nearby. The health hazards should be kept at its minimum with all the safety precautions taken as one of the priority in the construction of the plant.

9. Climate

The characteristics features of the climate of Malaysia are uniform temperature, high humidity and copious rainfall with winds that are generally light. A suitable climate can ensure the plant to operate smoothly and productively. Some natural disaster such as flood, earthquake, typhoon, etc. that occur at the plant location may increase the cost of operation. Thus, careful site consideration needs to be taken to avoid choosing site with adverse climatic conditions. In Malaysia, cases where major disasters such as earthquake or typhoon occur very little; the weather condition is influenced by the Northeast and Southwest monsoon. The Southwest monsoon season usually occur in end of May to September with wind flow is generally light below 15 knots. Meanwhile, the Northwest monsoon occurs in early November to March with wind speed ranging from 10 to 20 knots. During the two inter-monsoon seasons, the winds are generally light and variable. Stronger structure need to be built at locations subject to high winds. Annual rainfall in Malaysia is found to be around 2500 mm per year. Rain falls most heavily during the monsoon season, which is from the end of September to early January for East Malaysia and December to March for West Malaysia. Malaysia is a tropical country that has a daily temperature that varies around 25 to 27 degrees Celsius. The maximum is about 32oC, while the minimum is about 21oC daily. Highest humidity is achieved during the night and dawn, while the relative humidity value drops to minimum around midday where bright sunlight appears.

10. Political & Strategic Considerations

Subsidies and concessions from the government are provided for industries located in certain notified areas. Those areas are the ones that have been declared as industrially backward where low wages, cheap power and tax concessions are offered by the government.

The Several Strategic Locations as the Site For The Manufacture Of Chlorobenzene

In order to find the most suitable site location for the production of Chlorobenzene (with 20000KMT/year of Mono-Chlorobenzene and not less than 2000KMT/year of Di-Chlorobenzene), all the 10 factors stated previously has been considered during the survey of several possible sites. The three main sites that have been considered are as listed below:

i. Tanjung Langsat, Johor

ii. Gebeng Industrial Estate, Pahang iii. Kerteh Industrial Park, Terengganu

Tanjung Langsat Industrial Complex, Johor

Iskandar Malaysia which is a development corridor conducted in the southern part of Johor. It is also known as the South Johor Economic Region (SJER). One of the main components of Iskandar Malaysia is as the centre of industrial and manufacturing activities which covers up to 31,132 hector of Pasir Gudang region. The Major Economic Zone D includes the Pasir Gudang Port, Pasir Gudang Industrial Park, Tanjung Langsat Port as well as the Tanjung Langsat Industrial Complex.

It is located for about 48km in eastern of Johor Bahru and 8km from the Pasir Gudang industrial area with population of around 100,000 people. One of the main economic activities of Pasir Gudang involves chemicals, oleo chemicals, biofuels and etc. The Tanjung langsat Industrial Complex symbolizes the continuation of the existence of the industrial area of Pasir Gudang and it covers an area of 4,198.52 acres which is reserved for light, medium, and heavy industries. On the other hand, the Tanjung Langsat Industrial Park which covers up to 3764 acres of land has been one of the most successful industrial estates in Malaysia with a tank farm facility being developed for the chemical storage.

This location has good connectivity in terms of the transport facilities. It currently is connected by the four-lane Pasir Gudang Highway, a trunk road and a railway line to Johor Bahru. This would therefore ease the transportation process of raw materials (chlorine and benzene) since the supplier of these raw materials are also available in Johor Bahru (HG Chemicals Technology

Sdn. Bhd.) which is only 48km away from Tanjung Langsat. Other than that, the Senai-Desaru Expressway makes it possible for the traffic from the north of Johor Bahru to have an easy access to the Tanjung Langsat Industrial Complex through the 5km four-lane dual carriage road that links Tanjung Langsat to the expressway. Also, this location has seaport nearby (Tanjung Langsat Port that is located adjacent to the 4,000 acres of the industrial land) which would make it easier for the import and export activity of the Chlorobenzene product. Tanjung Langsat Port is designed especially to handle the bulk cargo (LPG and hazardous chemicals). Other than that, Senai Airport is also available for personal businesses.

