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CHAPTER 1: INTRODUCTION

1.1 Background of The Project Maleic Anhydride is widely used in industries as fumaric acid, agricultural chemicals, alkyd resins, lubricants, copolymers, plastics and agriculture chemicals. Maleic Anhydride is used mainly in the production of unsaturated polyester resins which is a vital component in housing, automobiles and construction industries. This product has a variety of applications in automobile bodies, building panels, molded boats, chemical storage tanks, lightweight pipe, machinery housings, furniture, radar domes, luggage, and bathtubs.

In 1997, TCL has set up a Maleic Anhydride plant of 35,000MT capacity. Based on the credibility of this plant, we expected our plant to produce 35,000MT per year. Based on the research,the product is expected to be exported high at Middle East as the market demand is highly consumed for butanediol. China is a one of the country that has a high percentage of consumption of Maleic Anhydride, but we did not expect to export because there are lots of Maleic Anhydride plants at China.

Due to widely applications of Maleic Anhydride in industries, there are many researches on alternatives route process. Among all, we choose catalytic oxidizing as our process because this process requires the usage of catalyst. The usage of catalyst promotes the desired product besides our process is an exothermic that involving the high temperature.

1.2 Problem Statement Benzene and normal butane are the main fees stocks for Maleic Anhydride production. Due to the rising cost and health hazard issue of benzene, the normal butane became the most chosen alternative. This is due to the low cost, easy availability and less hazardous to the health. The team will have to design the most cost-effective process plant while considering the following relevant issues: Select the most economical butane derivative product. Determine an appropriate plant capacity. Construct the plant at the best location in Malaysia. Design a plant that is environmental friendly possible. Recover and recycle process materials to the maximum economic extent. Minimize energy consumption to the extent economically justified. Design a plant that is simple and safe to operate, which follows the corporate HSE guidelines.

1.3 Objectives The main objective of this project is to select the most economical butane derivative product and develop a complete plant design of the product. The other objectives are as follow: To develop process flowsheeting. Perform MEB for the process. To carry Heat Integration for optimized flowsheet. To perform preliminary economic potential for the process.

1.4 Scope of Design Work The feed for the new plant has already indicated. A research is then been conducted to select the best product. A literature survey is then conducted, covering all aspects of the design problem. By taking general design considerations into account, a process flow sheet is generated. Material balance is then calculated for the chosen flowsheet. At this stage, predesign cost estimation is also prepared. A pre-simulation using HYSIS is also generated to aid in the design and material balance. Preliminary heat integration is also done after the flow sheet is prepared with the aid of SPRINT.

CHAPTER 2: LITERATURE REVIEW


2.1 Alternative Process Routes In the production of Maleic Anhydride, there are many of process routes introduced in producing maleic anhydride. According to the research article by Barone et al.,U.S. Pat. No 4,565,880 Maleic Anhydride Process., Maleic anhydride is produced commercially, by catalytic oxidation of a hydrocarbon (benzene or butane) at high temperature and using air/oxygen as the oxidizing agent and over the suitable catalyst to produce a gaseous effluent of maleic anhydride together with impurities. The catalyst is generally,V2O5 or V2O5-MnO2. The exothermic heat of reaction is removed by circulating molten salt or by generating steam in the shell side of the reactor. Apart from that, Maleic anhydride is also formed as a byproduct from phatalic anhydride process.

In the process using benzene as feedstock and vaporized benzene and air are mixed and heated before entering the tubular reactor, the benzene/air mixture is reacted with the catalyst which is vanadium pentoxide(V2O5). The effluent maleic anhydride gas is partially condensed and the gas is further scrubbed with water. Pure maleic anhydride is produced through a series of thin film evaporator, dehydrator and a distillation column. Maleic Anhydride is produced using air oxidation of benzene, illustrated by the following chemical reaction: V2O5 2C6H6 + 9O2 2C4H2O3 +H2O +4CO2 (Benzene) (MAN)

Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphorus oxide catalyst. The butane oxidation reaction to produce maleic anhydride is very exothermic and the reaction temperature is 350-400 C. The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows:

C4H10 + 3.5 O2 C4H2O3 + 4 H2O C4H10 + 6.5 O2 4 CO2 + 5 H2O C4H10 + 4.5 O2 4 CO + 5 H2O

DH = -1236 kJ/mol (-295.4 kcal/mol) DH = -2656 kJ/mol (-634.8 kcal/mol) DH = -1521 kJ/mol (-363.5 kcal/mol)

For the past few years , Butane were found to be better feedstock for the production of maleic anhydride due to higher prices of benzene, restriction imposed on benzene emission control standards, low cost and easy availability of butane feed stock and also being less hazardous to health. (Shyamal K.Bej and Musti S.Rac,1991)

2.2 Physical And Chemical Properties Maleic anhydride (cis-butenedioic anhydride, toxilic anhydride, 2,5-dioxofuran) is an organic compound with the formula C2H2(CO)2O. It is a compound that is briquettes in physical state, colourless, has pungent odour and the boiling point for maleic anhydride is 2020C (Thirumalai Chemicals Limited, 2006). Besides, maleic anhydride may be combustible at certain high temperature. In addition, it is combustible when exposed to heat or flame. This compound in powder form is capable of creating a dust explosion. When heated to decomposition it emits acrid smoke and irritating fumes. In this case the auto ignition temperature for this compound is 476.67C (Material Safety Data Sheet Maleic anhydride, 2005). In term of toxicity, the substance of maleic anhydride is toxic to human lungs and mucous membrane. Apart of that, it is very hazardous in case of ingestion and hazardous in case of skin contact (irritant, permeator), of inhalation (Material Safety Data Sheet Maleic anhydride, 2005). Butane (C4H10) comes from alkane group with four carbon atoms. The term may refer to either of two structural isomers, n-butane or isobutane (or "methylpropane"), or to a mixture of these isomers. Butanes are highly flammable, colorless, and easily liquefied gases. The boiling point for butane is -10C (Material Safety Data Sheet Butane, 2006). This product is considered to be non-toxic by inhalation. At high concentrations, butanes are asphyxiants and it will displace oxygen from the breathing atmosphere, particularly in confined spaces. Signs of asphyxiation will be noticed when oxygen is reduced to below 16%, and may occur in several stages. Symptoms may include rapid breathing and pulse rate, headache, dizziness, visual disturbances, mental confusion, incoordination, mood changes, muscular weakness,
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tremors, cyanosis, narcosis and numbness of the extremities (Material Safety Data Sheet Butane, 2006). The tables below shows the physical and chemical properties of feed(Table 2.1) and physical and chemical of product (Table 2.2).

PROPERTIES

I-BUTANE

N-BUTANE

OXYGEN

MALEIC ANDHYDRIDE

WATER

MOLECULAR FORMULA

C4H10 C4H10 (CH3)CHCH3 O2 C4H2O3

H2O HOH

MOLECULAR STRUCTURE

MOLECULAR MASS (g/mol) CAS NUMBER APPEARANCE 75-28-5 Colourless Gas 106-97-8 Colourless Gas 7782-44-7 Colourless (Gas) 108-31-6 7782-18-5 58.1 58.1 32.0 98.1 18.01

Pale Blue (Liquid) Aqua Hydrogen Hydrate 2-Methylpropane OTHER NAMES 1,1-Dimethylethane Trimethylmethane Butane 2,5-Furandione Dihydro-2,5-dioxofuran Cis-Butenedioic anhydride Oxidane Hydric acid hydroxide

Dihydrogen monoxide Hydroxyl Dihydrogen Hydrohydroxic -Oxido acid oxide acid

dihydrogen

Light Water BOILING POINT -12 (C) MELTING POINT -160 (C) 154.59 K CRITICAL POINT 5.043 MPa RELATIVE 0.6 0.6 1429 0.0015 22.1 MPa 1 647 K -138 -218.4 53 0 -0.5 -183 202 100

DENSITY (WATER=1) SOLUBILITY IN WATER (g/mol AT 20C) VAPOUR

(when liquid)

(AT 4C)

Insoluble

0.0061

3.1

Reaction

25 PRESSURE (kPa AT 20C) RELATIVE VAPOUR 2 DENSITY (AIR=1) FLASH POINT Flammable Gas (C) AUTO-IGNITION 460 365 477 -60 102 2.1 1.1 3.4 304 213.7 (AT 25C) 2.34

TEMPERATURE (C) EXPLOSIVE LIMITS 1.8-8.4 (VOL % IN AIR) 1.8-8.4 1.4-7.1

Table 2. 1:Properties of feed & product

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2.3 Market Study Of Raw Material And Product

Latest updated price of Maleic Anhydride from AliBaba.com the global trade website, ranges from RM 4430.76- RM 4707.69, with China being the largest manufacturer. In Malaysia, one of the existing plants that manufacture maleic anhydride is Thirumalai Chemicals Ltd Sdn Bhd. in Kemaman, Terengganu. The company is founded in India and on 1997 a plant is set up in Malaysia to produce maleic anhydride with a plant capacity of 35000 tones per annum. Both industrial analysts, ICIS and Platts, have noted that demand for butane, benzene and Phthalic Anhydride (PA) have lowered in the year 2012. According to ICIS, market intelligence for global chemical, energy, and fertilizer, price for benzene is around RM 3330-RM 3390/tonne, while for PA the price ranges from RM 4520 - 4800/tonne for liquid, and RM 4400- 4600 /tonne for flakes. As for butane, Platts, leading provider of energy, petrochemicals and metals

information, states that the price is RM 2227.50. The higher growth of the demand for maleic anhydride is due to the increased interest in maleic anhydride as been exhibit by the producers of 1,4-butanediol. In general, demand for maleic anhydride is governed by the economic situation in the country. The historical price for maleic anhydride from 1997 to 2002 is as tabulated in the table below:

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Demand Maleic Anhydride Year (millions of pounds) 1997 1998 1999 2000 2001 2002 470 488 515 523 479 489

Price* ( per pound) 40.5 43.6 45.2 47.2 45.3 40.5

Table 2. 2:Data for Maleic Anhydride Demand (1997 2002)

Based on the maleic anhydride market research; producers of 1,4-butanediol exhibit increased interest in maleic anhydride, which results in the higher growth of the demand for maleic anhydride. According to IHS.com, approximately 52% of maleic anhydride consumed in 2010 was for the production of unsaturated polyester resins. Chinese consumption of maleic anhydride slowed and the developing country will experience the highest growth since a considerable amount of unsaturated polyester resin goes into infrastructure. Maleic anhydride consumption for butanediol will grow primarily in Asia and the Middle East. Nevertheless global maleic anhydride consumption grew by 6-7% a year to 1.5m MT/y in 2006. Maleic anhydride consumption is expected to grow to 2.6% in 2007The increase demand in Maleic Anhydride is due to various applications of it. Below shows the applications of maleic anhydride:

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Chemicals

Usage

Unsatureted polyester resins Fumaric & malic acid

General

construction

,tanks,

pipes,

electric

component, paints & coating Paper sizing resins, food & beverage acidulants, pharmaceuticals

Lubricating additives Tartaric acid

oil

Gasoline & diesel engine

Chemical intermediate in the synthesis

Vinyl copolymer

Paper

treatment,

emulsifiers,

detergents,

cosmetics, toileteries Agriculture chemicals Herbicide,pesticide,soil sterilizer

Table 2. 2:Application of maleic anhydride(Thirulaichemicals

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2.4 Plant Location Tanjung (Bintulu) Kidurong Pengerang, Johor

Gebeng Location 30 km from Kuantan City. 5 km from Kuantan Port.

