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EXECUTIVE SUMMARY

1.0 PROCESS BACKGROUND AND SELECTION

1.1 Introduction

Acrylonitrile (AN) or also known as 2-propenenitrile has a chemical compound with formula CH2CHCN and 53.09 g/mol as it molecular weight. Acrylonitrile is a colourless liquid with a faintly sweet and pungent odour which dissolves readily in water. It melts at - 830C and boils at 770C. It is explosive and flammable. Acrylonitrile was first synthesized in year 1893 by Charles Moureu. Later, the production of acrylonitrile was improved by improvement of manufacturing process discovered by scientists and engineers at The Standard Oil Company, or Sohio. The new process was known as SOHIO Process. SOHIO technology involving ammoxidation of propylene, ammonia, and air that are reacted over catalyst in fluidized bed reactor to form some hydrogen cyanide (HCN) and acetonitrile (ACN), which is separated from acrylonitrile by distillation. The resulting acrylonitrile containing water and impurities is then further distilled to achieve a purity of 99%.

1.2 Process selection

Currently, there are two common types of process can be used to produce acrylonitrile. The first method that has been used widely is known as SOHIO ammoxidation of propylene and propane and second method that can be used to produce acrylonitrile is by hydrogenation of hydrogen cyanide (HCN) with acetylene. One of the differences that can be used to distinguish these two processes is that SOHIO process will produce toxicity material HCN as a by product while hydrogenation process required toxicity material HCN as a raw material.

1.2.1 Ammoxidation of propylene (SOHIO)

Majority of acrylonitrile manufacturers uses ammoxidation of propylene to produce acrylonitrile. The chemical reaction involved in this process is shown as below:

CH2=CH-CH3 + NH3 + 3/2 O2 CH2=CH-CN + 3H2O

(1.1)

The reaction between ammonia and propylene in this process is highly exothermic and it occurs in gaseous phase over a suitable catalyst at temperature of 300 - 500C and pressure at 1.5 - 3 bar. Fluidized bed reactor or fixed bed reactor is used in order for the reaction to take place. The selection of catalyst used in this process is highly important to enhance acrylonitrile production or higher yield of products can be achieved. Common catalysts used by manufacturer suitable with the selected process contain molybdenum or antimonium oxides mixed with transition metals (Fe, Ni, Co, V). Acrylonitrile production yields can achieve up to 80 - 82 % if the best catalyst has been used in the process and the yields cannot be achieved higher than that because some of the propylene loss in combustion.

1.2.2 Ammoxidation of propylene (SOHIO)

Same method as the above method but the difference is only the type of raw material used in the reaction. In this process, propane is used as the basic raw material instead of propylene. The chemical reaction of this process is shown as below:

C3H8 + NH3 + 2O2 CH2=CH-CN + 4 H2O

(1.2)

Before further reaction of acrylonitrile production can be precede, the propane must undergo another reaction which is dehydrogenation to convert the propane to propylene.

C3H8 C3H6 + H2

(1.3)

The overall ammoxidation of propane is exothermic. Over oxidation reactions may results in carbon monoxide and carbon dioxide formation. Based on experiences faced at early years, the conversion of propane is lower than that of propylene. By using propane, larger gas flows are required in order to obtain large capacity and much heat is generated although it is cheaper than propylene

1.2.3

Hydrogenation of acetylene

This process occurs in the presence of an acidic aqueous cuprous chloride complex as catalyst. The chemical reaction involves in the production of acrylonitrile from HCN and acetylene is shown as below:

C3H3 + HCN CH2=CH-C=N

(1.4)

The reaction can be carried out either in strictly gas phase or using a liquid reaction medium, but the latter is preferred as it can simplify the apparatus required and the more favourable contact can be achieved between reactants and results in higher product yields. Catalysts that can be used in the reaction are such as activated carbon, silica gel and metal cyanides and usually the operating temperature for this reaction to take place effectively is in the range from 450C to 700C. .

1.2.4 Summary of comparison for all method

Please refer to appendix A

1.3 Selected method

It can be concluded that synthesis of acrylonitrile through the ammoxidation of propylene will be chosen as a process for this project. The manufacturing of acrylonitrile by ammoxidation of propylene remains highly competitive because the high performance with the modern catalysts is based on molybdenum oxides. The conversion of propylene is practically complete, while the ammonia and oxygen are used in amounts close to stoichiometry. Hence, the yield of acrylonitrile produced is much greater. So, this method is the best process to produce acrylonitrile. Compared to the ammoxidation of propane, even though propane is cheaper than propylene, we are not interested to use propane as raw material because the problem of selectivity becomes more challenging. Catalyst should perform in-situ dehydrogenation simultaneously with ammoxidation. Numerous catalysts have been patented, but their performance is still insufficient to justify the massive replacement of current technologies. Besides, the conversion is low when mainly propane is used as feed. Consequently larger gas flows are required to obtain an equally large capacity compared with propylene feeds. Moreover, when propane is used as feed, relatively much heat is generated. This implies that a large reactor is required with a large heat-exchanging surface area. For acetylene and hydrogen cyanide process, process design for preparing acrylonitrile is using old method. This method was established in 1940 and produce higher amount of by-product compared to the other process

1.4 Process flow diagram

Please refer to appendix B

2.0 MASS BALANCE

2.1 Assumption

The major assumptions are: 1. The production of acrylonitrile more than 100 000 metric tonnes per year. 2. Total plant operating days are 351 days per year. 3. The plant is operating at 24 hours per day. 4. All calculations are performed in kg/hr. 5. No defect on the system that can affect the amount of the production such as pipe and vessel leakage. 6. All components are in steady state condition. 7. Reaction only occurs in the reactor and H2SO4 quench only. 8. Amount of catalyst does not have any impact to the mass balance. 9. To proceed with this calculation, an estimation of production of acrylonitrile for this plant is assumed 20% above the minimum production. This is because of some factors and considerations during this process such as losses of product in piping, inefficiently separation, or due to some internal and external problems.

Hence, the production of acrylonitrile is (1.2)(100,000 tonnes per year) = 120,000 tonnes / year This plant should produce 120,000 tonnes per year of acrylonitrile.

2.2 Overall process mass balance S1 SIMULATION ( kg/hr) MANUAL ( kg/hr) ERROR (%) 220,931.02 220,931.02 0.00 S2 220,920.47 220,931.02 0.13 S3 16630.00 5406.45 67.49 S4 259,986.26 267,302.98 2.74 S5 155,103.24 153,401.49 1.11 S6 104,883.02 113,901.49 7.92 S7 153,121.28 151,138.45 1.31

S8 SIMULATION ( kg/hr) MANUAL ( kg/hr) ERROR (%) 2081.95 2363.04 11.90

S9 19,800.00 17,224.18 14.95

S10 137,548.83 149,040.35 7.71

S11 2.484.37 1,984.33 25.20

S12 1,783.92 1,918.91 7.03

S13 132,916.54 145,137.11 8.42

S14 -

S15 SIMULATION ( kg/hr) MANUAL ( kg/hr) ERROR (%) 674.9 702.11 2.44

S16 1,109.01 1,216.80 8.86

S17 916.7 1467.78 37.54

S18 21,367.68 17,740.73 20.44419818

S19 8.194 14.27 42.58

S20 21,140.00 17,726.46 19.26

S21 3,608.00 3,685.13 2.14

S22 SIMULATION ( kg/hr) MANUAL ( kg/hr) ERROR (%) 17,720.00 14,041.33 26.19

S23 50,004.94 50,000.00 0.01

S24 53,878.27 50,000.00 7.76

ACN PURE 1,783.92 3,903.24 54.30

3.0 ENERGY BALANCE

3.1 Assumption

There are several assumptions for this process which are: 1. The system is system at steady state, all variable not change with time 2. Open system (input = output) 3. There are no moving parts in the system (negligible shaft work) 4. The linear velocities of all streams are the same (negligible change in kinetic energy) 5. All streams enter and leave the process at a single height (negligible change in potential energy) 6. Negligible heat of mixing and effect of pressure on enthalpy

3.2 SUMMARY OF ENERGY BALANCE

HEAT FLOW (kJ/hr)

HEAT EXCHANGER (Q1)

REACTOR (Q2)

HEAT EXCHANGER (Q3)

QUENCH (Q4)

MANUAL HYSYS ERROR (%) 1.320 108 99.99 92.52 99.99 152.83

HEAT FLOW (kJ/hr)

HEAT EXCHANGER (Q5)

DECANTER 1 (Q6)

HEAT ECXHANGER (Q7)

STRIPPING COLUMN (Q8)

COMPRESSOR 1 (Q9)

MANUAL HYSYS ERROR (%) 99.72 91.23 1000 68.20 99.65

HEAT FLOW (kJ/hr) MANUAL HYSYS ERROR (%)

DECANTER 3 (Q14)

DECANTER 2 (Q17)

COMPRESSOR 2 (Q18)

ABSORPTION COLUMN (C1)

STRIPPING COLUMN (C2)

79.66

108.72

68.30

99.07

99.22

HEAT FLOW (kJ/hr) MANUAL HYSYS ERROR (%)

DISTILLATION COLUMN (C4)

DISTILLATION COLUMN (C5)

DISTILLATION COLUMN (C3)

DISTILLATION COLUMN (C6)

99.89

1.79

111.1

100.1

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4.0 MARKET ANALYSIS

4.1 Demand on acrylonitrile

Global demand for acrylonitrile has been showing rising trend since 2003. Acrylonitrile demand growth is forecast at 3.7% per year on average for the period 20082018. Global demand for acrylonitrile is expected to grow by 1-2% per year, with strongest demand in Asia pulled by the growth in ABS. The total demand for acrylonitrile in 2018 is predicted at 6.516 million tons. The acrylonitrile supply and demand balance is forecast in order to improve over the coming years as capacity is added slightly behind forecast demand growth.

Figure 4.1

Acrylonitrile (2018): Production vs. Demand ( Source : latest news

(online) form www.pci-acrylo.com .retrieved 25 July 2010) ) Nowadays, production of acrylonitrile has a very bright prospect in Malaysia. The growth of the petrochemical industry is regarded as one of the major catalysts that contribute to the sustenance of the countrys economic growth. The market of acrylonitrile in Malaysia has increased year by year due to increased demand of acrylonitrile. Basically, acrylonitrile is used in Malaysia for the manufacture of styrene acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS) and fibers.

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Acrylonitrile can be transformed into clothes, carpet, computer casing, housing appliances and many others. Due to high profitability of these industries, production of acrylonitrile in Malaysia has a very high demand. The production capacity of propylene and ammonia in Malaysia also rise by years.

4.2 PROCESS ECONOMICS ANALYSIS AND ESTIMATION.

The market analysis on the acrylonitrile plant can be summarized as follow:

The total capital investment is RM 198,770,172.40 The revenue gained from product selling per year is RM 1,054,855,200.44 The plant life analysis is done for 21 years with 2 years as start-up. The rate of return on investment obtained after tax is 15 %. The total utilities cost is RM 1,743,824.00 The total operating labor cost is RM 1,400,000.00 The breakeven point for this project is 81,983.27 tonne/year The payback period is estimated to be 3.33 years after start-up period, which is reasonable because the payback time for typical chemical plant is normally between 2 to 5 years from start-up.

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4.3 BREAKEVEN ANALYSIS

Total Product Selling price per year = RM 1,054,855,200.44 Selling Price per tonne = RM 8,790.46 / tonne

Annual Production Costs

= Operating Costs = RM 992,958,128.73

Production Cost per tonne

= RM 8,274.65 / tonne

Fixed Cost

= RM 42,653,637.54 / year

Break Even Point

= 82,692.71 tonne/year

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4.4 PAYBACK PERIOD

Cumulative Non-Discounted Cash Flow Diagram


700,000,000.00 600,000,000.00 Cumulative Cash Flow (RM) 500,000,000.00 400,000,000.00 300,000,000.00 200,000,000.00 100,000,000.00 (100,000,000.00) (200,000,000.00) (300,000,000.00) Time (Year) 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Figure 4.4 Cumulative Non-Discounted Cash Flow Diagram

Payback period = 3.33

Cumulative Cash Ratio (CCR) = 4.07

Rate of return on Investment (ROROI) = 15 %

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5.0 SITE SELECTION

5.1 List of site and selected site

According to the factors that are listed in Chemical Engineering Design, vol. 6, 4 th edition, R. K. Sinnott,( P: 892), three suitable places were found to become the site for this plant. All the listed plant are ensure located in Malaysia, this is because according to Asia Petrochemical Industry Conference 2006 (Report from Malaysia) written by Malaysia Petrochemical Association, Malaysia is already a well known country exporting major petrochemical product. The listed sites are: 1. Kerteh, Terengganu 2. Tanjung Langsat, Johor 3. Bintulu, Sarawak

With a price range of RM8-22 per square feet (MIDA, 2010), Tanjung Langsat site is considered as suitable site for heavy type industry. This is because Tanjung Langsat is located in Iskandar Malaysia (Flagship Zone D) where this region is under government supervision which means that there is strong support in terms of economic growth that has been developed by the government. This site is located near to Tanjung Langsat port, which specially designated to handle bulk cargo such as liquefied petroleum gas (LPG) and dangerous chemicals. Situated 12 nautical miles (22 km) from the international shipping lane, 8 km from Johor Port and 45 km from Johor Bahru, this port that expected to complete its construction on 2012 will provide petrochemicals and chemical as well as liquid bulk handling services. Besides that, this port is targeting petroleum-based liquid bulk cargo from the industrial area around Pasir Gudang as well as the adjacent Tanjung Langsat Industrial Estate developed for petrochemical facilities, (Asia Petrochemical Industry Conference 2006: Country Report- MALAYSIA). Therefore, this facility will give an extra credit when site evaluation is made.

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This site is near to Titan Tanjung Langsat which provides propylene as a raw material. The distance between the plant site and Titan Tanjung Langsat is only about 5.4 km through the main road. The close distance not only will reduce the cost of raw material but also reducing time for transportation. Although ammonia supply can be obtained from Selangor, it is preferable to get the supply from Singapore as this site is located near to Singapore. This option can lessen the cost of transportation.

5.2 Summary data for site location

Please refer to appendix C.

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6.0 ENVIRONMENTAL AND SAFETY CONSIDERATION

6.1

Waste treatment

In acrylonitrile production process, only wastewater or liquid wastes and gas wastes are produced as solid waste does not being generated. Since almost of product produce in this plant poisonous, all waste will be treated with a help of guidance from department of environment.

6.1.1 Wastewater treatment

In acrylonitrile production, ammoxidation of propylene used large volume of processing water in the primary separation stages. Water are largely consume in the first separation step which process of acrylonitrile recovery from the reactor off-gas occurs. Water that needs to be treated comes from the quench column and acetonitrile column.

Since water has been used in a large amount, some of the water used can be recycled back to the system without undergoing any treatment. In the acrylonitrile production, water from the acetonitrile column specifically C4 and C5 are being recycled back to the stripping column and quench column.

For this plant ,activated sludge system is chosen to be used in treating the wastewater in the acrylonitrile because of the organic materials content in the wastewater containing acetonitrile. This system typically is a biological wastewater treatment. This system consists of primary clarifier, aeration tank, secondary clarifier or settling tank and finally disinfection section. The process flow diagram illustrated the wastewater treatment using this system is shown as below:

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Figure 6.1: Activated sludge system (Source: (2009) Biological Wastewater Treatment with Activated-Sludge Process ( online) retrieved from http://www.lenntech.com/wwtp/wwtp-overview.htm#ixzz14gM82Iaz )

The process is started as the wastewater containing acetonitrile is passes through the primary clarifier. Any heavy organic materials that present in the wastewater can sediment in this section. The wastewater is then routed to the aeration tank containing oxygen which can be supplied by bubbling either compressed air or pure oxygen gas. The activated sludge is the sludge containing in the aeration tank and it consists of bacteria flocs. Biological reaction occurs in this section as the flocs of bacteria consume the biodegradable organic substances in the wastewater containing organic materials (acetonitrile). The organic substances that are consumed by the bacteria are important for their growth, energy and reproduction in the presence of oxygen . Typically the activated sludge in the aeration tank consists of community of microorganism and it mainly comprise of bacteria and fewer percentage of higher organisms such as protozoa and rotifers. Usually, the wastewater is retained in the aeration tank for few hours before entering the secondary clarifier for separation process (UNEP, 2008).

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The secondary clarifier will separate the biological flocs and the treated wastewater by allowing the biological flocs or sludge to settle. Some of the activated sludge is recycled back to the aeration tank for later use and usually the amount of recycled activated sludge has increases because of growth and reproduction in previous reaction. Some of the excessive sludge also removed in the process as waste sludge. The final process of the wastewater treatment is the disinfection process which is to get rid or make the clear treated water free from any microorganisms that may cause disease. Thus, the treated water can safely be used back in the acrylonitrile production process or can be safely release to water bodies (Source : (2009) Biological Wastewater Treatment with Activated-Sludge Process ( online) retrieved from http://www.lenntech.com/wwtp/wwtpoverview.htm#ixzz14gM82Iaz). Ammonium sulphate which generated in the quench section from the neutralization of excess ammonia with sulphuric acid can be treated in a way whether to produce saleable product or just dispose it. The ammonium sulphate can be treated by using crystallization process to form valuable product that can be marketed to the fertilizers industries. Other than that, another option is by setting a treatment unit to generate back sulphuric acid. Waste treatment may be costly but there are advantages of waste treatment unit being installed. One of the advantages is that the saleable product generated can be the source of earnings. But it depends on the amount of wastes being produced. If such waste is produced in a smaller fraction, then disposal is the best way to be done. Each country has its own limits of effluent parameter standards which indicate that the water treated in their industries are safe to be discharged in the water bodies. The important parameters need to be tested in the treated water from wastewater treatment plant are such as temperature, pH, chemical oxygen demand(COD), biochemical oxygen demand (BOD) and organics compound. Below table shows the maximum effluent parameter limits Standards A and B according to Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979

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6.1.2 Air treatment

In acrylonitrile production, a major source of pollution mostly contributed by the offgas leaving the absorber, miscellaneous vent streams and fugitive emissions. The emission of gaseous is occurred mainly in the absorber vent gas. The absorber vent gas contains nitrogen, carbon oxides (due to total oxidation of propylene), propane (due to impurities in the propylene feed), unconverted propylene, hydrocarbon impurities, small quantities of acrylonitrile, hydrogen cyanide, acetonitrile and other organics (IPPC, 2006).

Thermal oxidation comprised of various type of system depending on its efficiencies. The suitable type of thermal oxidation system to be installed and treat the gas wastes in the absorber is recuperative thermal oxygen. This is because it has low operating cost and the destruction efficiency can reach up to 99% (Source: (2009), thermal recuperative oxidizer (TO) ( online) retrieved from

http://www.thecmmgroup.com/Thermal_Recoup_Oxidizers.aspx?print=yes).

Figure 6.2: Thermal recuperative oxidation flow of process( Source: (2009), thermal recuperative oxidizer (TO) ( online) retrieved from http://www.thecmmgroup.com/Thermal_Recoup_Oxidizers.aspx?print=yes) 20

Above diagram shows the typical work principle of thermal recuperative oxidizer adapted from the CMM Group which is the manufacture company that has the experience and expertise in producing cost-efficient equipment. Basically, the basic concept about this thermal oxidation system is the same used in various industries. The difference is that only the specific design equipment incorporated by different supplier of this equipment. To illustrate the system to be used in our plant, it is wise enough to demonstrate the work principle in standard by referring to the CMM Group design equipment .

The thermal recuperative oxidizer consists of a combustion chamber with shell and tube heat exchanger. The major factors need to be considered in this system are the temperature, residence time and turbulence in order to achieve efficient destruction. In thermal oxidation, the basic concept is to promote oxidation by the reaction between the gas waste and oxygen at elevated temperature. The destruction process is achieved when the gas waste converted into carbon dioxide, water vapor and heat in the combustion chamber

The work principle of this system is started as the gaseous waste drawn into the system fan and passes through into the inlet of the heat exchange media where the gaseous waste is preheated in the tube side of the heat exchanger. The waste is then undergo heating process as it passes the fired burner where it is raised to typical thermal oxidation temperature ranging from 1400 - 1500F and finally an exothermic reaction takes place. The typical residence time in this system is ranging from 0.5 1.0 seconds. The conversion of the gas wastes to carbon dioxide, heat and water vapor is occurring in the combustion chamber .

The hot clean air is then routed back to the shell side of the heat exchanger where the energy released continuously preheats the incoming gas wastes. The cooled clean air will exit the heat exchanger and finally routed to the exhaust chamber and exhaust into the atmosphere. The material of construction of the standard thermal recuperative units is stainless steel. The main advantages in proposing this type of air pollution control method are the ease of operation and ease of install as well as low operating cost. The destruction efficiencies of this technique can reach 99% (Source : (2009), thermal recuperative oxidizer (TO) ( online) retrieved from

http://www.thecmmgroup.com/Thermal_Recoup_Oxidizers.aspx?print=yes)

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Gaseous leak contain in the storage tank specifically acrylonitrile storage tank, also can occurs in this industry. Acrylonitrile gas shows toxicity characteristic thus it is important to prevent this type of problem from arises. This problem can be controlled by double-sealed the floating roofs or use water scrubbers. Sometimes, emissions from product transport loading vents occurs but it can be controlled by gathering the escaped gaseous and send it to a flare or incinerator for destructions (IPCC, 2006).

Besides that, fugitive emissions can contributed to air pollution and this can be occur when there is a leaking problem from piping, valves, pumps or compressors. Usually fugitive emission comprise of propylene. This problem can be avoided by performing regular monitoring on the equipment such as using a detector to detect any leaking and maintenance should be directly taken whenever a flaw has been occurred (IPCC, 2006).

All in all, all type of gaseous emission in this production must be taken into full consideration because without treating the emitted gaseous, it can contribute to air pollution. All the gaseous should be treated in correct manner or methods before it can be emitted to the environment. To verify that the gaseous is safe enough, monitoring activity need to be done in order to test that the emission of gas complies with the regulated law that the Malaysian Government has set. The standards of parameters referring to this law are stated in the Environmental Quality (Air) Regulations, 1978.

6.2 Material safety data sheet (MSDS)

The legal obligations of suppliers and employers are specified by the Occupational Health and Safety (Hazardous Substances) Regulation 1996. MSDS for hazardous substances supplied are required to be provided by suppliers, and this includes importers and manufacturers. Employers must ensure that the MSDS are accessible to employees who may be exposed to certain hazardous chemicals and to enhance the safety in workplace the MSDS must be regularly update

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7.0 PROCESS SIMULATION

7.1 Process flow diagram (HYSYS Simulation)

Please refer to appendix D

7.2 Data summary for process simulation

Please refer to appendix D

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