The available area for the industrial activities in Tanjung Langsat is about 2709.94 acres with the price ranging from RM12 – RM14 per square feet (for a 30yr + 30yr lease period). In terms of the available utilities, the current water supply by the Syarikat Air Johor Holdings Bhd (SAJH) to the industrial areas in Iskandar Malaysia is adequate. On the other hand, natural gas is used for the power generation in Malaysia with 24% of the NG being used in heavy industries whereas 4% is used in the housing, commercial and other industrial areas. Supply of NG is made by the Petronas Gas Bhd via pipelines to the factories.

In reference to Ramli, Abdul Rahim (2007), the environmental impact of the industrial activities in the Tanjung Langsat area has showed that the industrial development had given positive impacts to the local community in terms of their income, infrastructure as well as public facilities. However, it also creates negative impacts such as pollution of air & water and limitation of area for fishing activities around the Tanjung Langsat. Next, considering the climatic factor, as stated earlier, a suitable climate can ensure the plant to operate smoothly and productively. Natural disasters that occur at the plant location may increase the cost of operation. Thus, it is important to avoid choosing site with adverse climatic conditions. The possibilities of the occurrence of natural disasters in Malaysia are very low. Thus, it could be concluded here that in terms of climatic factor, Tanjung Langsat is also suitable for the site location. Next, the rapid development of the industry in the Pasir Gudang Tanjung Langsat has led to the shortage of manpower or labor to carry out all the operations in the plant. Though some industries have implemented the automated systems, but the need of manpower is still high.

Lastly, it is important to have the targeted marketing area as close as possible to the site location. Chlorobenzene is used mostly in the manufacture of pesticides, dyes, and rubber. Thus, it is

important to have the site close to the manufacturer of these three materials. In Johor, there are few rubber industries which are located at Skudai, Johor Bahru which are LekSeng Rubber Industries and N.K. Rubber (M) SDN. BHD.

Gebeng Industrial Estate, Pahang

Gebeng Industrial Estate (GIE) has developed rapidly over the past 20 years where it first started in early 90s by the Pahang State Development Corporation (PSDC). GIE is located in Kuantan, Pahang, Malaysia which consist of four development phases that have about 8600 hectares of land and is a world-class petrochemical and chemical industrial zone. It is located 25 km from Kuantan Town and 250 km from Kuala Lumpur; and is strategically located only 5 km from the Kuantan Port. GIE also offers a wide variety of facilities for the investors. For example, the Gebeng bypass that links Kuala Lumpur and Kuantan directly via the East Coast Highway which eases the trafiic flow from the industrial estate to Kuantan Port. Pahang State Government has continuously upgrading the infrastructures around the area mainly its transportation facilities. For example, the railway link that connects Kuantan Port-Gebeng-Kerteh to ensure the import and export activities runs smoothly.

1. Location, with respect to the marketing area

 Distance from nearest town : o 25 km from Kuantan town o 250 km from Kuala Lumpur city

- Using land transport is 2 hours drive and by air is 45 minutes.

 Distance from nearest port : o 5 km from Kuantan Port

- This is very strategic; close proximity to the port save the logistics costs and promotes imports-exports activities.

 Market Demand:

o Chlorobenzene is widely used in pesticide business. Within the Pahang State itself, there are many pesticide or pest control company that required chlorobenzene for its production, for example:

- Rentokil Pest Control Kuantan, BINS Pest Control, Kilpest (Pahang) Sdn Bhd, Prima Pest Control & Services, etc. which is all located in Kuantan, Pahang.

o Chlorobenzene also used in synthesis of rubber for example in manufacturing of tire and furniture. There are a lot of tires and rubber-based furniture company in area near to Gebeng such as Uts Tyre Service (Kuantan) Sdn Bhd and TWINS Furniture Manufacture.

o Other than that, chlorobenzene also involve in the production of herbicide that widely used to kill weed. Weed killer is popular among farmers and also landscape designer.

2. Raw material supply

 The raw materials needed for production of chlorobenzene are chlorine and benzene. There are many suppliers for benzene near to Gebeng, for example PETRONAS Chemicals Group Berhad (PCG) which is located at Gebeng too. Since Gebeng Industrial Estate is located near to Kuantan Port, the availability of raw materials should not be a problem as it can be exported from outside of Gebeng.

3. Transport facilities a) Road facilities: i. Highway

- East Coast Highway that links Kuantan and Kuala Lumpur which is only 2 hours drive away.

- Gebeng Bypass Road is being planned to further enhance the traffic flow between the main road and Gebeng.