Pasir Gudang

Tanjung Langsat

36 km from Johor Bahru City. Johor Port.

42 Johor City.

km

from Bahru

km

from

109 km from Johor Bahru

Bintulu city 3.4 km from Bintulu

78.3 km from Kota Tinggi

5 km from Johor Port

MLNG port

Area Still Available 1618.78 hectares Electricity Tenaga Berhad Nasional (800MW), Sultan Iskandar Power Sultan Iskandar Sarawak Electricity Supply Corporation (SESCO) MLNG Power Pengerang Cogeneration Plant (2000 MW) Tenaga Nasional Berhad 27.0 hectares 1814.20 hectares 1600 hectares

Power Station. IPPYTL

Tanjung Gelang.

Generation Sdn.Bhd (404 MW).

Power Station

Plant (102 MW)


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Water Supply Loji Air Semambu Syarikat Air Johor Loji Layang Road Facilities Karak Highway PLUS Highway PLUS Highway Panhighway Borneo Pengerang Highway Tinggi Rengit) from Senai-Desaru Expressway (from (Kota Sungai Air Sungai Syarikat Johor Loji Air Sungai Layang Air Bintulu Supply Treatment Plant Water Syarikat Air Johor

(Kuala Terengganu Kuantan KL) East-West Highway (federal Road Kuala Terengganu Kerteh Telok Kalong Gebeng Kuantan KL Airport Kuantan Airport

(from Bukit Kayu Hitam Singapore) Pasir Gudang Kim Kim River Highway from Pasir Gudang Tanjung Kupang Singapore. Tuas

(from Bukit Kayu Hitam Singapore) Pasir Gudang Kim Kim River Highway Pasir Gudang Tanjung Kupang Tuas Singapore

Pengerang to Pasir Gudang)

Senai

International

Senai

International Bintulu Airport ,(5.5 km)

Changi International Airport, (29.4km) Spore

Airport, Johor (50 km)

Airport, Johor (50 km)

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Changi International Airport, Spore (60 km)

Changi International Airport, (60 km) Spore

Senai International Airport, Johor (111 km)

Land Price (per meter square)

RM86.10 RM172-RM193 Developer

RM107.60-RM183

RM285 - 2,400 per ha US$79 - 667 per ha

RM2,400 per ha.

PKNP Kemajuan Pahang) (Perbadanan Negeri PBTG (Perbadanan Pasir PBTG (Perbadanan Pasir

Bintulu Development Authority

Johor State Government (Sourthen Johor

Tempatan Gudang)

Integrated Development Plan) PETROLIAM Nasional Berhad (PETRONAS)

Tempatan Gudang)

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Government Incentive Investment Tax Allowance (ITA) Infrastructure Allowance. Five-year exemption on import duty. 5 % discount on monthly electricity bills. Very and over developed Industrial Area The Industrial Park has been growing more than 12% per year. Attractive tax incentives Pioneer status. Partial exemption from income tax. Investment tax allowance. Research and technology incentives. exemption of corporate and withholding taxes for 10 years

100 per cent investment tax allowance for 10 years for new companies entering the country's petroleum refining sector

Table 2. 4: Plant location alternatives (Petrochemical & Polymer Industries Division, MIDA, 2005)

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The selection of plant location is made based on six major factors including (1) raw material (2) markets, (3) energy supply, (4) climate change, (5) transportation and (6) water supply. However, the preliminary survey of the plant site is focusing on four main basis which are availability of raw material, markets, energy availability and climate.

1) Raw material availability:

Five locations have been identified as the maleic anhydride plant location. All the locations are near with the natural gas (butane) suppliers which are Gebeng, Pasir Gudang, Tanjung Langsat, Tanjung Kidurong and Pengerang. But, natural gases produced in Tanjung Kidurong are for export purpose. Therefore, Tanjung Kidurong is being deduced from first selection step.

a) Gebeng Pengerang

b) Pasir Gudang

c) Tanjung Langsat

d) Tanjung Kidurong

e)

2) Markets

Areas identified are also based on market potential since it gives effect to the product distribution and time required for shipping. Therefore, based on the table, the nearest area to the city is Tanjung Kidurong.

3) Energy supply or availability

The second factor to be considered is energy supply. All the three locations are having power generation to supply electricity.

4) Transportation facilities

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The common facilities for industrial concern are water, railroads and highway. All the areas were near to port, having road facilities and airport. Therefore, the distance between the plants sites with the transportation are taken into consideration for choosing the suitable location.

5) Land availability The availability of land is one of the most important factor. This is because the plant should be built in larger area to accommodate all the facilities. Based on the table, the largest area available is in Tanjung Langsat with 1814.20 hectares.

6) Land Price

The land price is based on Malaysia Invest Development Authority. This is to ensure that the effective and cheapest cost invested on land.

Table below summarize the weightage for each factor considered for four plant location.

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Table 2.5: Plant Location Ranking Gebeng Pasir Gudang Tanjung Langsat Tanjung Kiduron g (Bintulu) 2 5 3 4 4 3 4 5 3 5 4 42 76 3 Pengerang

Factors Raw material availability Markets Energy supply Climate change Transportation facilities Waste disposal Labor supply Land availability Land price Incentives By Local Gov. Community factor TOTAL MARKS PERCENTAGES (%) RANKING

4 4 3 2 3 3 4 4 5 3 3 38 69 4

3 3 2 4 4 3 3 3 3 2 4 34 62 5

5 3 4 3 4 3 5 5 4 4 3 43 78 2

2 3 5 3 4 4 5 5 4 5 4 44 80 1

Based on the weightage calculated, the most preferable location is in Pengerang, Johor.

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Table 2.5: Plant Layout

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2.5 Summary of previous accidents Throughout the study, there are 3 accidents involved the explosion of the the chemicals above. Two explosion and fire occurred in 2 plants which are Sunrise Propane Industrial Gas and Picnic Point Wastewater Treatment. Another accident happened at the railway station situated at Kuybyshev Railway, Soviet Union. All of these accidents occurred by the propane gas that has leaked to produce explosion and fire.

Case 1 : UFA Train Disaster According to New York Times on June 5,1989, on 1:15(local time) in the Soviet Union, about 50km from the city if Ufa, there was an explosion on the Kyubyshev Railway on June 4,1989. The explosion occurred when 2 passenger trains passing each other nearby that produced spark that ignited a highly flammable cloud sourced by the leaking of natural gas which are propane and butane. The trains were occupied by many children and the location of explosion was near the town of Asha. The explosive range is from 250-300 tonnes of TNT equivalent up to 10 000 tonns of TNT equivalent. Official figures reported that 575 people died and more than 800 people were injured. Before the accident, the engineers noticed the pressure drop at the pumping end of LPG pipeline. The emergency action taken by the engineer was increasing the pressure back to the normal instead of checking for the leakage.(Robin & Mark L) Several explosions took place followed by a ball of fire which came from both directions and broken as far away as 8 miles. Most of the remaining passengers were hospitalized, some caused by 70-80% of burn injuries. Lesson learnt The implementation of leak detection devices should follow tight mathematical models of pressure variance, with automatic shutdown mechanism. This is to prevent large leakage. The inspectors of robot pig pipe should be done to check the interiors problems. The pipe
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construction includes enamel to prevent corrosion. These improvements lead to the reduction of leakage incidents. Case 2 : The Explosion of Sunrise Propane Industrial Gas In 2008, there was a propane explosion caused by illegal transfer tank to tank along with a leak hose. It was reported that the Sunrise has no right licence to perform that type of transfer and was previously barred by Technical Standards and Safety Authority in November 2006. (Freeman & Taylor , 2008) After the first explosion, some residents are allowed to return to their home but most of them were stoped at the police check points and turned back. The effect of the explosion was Toronto executed an official plan on reviewing all industrial areas that could threaten the resident areas to prevent this situation from reoccurring. TSSA and Ontario Fire Marshall were investigating the main cause of the explosion. (Kooren,2008)

Lesson learnt Propane has no natural odour and colourless. An odourant has to be added to this tank so that it can be detected. A chemical which is Mercaptan is flammable, has pungent odour and can be detected as low as 20% of the lower explosive level (2.4%). Ensure the propane line has been disconnected from the propane storage tank and the gas line shut off valve is locked off. If gas is detected inside a house, then the hydro service should be shut off from the outside by having the meter pulled.

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CHAPTER 3 : CONCEPTUAL DESIGN ANALYSIS

In choosing the best process for production of maleic anhydride, a technical and economic evaluation is the most important factors to consider. Therefore, this chapter will concisely explain four important parts in evaluating and selecting the best process which are preliminary reactor optimization, process screening, economics evaluation and process flow sheeting. 3.1 Preliminary Reactor Optimization

Basically, there are two heuristic methods used for determining the best flow sheet which are Douglass Hierarchical and Onion Model. For Onion Model, the core of the onion will involve rector design considering selectivity and capacity. Separation subsystem will be the next layer for the onion followed by heat exchanger networks which define the energy requirement. As heat recovery between process streams is insufficient to meet required energy needed, utility system is the final layer of the onion.

Reactor

Separation and recycle stream Heat exchanger network Utilities

Figure3. 1: Onion model

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Douglas Hierarchical is a procedure for synthesising process flow sheet and it consists of decision level and more fine structure is added to the flow sheet at each level. In this project, Douglas method is chosen as the basis of conceptual design since it is more systematic. Douglas hierarchical procedure is based on the following level: Level 0: Input information Level 1: Batch continuous Level 2: Input output Level 3: Recycle structure Level 4: Separation system Level 5: Heat Exchanger

3.1.1 Reaction information

In general, there are two process routes for production of maleic anhydride either through catalytic oxidation of benzene or butane. The chemical reaction for producing maleic anhydride using air oxidation of benzene is illustrated as follow: General process description V2O5 2C6H6 + 9O2 2C4H2O3 +H2O +4CO2 (Benzene) (MAN)

However, due to health hazard and rising cost of benzene, butane emerged as alternative replacing benzene due to its low cost, less hazardous to health and easy availability. Hence, the main focus of this process is to produce maleic anhydride from butane
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Reaction Chemistry The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows: C4H10 + 3.5 O2 = C4H2O3 + 4 H2O C4H10 + 6.5 O2 = 4 CO2 C4H10 + 4.5 O2 = 4 CO + 5 H2O + 5 H2O DH = -1236 kJ/mol (-295.4 kcal/mol) DH = -2656 kJ/mol (-634.8 kcal/mol) DH = -1521 kJ/mol (-363.5 kcal/mol)

Reactor condition

Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphorus oxide catalyst. The butane oxidation reaction to produce maleic anhydride is very exothermic. The reaction conditions are as follow: Reaction type: exothermic Reactor pressure: 300 kPa (3 bar) Reactor temperature: 350oC 400oC

a) Reaction description For production of 35000 tonne per annum of maleic anhydride, only one reactor is used. N-butane is heated to reaction temperature of 400 oC and air is supplied through compressor and mix with butane before it enters the reactor. High pressure at 3 is supplied as by generating the high pressure, the exothermal reaction can be removed to stay close to isothermal. Then, the reactor effluent is cooled. Then, maleic anhydride is recovered from the maleic acid and been purified by distillation under lower pressure. The reaction has a conversion of 82.2%.

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b) Production rate The production rate of maleic anhydride is 35,000 tonnes per year. The plant is to be assumed to be operating for 330days/year and 24 hours per day. The calculation as below: The rate of production = x =44.643kmol/year Therefore, the rate production to achieve the target of 35,000 metric ton maleic anhydride per year is 44.643kmol/year. In designing new plant, the production rate from existing plant in Malaysia is used as an estimate. For this project, Thirumalai Chemical Ltd. producing maleic anhydride is used as reference. x x

c) Product purity Approximately 99% of product purity is achieved based on the process flow design. This equal to 44.643 kmol/year.

d) Raw materials The main raw material to be used is n-butane. This raw material must be free from the impurities to make sure the efficiency of the product is sustained. e) Catalyst Rate of chemical reaction can be increased by using catalyst. Catalyst can promote the production of selected product. In general, there are two types of catalyst which are heterogeneous and homogeneous catalyst. A major different between these two types of catalyst are; in homogeneous catalyst, the catalyst is in liquid phase meanwhile in heterogeneous catalyst,
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solid or gas catalyst are used. The comparison between homogeneous and heterogeneous catalyst are as follow: Homogeneous Phase Temperature Activity Catalyst recycle Catalyst modification Liquid Low (< 250 oC) Moderate Expensive Easy Heterogeneous Gas or solid High ( 250- 500 oC) High Simple Difficult

Table 3. 1:Major difference between homogeneous and heterogeneous catalyst

The oxidation of n-butane for producing maleic anhydride occurs at 400 oC. Therefore, heterogeneous catalyst is used. Typically, the reaction is catalysed by vanadium-phophorus mixed oxides. The butane oxidation reaction produce byproduct which is carbon monoxide and carbon dioxide. Due to this, only kinetic control by a catalyst will enhance the formation of maleic anhydride. The chemical reaction rate, k is expressed as follows: k = A exp (- Ea / R T) -- Arrhenius equation Whereby A is a constant (frequency factor or pre-exponential factor), Ea is the activation energy, T is temperature in Kelvin and R is universal gas constant ( 8.3144e-3 kj mol-1 ).

Level 1 : Batch versus continuous There are several guidelines from Douglas to help us to select the batch process or a continuous process. According to Douglas, the criteria that differentiate between these two processes are production rates, market forces and operational problems.

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a) Production rates The continuous process applicable for the plant which has a capacity more than 10x106 lb/year ( 4.5x10-3 tonnes/year ) whereas the batch process is for the plant with capacity less than 1x106 lb/year (4.5x10-4 tonnes/year). It is required to produce maleic anhydride for capacity of 77x106lb/year (35x103 tonnes/year). Therefore, a continuous process is the best choice for the design. b) Market forces For Batch plants often are preferred for products with a seasonal demand so that the plant could be used to make other products during periods of no demand .However, maleic anhydride is not a seasonal product, so it is decided to choose the continuous process. c) Operational problems Batch reactor requires long reaction times as the chemical reactions are slow. As batch reactor can cause rapid fouling materials, frequent cleaning is required. Therefore, continuous process is more preferable.
Table 3. 2:Comparison between batch operation and continuous operation

Batch operation Usually better for small-volume production

Continuous operation Better for indefinitely long production runs of one product or set of product

Unsteady-state operation means process control and obtaining uniformity of product is more difficult Obtaining uniform product quality is more difficult due to unsteady-state operation Inherent down-time between batches

Operating cost is relatively low

Steady-state operation allows uniformity of product easier No down-time except for schedule and

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emergency maintenance Easy to shut down and clean for fouling service Shut down for cleaning very demanding and costly

Due to more advantages of continuous operation compared to batch operation, therefore continuous operation is chosen.

Level 2: Input-Output Structure Decision for the input-output structure is according to following alternatives: 1)
Product Feed streams Process By-product No-reactant

Figure3. 2:: No recycle of by-product

2)
Purge Product Feed streams Process By-product No-reactant Figure3. 3:Recycle of by-product

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Alternative 1 is chosen if inexpensive reactant such as air and water involved. Meanwhile alternative 2 is proposed when gaseous reactant and inert gaseous feed impurity or inert gaseous reaction by-product involved. Douglas hierarchical for level 2 decision is based on the following:

1) Should we purify the feed streams before they enter the process? 2 ) Should we use a gas recycle and purge stream? 3) Should we not bother to recover and recycle some reactants?

Table 3. 3:Level 2 decision

1) Purification of feed To avoid any reaction of impurities occur, feedstock need to be purified at first before it is fed into the reactor. The desired fed is only n-butane, therefore it is best to remove any feed impurities. This is because reaction of impurities will cause more complicated separation to recover additional by-product and lead to raw-material losses. 2) Gas recycle and purge Gas recycle and purge stream is proposed whenever a light reactant and either a light feed impurity of a light by-product boil lower than propylene (-48.333 oC). This is because lower boiling point component normally cannot be condensed at high pressure with cooling water. In this process, unreacted n-butane with boiling point (-1 oC) is purged out together with other byproduct such as oxygen, nitrogen, carbon dioxide and carbon monoxide. This is because additional equipment is required for purifying n-butane from other gas component. 3) Do not recover and recycle some reactants which are inexpensive such as air and water For getting the best flow process with maximum profit, inexpensive reactant such as air and water is not recovered and recycle. This is because it is often to feed them as an excess to

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make them react completely. Therefore, in the reaction producing maleic anhydride, air which is fed for oxidation of n-butane is not recycled.
Table 3. 4: Level 3 decisions

1. How many reactor systems are required? If multiple reactors are used, which feed streams and recycle streams are associated with each reactor and is there any separation between reactors? 2. How many recycle streams are required? 3. Do we want to use an excess of one reactant at the reactor inlet? 4. How does the reactor cost affect the economic potential?

Level 3: Recycle structure of the flow sheet Level 3 focus on determination of recycle flows. The decision make at level 3 are: 1) Number of Reactors The main reaction producing maleic anhydride takes place in only one reactors, operating at temperature and pressure of 400oC and 3 bar respectively. Fluidize bed reactor and fixed bed reactors are 2 alternative types of reactor to be chosen for the system. Selection of reactor As the operation is continuously performed, two types of reactors are considered i.e fixed bed and fluidized bed reactor. Fixed-bed reactor: fixed bed reactor has been used in commercial industry and typically it contains catalyst in pellet form, in fixed location. In fixed-bed reactor, gas-solid reaction occurs in which the syngas is passed over the catalyst, allowing the reaction to take place. Fluidized bed reactor: in fluid-bed reactor, the catalyst material is in fluid state instead of fixed-bed. The fluid will flow from bottom of the reactor to the top, causing particles of catalyst to be suspend
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The characteristic of the two reactors are summarized in table below:


Table 3. 5: Comparison between Fixed and Fluidized Bed Reactors

Characteristics Conversion

Fixed Bed High conversion per unit mass of catalyst

Fluidized Bed Require more catalyst for high gas conversion

Operating cost

Low operating cost

High cost of the reactor and catalyst regeneration equipment

Operation

Continuous operation

Continuous

operation

yields uniform product Maintenances Fixed-bed device will The catalyst can be

have to be taken offline to regenerate the catalyst by means of shutting down the plant or using standby suitable reactor. for Not

continuously from the

removed reactor bed,

regenerated and recycled back to the bed. Useful for frequent regeneration. catalyst

frequent

catalyst regeneration.

Temperature Control

Poor temperature control

Good

uniformity

of

temperature

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Table 3.5 shows the comparison between the fixed bed reactor and fluidized-bed catalytic reactor for maleic anhydride production. Since fluidize-bed reactor cost more and is more difficult to operate, requires extensive provision for dust recovery and suffer from back mixing. Therefore, it is advantageous to select fixed-bed reactor to carry out the reaction. 2) Number of Recycle Streams In this process, there is only one recycles stream has been considered as it is economical to be recycle back to the production system. Dibutyl phthalate (DPA) solvent is purified and recycled back to the DPA feed stream. DPA solvent is costly and since the amount used is in a large volume, it is not feasible to discard as hazardous waste as this will cause immense loss in raw material and its costing.

3) Excess of reactant Oxygen is fed for oxidation of n-butane. To achieve complete reaction, the air is fed in excess since that reactant is inexpensive. Reactor performance Reactor performance is measured through its conversion, yield and selectivity. The main reaction involved is: C4H10 + 3.5 O2 C4H2O3 + 4 H2O Therefore, to calculate conversion ( Felder and Rosseau, 2000) is:

Components

Reactor Inlet (kmol/hr) 78.225 3913.26

Reactor Outlet (kmol/hr) 13.9312 3651.909

Conversion (%)

Butane Oxygen

82.2% 6.7%

34

Table 3.6: Calculation for conversion of butane and oxygen

Conversion of butane:

Conversion of oxygen:

To calculate selectivity ( Felder and Rosseau, 2000) of maleic anhydride based on n-butane:

Components

Reactant consumed (kmol/hr) 64.2938 261.351 -

Desired product (kmol/hr) 47.054

Selectivity (%)

Butane Oxygen Maleic anhyride

73.2%

Table 3. 7: Calculation for selectivity of maleic anhydride

1mol of butane produced 1mole of maleic anhydride: Selectivity based on butane:

35

The reactor yield ( Felder and Rosseau, 2000) is calculated based on the following formula:

Components

Reactant feed (kmol/hr) 78.225 3919.26 -

Desired product (kmol/hr) 47.054

Yield (%)

Butane Oxygen Maleic anhyride

60.2%

Table 3. 8: Calculation for yield of maleic anhyride

Yield based on butane:

Reactor optimization The main focus of designing the process flow is to maximize the profit. Several methods can be applied for maximizing the profit such as increasing the amount of product produced by increasing yield and conversion or reduce the raw material and utilities cost with more efficient technology, better process route and selectivity. Two alternatives are proposed in this project which are: 1) Recycle dibutyl phthalate only 2) Recycle n-butane and dibutyl phthalate

36

Alternative 1)

DPA

Oxygen CO CO2 Unreacted n-butane

n-butane oxygen

Reactor

Separation

Separation

MAN

DPA

Figure 3. 4: Unreacted butane is not recycled to reactor

37

Alternative 2)
Unreacted n-butane
Purge

DPA

n-butane oxygen

Reactor

Separation

Separation

MAN

DPA

Figure3. 5: Recycle unreacted butane to reactor

38

Although putting unreacted raw material is economically important, another factor should be taken into consideration. Comparing between alternative 1 and 2 for increasing reactor performance, alternative 1 is chosen since alternative 2 is more complex and require more equipment for purification of raw material.

Economic potential analysis of reactor For calculation of reactor cost, data is extracted from section 4.4 Economic evaluation. To select the best reactor configuration producing high profit, economic potential (EP) is calculated for two alternatives; unrecycle n-butane and recycle n-butane. Detail calculation is explained in economic evaluation. Alternative 1 (unrecycled n-butane) Revenue RM/ yr RM161,075,426.40 Raw material cost RM 18,193,684.28

EP1 (RM/year) = Production Value Raw Material Cost = 161,075,426.40 - 18,193,684.28 = RM 142,881,742.12 /yr Alternative 2 (recycle n-butane) Revenue RM/ yr RM167,139000 Raw material cost RM 18,193,684.28

EP1 (RM/year) = Production Value Raw Material Cost = 167,139000 - 18,193,684.28


39

= RM 148,945315.7/yr Economical potential calculation for reactor clearly indicates that alternative 2 with recycle raw material gives higher profit to non-recycle process. However, recycling of raw material requires additional equipment for purification of n-butane. Hence, the overall cost for installation of equipment and labor cost will increase. Therefore, alternative 1 is chosen due to higher profit for overall process flow compared to others.

Therefore, from preliminary reactor optimization, it can be concluded that: Reactor type: Fixed bed reactor is chosen over fluidized bed mainly because of low operating cost and high conversion. Mode of operation: Continuous operation is selected over batch operation based on three factors which are production rate, market force and operational problem which favour the continuous operation. Type of phase: Reaction is carried out in gas phase. This is because based on the literature research , the operating temperature of reactor is 400o C in which all the materials present in gas phase. Non recycle for raw material entering reactor is chosen.

3.2 Process Screening 3.2.1 Separation System Synthesis

In designing chemical processes, separation is a crucial part whereby it determines how much product can be recovered. Therefore, in this design project, the main focus is to produce an effective separation in order to maximise the recovery of product as well as minimizing the waste. Higher capital cost is required to be invested in separation equipment. Hence, effective separation can lead to higher profit.

40

This project is aimed at producing maleic anhydride from n-butane. However, the problem associated with this process is the production of side product .In order to provide the best flow sheeting with minimum side product, several alternatives have been designed to produce high purity of maleic anhydride (MAN) and maximise the profit. There are two methods that can

be used to compare between the alternatives and select the best separation train sequence, which are heuristic approach and minimum vapour flow. For this design project, heuristic approach has been used. The products out of reactor consist of maleic anhydride (MAN), unreacted butane, water, nitrogen, carbon monoxide, carbon dioxide and oxygen. These products will then enter absorber to separate the main product (maleic anhydride) with other components. Dibutyl phthalate is used to recover maleic anhydride from other gas mixture by absorbing it. The concern of the separation synthesis is to separate maleic anhydride from other component. Products in distillation column are separated based on their boiling point. Product with low boiling point will enter to the top and high boiling point will enter to the bottom. Several alternatives have been introduced in order to get the best process. The selection of the best alternative is based on the highest purity with maximum profit and recovery of maleic anhydride. The alternatives are described based on the following: In general, feedstock which consist of propane, isobutane, isobutene, 1-butene, nbutane, neopentane, isopentane and n-pentane are separated in distillation column. This is the first stage for this process whereby the purpose is to separate n-butane, which is the main feedstock for maleic anhydride (MAN) from other components.Bottom products containing nbutane will then enter reactor whereby reaction through oxidation of butane to produce maleic anhydride occur. Alternative 1, 2 and 3 are introduced based on the products from the reactor.

41

Alternative 1 For alternative 1, none of the products are recycled. Product such as water, dibutyl phthalate (DPA) and n-butane are discharged. Only main product, MAN is recovered.

n-butane Propane iso-butane Distillati -on column Isobutene O2 1-butene N2

DPA

O2 CO CO2 MA water

Propane iso-butane Isobutene 1-butene n-butane Neopentane Isopentane n-Pentane

Reactor

n-butane Absorber N2 DPA

O2 n-butane Neopentane Isopentane n-Pentane n-butane I MA water CO CO2 Water

Water

MA

II

MA DPA

Distillati -on column Distillation column MA DPA

water CO CO2

III
n-butane Propane iso-butane Distillati -on Isobutene O2 1-butene N2

DPA

Figure3. 6: Process flow for alternative 1


DPA O2 CO CO2 MA water

42

I:

Products from reactor which consist of oxygen, butane , maleic anhydride (MAN) , water , carbon monoxide and carbon dioxide are separated in absorber based on their boiling point. As the feed temperature to the absorber is 120 oC, products with lower boiling point such as carbon monoxide, carbon dioxide and butane will enter to the top meanwhile products with higher boiling point such as MAN, dibutyl phthalate (DPA) and a small amount of water will settle at the bottom. As the main component is maleic anhydride, bottom products will be separated to recover maleic anhydride.

II:

As the mixture between water and maleic anhydride will from maleic acid, the small amount of water at the bottom will be separated from maleic anhydride. Three components which consist of MAN, water and DPA are separated based on their boiling point. Water will enter to the top of column meawhile MAN and DPA will enter to the bottom.

III:

Maleic anhydride is separated from dibutyl phthalate by using another distillation column. This is to ensure that all maleic anhydride is recovered throughout the process.

43

Alternative 2 For alternative 2, DPA which is separated from water and MAN is recycled. As the price for DPA is high, much of the profit is generated as compared to the first alternative.

n-butane Propane iso-butane Distillati -on column Isobutene O2 1-butene N2

DPA

O2 CO CO2 MA water Water

Propane iso-butane Isobutene 1-butene n-butane Neopentane Isopentane n-Pentane

Reactor

n-butane Absorber N2 DPA Distillation column

O2 n-butane Neopentane Isopentane n-Pentane

n-butane MA water CO CO2

II

Water MA DPA

III

Distillati -on column

MA

DPA

Figur Figure 3. 7: Process flow for alternative 2

44

I:

Reaction between butane with oxygen producing oxygen, maleic anhydride (MAN), water, and side products such as carbon monoxide and carbon dioxide. These products will then enter absorber to separate maleic anhydride from other component based on their boiling point. In order to recover maleic anhydride, dibutyl phthalate is used in absorber to absorb maleic anhydride from the gas mixture. As the feed temperature to the absorber is 120 oC, products with lower boiling point such as carbon monoxide, carbon dioxide and butane will enter to the top meanwhile products with higher boiling point such as MAN, dibutyl phthalate (DPA) and a small amount of water will settle at the bottom.

II:

Bottom products which consist of maleic anhydride, dibutyl phthalate and a small amount of water are sent to distillation column in order to separate dibutyl phthalate (DPA) with other components. Dibutyl phthalate with higher boiling point will settle to the bottom meanwhile maleic anhydride and water will enter to the top. As the main purpose of alternative 2 is to maximise the profit, DPA is recycled and send to the absorber.

III:

Top product containing maleic anhydride and water are separated in the next distillation column to recover maleic anhyride. Through this process, maleic anhydride with 99% purity is achieved.

45

Alternative 3 In Alternative 3, several products are being recycled such as DPA, amine and unreacted butane. This is the most complicated process as compared to the other two alternatives with most number of equipments.

Purge

Unreacted butane

n-butane Propane iso-butane Isobutene Distillati -on column 1-butene

Amine solvents DPA O2 CO Stripper Gas Scrubber CO2 CO

Propane iso-butane Isobutene 1-butene n-butane Neopentane Isopentane n-Pentane

IV
Reactor
Absorber

CO2 MA water n-butane

V
Water

Amine

O2 n-butane Neopentane Isopentane n-Pentane n-butane MA water Water MA DPA

N2 DPA

MA Distillati -on column Distillation column MA DPA

CO CO2

II

DPA

III
Figure3. 8: Process flow for alternative

46

I:

Reactor effluent leaving reactor contains oxygen, maleic anhydride (MAN), water, and side products such as carbon monoxide and carbon dioxide. These components will enter absorber in order to separate maleic anhydride from other component based on their boiling point. Dibutyl phthalate is used in absorber to absorb maleic anhydride from the gas mixture. As the supplied temperature to the absorber is 120oC, offgas with low boiling point such as oxygen, carbon dioxide, carbon monoxide, water, n-butane will be released at the top of the column meanwhile maleic anhydride, dibutyl phthalate and small amount of water with boiling point higher than supplied temperature will settle at the bottom.

II:

Maleic anhydride, dibutyl phthalate and small amount of water which are discharged at the bottom are then separated. Heuristic 2 which favours direct sequence is applied. Water is separated from MAN and DPA will then enter to the top meanwhile MAN and DPA will go down to bottom of column.

III:

Maleic anhydride is recovered from dibutyl phthalate by separating it in distillation column. Dibutyl phthalate discharged at the bottom of column is recycled and send to the absorber.

IV:

Off gas containing carbon dioxide, carbon monoxide, oxygen, water and n-butane are released through the top of the column. Carbon monoxide and carbon dioxide are treated in the gas scrubber by supplying amine solvent. Unreacted butane released from the top of the gas scrubber is recycled and send to the reactor. Meanwhile bottom product containing carbon monoxide and carbon dioxide are sent to stripper for further separation.

V:

In the stripper, treated carbon monoxide and carbon dioxide are released at the top of the column meanwhile bottom product containing amine solvent is recycled. This recycled product will be sent to the gas scrubber and thus reducing the amount of amine supplied.

47

Level 5: Heat Exchanger Network Douglas hierarchical proposed for heat exchanger to be carried out after reactor and separator synthesis has been conducted. The heat exchange network is important for heat recovery. The target is to recover the heat as much as possible as well as minimizing the external utility consumed. By doing this, the energy cost can be reduced. The heat exchanger is conducted to exchange heat between the steam that needed to be heated and cooled. For designing heat exchanger network, Cp rule for above and below pinch should be followed and priority is given for minimizing the number of heat exchanger used. Detail for designing the heat integration is discussed in following pages.

3.4 Process Flow Sheeting

Summary of process flow sheeting is presented in this section. Details will be elaborated in Chapter 6.

For production of maleic anhydride, the raw materials involved are n-butane in the presence of oxygen and vanadium phosphorous oxide catalyst. However, as the feedstock consist of propane, iso-butane, n-butane, iso-butene, 1-butene, neopentane, isopentane and n-pentane, -butane needs to be purified at first. Distillation column is used, separating the n-butane with 1butene. The n-butane settle at the bottom due to high boiling point meanwhile 1-butene enters to the top of column.

The product containing n-butane is then fed to reactor. For reaction producing maleic anhydride, oxygen is supplied to fixed bed reactor with the presence of vanadium phosphorus oxide catalyst to speed up the reaction and promote the selection of desired product. Since the selective oxidation of n-butane for producing maleic anhydride is highly exothermic, fixed-bed
48

reactor must contain a facility in order to remove the reaction heat. However, the drawback of fixed bed reactor is the hot spots which can occur easily. Therefore, larger catalyst body is used to prevent it.

Products leaving the reactor consist of maleic anhydride, unreacted n-butane, water, oxygen, carbon dioxide and carbon monoxide is then fed to absorber to separate maleic anhydride from other component. This is because mixture of maleic anhydride with water can lead to formation of maleic acid. In addition, dibutyl phthalate is fed to absorber for recovery of maleic anhydride. Oxygen, carbon dioxide, carbon monoxide, water and small amount of unreacted n-butane is purged out at the top of column meanwhile the bottom product consist of maleic anhydride, water and dibutyl phthalate are sent to distillation column. In the distillation column, maleic anhydride and water are separated from dibutyl phthalate (DPA) due to low boiling point. As dibutyl phthalate is very costly, it is recovered and recycled to DPA stream. Maleic anhydride and water which enters to top of column goes to the next distillation column.

Maleic anhydride is recovered by separating it from water. Approximately 99% purity of maleic anhydride is achieved through this designed process.

49

3.5 HEAT INTEGRATION

3.5.1 Introduction In industry, there are many kind of heat exchanger are used. But, the most common use is the shell tube heat exchanger. Heat integration emphasizes on energy conservation which is very crucial in process designing Heating and cooling duties for heat recovery system are done after the acceptance of major processing steps (reactors, separators and recycles). Targets can be set for the heat exchanger network to assess the performance of complete process design. These targets allow both energy and capital cost for heat exchanger network to be assessed. The energy used during heating and cooling process is maximized to its full potential by using pinch analysis.

3.5.2 Stream Identification

The analysis of heat integration is beginning with analysis of stream. We start to identify with source of heat (hot stream) and source of sink (cold Stream). Figure 3.9: Stream Identification

50

3.5.3 Minimum Temperature Difference, Tmin

The minimum temperature difference, Tmin is the driving force for heat transfer. The importance of Tmin is that it sets the relative location of the hot and cold streams, and therefore the amount of heat recovery. As the energy target (and hence Tmin) is increased, the capital cost decreases. The optimum Tmin varies in different industries. Industrial sector Optimum Tmin (oC) 20 40 values Remarks

Oil refining

Relatively low heat transfer coefficients, parallel composite curves in many applications, fouling of heat exchangers

Petrochemical

10 20 10 20

Reboiling and condensing duties provide better heat transfer coefficients, low fouling

Chemical

As for petrochemicals Power requirement for refrigeration system is very expensive. Tmin decreases with low refrigeration temperatures

Low temperature 3 5 Processes

Table 3.9: Optimum Tmin in different industries

Source: Pinch Analysis Foundation Training Course (1997) As production of Maleic Anhydride is in petrochemical industries, Tmin of 10oC is chosen.

51

3.5.4 Pinch Technology Method 3.5.4.1 Introduction

Pinch Technology Method is used to determine the energy requirement from the process and the amount of energy recovery. This section will analyse on how to calculate the amount of energy for the process by constructing composite curves to set energy target or develop the problem table algorithm and heat cascade diagram. Composite curves are useful in providing the conceptual understanding of the process but the problem table algorithm is a more convenient calculation tool. The term Pinch Analysis is used corresponding to application of the tools and algorithms of Pinch Technology related in industrial process. The application of First and Second Law of Thermodynamics determine the direction of Pinch Analysis application. Heat energy only flows in the direction of hot to cold. This prohibits the temperature crossovers of the hot and cold stream profiles through the exchanger unit. There is two main important things in dealing with transfer of heat between hot and cold stream which are, heat load and temperature. The minimum heat load between the two streams is selected when comparing their value while in a heat exchanger unit a hot stream cannot be cooled below cold stream supply temperature nor a cold stream can be heated to temperature more than hot stream supply temperature. 3.5.4.2 Pinch Temperature

The corrected temperature for hot streams and cold streams need to be determined first before calculating the minimum utility requirement. For hot stream, Corrected temperature = T (Tmin)/2 For cold stream, Corrected temperature = T + (Tmin)/2
52

After the shifted temperatures for both hot and cold streams are determined, the minimum heating requirements, QH,min, minimum cooling requirements, QC,min, and pinch temperature are determined.

53

Figure 3.10: Problem Table Algorithm *Tmin = 10.0000 [C] [kW] [kW] [kW]

12 13 14 15 16 17

138.50000 135.90000 131.90000 130.90000 125.00000 121.90000 115.00000 113.90000 37.120000 36.120000

7311.9100 7303.5300 7421.6600 1240.1900 1414.4300 1427.1100 1468.6700 1457.9800 1814.3600 0.0000000

Minimum Hot Utility =

1829.73

Minimum Cold Utility = 2728.24 Process heat recovery= 16573.3

Interval Temperature* [C] [kW]

Enthalpy

18 19 20 21

-------------------------------------------------------------------1 2 3 4 5 6 7 8 9 10 11 405.00000 398.40000 240.60000 231.40000 215.00000 202.20000 201.20000 185.00000 148.50000 147.50000 139.50000 1829.7300 1734.9600 1952.9900 2036.7900 2647.8300 2705.4600 8476.9700 8549.9100 8432.2400 7244.0100 7218.2200

Pinch 22 23 24 25 30.000000 20.000000 14.420000 13.420000 28.406500 329.24300 329.24300 2728.2400

54

Figure 3.11: Pinch Temperature


405 QHMIN=1.829MW

ABOVE PINCH

36.12

PINCH= 0 MW

BELOW PINCH

25

QCMIN=2.728MW

55

Figure 3.12: Composite Curve

QHMIN

PINCH POINT=36.120C

QCMIN

In order to set the energy targets, the temperature enthalpy (T-H) plot or known as composite curves is used. The hot composite curve shows the heat availability in the process while the cold composite curve shows the heat demands in the process. Both of the stream combined in a one graph to estimate the pinch temperature based on Tmin which is equal to 10oC. Also, from this figure we can also indicate the enthalpy for hot utilities QHmin and cold utilities QCmin. The pinch temperature can be determined from smallest interval between two composite curves which is at 41.120C for hot stream and 31.120C for cold stream.

56

Figure 3.13: Grand Composite Curve

QHMIN

PINCH POINT=36.120C

QCMIN

The Grand Composite Curve is a plot of interval temperatures against corresponding heat flow quantities. The temperatures of the hot and cold process streams are divided into interval temperatures according to the supply and target temperatures of the hot and cold streams, respectively. The Grand Composite Curve plot depends on the process stream conditions as well as the minimum temperature approach. The Grand Composite Curve approach is based on the same stream data as used in the composite curves and Problem Table Algorithm but is a more appropriate aid for representing the interface between the process and utility system. It provides the same overall energy target as the composite curves. From the Grand Composite Curve, a solution to heating and cooling requirement to the process can be defined and thus provides an optimum solution for the utilities needed. From the Grand Composite Curve above, it show the amount of QH and QC for the whole process. The line or slope above the pinch temperature is defined as heat sink or region where heat is less and required more heat. While the line or slope below the pinch is defines as heat source or region where the heat is in excess.

57

3.5.5 Heat Exchanger Network Pairing of streams is determined from the Maximum Energy Recovery (MER) method, for the above pinch region, CPc > CPH for the below pinch region, CPH > CPc The hot stream can only be matched with any cold stream without a violation of Tmin. However, the limitations that could prevent this should be considered. As a rule of thumb, do not transfer heat across pinch. Heat Exchanger Network Diagram shows how the heat transfers operations. Hot streams run from the left to the right. Cold streams run from right to the left. A heat exchanger transferring heat between the cold and hot streams are indicated by a vertical line connecting two circles on the two matched streams.
Figure 3.14: Grid Diagram for Heat Exchanger Network

58

From the figure, we can state that, there are 10 heat exchanger used to fully utilize the heat provided from the hot streams to bring the cold streams to the desired temperatures. The minimum hot utility is 1.829 MW meanwhile for minimum cold utility is 2.728 MW. 3.5.6 Advantages and Disadvantages of Heat Integration There are certain advantages and disadvantages when heat integration is applied in the Advantages After Integrati on decreased. Disadvantages need to be installed-

Cooling and heating utility is Extra units of heat exchanger

installation costs needed.

Process Flow Diagram. Table 5.2 below provides the advantages and disadvantages of heat integration when applied to the whole plant.

59

Saving of cold and hot utility - Cost savings.

Hot streams are kept hot and cold streams are kept cold.

Offers trade-off between energy Degree of freedom become usages with capital costs. less, therefore complex

control systems are needed, to decrease disturbances.

Table 3.10: Advantages and Disadvantages of Heat Integration

60

Figure 3.15: Process Flowsheeting Before Heat Integration 61

Figure 3.16: Process Flowsheeting After Heat Integration

62

CHAPTER 4: INSTRUMENTATION AND CONTROL

4.1 INTRODUCTION

The plant control strategy The word control in industries or engineering aspect refers to measurement and adjustment which is to maximize unit profitable and operability while ensuring operating safety. When pursuing these task, typically process disturbances and constrains are encountered and kept continuously under control, enabling to approach confidently the units design limit. The plant control strategy is divided into several sections involving the control of different unit operations. The control of a process is accomplished by measuring the variables (controlled variables), comparing this measurement with the desired set value (set point), and adjusting certain variables (manipulated variables) which has a direct or indirect effect on the controlled variables. A control system basically consists of four components which include; primary elements, controllers, final control elements and processes. Each of the components must be well understood to comprehend the workings of a control system. These individual components are described as below: a) Primary elements The instruments used to measure variables in a process such as level, flow,

temperature and pressure. Consists of sensor or transmitter

b) Controllers The instrument whose control law and tuning drive the corrective action
63

and influence the response of the control system. c) Final control elements (FCE) Also known as control valve The instrument manipulated by a control loop to affect the process. They regulate the flow of material or energy into the system.

d) Processes The important operation that is used to change raw materials into product. Without a process, a), b) and c) is of no use.

Meanwhile, the basic elements for control configurations are as follow: a) Process variable (PV) - Sometimes known as controlled variable (CV) - It is the variable that is important to maintain under control. b) Set point (SP) - The desired value of the PV. c) Error (e) - A measure of the difference between the PV and the SP. d) Manipulated variable (MV) - Represents the variable in the process to which the PV is sensitive and to which the final control element is attached.

Piping and Instrumentation A process flow sheet shows the arrangement of the major piece of equipment and their interconnection. The Piping and Instrumentation diagram (P & ID) shows the engineering details

64

of the equipment, instrumentations, piping, valves and fittings; and their arrangement. It is often called the Engineering. Flowsheet or Engineering Line Diagram.

The P and I diagram should include: 1. 2. All process equipment identified by an equipment number. All pipes, identified by a line number. The pipe size and material of construction should be shown. 3. All valves, control and block valves, with an identification number. The type and size is usually shown. 4. Ancillary fittings that are part of the piping system, such as inline sight-glasses, strainers and steam traps; with an identification number. 5. 6. Pumps, identified by a suitable code number. All control loops and instruments, with an identification numbers.

Several types of indicator controllers are used in the control system of the proposed plant: 1. Temperature indicator and controller (TIC) 2. Pressure indicator and controller (PIC) 3. Flow indicator and controller (FIC) 4. Level indicator and controller (LIC) 5. Ratio controller (RC) 6. Speed controller (SC)

65

Piping and Instrumentation Symbol and Legend Table 4.1 : Piping and Instrumentation Symbol and Legend TT TIA CT PA PT PIA FT FC LT TC TA TIC Instrument Balloon: Local mounted Temperature sensor and transmitter Temperature indicator alarm Composition sensor and transmitter Pressure alarm Pressure sensor and transmitter Pressure Indicator alarm Flow meter and transmitter Flow controller Level sensor and transmitter Temperature controller Temperature alarm Temperature Indicator Controller

Main panel mounted

Instrument Signal Line: Pneumatic signal

66

Valve: Control valve

Alarm: H L High Low

4.2 REACTOR CONTROL SYSTEM

The control of chemical reactor offers one of the most challenging problems in chemical engineering, since it is where the reaction is taking place in which n-butane converts to Maleic Anhydried. The stability efficiency of reaction operation is playing significant role to

productivity and profitability of the entire plant. The reaction employed in the plant is highly exothermic and runaway operation may cause high risk and high potential damage to the plant. Thus, an effective, well-designed control system is essential to sustain and assure stable operating condition.

The control system objectives are defined as: To maintain the reactor operation at optimum temperature and pressure. To sustain and ensure the maximum production rate can be maintained at the annual

production rate of 35,000 metric ton per year (kmol/hr) Provide the safeguards against the process runaway and maintain the safe operation. To maintain optimum feed condition to ensure high production rate.

67

Production of maleic anhydride is an oxidation reaction between n-butane and oxygen in which exhibit exothermic reaction with the temperature in the range of 320 400C. The heat removal system of reactor includes molten salt and cooling water. Molten salt is used to remove heat of reaction continuously in order to maintain the temperature of the reactor and to prevent catalyse from the hot spot which might result in the degradation of the catalyse before reaching its useful life. On the other hand, cooling water used as the coolant to removes the heat of the spent molten salt via heat exchanger and recycle back to the reactor. The temperature in the reactor is detected by placing several thermocouples along the length of reactor.

The butane oxidation reaction to produce maleic anhydride is based on the stoichiometries with the ratio of 1:10 n-butane to oxygen . The control system of reactor also aims to controls the feed ratio of the two feed stream through the reactor in order to to retain the conversion of product at its highest value of 82%.

68

RS 1001

FIC 1005

FIT 1005 FIT 1006 FCV 1005

n-butane

Inlet Air
PSV 1004

TIC 1004

TCV 1005 TIC 1005

TIT 1004

E-1004
TIT 1005 TIC 1006 FIC 1004 FIT 1004 FCV 1004 TIT 1006

Molten salt R-1001

69

70

Table 4.2: Reactor, R-1001 Control System Details

No

Control Objective

Controlled Variable Temperature inside reactor

Manipulated Variable Molten salt

Disturbance Variable - Changes in

Control Strategy Cascade control - TIC (master loop) - FIC (slave loop)

To control Operating temperature Inside reactor

inlet flow rate reaction temperature Change in feed inlet temperature -Change in malten salt inlet temperature

To control inlet -Inlet temperature of molten salt to reactor

-Inlet flow

Change in

Combination of feed farward

temperature of rate of cooling outlet molten salt to the rector, water to the cooler

temperature of and feedback malten salt from the reactor control

To maintain a stiochiometric ratio of reactants to reactor

Ratio of the

Flow rate of

Changes in

Ratio control

inlet flow rate inlet air to the inlet flow rate of n-butane to reactor air flow rate of n-butane feed to reactor

71

1. To control Operating temperature Inside reactor

Due to the slow dynamic response of temperature control system, a cascade control is applied to control the temperature inside the reactor at a safe and allowable limit .The cascade control structure consists of a primary control loop (utilizing TT and TC) and a secondary control loop that control the malten salt inlet flow rate via FT and FC.The primary measurement is the reactor temperature that is used by the master controller (TC) to establish the set point for the secondary (slave) loop controller.This secondary measurement is the malten salt inlet flow rate ,which is transmitted to the slave controller (FC).The output signal from the master controller will serve as the set point for the slave controller based on the deviations of the reactor temperature from its set point. Flow control valve is then adjusted by the output signal from the slave controller (FC).

2. To control inlet temperature of molten salt to reactor In this control strategy to control the inlet temperature of malten salt to the reactor ,Feed forward control in combination with feedback control is chosen. Temperature of outlet malten salt stream from reactor which feed to the cooler is a significant disturbance variable while the inlet temperature of the malten salt feed to reactor is the control variable that required to maintain at its set point. Temperature of the outlet malten salt stream from reactor (disturbance) will transmit and sent to the Feedforward temperature controller.Feed forward control will provide corrective action before the process is upset .On other hand, the feedback control will maintain the temperature of inlet malten salt feed to reactor (control variable) at its set point despite disturbance and provide the corrective action regardless of the source and type of disturbance. The feedforward control will attemps to eliminate the effects of the measurable disturbance (outlet temperature of malten salt from reactor or inlet to cooler) while the feedback control will provide the signal to corrects for unmeasurable disturbance and modelling errors.

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The output signal of corrective action from these two controllers are added together and the sum is the signal that is sent to the flow control valve to adjust the cooling water flow rate feed to the cooler,hence by implementing this control strategy ,the inlet temperature of malten salt is maintained at its set point. 3. To maintain a stiochiometric ratio of reactants to reactor A certain mix of ratio of n-butane and air stream is required to make sure desired reaction occurs based on its stoichiometric. The flow rate of n-butane stream as the disturbance variable is measured and transmitted to the ratio station. The output signal from the ratio station is served as a set point for the air steam flow controller to adjust the flow rate of the air inlet stream feed to reactor.

** A safety valve is added to provide an outlet for over-pressurised fluids to prevent rupture of pipelines and equipments. The safety valve will pop open to release the excess pressure when the operating pressure exceeds the set pressure.

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4.3 SEPARATION UNITS CONTROL SYSTEM

4.3.1 Distillation Column The effective operation of a distillation column is determined by the control of many variables, its control is typically a 5x5 multivariable problem. Among the five controlled variables three are for basic inventory and two for remaining are for quality control.

Table 4.3: Typical variables that have to be maintained in The five manipulated variables are: Distillate flow : D Bottom product : B Boil up V or reboiler duty : Qr Condenser duty : Qc and Reflux flow : L

There are three distillation columns use in production of maleic anhydride process :
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1. Mix butane - Distillation Column (C-1001) This column is used to extract n-butane from the mix butane feed as a bottom product with 98.67% purity.And iso-butane and other components is the distillate product with 92.66% purity.

2. DPA Distillation Column (C-1002) This column is used to extract DPA from the maleic anhydride and gases stream as a bottom product with 99% purity . And for maleic anhydride + water stream is the the distillate product with MAN 87.88 % purity and water 9.17% purity. 3. Maleic Anhydride Distillation Column (C-1003) This column is used to extract Maleic Anhydride product from MAN and H2O stream as a bottom product with 98.77% purity .And water is the distillate product with 81.49% purity.

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PIC 1002

PCV 1002 PIT 1002

coolant
PCV 1002

E-1001

Flare
FIT 1002 LIC 1001 FIC 1002 FCV 1002

V-1001
LIT 1001

TIT 1001

TIC 1001

LIT 1002

LICA 1001

T-1001

LG 1001 FICA 1003

C-1001
PSV 1002

FCV 1003

Isobutane

flare

LIT 1003

LIC 1003

TIT 1002

TIC 1002

TCV 1002

Steam

E-1002

LCV 1003

The control strategy for all the distillation column in the production of Maleic anhydride process are use the same principle and control scheme as shown in the table belows:

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No 1

Control Objective Controlled Variable To control pressure of the column

Manipulated Variable

Disturbance Variable

Control Strategy

Pressure in column

flow rate of Amount of coolant/cooli vapour in the ng water to column the condenser The bottom flowrate
Feed inlet flow rate

Feedback Control

To control column base level

Liquid level at the base of the column.

Feedback Control

To control level in the reflux drum

Condensing liquid Flow rate of level in reflux drum reflux to column

-Changes in inlet flow rate of condensing liquid to reflux drum -Change in distillate flow rate

Feedback Control

To control flow rate of distillate

Distillate flow rate

Distillate flow rate

Reflux flow rate

Feedback Control

To control top product composition To control bottom product composition

Liquid temperature near the top of the column

Distillate flow rate

Feed back control

Liquid temperature Vapor near the bottom of flow/steam the column flow

Feed back control

Table 4.4: Distillation Column Control System Details

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1. To control pressure of the column A change in pressure will affect relative volatility (), the temperature difference across the reboiler and condenser as well as process safety. Therefore, it is important to control pressure of the column. In this control scheme, pressure is regulated using the flow rate of coolant to the condenser. The change in water flow rate (increasing or decreasing) will alter the temperature of the condensing liquid and hence the amount of vapour in the column. This, inturn, alters the pressure in the column. This will be a slow loop as the dynamics effects of the cooling can be slow in comparison to simply venting the system by e.g. opening a valve. In this control scheme also include a safety valve as a safety mechanism, in case a situation of excessive pressures arose.

2. To control column base level To ensure that the material balance is maintained around the column base.The Richrdson Rule is applied.As the rule state that: Use the largest flow to control a level. Since, all the distillation columns in the process are having a large bottom flow rate (B) and a small distillate flow rate (D). Therefore, to ensure that the level remains constant (and that an

appropriate change is made to B) a level controller is required with its manipulated variable being B.

3. To control level in the reflux drum To ensure that the material balance is maintained around the reflux drum.The control strategy also apply the Richrdson Rule which state that : Use the largest flow to control a level. Since column (C-1101 and C-1401) are having the reflux ratio(L/D) which is greater than 1 or having reflux flow larger than distillate flow.Therefore to ensure that the level remains constant (and that an appropriate change is made to L) a level controller is required on the reflux drum with its manipulated variable being L.

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For the reflux drum level control in C-1301 which having reflux ratio (L/D) less than 1 or having the distillate flow larger than reflux flow.A level controller is required on the reflux drum with its manipulated variable being D.

4. To control flow rate of distillate Flow control is place to the distillate flow line in order to maintain and ensure the steady state of the product. 5. To control top product composition Temperature is often used as an indication of composition. Composition is often regulated indirectly using temperature control .This due to there is a direct relationship of temperature and composition at constant pressure. Therefore, to control the composition of the top product ,a liquid temperature near the top of the column is measured and transmitted to the temperature controller. The signal from temperature controller then supply to the distillate flow control valve to regulate the top product composition.

6. To control bottom product composition This control scheme also use the same principle as to control the top product.Bottom product composition is controlled through a liquid temperature near the bottom of the column and is regulated by adjusting vapour flow or steam flow.

** A safety valve is added to provide an outlet for over-pressurised fluids to prevent rupture of pipelines and equipments. The safety valve will pop open to release the excess pressure when the operating pressure exceeds the set pressure.

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4.3.2 Gas Absorber The maleic anhydride and gases from reactor outlet stream is fed into gas absorber to remove the sour gas (CO and CO2) from the product stream by using dibutyl pathalate solvent(absorbent), In order to attain product quality, the operational conditions in the gas absorber should be controlled. This can be accomplished based on the operating parameters such as pressure and ratio of feed . An appropriate ratio between product effluent and DPA solvent is obtained. The control of liquid level in absorber is vital to prevent flooding.

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PIC 1005

PCV 1005

Purge gas
PIT 1005 PSV 1006

Flare

RS 1002

FIC 1010

FIT 1011

MAN + gas mixture


FIT 1010 FCV 1010

DPA feed

C-1002

LIT 1007

LICA H 1007 L

FCV 1013

FIC 1013

MAN + H2O

No

Control Objective

Controlled Variable

Manipulated Variable flow rate of

Disturbance Variable Product stream flow rate

Control Strategy Ratio Control

To control feed ratio of product stream Feed ratio of

DPA solvent

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: DPA solvent

product stream : DPA solvent

To control liquid level in absorber column of liquid of outlet stream Level Flow Feed flowrate Cascade Control

To control pressure of the column of the column Pressure

Flow of purge gas stream

Amount of CO/CO2 absorbed Control Feedback

Table 4.5: Gas Absorber Control System Details 1. To control feed ratio of product stream : DPA solvent To absorb CO , CO2 gas from the mixture gas of the product stream, dibuty pathalate (DPA) is used as the absorbent with an appropriate ratio between mixture gas stream and DPA solvent.Therefore,this feed ratio is needed to maintain at its certain ratio to ensure that the absorption reach its efficiency to remove CO and CO2 gas from the product stream. Flow transmitters are place on gas mixture inlet streams to measure and transmit flow rate and sent the signal to ratio station. The output signal from the ratio station is served as a set point for the DPA flow controller to manipulate the flow rate of the DPA inlet stream feed to absorber.

2. To control liquid level in absorber column


In this control scheme,level indicator transmitter is used to detect the level of liquid inside the column and transmit the signal to the level indicator control alarm (LICA). LICA have 2 functions both control and alarm. If the level is exceed the HIGH limit or lower than LOW limit ,alarm will start warning. The output signal from the controller will sent to flow controller and the output from the flow control will sent to flow control valve to regulate the flow of the outlet stream.

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3. To control pressure of the column The pressure of absorber column is control by pressure controller.Pressure transmitter detect the pressure in the column and transmit to pressure controller which output signal is sent to the pressure control valve to manipulate the flow of the purge gas, hence this will release pressure from the column or build up the pressure to the column.

** A safety valve is added to provide an outlet for over-pressurised fluids to prevent rupture of pipelines and equipments. The safety valve will pop open to release the excess pressure when the operating pressure exceeds the set pressure.

4.4 HEAT EXCHANGER CONTROL SYSTEM

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The main objective of heat exchanger control system is to maintain the desired outlet temperature of its outlet stream either by providing heating or cooling utility. The measurement of the outlet temperature will measured by temperature transmitter and its deviation to the set point will transmitted to the temperature controller. The corrective action signal from the controller will sent to the final control element in order to regulate temperature by manipulating the flow rate of utility.

Table4.6: Heat Exchangers Control System Details No Control Objective 1 To control Controlled Variable Outlet stream Manipulated Variable flow rate of coolant/steam Disturbance Variable feed flow rate Control Strategy Feedback Control

temperature of temperature outlet stream

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4.5 COMPRESSOR CONTROL SYSTEM

The purpose of the compressor control system is to maintain the desired outlet stream pressure. Several control variables are required to be controlled for the compressor, such as flow rate across compressor, speed of compressor and pressure of outlet stream.

CCP 1001 FCV 1001

FIT 1001

PDIT 1001

PSV 1001

K-1001
PIT 1001

PIC 1001

The control strategy is shown in table below:

Table 4.7: Compressor Control System Details No 1 Control Objective To control inlet flow rate and the pressure different across the compressor Controlled Variable Manipulated Variable Disturbance Variable Control Strategy

inlet flow rate and the flow of feed flow rate pressure Recycle stream different across the compressor

Feedback Control

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To control pressure of an outlet stream

Pressure at outlet stream

Speed of compressor

Speed of compressor

Cascade Control

1. To control inlet flow rate and the pressure different across the compressor The differential pressure and flow rate measured across compressor are transmitted to a surge controller. The surge controller will calculates the optimum pressure drop and flow rate to avoid surging in the compressor If the flow rate is too low, flow reversal would occur which will destroy the blades of compressor. The signal from surge controller will sent to the flow control valve to manipulate the flow rate across the compressor based on the set point provided by surge control via a recycle stream. To control pressure of an outlet stream To ensure the pressure of the outlet stream is the operating condition. Pressure transmitter is placed on the outlet stream of the compressor to measure and transmit the signal to the pressure controller. Pressure controller output signal is served as the set point to the speed controller. Hence, the compressor speed is manipulated for regulating the outlet stream pressure.

** A safety valve is added to provide an outlet for over-pressurised fluids to prevent rupture of pipelines and equipments. The safety valve will pop open to release the excess pressure when the operating pressure exceeds the set pressure.

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4.6 STORAGE TANK CONTROL SYSTEM

MAN
Flare
PSV 1008

LICA 1010

FICA 1015

T-1002

LIT 1010

FCV 1015

To MAN export

Table 4.8:Storage Tank Control System Details No Control Objective 1 To control liquid level in tank Controlled Variable Manipulated Variable Disturbance Variable feed inlet flow rate Control Strategy Feedback Control

Liquid level in flow rate of tank outlet stream

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In this control scheme,level indicator transmitter is used to detect the level of liquid inside the tank and transmit the signal to the level indicator control alarm (LICA). LICA have 2 functions both control and alarm. If the level is exceed the HIGH limit or lower than LOW limit ,alarm will start warning. The output signal from the controller will sent to flow controller and the output from the flow control will sent to flow control valve ,hence,the level in the tank is controlled by regulating the flow of the outlet stream.

4.7 PIPE SIZING

Piping is an important item in chemical plant because of its important role and contribution to the overall cost. The economy in designing a piping system is an absolute necessity as the process industries become more competitive nowadays. A piping system should be designed so that maintenance and inspection can be accomplished easily. Factors that should be considered when developing the design for a piping system including choices of material and sizes, effects of temperature level and temperature changes, available support and anchorage, flexibility of the system for physical, maintenance and inspection, ease of installation and safety. In particular case for this maleic anhydride plant, stainless steel pipes have been selected due to its excellent heat resistance and corrosion-resistance properties, which are suitable for the process nature.

Optimum Economic Pipe Diameter The capital cost of a pipe is increased with diameter. For stainless steel pipe, the approximate optimum diameter, doptimum:

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Where, G = Fluid flowrate, kg/s = Fluid density, kg/m3

According to equation above, the optimum diameter of a pipe is depends on the fluid flow rate and density that flow inside the pipe.

Table 4.9: Pipe sizing for Maleic Anhydride production plant.

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Stream 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Phase vapour vapour vapour Liquid vapour vapour vapour vapour vapour vapour Liquid Liquid Liquid Liquid vapour Liquid Liquid vapour Liquid vapour Mix vapour Liquid Liquid Liquid Liquid Liquid Liquid

Mass flow kg/h 6721 6721 2101 4620 111800 111800 111800 4620 116400 4018 2764 52540 52540 52540 111900 57050 57050 4652 52400 4652 4652 122.7 4529 4529 52400 52400 49780 2620

Mass flow kg/s 1.867 1.867 0.584 1.283 31.056 31.056 31.056 1.283 32.333 1.116 0.768 14.594 14.594 14.594 31.083 15.847 15.847 1.292 14.556 1.292 1.292 0.034 1.258 1.258 14.556 14.556 13.828 0.728

Density Kg/m3 2.434 6.671 7.724 565 1.18 2.349 1.545 3.143 1.544 2.662 1282 1282 1266 1266 5.735 1182 968 0.1847 1036 2.195 6.813 0.2316 1212 1331 1282 1282 1282 1282

d,optimum mm 258.835 178.242 92.227 28.383 1459.787 1131.512 1321.242 193.773 1349.560 191.626 16.046 74.205 74.550 74.550 813.636 79.814 85.936 554.978 80.180 222.095 146.061 77.080 21.180 20.458 74.102 74.102 72.152 15.606

d,optimum in 10.190 7.017 3.631 1.117 57.472 44.548 52.017 7.629 53.132 7.544 0.632 2.921 2.935 2.935 32.033 3.142 3.383 21.850 3.157 8.744 5.750 3.035 0.834 0.805 2.917 2.917 2.841 0.614

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Figure 4.1: Piping & Instrumentation Diagram for Maleic Anhydride Plant

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CHAPTER 5: SAFETY AND LOSS PREVENTION

5.1 Introduction Ensuring safety in chemical plant is a must. This concern is related to the industry potential to cause accidents and deaths. For an example, the Bhopal, India tragedy causes more than 2000 civilian casualties due to the released of methyl isocyanate (MIC) to atmosphere. MIC is considered as an extremely dangerous compound which is reactive, toxic, volatile and flammable. 25 tons of toxic MIC vapor estimated was released, the toxic cloud spread to the adjacent town, killing more than 2000 civilians and injuring an estimated 20,000. (D.A Crowl, 2002) From this incident, it can be seen that guaranteeing safety is not only important for the company but also for the civilians. Knowing how an incident can lead to deaths of people, safety at the workplace should not be taken lightly. 5.2 Safety Issues in Chemical Plants Considered as one of the most critical issues in chemical plants safety must be practiced in line with the safety regulations in order to eliminate accidents and probability of accidents. Safety starts with people, safety awareness among the workers and civilians would result in better understanding of the importance of safety. Safety is an undeniably a very crucial element in a chemical plant. It protects workers from illness, injuries and deaths while ensuring the survival of company business. Therefore, it is a necessity to establish safe working environment in a chemical plant. Thus, a management team to cater health safety and environment (HSE) must be developed. The aim of establishing this team is to reduce and eliminate any undesired accident in the plant. 5.2.1 Operational Procedures 5.2.1.1 Personal Protective Equipment

Personal Protective Equipment (PPE) includes all clothing and other work accessories designed to create a barrier against workplace hazards. Occupational Safety and Health

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Administration, (OSHA) requires the use of PPE to reduce operators exposures to hazards when engineering and administrative controls are not feasible or effective in reducing these exposures to acceptable levels. Employers are required to determine all exposures to hazards in their workplace and determine if PPE should be used to protect their workers. Protective equipment must include eye and face protection, head protection, foot protection, and hand protection. Any worker required to wear PPE shall receive training in the proper use and care of PPE. Periodic retraining shall be offered by OHS to both the employees and the supervisors, as needed. The training shall include, when PPE is necessary to be worn, what PPE is necessary, the limitations of the PPE, the proper care, maintenance, useful life and disposal of the PPE. After the training, the employees shall demonstrate that they understand the components of the PPE Program and how to use PPE properly, or they shall be retrained. Written records shall be kept of the names of persons trained, the type of training provided, and the dates when training occurred. The supervisor or employer shall maintain the operators training records. All personnel entering the process area are subjected to wear the appropriate PPE and provide their names and details before permitted to enter the process area. This is to ensure the minimum safety requirements are fulfilled and for the managers monitor the number of personnel entering and going out from the plant. In case of emergency, it will be easy to carry out the emergency response plant and locate the personnel.

5.2.1.2 Handling, storage and transportation

The availability of MSDS is very important when handling any hazardous chemicals. For the plants acrylic acid production, propylene is the primary chemical as feed-stock to the process, whereas acrylic acid and propylene also is being handle in bulk capacity. Storage tanks for raw material and finished products are located in isolated area. Storage area is also located between the loading and unloading area and the processing units it serves.

5.2.1.3 Process Safety

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Process safety is about minimizing the risks involved in our plant operations, so that the likelihood of any accident occurring is reduced. It covers all areas of manufacturing, from incoming raw materials to the finished product. It includes defining and assessing risks, learning from our plant operators and contractors, and acting to reduce risks.

5.2.1.4 Standard Operating Procedures

The Standard operating procedure is available for start-up and shut-down and therefore need to be followed by the operators when carrying out the duty. This document is regarded as an important reference where safe conduct is taken high priority at any part of the process.

5.2.1.5 Plant Process Control Systems

The overall plant control systems administer an effective and efficient control strategy. Among its main concern are using temperature indicator to prevent runaway reaction and pressure indicator to prevent over pressure in the vessel and tank. Alarm is set to low level, intermediate level, high level and very high-level alarm. Levels of alarm will be triggered if any of the system is attention depending of the systems critical level.

5.3 HAZARD AND OPERABILITY STUDIES (HAZOP)

5.3.1 Introduction

Hazard and operability (HAZOP) analysis was established in the late 1960s at ICI in UK based on the basic principle of that hazards arise in a plant due to deviations from normal behaviour. Thus, a group of experts thoroughly identify every possible deviations from design intent in a plant, find all the possible abnormal causes and adverse hazardous effects of the deviations (V. Subramaniam et al, 2000) In HAZOP analysis, hazards assume to arise in a process plant due to deviations from designers intent or from acceptable normal behaviour. It is performed by systematically examining the process P&IDs in order to determine abnormal
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causes and adverse consequences for every conceivable abnormal behaviour of the process plant. To cover all possible malfunctions in the plant, the process deviations for HAZOP analysis are generated by systematically applying a set of guide words for examples MORE OF, LESS OF, NONE, REVERSE, PART OF, AS WELL and OTHER THAN. (R. Vaidhyanatham et al, 1995).

Table 5.1: Definition of the terms in HAZOP Studies Terms Nodes Definition Specific location in the process where the deviations of the design/process intent are evaluated. Examples: separators, heat exchangers, scrubbers, pumps, compressors, and interconnecting pipes with equipment. Intention Description on how the process is expected to behave at the node; either qualitatively such as feed, reaction, sedimentation or quantitatively such as temperature, flow rate, pressure, and composition. Deviation A way where the process conditions may depart from their design/process intent. Parameter Relevant parameter for the condition of the process such as pressure, temperature, composition. Guide Words A short word to create the imagination of a deviation of the design/process intent. The guidewords are applied to all the parameters in order to identify unexpected and possible deviations from the design/process intent. Causes The reasons why the deviation could occur. Several causes may be identified for one deviation. It is often start with the causes that may causes the worst possible consequence. Consequences The results of the deviation, in case it occurs. May cause process hazards and operability problems, like plant shut-down or reduced quality of the product. Several consequences may follow from one cause and, one consequence can have several causes. