Chapter One

CHAPTER ONE

INTRODUCTION

1.1 Introduction to maleic anhydride Maleic anhydride (butenedioic anhydride, toxilic anhydride, 2,5-dioxofuran), an organic compound with the formula C2H2(CO)2O is the acid anhydride of maleic acid. In its pure state it is a colourless or white solid with an acrid odour. Maleic anhydride is a solid at room temperature. Above 52.9 °C it becomes a clear, colourless, low viscosity liquid. Maleic anhydride is soluble in water forming maleic acid. In the United States, one plant uses only n-butane and another uses n-butane for 20 %of its feedstock, but the primary raw material used in the production of Maleic Anhydride is benzene. The Maleic Anhydride industry is converting old benzene plants and building new plants to use n-butane. Maleic Anhydride also is a by-product of the production of phthalic anhydride. It is a solid at room temperature but is a liquid or gas during production. It is a strong irritant to skin, eyes, and mucous membranes of the upper respiratory system Table 1.1 further explains some physical and chemical properties of industrial maleic anhydride. (McKetta, J. J.1985)

1

Table 1.1 Physical and Chemical Properties for Industrial Maleic Anhydride Property

Maleic Anhydride

Formula

C4H2O3

Formula weight, g

98.06

Melting point, oC

52.85

Boiling point, oC

202

Heat of formation, kJ/mold

-470.41

Heat of combustion, kJ/ mold

-1389.5

Heat capacity,kJ/(K mol)d Solid

0.1199

Liquid

0.164

Heat of sublimation, kJ/ mold

71.5

Heat of vaporization, kJ/ mold

54.8

Heat of fusion, kJ/ mold

13.55

Heat of hydrolysis, kJ/ mold

-34.9

1.2 Production of maleic anhydride In the early 1930s, maleic anhydride was first commercially produced by the vapour-phase oxidation of benzene. The use of benzene as a feedstock for the production of Maleic anhydride was dominant in the world market well into the 1980s. Several processes have been used for the production of Maleic anhydride from benzene with the most common one from Scientific Design. Small amounts of maleic acid are produced as a by-product in production of Phthalic anhydride. This can be converted to either Maleic anhydride or fumaric acid. Benzene, although easily oxidized to maleic anhydride with high selectivity, is an inherently inefficient feedstock since two excess 2

carbon atoms are present in the raw material. Various C4 compounds have been evaluated as raw material substitutes for benzene in the production of maleic anhydride. Fixed- and fluid-bed processes for production of maleic anhydride from the butene present in mixed C4 streams have been practiced commercially. None of these processes is currently in operation because of rapid increases in the price of benzene and the recognition of benzene as a hazardous material intensified the search for alternative process technology in the United States. These factors led to the first commercial production of maleic anhydride from butane at Monsanto's J. F. Queenly plant in 1974 (McKetta, J. J.1985). By the early 1980s, the conversion of the U.S. maleic anhydride manufacturing capacity from benzene to butane feedstock was well under way using catalysts developed by Monsanto, Denka, and Halcon. One factor that inhibited the conversion of the installed benzene-based capacity was that early butane-based catalysts were not active and selective enough to allow the conversion of benzene-based plant without significant loss of nameplate capacity. In 1983, Monsanto started up the world's first butane-to-Maleic anhydride plant, incorporating an energy efficient solvent-based product collection and refining system. This plant was the world's largest Maleic anhydride production facility in 1983 at 59,000t/year capacity, and through rapid advances in catalyst technology has been debottlenecked to a current capacity of 105,000t/year in 1999. Advances in catalyst technology, increased regulatory pressures, and continuing cost advantages of butane over benzene have led to a rapid conversion of benzene- to butane-based plants. By the mid-1980s in the United States 100% of maleic anhydride production used butane as the feedstock. (Chem Systems PERP Program 2009) Coincident with the rapid development of the butane-based fixed-bed process, several companies have developed fluidized-bed processes. Two companies, Badger and Denka, collaborated on the development of an early fluid-bed reaction system which was developed through the pilot-plant stage but was never commercialized. Three fluid-bed, butane-based technologies were commercialized during the latter half of the 1980s by Mitsubishi Kasei, Sohio (British Petroleum). Europe has largely converted from benzene-based to butane-based Maleic anhydride technology with the 3

construction of several new butane based facilities by CONDEA-Huntsman, Pantochim and Lonza. Growth in the worldwide maleic anhydride industry I predominantly in the butane-to-maleic anhydride route, often at the expense of benzene-based production. Only a few newer benzene-based fixed-bed processes have been built since the early 1980s and these were built where the availability of butane was limited. The fluidized-bed butane-based process is experiencing some growth, but based on growth rates from it does not appear destined to challenge fixed-bed technology. The announcement from Huntsman Specialty Chemicals Corp., formerly Monsanto, and DWE that they intend to cooperate in the development of catalyst and reactor technology to permit operation at 50% higher productivity than the standard nonflammable fixed-bed butane process indicates that the largest companies in fixed-bed technology are confident that further advances are possible. Three fixed-bed processes, from Huntsman Pantochim, and Scientific Design and two fluidized-bed processes, from Alusiusse-Lummus (ALMA) and BP Chemicals, are currently offered for license (Kirk, et al. 2005) 1.3

Usage of maleic anhydride.

Maleic anhydride is truly a remarkable molecule in that it possesses two types of chemical functionality making it uniquely useful in chemical synthesis and applications. Maleic anhydride itself has few consumer uses but in derivative form,it is extremely versatile in the consumer uses in which it is found. The majority of the maleic anhydride produced is used in unsaturated polyester resin. Unsaturated polyester resin is then used in both glass-reinforced applications and in unreinforced applications. Another significant use of maleic anhydride is in the manufacture of alkyd resins, which are in turn used in paints and coatings. Other applications where maleic anhydride is used include the production of agricultural chemicals, maleic acid, copolymers, fumaric acid, lubricant additives, surfactants and plasticizers. It is also used as a co-monomer for unsaturated polyester resins, an ingredient in bonding agents used to manufacture plywood, a corrosion inhibitor, and a preservative in oils and fats (Greiner, E., et al. 2002).

4

CHAPTER TWO

ECONOMY ASPECTS

2.1

Supply and demand of maleic anhydride

Economic crisis of 2007 through most of 2009 contributed to a large drop in consumption of maleic anhydride in most regions. Chinese consumption of maleic anhydride slowed, but did not decline during the same period. The unsaturated polyester resin market, maleic anhydride's largest consuming market, took a large hit from the weak housing, construction, automotive and boating industries. At the end of 2009, several markets started to improve and there was a significant increase in demand in 2010. Unsaturated polyester resins will continue to have the largest market share and will drive refined maleic anhydride consumption on a global scale. The developing regions will experience the highest growth in maleic anhydride for unsaturated polyester resin production since a considerable amount of unsaturated polyester resin goes into infrastructure. Overall economic health will affect the unsaturated polyester resin market because it is tied to the construction, automotive and marine industries. Maleic anhydride consumption for butanediol will grow primarily in Asia and the Middle East. Maleic anhydride consumption for butanediol is not included in the United States since maleic anhydride is not refined. A plant in the Republic of Korea uses refined maleic anhydride for butanediol production. Maleic anhydride consumption for butanediol production is included in Other Asia and the Middle East, in cases where refined maleic anhydride is believed to be used.