- Kuantan Bypass Road will be widened to eased the traffic congestion. - Federal Road (Kuantan-Kerteh-Kuala Terengganu)

- Federal Road (Kuantan-Segamat)

ii. Railway

- Have a railway link that connects the integrated petrochemical complex in Kerteh (Terengganu) to Gebeng and Kuantan Port. This railway link has strengthen the chemical and petrochemical linkage between Gebeng and other industrial centers by which it ensures a much more safer form of transporting dangerous goods by train rather than by road.

b) Airport facilities:

- The nearby airport to Gebeng is the Kuantan Airport. Since airport transportation is used to ease the movement of personnel and essential equipment and supplies from Gebeng to other places, Kerteh Airport and Kuala Lumpur International Airport (KLIA) also available for this purpose.

c) Seaport facilities:

- The main seaport facility in Gebeng is Kuantan Port which is only located 5 km from the industrial estate. (*More details about Kuantan Port are described in

latter section.)

- Other seaports that connect with Kuantan Port are Kemaman Port and Kerteh Minor Port for better transport of goods for import and exports activities.

4. Availability of labour

 Labors, of both the skilled and semi-skilled labors are needed for the construction as well as for running the plant. Training institution with customized courses are available such as:

- Universiti Teknologi Malaysia, Indera Mahkota - Institut Latihan Perindustrian

- Politeknik Sultan Ahmad Shah (POLISAS) - Institut Kemajuan Ikhtisas Pahang (IKIP)

5. Availability of utilities

a) Electricity

 The main electricity supplier in Gebeng Industrial Estate is Tenaga Nasional Berhad (TNB) which supply 132/11 kV main intake for Phase I and II; and for Phase III, there are two sources of electricity available which are Centralized Utility Facilities (CUF) and 12/275 kV main intake.

 Other sources of electricity may be from the nearest electric generators which are: - Paka Power Plant

- IPP YTL Power Generation Sdn. Bhd. - Tasik Kenyir Hydro-Electric

b) Water Supply

 The main water supply in Gebeng Industrial Estate is from the Semambu Water Treatment Plant with capacity of 2 MG/D.

 Others are from the reservoirs at Bukit Penggorak with capacity of 2 MG/D and 1.5 MG/D; and reservoirs at Bukit Merah with capacity of 0.5 MG/D and 1.0 MG/D.

 Government of Pahang have taken few steps in order to ensure efficient water supply in Gebeng which are:

i. Increase the water supply to 64 MG/D

ii. Building of a new 200 acres dam in Sungai Lembing, Kuantan iii. Building of new pipes and water tanks in Gebend Industrial Estate

c) Natural gas utility

 The current natural gas suppliers for Gebeng Industrial Estate are Gas Malaysia and Petronas Gas Berhad which supply gases within the estate to fulfil the tremendous demand for existing and further petrochemical projects in the area.

 Other than that, availability of natural gases, Butane and Propane are supplied by the Peninsular Gas Utilization Network (PGU).

d) Telecommunications

 Telecommunication services such as Integrated Systems Digital Network (ISDN), digital line, MAYPAC, Internet and video conferencing in Gebeng is supplied by the Telekom Malaysia.

e) Fire Fighting facilities

 As one of the most developed industrial estate in the nation with various kinds of plant, factory, buildings, etc., Gebeng Industrial Estate is built near to the Pahang Fire and Rescue Department in order to handle any emergencies. In addition, near to Gebeng area is also the Petronas Centralized Emergency Facilities. Both of these stations are equipped with HAZMAT (hazardous material) facilities.

 Alliance between Government agencies and private manufactures in Gebeng has set up a voluntary crisis management organization called the Gebeng Emergency Mutual Aid (GEMA) which is to execute proactive action and offer expert services to overcome emergencies situation.

f) Piperack link

 Centralized Tankage Facilities which is located at Kuantan Port links Gebeng and Kuantan Port with a common piperack / pipeline network to transport gases.

6. Availability of suitable land

 The preferable type of industrial activities in Gebeng Industrial Estate is chemical, petrochemical and general.

 The land / site available are originated from the State Land.

 There are four development phases available in Gebeng Industrial Estate, which is very convenient for additional space needed for future changes such as expansion of plant and so on. They are Gebeng Phase I with space 700 acres (283.28 hectares), Gebeng Phase II with 1400 acres (566.57 hectares), Gebeng Phase III with 2500 acres (1,011.73 hectares) and Gebeng Phase IV with 4000 acres (1,618.76 hectares).

 Land price (RM psf) : (Note: Price change without notice)

- RM16.00 per square feet (Industrial Lot Ready Land) - RM20.00 per square feet (Small Medium Enterprise- SME

Lot 129 Complete with infrastructure) - RM12.00 per square feet (Raw Land)

 The leasehold for the site is 99 years upon the issuance of titles.

 Total Planned Area is about 2468.60 hectares, Total Land Developed around 2408.08 hectares; and the Total Land Available is 1,528.5 hectares.

 Quit Rent per Annum (RM) is subjected to RM15.00 for every 100 m2 portion of it for the first 2 hectares and RM10.00 for every 100 m2 or portion of it subject to a minimal taxation of RM150.00 per ownership.

 The Annual Assessment is 7% of the property / land value.

Kerteh Industrial Park, Terengganu

Kerteh also known as Kertih, is a town in the district of Kemaman in southern Terengganu, Malaysia. Kerteh is the base of operations for Petronas in Terengganu, overseeing the oil platform operations off the state's coast as well as petrochemicals production and crude oil refining in nearby Paka.

Terengganu is known with its industrial land being the cheapest among the other lands in Malaysia. It ranges from RM0.18 – RM5.60 per square foot. Other states land price usually ranging from as low as RM2.00 – RM4.50 psf to as high as RM18.00 – RM22.00 psf. The land price in Kerteh Industrial Area is ranging from RM9 - RM14 psf. While for land with ready-built factories with pre-installed facilities like broadband, water and power, which reduces the time required to get a project off the ground is ranging from RM45 - RM60 per square meter.

As for the utilities supply, the Centralized Utility Facility (CUF) which is located in Kerteh operates independently of the national grid. CUF supplies wide range of industrial utilities to the selected industrial area. This includes the electricity, steam, industrial gases as well as other by-products (de-mineralized water, raw water, cooling water, effluent treatment and etc.). Since

power is generated by CUF from natural gas. Thus, it is less prone to lighting and power surges in the grid, and therefore making it an efficient source of utilities. The availability of this facility allows the Kerteh industrial area to save up to 20% of its operating and investment costs since they do not need to build any extra infrastructure to generate utilities.

In terms of closeness of the plant with the targeted markets, for the Kerteh Industrial Park, this location is quite close with the Mardec Processing Sdn. Bhd. (MPSB) Kuala Berang Factory which manufactures rubber (one of the product in which the process of the production uses chlorobenzene). The distance between Kerteh and Kuala Berang is about 108km difference. Another targeted market is the manufacturer of pesticide which is the Felda Agricultural Services Sdn Bhd located Kuala Lumpur. The distance between Kerteh and Kuala Lumpur is about 326km difference.

One of the raw materials suppliers that provide benzene for production of chlorobenzene in Kerteh Industrial Park is Aromatics Malaysia Sdn Bhd in conjunction with PETRONAS, MJPX Co. Ltd. that was built in July 2000. It has a capacity of 188,000 tonnes per annum (tpa) Benzene. Meanwhile, liquid chlorine may be supplied by Malay-Sino Chemical Industrial Sdn Bhd which is located in Kemaman Terengganu. This somehow increases the transportation cost of raw materials since raw materials are obtained from two different suppliers.

As a developed town, Kerteh is equipped with a good transportation facility. As for road facilities, Kerteh Industrial Area is located within the East Coast Industrial Corridor (ECIC) of Pennisular Malaysia and also Kerteh-Kuantan Port Railway Line is available for transportation of goods via train. The railway is 77 km is a single-track line that links Kerteh Petrochemical Complex in Terengganu with Kuantan Port in Pahang with a direct connection to Gebeng Industrial Estate. East Coast Expressway is the highway that connects Kerteh, Terengganu with Kuala Lumpur. As in terms of airport facility, Kerteh Airport is available, that is only 3.54 km to Kerteh town center. This airport is owned and operated by Petroleum Nasional Berhad (Petronas), and was built to serve the purpose of airlifting its employees and ExxonMobil employees to their various oil platforms located 100–200 km offshore South China Sea. Other than that, this airport is also used to transport Petronas and ExxonMobil employee from Kerteh to Sultan Abdul Aziz Shah Airport, Subang near to Kuala Lumpur. As for seaport facility, Kertih

Port Marine Terminal which is operated by Petronas Penapisan Sdn Bhd is available in the South China Sea. The supporting Kerteh marine facilities include six berths that can accommodate chemical tankers of up to 40,000 tonnes. Another port is the Kemaman Port which is situated only 7 km from Kerteh, about 9 minutes of travel via road.

Comparison Among The Possible Sites (Using Concept Screening & Scoring)

For the concept screening of the potential sites, only five main criterions are considered and evaluated. The criterions are as follow:

Criterion Alternatives

1 (Gebeng) 2 (Reference:Kertih) 3 (Tanjung Langsat) 1  Kuantan Town

(25 km)

 Kuala Lumpur (250 km)

 Targeted markets are mainly located in Kuantan, Pahang

+

 Kuala Berang (108km)

 Kuala Lumpur (326km)

0

 Targeted markets are located in Skudai, Johor

+

2  Benzene supplied from PETRONAS Chemicals Group Berhad (PCG) in Gebeng itself. --  2 suppliers: Kemaman, 41.9km and in Kerteh  Increase in transportation cost 0  48km from Tanjung Langsat +

3  East Coast Highway

 Gebeng Bypass Road

 Kuantan Bypass Road

 Federal Road  Kerteh-Kuantan Port Railway Line  Kuantan Airport  Kuantan Port +  Kerteh-Kuantan Port Railway Line

 East Coast Expressway

 Kerteh Airport

 Kertih Port Marine Terminal

0

 Four-lane Pasir Gudang Highway, a trunk road and a railway line

 Senai-Desaru Expressway

 Tanjung Langsat Port

 Senai Airport

+

4  Centralized Utility Facility (CUF)  Centralised Tankage Facilities +  Centralized Utility Facility (CUF) 0

 SAJH (water supply)

 Petronas Gas Bhd. (power supply) 0 5  RM12 – RM16 -- RM 9 – RM 14 0  RM 12 - RM14 -- Total 2 0 2 Rank 1 3 1

Where the criterion are as follow:

 1 = Location, with respect to the marketing area

 2 = Raw material supply

 3 = Transport facilities

 4 = Availability of utilities

 5 = Availability of suitable land

Based on the concept scoring, both proposed sites which are in Gebeng Industrial Estate, Pahang and Tanjung Langsat Industrial Complex, Johor has a higher ranking than the reference site in Kerteh Industrial Area, Terengganu. Therefore, both proposed sites are further judged in the concept scoring as shown below.

Criterion Weight Alternatives 1 3 1 35% 5 4 2 25% 2 4 3 15% 5 4 4 20% 5 3 5 5% 2 2 Total Score 4.10 3.70 Rank 1 2

By comparing both proposed sites that have passed the concept scoring, it was found that the best alternative is the one with the highest score which is the Gebeng Industrial Estate with total score of 4.10 against Tanjung Langsat Industrial Complex with total score of 3.70. Thus, Gebeng Industrial Estate has been chosen as the site location for the production of Chlorobenzene.

Process Flow Diagram (PFD)

Heat and Material Balance Table

Stream ID B--OUT B-1 B-2 B-FEED B-IN CL2-FEED CL2-OUT COND-OUT DIST-1 DIST-2 HCL-OUT MIX-OUT R1-OUT R2-OUT RECYCLE SPLIT-1 SPLIT-2 W-OUT

From SEP1 SEP3 DC1 HEATER HEATER2 CONDNSER SEP2 DC1 SEP2 MIXER REACTOR1 REACTOR2 SEP3 SPLITER SPLITER SEP1

To HEATER DC1 MIXER REACTOR1 HEATER2 SPLITER SEP2 SEP3 SEP1 REACTOR2 CONDNSER MIXER REACTOR1 REACTOR2

Phase LIQUID LIQUID LIQUID LIQUID VAPOR VAPOR VAPOR MIXED LIQUID LIQUID VAPOR LIQUID MIXED MIXED VAPOR VAPOR VAPOR LIQUID

Substream: MIXED Mole Flow lbmol/hr

C6H6 70.21297 0.0 0.0 62.34210 70.21297 0.0 0.0 7.870874 7.870874 0.0 0.0 70.21297 41.42565 7.870874 7.870874 0.0 0.0 0.0 CL2 0.0 0.0 0.0 0.0 0.0 139.0676 139.0676 73.01193 0.0 0.0 73.01193 0.0 40.74648 73.01193 0.0 69.53380 69.53380 0.0 HCL 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66.05566 0.0 0.0 66.05566 0.0 28.78732 66.05566 0.0 0.0 0.0 0.0 C6H5CL 0.0 58.62853 .0165002 0.0 0.0 0.0 0.0 58.62853 58.62853 58.61203 0.0 0.0 28.78732 58.62853 0.0 0.0 0.0 0.0 P-DIC-01 0.0 3.713564 3.555722 0.0 0.0 0.0 0.0 3.713564 3.713564 .1578421 0.0 0.0 0.0 3.713564 0.0 0.0 0.0 0.0 H2O 0.0 0.0 0.0 .3132769 0.0 0.0 0.0 0.0 0.0 0.0 0.0 .3132769 0.0 0.0 0.0 0.0 0.0 .3132769 Total Flow lbmol/hr 70.21297 62.34210 3.572202 62.65538 70.21297 139.0676 139.0676 209.2806 70.21297 58.76990 139.0676 70.52625 139.7468 209.2806 7.870874 69.53380 69.53380 .3132769 Total Flow lb/hr 5484.591 7145.040 524.5567 4875.412 5484.591 9860.644 9860.644 15345.23 7759.862 6620.482 7585.372 5490.235 10414.91 15345.23 614.8226 4930.322 4930.322 5.643771 Total Flow cuft/hr 104.9297 109.3135 7.829402 89.47071 33431.60 53581.76 60176.79 87193.84 121.4675 110.9598 65951.02 104.9700 12598.08 24653.12 3648.030 30088.40 30088.40 .0941140 Temperature F 138.0930 184.7300 384.5992 76.73000 201.0930 67.73000 130.7300 184.7300 184.7300 306.0184 184.7300 138.0930 130.7300 130.7300 184.7300 130.7300 130.7300 138.0930 Pressure psia 14.50377 14.50377 24.65642 14.50377 14.50377 14.50377 14.50377 14.50377 14.50377 24.65642 14.50377 14.50377 34.80906 34.80906 14.50377 14.50377 14.50377 14.50377 Vapor Frac 0.0 0.0 0.0 0.0 1.000000 1.000000 1.000000 .8830702 0.0 0.0 1.000000 0.0 .5022436 .6563256 1.000000 1.000000 1.000000 0.0 Liquid Frac 1.000000 1.000000 1.000000 1.000000 0.0 0.0 0.0 .1169298 1.000000 1.000000 0.0 1.000000 .4977564 .3436744 0.0 0.0 0.0 1.000000 Solid Frac 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Enthalpy Btu/lbmol 23377.86 7694.139 3344.977 20857.45 38298.11 -108.7071 410.5660 -5323.835 9618.068 13315.22 -18048.10 22758.96 632.5283 -9539.589 37895.68 410.5660 410.5660 -1.2252E+5 Enthalpy Btu/lb 299.2802 67.13311 22.77911 268.0454 490.2871 -1.533129 5.790335 -72.60725 87.02643 118.1989 -330.8876 292.3561 8.487232 -130.1023 485.1353 5.790335 5.790335 -6800.626 Enthalpy Btu/hr 1.64143E+6 4.79669E+5 11948.94 1.30683E+6 2.68902E+6 -15117.63 57096.43 -1.1142E+6 6.75313E+5 7.82534E+5 -2.5099E+6 1.60510E+6 88393.78 -1.9965E+6 2.98272E+5 28548.22 28548.22 -38381.17 Entropy Btu/lbmol-R -56.41256 -55.26235 -49.08018 -59.44399 -32.88386 -.1537557 .7762084 -9.876595 -54.42879 -48.51741 3.913583 -56.24713 -26.65722 -17.91827 -33.50052 .7762084 .7762084 -38.00291 Entropy Btu/lb-R -.7221858 -.4821766 -.3342333 -.7639324 -.4209746 -2.1685E-3 .0109471 -.1346985 -.4924839 -.4306881 .0717502 -.7225372 -.3576852 -.2443720 -.4288690 .0109471 .0109471 -2.109482 Density lbmol/cuft .6691428 .5703057 .4562548 .7002893 2.10020E-3 2.59543E-3 2.31098E-3 2.40018E-3 .5780390 .5296502 2.10865E-3 .6718707 .0110927 8.48901E-3 2.15757E-3 2.31098E-3 2.31098E-3 3.328696 Density lb/cuft 52.26918 65.36284 66.99831 54.49171 .1640541 .1840299 .1638612 .1759899 63.88425 59.66557 .1150152 52.30290 .8267063 .6224461 .1685355 .1638612 .1638612 59.96739 Average MW 78.11364 114.6102 146.8441 77.81315 78.11364 70.90540 70.90540 73.32374 110.5189 112.6509 54.54450 77.84668 74.52704 73.32374 78.11364 70.90540 70.90540 18.01528 Liq Vol 60F cuft/hr 99.54653 102.8150 6.490596 88.47795 99.54653 113.3212 113.3212 230.1390 113.9742 96.32442 116.1649 99.63711 163.8012 230.1390 11.15917 56.66059 56.66059 .0905787

Material Balance

Basis being used: 330 days/year of operation.

In which, it is required to produce 50000 metric tonne/year of monochlorobenzene (MCB) with not less than 2000 metric tonne/year of dichlorobenzene (DCB).

Balance Around Reactors

The reaction that occurred around the reactor is as follow: Reaction 1 : C6H6 + Cl2 C6H5Cl + HCl

Reaction 2 : C6H5Cl + Cl2 C6H4Cl2 + HCl

 The balance around Reactor 1:

 Inlet streams: 𝑛 Cl2 = 69.53380 lbmol/hr 𝑥o B = 0.2964 𝑥0 Cl2 = 0.2916 𝑥o HCl = 0.2060 𝑥o MCB = 0.2060 𝑥 B = 1 𝑛 tot = 139.7468 lbmol/hr 𝑛 tot = 70.21297 lbmol/hr

R1

B-IN = 1 B

SPLIT-1 = Cl2

 Components in outlet R1-OUT stream:

B = Cl2 = HCl = MCB =

 The balance around Reactor 2:

 Inlet streams:

For stream R1-OUT

= B = Cl2

= HCl = MCB

For stream SPLIT-2

= Cl2

 Components in outlet R2-OUT stream:

B = Cl2 = HCl = MCB = DCB = 𝑛 Cl2 = 69.53380 lbmol/hr 𝑥 B = 0.0376 𝑥 Cl2 = 0.3489 𝑥 HCl = 0.3156 𝑥 MCB = 0.2801 𝑥 DCB = 0.0177 𝑥 B = 0.2964 𝑥 Cl2 = 0.2916 𝑥 HCl = 0.2060 𝑥 MCB = 0.2060 𝑛 tot = 209.2806 lbmol/hr 𝑛 tot = 139.7468 lbmol/hr

R2

Balance around Separator & DC

 The balance around the first separator 1:

Assumption is that all the water contained in the liquid benzene fed to the inlet stream of this separator goes to the top stream of the separator:

Balance for each component is as follow:  B: inlet = outlet 70.215935 70.21297  H2O: inlet = outlet 0.3103155 0.3132769

 The balance around the separator 2:

𝑥 B = 0.9956 𝑥 H2O = 0.0044 𝑛 tot = 70.52625 lbmol/hr 𝑥 H2O = 1 𝑛 tot = 0.3132769 lbmol/hr 𝑛 tot = 70.21297 lbmol/hr 𝑥 B = 1

Sep1

Where hydrochloric acid and chlorine are removed in this step:

Balance for each component is as follow:

 B: inlet = outlet 7.86895 7.87087  Cl2: inlet = outlet 73.01800 73.01049  HCl: inlet = outlet 66.04896 66.05711  MCB: inlet = outlet 58.61950 58.62783  DCB: inlet = oulet 𝑥 B = 0.0376 𝑥 Cl2 = 0.3489 𝑥 HCl = 0.3156 𝑥 MCB = 0.2801 𝑥 DCB = 0.0177 𝑛 tot = 209.2806 lbmol/hr 𝑥 B = 0.1121 𝑥 MCB = 0.8350 𝑥 DCB = 0.0529 𝑛 tot = 70.21297 lbmol/hr 𝑛 tot = 139.0676 lbmol/hr 𝑥 HCl = 0.4750 𝑥 Cl2 = 0.5250

Sep 2

3.70427 3.71427