5

Regionally, smaller end-use applications will experience higher-than-average growth, such as maleic copolymers in the United States. New product development— driven by increasing the use of renewable or replacing one petroleum-based chemical with a more environmentally friendly one—will drive maleic anhydride consumption in this application. The use of maleic anhydride and maleic anhydride copolymers will stand to gain from the increasing importance of recyclability, biodegradability and the use of more sustainable chemicals (Greiner, E., et al. 2002). However, world demand for maleic anhydride last five years growing rapidly, world demand for maleic anhydride rapid growth, annual growth rate of 7.3%, of which the average annual growth in North American demand for maleic anhydride rate of 4%, while demand in Western Europe and Japan, the growth rate of maleic anhydride, respectively, 12% and 6.5% . Maleic anhydride in 2000 global production capacity has reached 137 million tons. A few years ago the production capacity of maleic anhydride in Asia only the world’s total production capacity of 24% in recent years as China, Malaysia, South Korea and China Taiwan maleic anhydride production capacity of rapid growth, the current production capacity of maleic anhydride in Asia already accounts for the world’s total production capacity of 44%, the Asian region into the world the largest production base of maleic anhydride at the same time, Asia has become the maleic anhydride production than to be pure output region of Asia maleic anhydride capacity growth, changed the world production of maleic anhydride regional capacity allocation pattern present, China’s annual production capacity of maleic anhydride has been close to 20 million tons, production capacity of maleic anhydride in Asia about 35% of the current market is very mature maleic anhydride, maleic anhydride downstream while new products are constantly land developed, such as Germany, Bayer has developed a biodegradable chelating agent, poly aspartic acid and biodegradable dispersant addition, without the use of refined or refined maleic anhydride, maleic or direct use acid as raw materials to produce 1,4 – butanediol. Unsaturated polyester resin was the largest end use market for maleic anhydride in 2012. However, the demand is strongest in BDO market due to the growing use in the production of elastic fibers, plant protection, thermoplastic polyurethanes, coatings, solvents, pharmaceuticals, and electronic chemicals. Increasing demand for maleic anhydride has triggered capacity expansion by companies mainly in Europe and Asia 6

Pacific. Continuous rise in raw material prices has increased the production cost thus bringing maleic anhydride prices under pressure. However, continuous efforts on research and development are expected to provide huge market opportunities such as bio-based maleic anhydride to the industry participants. Unsaturated polyester resins dominate the maleic anhydride consumption, accounted for 49.3 percent of the total consumption in 2012 and expected to grow at a CAGR of 5.3 percent from 2012 to 2018. The demand for unsaturated polyester resins was primarily driven by the increasing demand for general construction, pipes and ducts, corrosion resistant tanks, paints and coatings, bathroom fixtures and fibreglass reinforced plastics (Chem Systems PERP Program 2009). Asia Pacific dominated the global market for maleic anhydride in 2012.With over 52 percent global market shares in terms of both volume and revenue, Asia Pacific is

the

leading

consumer

of

maleic

anhydride. North

America and Europe together accounted for over 30 percent of total volume share in 2012. The global maleic anhydride market has witnessed significant capacity addition during the recent past. Asia Pacific is lucrative market for new plant establishments and capacity expansions. The following pie chart shows global production of maleic anhydride in 2012.

Figure 1: Global Consumption of Maleic Anhydride for Year 2012. Source: Maleic Anhydride (MA): 2013 World Market Outlook and Forecast up to 2017.

7

Capacity of malic anhydride (kilo tonnes)

3000 2500 2000 1500

Supply Demand

1000 500 0 2000

2005

2010

2015

2020

Year

Figure 2.1: Comparison of Demand and Supply of Maleic Anhydride for Global Market Figure 2.1 indicates the graph of demand and supply of malic anhydride (tonnes) against years from year 2000 to 2020. According to the chemical business, the demand of maleic anhydride was increased by 15% from year 2000 to 2005, and 15.38% from year 2005 to 2010. It is estimated that the demand will grow at a rate of 7.8% from year 2010 to 2015 due to the high demand of production of elastic fibers, plant protection, thermoplastic polyurethanes, coatings, solvents, pharmaceuticals and electronic chemicals. Its demand predicted to increase by 13.6% from 2015 to 2020. The supply of maleic anhydride was increased by 18.22% from year 2000-2005, and 18.18% from year 2005-2010. Its supply is predicted to rise by 35.74% from year 2010-2015, and increased by 11.11% from year 2015-2020. Based on the market analysis that our group has been made, we can conclude that the demand and supply of maleic anhydride will keep increasing in the coming years due to the multi usages of maleic anhydride. As we know, the demand is always greater than the supply of maleic anhydride for every five year. Thus, to make a target for the production capacity, the shortage must be first calculated. 8

Shortage = Average demand of maleic anhydride - Average supply of maleic anhydride To calculate the average demand and supply of maleic anhydride, we take the data from the line graph of Figure 2.1 in year 2015.

Demand of maleic anhydride: =2200000 tonnes/year

Supply of maleic anhydride: =1800000 tonnes/year

Shortage: = (2200000-1800000) tonnes/year = 400000 tonnes/year

Based on the value of the shortage that is 300000 tonnes/year, we had decided to produce maleic anhydride in industrial only 10% from the shortage which is about 40000 tonnes/year. This is due to the competitions in the market from various companies. Production capacity: =(10/100) x 400000 tonnes/year =40000 tonnes/year

9

2.2

Price of Maleic Anhydride per Tonne

Based on Asian market price for the end of August 2013, the price of maleic anhydride was assessed at $1,600–1,650/tonne, which is approximately RM8256-8514/tonne (ICIS 2013). 2.3

List of Companies in Malaysia That Produce Maleic Anhydride 1) Heller Industries Malaysia Sdn. Bhd. at Bayan Lepas, Pulau Pinang 2) Teleflex Medical Sdn. Bhd. 3) Gimmill Industrial (M) Sdn. Bhd. at Bukit Mertajam, Pulau Pinang 4) Orient Co One Cross Island Plaza

2.4

Current issue related to maleic anhydride

2.4.1 Economic issues on maleic anhydride plant In the end of 2009, BASF company plans to shut down a 115,000-metric-ton-peryear maleic anhydride facility in Feluy, Belgium. About 133 jobs will be affected. The facility closure effectively marked the end of all BASF activities in Feluy. About four years ago, the firm ended production of phthalic anhydride, plasticizers, fumaric acid, and butanediol at the Feluy site that it had purchased in 2001 from the bankrupt Italian firm SISAS. The maleic anhydride facility survived the 2005 cutbacks. But now, because of industry overcapacity, profit margins for maleic anhydride, a building block for unsaturated polyester resins, are unacceptably low, BASF says. Efforts to make the plant more efficient haven't succeeded in making the plant sustainably cost competitive, the firm adds.

10

Tom Witzel, BASF group vice president of European diols and polyalcohols, says, "A withdrawal from maleic anhydride production in Feluy would help us to focus on our core intermediates business," in vertically integrated value chains such as butanediol and its derivatives, and polyalcohols. BASF adds, it will work with union representatives to find "socially acceptable solutions" for employees affected by the plant shutdown (Reisch, M. S. 2009). 2.5

Conclusion

The demand for maleic anhydride is growing rapidly every year with an annual growth of 7.3% where the highest demand is a Western Europe followed by Japan. Of the total demand Asia produces about 44% of maleic anhydride for the global market. The maleic anhydride producing countries in Asia are China, Malaysia, South Korea, China and Taiwan. The economic crisis of 2007 through most of 2009 contributed to a large drop in consumption of maleic anhydride in most regions. Chinese consumption of maleic anhydride slowed, but did not decline during the same period. The unsaturated polyester resin market, maleic anhydride's largest consuming market, took a large hit from the weak housing, construction, automotive and boating industries. At the end of 2009, several markets started to improve and there was a significant increase in demand in 2010. Unsaturated polyester resins will continue to have the largest market share and will drive refined maleic anhydride consumption on a global scale. The developing regions will experience the highest growth in maleic anhydride for unsaturated polyester resin production since a considerable amount of unsaturated polyester resin goes into infrastructure. Overall economic health will affect the unsaturated polyester resin market because it is tied to the construction, automotive and marine industries. In future, smaller end-use applications will experience higher-than-average growth, such as maleic copolymers in the United States. New product development—driven by increasing the use of renewable or replacing one petroleum-based chemical with a more environmentally friendly one—will drive maleic anhydride consumption in this application. The use of maleic anhydride and maleic anhydride copolymers will stand to gain from the increasing importance of recyclability, biodegradability and the use of more sustainable chemicals.

11

CHAPTER THREE

PROCESS DESCRIPTIONS

3.1

Chemical reactions.

The following reactions occur during the reaction of butane with oxygen: C4H10+3.5O2

C4H2O3+4H2O

(1)

C4H10+5.5O2

2CO+2CO2+5H2O

(2)

C4H10+3.502

C3H4O2+CO2+3H20

(3)

C4H10+6O2

CH2O2+3CO2+4H2O

(4)

The conversion of butane is assumed to be 82.2 percent. The selectivity for maleic anhydride reaction is 70.0 percent, for carbon dioxide is 1.0 percent, for acrylic acid is 1.0 percent, and for formic acid is 1.0 percent (Preparation of Maleic Anhydride Using Fluidized Catalysts US 4317778). The process was simulated using the Peng-Robinson thermodynamic package for Kvalues and Peng-Robinson for enthalpy. UNIFAC thermodynamic suggested an azeotrope between maleic anhydride and water, which would not allow purification of the maleic anhydride to the purity obtained here. This should be considered when designing the separation units. 12

3.2

Process Flow Diagram

13

Figure 3 shows a PFD for the overall process. Pure butane, Stream 2, and compressed air, Stream 3, are mixed and fed to R-101, an adiabatic reactor, where butane reacts with oxygen to form maleic anhydride. The reaction is exothermic. Therefore, one could consider either a fluidized bed reactor or a packed bed reactor with heat removal to stay close to isothermal. The reactor effluent is cooled and sent to T-101, a packed bed absorber, where it is contacted with water, Stream 7, to remove the light gases and all of the maleic anhydride reacts to form maleic acid. The vapor effluent, which consists of non-condensable, Stream 8, must be sent to an after-burner to remove any carbon monoxide prior to venting to the atmosphere. This is not shown here. The liquid effluent, Stream 9, is then cooled and flashed at 101 kPa and 120°C in V-101. The vapor effluent from V-101, Stream 11, is sent to waste treatment. Stream 12, the liquid effluent, is sent to R-102 where maleic acid is broken down to maleic anhydride and water. The reactor effluent is then sent to distillation column, T-102, where maleic anhydride and water are separated. The distillate, Stream 14, is sent to waste treatment. Stream 15, the bottoms, consists of 99-wt percent maleic anhydride.

Equipment Summary C-101 Air Compressor E-101 Heat Exchanger E-102 Heat Exchanger E-103 Condenser E-104 Reboiler P-101A/B Reflux Pump R-101 Packed Bed Reactor R-102 Maleic Acid Reactor T-101 Absorbtion Tower T-102 Distillation Column V-101 Flash Vessel V-102 Reflux Vessel 3.3

Raw materials

This maleic anhydride plant use butane, water and air as the raw materials.

14

3.4

Material Safety Data Sheet (MSDS) for the production of product

-Attached in the appendix.

15

CHAPTER FOUR

ENVIRONMENTAL OF SAFETY ISSUES

4.1

Environmental issues faced by operating the maleic anhydride plant.

4.1.1

Long term effects because of environmental issues related to the maleic anhydride plant.

Exposure to maleic anhydride may occur from accidental release to the environment or in a workplace where it is produce or used and also from the contact with spills, fugitive emission, or vent gases. Chronic exposure to maleic anhydride has been observed to cause chronic bronchitis, asthma-like attacks, pulmonary oedema, upper respiratory tract irritation, eye irritation, and dermatitis in workers. In some people, allergies have developed so that lower concentrations can no longer be tolerated. However mostly exposure to maleic anhydride have cause irritation to several part of bodies. 4.1.1.1 Skin irritation A number of reports indicate that maleic anhydride is irritating to skin. First to second degree skin burns and itching, which became more severe on showering, were reported in two workers exposed by contact with contaminated clothing. Environmental Protection Agency. 2013).

16

(The Danish

4.1.1.2 Eye irritation Maleic anhydride as dust or vapour has been reported to cause conjunctivitis, inflammation and swelling of the eyelids, severe lachrymation and photophobia (HSE, 1996). According to data presented in IUCLID (2000), exposure to a concentration of 6-8 mg/m3(form of test material not described) resulted in eye irritation within 15 minutes (IUCLID 2000). 4.1.1.3 Respiratory irritation Two cases of respiratory irritation following exposure to maleic anhydride dust or vapour have been reported (HSE 1996). A threshold of 5.48 mg/m3for irritative effects has been reported in a review by Ruth (1986).According to data presented in IUCLID (2000), exposure to a concentration of 6-8 mg/m3(form of test material not described) resulted in nasal irritation within 1 minute; among workers repeatedly exposed to 5-10 mg/m3, ulceration of nasal mucous membrane, chronic bronchitis and in some cases asthma occurred (IUCLID 2000).An exposure chamber study in male volunteers (age 22-27 years) has been performed. Maleic anhydride vapour was produced by melting the solid; exposure concentrations were determined by atmospheric analysis. Three sets of investigations were performed (HSE, 1996). In the first set of trials (6 trials, twice/week), groups of 2-7 volunteers were exposed for 5 minutes to concentrations ranging from 22 to 270 mg/m3. In the second set, 6 volunteers were exposed to a concentration of 54 mg/m3for 1 hour. In the third set, 5 volunteers were exposed to 45 mg/m3for 1 hour. Table 4 shows the description made by the volunteers regarding their sensory responses on a standard form at regular intervals throughout the exposure periods:

17

Table 4 : Sensory response of volunteers exposed to maleic anhydride Concentration (mg/m3)

Description of sensory response

270

Nasal irritation, impairment of smell, eye irritation,

greater

than

moderate

pulmonary discomfort in 3/5 subjects. 179

Eye irritation, moderate pulmonary discomfort in 1/5 subjects.

54

Very occasional pulmonary discomfort and impairment of smell.

45

Very occasional pulmonary discomfort and impairment of smell

22

4.1.2

Response not described in HSE 1996.

Waste relevant to maleic anhydride plant.

Maleic anhydride plant is operated to produce maleic anhydride as the product. However, some waste products such as un-reacted butane, carbon monoxide gas, acetic, acrylic acids, water and carbon dioxide are obtained in this plant, as the plant is operated. 4.1.3

Waste treatment of maleic anhydride plant.

A small slipstream of the circulating solvent is purified to remove solvent degradation products in order to prevent the build up of impurities in the solvent recycle loop. The absorber offgas is combined with the light ends column distillate and vacuum system exhausts and fed to the incinerator, where unreacted butanes and reaction by-products (carbon monoxide, acetic and acrylic acids) are combusted. The waste heat is recovered as high pressure steam, which is combined with the steam from the reactor and superheated. A portion of this steam can be used to drive the air compressor, with the excess exported or used to generate electric power. 18

4.1.4

Current Issue Related to Maleic Anhydride.

4.1.4.1 Food Safety Issue Regarding Starch Containing Maleic Anhydride in Taiwan. May 2013, the issue of toxic starch in Taiwanese food had spread all over the world. Department of Health of China had announced that it had found maleic acid in food such as tapioca balls (the balls in bubble tea), rice noodles and oolian a Taiwanese night market staple inspired by Japanese tempura. Pointing out that the acid is formed after maleic anhydride comes into contact with water, the Food and Drug Administration (FDA) raised the possibility of maleic anhydride-grafted starch being used in food products to make them chewier (The Straits Times 2013). To cut synthesization costs and to reduce the water absorbency of the polymer, maleic anhydride-grafted starch which is an industrial compound was added to polymer plastics in part. The industrial starch is also used in polymeric films in the non-food contact layer of food packaging. The FDA bans the compound's use as a food additive, pointing out that the industrial substance maleic anhydride, which imparts chewiness, can cause kidney failure if taken in sufficient doses (The China Post 2013). Singapore's Agri-Food and Veterinary Authority (AVA) reported that it had detected maleic anhydride in eleven products imported from Taiwan out of sixty six tested. Besides, AVA said all products had been withdrawn from stores and consumers who bought the products were asked to return them to the retailers or discard them (Asia News Network 2013). However, as the solution, the Department of Health of China has demanded that all tainted food products be promptly removed from shelves and destroyed, and that a risk alert mechanism be established to enhance food safety inspections and management nationwide. The government will also implement border control measures whereby any company that is found to have manufactured products containing unapproved additives or industrial starch will have to present safety certificated before it can export products to other countries (Department of Health of Hong Kong 2013).

19

4.1.5

Pollution made by the maleic anhydride plant.

Maleic anhydride in soils is readily broken down. It does not bind particularly strongly to soil particles, so can leach to groundwater where it will be broken down naturally. In air, it reacts fairly quickly and so has a short life. Maleic anhydride does not accumulate in the environment. It is not considered likely that Maleic anhydride pollution has any effects on the global environment. 4.1.6

Environmental acts.

Releases of Maleic anhydride are controlled through the UK Pollution, Prevention and Control (PPC) Regulations. An upper limit for safe long term exposure to Maleic anhydride has been designated in amendments to the 1994 UK Control of Substances Hazardous to Health (COSSH) Regulations (SI 1996/3138) 4.1.7

The latest act on environmental quality.

4.1.7.1 Waste Avoidance and Resource Recovery Act 2001. In general, industries and industrial operations should be encouraged that are more efficient in terms of resource use, that generate less pollution and waste, that are based on the use of renewable rather than non-renewable resources, and that minimize irreversible adverse impacts on human health and the environment. The WARR Act sets out eight objectives which are to encourage the most efficient use of resources and to reduce environmental harm in accordance with the principles of ecologically sustainable development and ensure that resource management options are considered against a hierarchy of the following order: (i) Avoidance of unnecessary resource consumption. (ii) Resource recovery (including reuse, reprocessing, recycling and energy recovery). (iii) Disposal. Next is to provide for the continual reduction in waste generation, minimise the consumption of natural resources and the final disposal of waste by encouraging the avoidance of waste and the reuse and recycling of waste and to ensure that industry shares with the community the responsibility for reducing and dealing with waste. 20

Furthermore, this act also ensure the efficient funding of waste and resource management planning, programs and service delivery .Lastly, to achieve integrated waste and resource management planning, programs and service delivery on a Statewide basis and to assist in the achievement of the objectives of the Protection of the Environment Operations Act 1997. 4.1.7.2 Environmental Quality Act, 1974 Malaysia has had environmentally-related legislation since the early 1920s.But the legislation is limited in scope and inadequate for handling complex emerging environmental problems. So through EQA, 1974, a more comprehensive form of legislation and an agency to control pollution was established. EQA is an enabling piece of legislation for preventing, abating and controlling pollution, and enhancing the environment, or for other related purposes. Pollution, as declared in EQA, includes the direct or indirect alteration of any quality of the environment or any part of it by means of a positive act or act of omission. Pollution is ‘controlled’ through the mechanism of licences issued by the Department of Environment. The mode of control is by prescribing, by means of a ministerial regulation, that licences are mandatory for: 

The use and occupation of prescribed premises;



Discharging or emitting wastes exceeding acceptable conditions into the atmosphere, as well as noise pollution, polluting or causing the pollution of any soil or surface of any land;



Emitting, discharging or depositing any wastes or oil, in excess of acceptable conditions, into inland waters or Malaysian waters. The provision of "acceptable conditions" is controversial because the polluter is

not liable for prosecution if the discharge is within those acceptable conditions, even if the effluents are sufficient to severely damage the environment. Most people adversely affected by pollution do not want to seek legal remedy through common law because of the prolonged nature of such hearings and the costs incurred. Currently, 16 sets of regulations and orders are enforced by the Department of Environment under EQA. Despite government efforts to implement environmental laws and regulations, it has been found that enforcement measures need to be further 21

enhanced to ensure the full compliance with laws and regulations. With regard to monitoring and enforcement, surveillance capability will be strengthened. The penalty structure related to environment offences will be revised to ensure a more effective deterrent, especially in the case of repeat offenders. The enforcement function of agencies such as the Department of Environment, Health Department, Pesticide Board and local authorities will be rationalized and streamlined, and adequate training will be provided for their enforcement staff. 4.1.7.3 Control of agro-based water pollution 

Environmental Quality (Licensing) Regulations, 1977



Environmental Quality (Prescribed Premises) (Crude Palm Oil) Order, 1977



Environmental Quality (Prescribed Premises) (Crude Palm Oil) Regulations, 1977, and (Amendment) 1982



Environmental Quality (Prescribed Premises) (Raw Natural Rubber) Order, 1978



Environmental Quality (Prescribed Premises) (Raw Natural Rubber) Regulations, 1978

4.1.7.4 Control of municipal and industrial waste water pollution 

Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979



Environmental Quality (Prohibition on the Use of Controlled Substance in Soap, Synthetic Detergent and Other Cleaning Agents) Order, 1995

4.1.7.5 Control of industrial emissions 

Environmental Quality (Clean Air) Regulations, 1978



Environmental Quality (Compounding of Offenses) Rules, 1978

4.1.7.6 Control of motor vehicle emissions 

Motor Vehicles (Control of Smoke and Gas Emission) Rules, 1977 (made under the Road Traffic Ordinance of 1958)



Environmental Quality (Control of Lead Concentration in Motor Gasoline) Regulations, 1985 22



Environmental Quality (Motor Vehicle Noise) Regulations, 1987

4.1.7.7 Control of toxic and hazardous waste management 

Environmental Quality (Scheduled Wastes) Regulations, 1989



Environmental Quality (Prescribed Premises) (Scheduled Wastes Treatment) and Disposal Facilities) Order, 1989



Environmental Quality (Prescribed Premises) (Scheduled Wastes Treatment and Disposal Facilities) Regulations, 1989



Promotion of Investments (Promoted Activities and Products) (Amendment) (No. 10) Order, 1990 (made under the Promotion of Investments Act, 1986

4.2 Safety issues of the maleic anhydride plant. 4.2.1

Level Control

In any equipment where an interface exits between two phases (eg. Liquid vapor), some means of maintaining the interface at the required level must be provided. This may be incorporated in the design of the equipment, the control value should be placed on the discharge line from the pump. 4.2.2

Pressure Control

Pressure control will be necessary for most systems handling vapor or gas. The method of control depends on the nature of the process. 4.2.3

Flow Control

Flow control is usually with inventory control in a storage tank or other equipment. There must be a reservoir to take up the changes in flow –rate. To provide flow control on a compression or pump running at a fixed speed and supplying a near constant volume output, a by-pass would be used. 4.2.4

Heat Exchangers

Here, the temperature can be controlled by varying the flow of the cooling or heating medium. If the exchange is between two process streams whose flows are fixed, bypass control will have to be used. 23

4.2.5

Condenser Control

Temperature control is unlikely to be effective, unless the liquid stream is sub-cooled. Pressure control is often used, or control can be based on the outlet coolant temperature. 4.2.6

Reactor Control

The schemes used for reactor control depend on the process and type of reactor. If a on–line analyzer is available and the reactor dynamics are suitable, the product composition can be monitored continuously and the reactor conditions and feed flows controlled automatically to maintain the desired product composition and yield. More often, the operation is the final link in the control loop, adjusting the controller set points to maintain the product within specification, based on periodic laboratory analyzer. Regulating the flow of the heating or cooling medium will normally control reactor temperature. Pressure is usually held constant. Material balance control will be necessary to maintain the correct flow of reactants to the reactor and the flow of product and un-reacted materials from the reactor. 4.2.7

Distillation Column Control

The primary objective of distillation column control is to maintain the specified composition of the top and bottom products, and any side streams; correcting the effect of disturbances in: 1) Feed flow rate, composition and temperature. 2) Steam supply pressure. 3) Cooling water pressure and header temperature. 4) Ambient conditions, which cause changes in internal reflux. 5) Regulating reflux flow and boil-ups control the compositions. The column overall material balance should also be controlled; distillation columns have little surge capacity and the flow of distillate and bottom product must match the feed flows. 6)Column pressure is normally controlled at a constant value. The level of controller on a preceding column often sets the feed flow rate. It can be independently controlled if the column is fed from a storage tank. Feed temperature is not controlled unless a pre-heater is used.

24

4.3

First aid measures

4.3.1

Swallowed

For advice, contact a Poisons Information Centre or a doctor at once. Urgent hospital treatment is likely to be needed. 4.3.2

Eye

If this product comes in contact with the eyes: Immediately hold eyelids apart and flush the eye continuously with running water. Ensure complete irrigation of the eye by keeping eyelids apart and away from eye and moving the eyelids by occasionally lifting the upper and lower lids. For thermal burns: “Do not remove contact lens”. Lay victim down, on stretcher if available and pad both eyes, make sure dressing does not press on the injured eye by placing thick pads under dressing, above and below the eye. Seek urgent medical assistance, or transport to hospital. 4.3.3

Skin

If skin or hair contact occurs: Immediately flush body and clothes with large amounts of water, using safety shower if available. Quickly remove all contaminated clothing, including footwear. In case of burns: Immediately apply cold water to burn either by immersion or wrapping with saturated clean cloth. Do not remove or cut away clothing over burnt areas. Do not pull away clothing which has adhered to the skin as this can cause further injury. Do not break blister or remove solidified material. Quickly cover wound with dressing or clean cloth to help prevent infection and to ease pain. For large burns, sheets, towels or pillow slips are ideal; leave holes for eyes, nose and mouth. Do not apply ointments, oils, butter, etc. to a burn under any circumstances. Water may be given in small quantities if the person is conscious. Alcohol is not to be given under any circumstances. Reassure. Treat for shock by keeping the person warm and in a lying position. Seek medical aid and advise medical personnel in advance of the cause and extent of the injury and the estimated time of arrival of the patient. 4.3.4

Inhaled

If fumes or combustion products are inhaled remove from contaminated area. Lay patient down. Keep warm and rested. Inhalation of vapors or aerosols (mists, fumes) 25

may cause lung oedema. Corrosive substances may cause lung damage. To extinguish the media, do not apply direct a solid stream of water or foam into burning molten material; this may cause spattering and spread the fire. Dry chemicals are not recommended to be used because they contain alkalis which may cause rapid exothermic reactions. 4.4

Accidental release measures

4.4.1

Minor spills

1) Remove all ignition sources and clean up all spills immediately. 2) Avoid contact with skin and eyes. 3) Control personal contact by using protective equipment. 4) Use dry clean up procedures and avoid generating dust. 5) Place in a suitable, labelled container for waste disposal. 4.4.2

Major spills

1) Clear area of personnel and move upwind. 2) Alert Emergency Responders and tell them location and nature of hazard.

26

CHAPTER FIVE

MASS AND ENERGY BALANCE

5.1

Mass Balance

5.1.1

Introduction of mass balance

Mass balance is used to compare the inputs and the output of the processes. It is an application of the law of conservation of mass to analyze the physical system. Law of the conservation of mass states that the mass of a closed system will remain constant, regardless the processes occur in the system. This mean that the mass enter the system must equal to the mass leave the system. By accounting for material entering or leaving a system, mass flows can be identified which might have been unknown, or difficult to measure without this technique. The purpose for using the mass balance is to ensure that there is no mass loss during the entire reaction. 5.2

Calculation of Mass Balance for Reactor

Molecular weight of C4H10 =58 Molecular weight of O2 =32 Molecular weight of C4H2O3 =98 Molecular weight of CO2 =44 Molecular weight of CO = 28 Molecular weight of H2O =18 Molecular weight of N2=28 Molecular weight of CH2O2 =46 Molecular weight of C3H4O2=72

27

COMPRESSOR Figure 3 shows the raw materials, butane in stream 1 and compressed air in stream 2 are mixed. The components in the stream 2 are the same as in the stream 3 which contains oxygen, nitrogen and water. There is a mixer before the components in stream 1 and 3 flow into stream 4. Butane 1

4

2

3

Air C-101 Compressor

Figure 3

For stream 1 F1= 5130.9 kg/h F1C4H10= 5130.9 kg/h For stream 2 & stream 3 F2=F3= 95129.14 kg/h F2o2 =F3o2=18074.54 kg/h F2n2 = F3n3= 75152.02 kg/h F2H20 = F3H20=1902.58 kg/h

REACTOR Figure 4 shows the butane and air enter the reactor to form maleic anhydride. The material mass balance that needs to be considered is at the reactor. Based on the Principle of Conservation Of Mass, it shows that the amount of mass entering a system must be equivalent to the amount exiting the system. Hence, the mass at the inlet and outlet have to be determined to confirm the accuracy of the data, 28

4

R-101 Packed bed reactor

XC4H10=0.822

5

E-3

Figure 4

r1 r2 r3 r4

Conversion of C4H10=0.822 ( Preparation of maleic anhydride using fluidized catalysts US 4317778) XC4H10= - ∑α C4H10 rr / N4C4H10 0.822= -[(-1)r1+(-1)r2+(-1)r3+(-1)r4]/(5131.71÷58) 72.7287= r1+ r2 + r3+ r4

Selectivity of C4H203=0.7 ( Preparation of maleic anhydride using fluidized catalysts US 4317778) SC4H2O3 =∑αC4H203 r / N4C4H10 0.7= r1/(5131.71÷58) r1= 61.9339

29

Selectivity of CO2=∑αco2r/N4C4H10= 1.5320 2r1+r2+3r3/(5131.71÷58)=1.5320 r2=9.02526 Selectivity of C3H4O2= 0.01 (Preparation of maleic anhydride using fluidized catalysts US 4317778) SC3H4O2=∑αC3H4O2 r /N4C4H10 0.01=r3/(5131.71÷58) r3=0.88477

Selectivity of CH2O2 =0.01 ( Preparation of maleic anhydride using fluidized catalysts US 4317778) SCH2O2=∑αCH2O2 r /N4C4H10 0.01=r4/(5131.71÷58) r4=0.88477

For stream 4 F4=100260.04kg/h F4N2= 75152.02kg/h F4O2= 18074.54kg/h F4C4H10=5130.9kg/h F4H2O=1902.58kg/h

For stream 5 Component balance F4=Fi,F5=Fo

30

C4H10: NiC4H10 +αC4H10 r = NoC4H10 5131.71/58 + (-r1) + (-r2) + (-r3) + (-r4) = NoC4H10 88.4778 – 61.9339 – 9.02526– 0.88477- 0.88477 = NoC4H10 NoC4H10 = 15.7491 X 58 FoC4H10 = 913.4478kg/h

O2 : NIo2 +αO210 r= NoO2 18074.36/32 +( -3.5 r1) +( -5.5 r2) + (-3.5 r3) + (-6 r4) NoO2 = 564.82375 - 216.76865– 49.63893 – 3.096695 – 5.30862 NoO2 = 290 X 32 FOO2= 9280.34kg/h

C4H203: NIc4h2o3 +α C4H203 r = No C4H203 NoC4H203 = 0 + 61.9339X 98 FoC4H203 = 6069.5222kg/h

H2O: NIH2O +α H2O r = No H2O 1902.65/18 + 4 r1 + 5 r2 + 3 r3+ 4 r4= No H2O No H2O = 105.7028 + 247.7358+ 45.1263+ 2.65431+3.53908 No H2O = 404.75829 X 18 FOH2O = 7285.64922kg/h

31

CO : NICO +α CO r = NoCO O + 2 r2 = NoCO NoCO = 2(9.02526) X 28 FOCO = 505.41456kg/h

CO2 : NICO2 +α CO2 r = NoCO2 0 + 2 r2 + r3+ 3 r4 = NoCO2 NoCO2 = 2(9.02526) + 0.88477 + 3(0.88477) NoCO2=21.5896X 44 =949.9424 kg/h

C3H4O2: NIC3H402+α C3H4O2 r = No C3H4O2 O + r3 = No C3H4O2 No C3H4O2 = 0.88477X 72 FOC3H4O2 = 63.70344kg/h

CH202 : NICH2O2+α CH202 r = No CH202 0 + r4 = No CH202 0.88477 = No CH202 No CH2O2 = 0.88477 FoCH2O2=0.88477 X 46 FOCH2O2 = 40.69942kg/h 32

N2: FoN2= 75150.92kg/h F4=F5 75152.02+18074.54+5130.9+1902.58=913.4478+9280.34+6069.5222+7285.64922+5 05.41456+949.9424+63.70344+40.69942+75150.92 100260.04=100260.04(proven)

HEAT EXCHANGER Figure 5 shows stream 5 and stream 6. The components in both streams are the same as the purpose of having it is to lower the temperature of the reaction from 410°C to 95°C. 5

6

Heat exchanger

Figure 5 F5=F6

ABSORPTION TOWER To atmosphere

8

Water

7

Absorption tower 6

E-4 9

33

For stream 6 F6=100260.04kg/h F6N2=75150.92kg/h F6CO=505.41456kg/h F6O2=9280.34kg/h F6CO2=949.9424kg/h F6C4H10=913.4478kg/h F6H2O=7285.64922kg/h F6CH2O2=40.69942kg/h F6C3H4O2=63.70344kg/h F6C4H2O3=6069.5222kg/h

For stream 7 F7=1902.58kg/h F7H2O=1902.58kg/h For stream 8 F8=85886.623kg/h F8N2=75150.9266kg/h F8CO=505.41456kg/h F8O2=9280.34kg/h F8CO2=949.9424kg/h

For stream 9 F9=16275.60186kg/h F9C4H10=913.4478kg/h F9H2O=9188.229kg/h 34

F9CH2O2=40.69942kg/h F9C3H4O2=63.70344kg/h F9C4H2O3=6069.5222kg/h F6+F7=F8+F9 100260.04+1902.58=85886.623+16275.60186 102162=102162 (proven)

HEAT EXCHANGER Figure 7 shows stream 9 and stream 10. The components in both streams are the same as the purpose of having it is to lower the temperature of the reaction from 60 °C to 40°C.

9

10

Heat exchanger

For stream 10 F9=F10 =16275.60186kg/h F10C4H10=913.4478kg/h F10H2O=9188.229kg/h F10CH2O2=40.69942kg/h F10C3H4O2=63.70344kg/h F10C4H2O3=6069.5222kg/h

35

11

To waste treatment

10

Flash vessel

12

E-5

Distillation Column

F10=F11+F12 Make assumption all butane goes to waste treatment

For stream 11 F11=8428.085kg/h F11C4H10=913.4478kg/h F11H2O=7350.5832kg/h(80% selecrivity) F11CH2O2= 40.2924kg/h F11C3H4O2=63.0664kg/h F11C4H4O3=60.6952kg/h

For stream 12 F12=7847.5166kg/h F12H2O=1837.6458kg/h F12CH2O2=0.40699kg/h (1% selectivity) F12C3H4O2=0.637034kg/h (1% selectivity) F12C4H4O3=6008.82678kg/h (99% selectivity) 36

F10=F11+F12 16275.60186=8428.085+7847.5166 16275.601=16275.601 (proven)

Condenser

Reflux vessel

To waste treatment 13 12

Reflux Pump Distillation column Reboiler

14

Maleic Anhydride

F12=F13+F14 Assume top product contains 0.1% maleic anhydride, 0.8% water, 0.7% of acrylic acid and formic acid

For stream 13 F13=2071.730kg/h F13H2O=1470.11664g/h F13CH2O2=0.284893 kg/h F13C3H4O2=0.4459 kg/h F13C4H2O3=600.882678 kg/h

37

For stream 14 F14=5775.595257kg/h F14H2O=367.52916kg/h F14CH2O2=0.122097kg/h F14C3H4O2=0.19111kg/h F14C4H2O3=5407.944kg/h F12=F13+F14 (1837.6458+0.40699+0.637034+6008.82678=(1470.11664+0.284893+0.4459+600.8 82678)+( 367.52916+0.122097+0.19111+5407.9440) 7847.516=2071.730+5775.95257(proven)

Total mass flow rate in = Total mass flow rate out F1+F2+F7=F8+F11+F13+F14 5130.9+95129.14+1902.58=85886.623+8428.085+2071.730+5775.595257 102162=102162 (proven)

38

Stream

1

2

3

4

5

6

7

8

Temp. (°C)

20

20

147.9

121

410

95

45

59.9

Press(kPa)

275

101

275

275

275

200

170

170

Vapor Fraction

0

1

1

1

1

1

0

1

Total Flow 5130.9 95129.14 95129.14 100260.04 100260.04 (kg/h) 0

0

0

0

100260.04

85886.623 1902.58

Component Flow(kg/h)

0

0

Nitrogen

0

Carbon Monoxide

0

Oxygen

0

Carbon Dioxide

0

0

0

Butane

5130.9

0

0

Water

0

Formic Acid

0

0

0

0

40.69942

40.69942

0

0

Arcylic Acid

0

0

0

0

63.70344

63.70344

0

0

Maleic Anhydride

0

0

0

0

6069.5222

6069.5222

0

0

75152.02 75152.02 75152.02 75150.92066 75150.92066 0

0

0

0

0

0

75150.9266

505.41456

505.41456

0

505.41456

9280.34

9280.34

0

9280.34

0

949.9424

949.9424

0

949.9424

5130.9

913.4478

913.4478

0

0

18074.54 18074.54 18074.54

1902.58 1902.58 1902.58 7285.64922 7285.64922 1902.58

39

0

5.2

Energy Balance

5.2.1

Introduction of energy balance

The energy balance is the arithmetic balancing of energy inputs versus outputs for an object, reactor, or other unit processing. It determine the heat released or absorbed during the reaction. The reaction is exothermic if the heat is released and is endothermic if heat is absorbed. The concept of energy balance is generally the same for all process but only with different approach. The energy balances are used to quantify the energy used or produced by a system. This can be used to build complex differential equation models to design and analyze real systems. To make an energy balance for a system is very similar to making a mass balance but there are a few differences. The law of conservation of energy states that energy can neither be created nor destroyed; it can only be changed from one form to another or transferred from one body to another. Therefore the sum of all the energies in the system remains constant. The purpose is to carry out the calculation of energy balance is to determine the heat change of the unit processing which being analyzed. 5.2.2

Calculation of energy balance of the reactor Stream 4

121oC

Nitrogen gas Oxygen gas Water n-butane Reactor 1

Stream 5 410oC

40

Nitrogen gas Oxygen gas Water n-butane Carbon monoxide gas Carbon dioxide gas Formic acid Acrylic acid Maleic anhydride

Table 5.3 Properties data of each component Liquid-Phase Heat Capacity: Cp = A + BT + CT2 + DT3 + ET4 Liquid-Phase Heat Capacity (J/kmol.K) Component A

B

C

D

Water

92.053

-3.9953e-2

-2.1103e-4

5.3469e-7

Maleic anhydride

-3.123

0.08323

-5.217X10-5

1.156X10-7

n-butane

3.96

37.15X10-2

-18.34X10-5

35X10-9

Oxygen

25.48

1.520X10-2

-0.7155X10-5

1.312X10-9

Nitrogen

28.90

-0.1571X10-2

0.8081X10-5

-2.873X10-9

Carbon dioxide

22.26

5.981X10-2

-3.501X10-5

7.469X10-9

Carbon monoxide

28.16

0.1675X10-2

0.5372X10-5

-2.222X10-9

Cp acrylic acid = 2050 J/kmol.K Cp formic acid = 101.3 J/kmol.K

Stream 4 394

Ĥi Oxygen

394

= ∫ Cp dT = ∫ 298

A + BT + CT2 + DT3 dT

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 25.48(394-298)+(1/2)(1.52X10-2)(3942-2982)+(1/3)(-0.7155X10-5) (3943-2983)+(1/4)(1.312X10-9)(3944-2984) = 2873.52 J/kmol.K

41

394

Ĥi Nitrogen

394

= ∫ Cp dT = ∫ A + BT + CT2 + DT3 dT 298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

=28.90(394-298)+(1/2)(-0.1571X10-2)(3942-2982)+(1/3)(0.8081X10-5) (3943-2983)+(1/4)(-2.873X10-9)(3944-2984) = 2804.05 J/kmol.K 394

Ĥi Water

394

= ∫ Cp dT = ∫ A + BT + CT2 + DT3 dT 298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

=92.053 (394-298)+(1/2)( -3.9953e-2)(3942-2982)+(1/3)( -2.1103e-4) (3943-2983)+(1/4)( 5.3469e-7)(3944-2984) = 19302287.84 J/kmol.K 394

Ĥi n-butane

=∫

394

Cp dT

=∫

A + BT + CT2 + DT3 dT

298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

=3.96 (394-298)+(1/2)( 37.15X10-2)(3942-2982)+(1/3)( -18.34X10-5) (3943-2983)+(1/4)( 35X10-9)(3944-2984) = 10740.43 J/kmol.K Stream 5 683

Ĥo Oxygen

=∫

683

Cp dT

=∫

298

A + BT + CT2 + DT3 dT

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 25.48(683-298)+(1/2)(1.52X10-2)(6832-2982)+(1/3)(-0.7155X10-5) (6833-2983)+(1/4)(1.312X10-9)(6834-2984) = 12052.23 J/kmol.K 42

683

Ĥo Nitrogen

=∫

683

Cp dT

=∫

298

A + BT + CT2 + DT3 dT

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 28.90 (683-298)+(1/2)( -0.1571X10-2)(68322982) +(1/3)( 0.8081X10-5)(6833-2983)+(1/4)( -2.873X10-9)(6834-2984) = 11466.33 J/kmol.K 683

Ĥo water

=∫

683

Cp dT = ∫ A + BT + CT2 + DT3 dT 298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 92.053(683-298)+(1/2)( -3.9953e-2)(6832-2982)+(1/3)( -2.1103e-4) (6833-2983)+(1/4)( 5.3469e-7)(6834-2984) = 251811.59 J/kmol.K 683

Ĥo n-butane

683

= ∫ Cp dT = ∫ A + BT + CT2 + DT3 dT 298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 3.96 (683-298)+(1/2)( 37.15X10-2)(6832-2982)+(1/3)( -18.34X10-5) (6833-2983)+(1/4)( 35X10-9)(6834-2984) = 55654.68 J/kmol.K 683

Ĥo carbon monoxide = ∫

683

Cp dT

=∫

298

A + BT + CT2 + DT3 dT

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 28.16(683-298)+(1/2)( 0.1675X10-2)(6832-2982) +(1/3)( 0.5372X10-5) (6833-2983)+(1/4)( -2.222X10-9)(6834-2984) = 11564.55 J/kmol.K

43

683

683

Ĥo carbon dionoxide = ∫ Cp dT = ∫ A + BT + CT2 + DT3 dT 298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= 22.26 (683-298)+(1/2)( 5.981X10-2)(6832-2982)+(1/3)( -3.501X10-5) (6833-2983)+(1/4)( 7.469X10-9)(6834-2984) = 16847.01 J/kmol.K 683

683

Ĥo maleic anhydride = ∫

Cp dT = ∫ A + BT + CT2 + DT3 dT

298

298

298.1 298.15 3 = AT + BT2/2 + CT /3 + DT4/4 5

= -3.123 (683-298)+(1/2)( 0.08323)(6832-2982)+(1/3)( -5.217X10-5) (6833-2983)+(1/4)( 1.156X10-7)(6834-2984) = 15495.6 J/kmol.K 683

Ĥo formic acid

=∫

683

Cp dT

=∫

298

101.3 dT

298

298.1 298.15 J/kmol.K =39000.5 5 683

683

Ĥo acrylic acid

=∫

Cp dT

=∫

298

2050 dT

298

298.1 298.15 J/kmol.K =789250 5

Stream 4

Component

Molar flow rate, N

Enthalpy, Ĥi

Nitrogen gas

(kmol/h) 2684

(kJ/kmol.K) 2.804

Oxygen gas

564.83

2.874

n-butane

88.28

10.74

Water

105.70

19302.29

44

Nnitrogen Ĥinitrogen = 7525.94 NOxygen ĤiOxygen = 1623.32 Nn-butane Ĥin-butane = 948.13 Nwater Ĥiwater = 2040252 ∑Ĥ4 = 2050349.39

Stream 5

Molar flow rate, N

Enthalpy, Ĥo

Nitrogen gas

2683.96

(kJ/kmol.K) 11.47

Carbon monoxide

18.05

11.56

Oxygen

290.01

12.05

Carbon dioxide

21.59

16.85

n-butane

15.72

55.65

Water

404.76

251.81

Formic acid

0.8842

39.00

Acrylic acid

0.8840

789.25

Maleic anhydride

61.896

15.5

Component

Nnitrogen Ĥonitrogen= 30785.02 NCarbon monoxide ĤoCarbon monoxide = 208.66 Noxygen Ĥooxygen = 3494.62 NCarbon dioxide Ĥocarbon dioxide = 363.79 45

Nn-butane Ĥon-butane = 874.82 Nwater Ĥowater = 101922.62 Nformic acid Ĥoformic acid = 34.48 N Acrylic acid Ĥo Acrylic acid = 666.13 N Maleic anhydride Ĥo Maleic anhydride = 959.39 ∑H5 = 139309.53

Q= Ĥout-Ĥin+r(∆Hof) (∆Hof) = -a(∆Hofn-butane) –b(∆HofO2) +c(∆Hofmaleic anhydride) +d(∆Hofwater) = -1(-125kJ/mol) -3.5(0) +1(-398.076) +1(-286kJ/mol) =-559.08 kJ/mol r(∆Hof) = 61.9339 (-559.08 kJ/mol) = - 34626 kJ/mol Q

= 139309.85-2050349-34626 ≈ -1945665.15 kJ/hour (exothermic reaction)

Therefore, the reactor need to release 1945665.15 kJ/hour of heat in order for the process to occur.

46

CONCLUSION Maleic anhydride has been use a lot in industry to produce various kind of product. However majority of it is use in unsaturated polyester resin which is then used in both glass reinforced applications and in unreinforced applications. Other than that it also use in manufacture of alkyd resins, production of agricultural chemicals ,maliec acid, copolymers and etc. Even though unsaturated polyester resin was the largest end use market for maleic anhydride in 2012 but, the demand is strongest in the BDO market due to the growing use in the production of elastic fibers, plant protection, thermoplastic polyurethanes, coatings, solvents, pharmaceuticals, and electronic chemicals. Increasing demand for maleic anhydride has triggered capacity expansion by companies mainly in Europe and Asia Pacific. Continuous rise in raw material prices has increased the production cost thus bringing maleic anhydride prices under pressure. However, continuous efforts on research and development are expected to provide huge market opportunities such as bio-based maleic anhydride to the industry participants. Mass and energy balance of maleic anhydride can be calculated either using manual or iCON software. Although it might be a difference between these two values, but the changes is too small. Exposure to maleic anhydride can effect someone health if he/she expose to maleic anhydride exceed the warning concentration. Thus, there’s a lot of precaution need to be carried out during working with maleic anhydride. In conclusion, maleic anhydride is one of the products that has been use widely all over the world to produce another kind of product. Market of maleic anhydride also increase from year to years.

47

REFERENCE

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APPENDIX

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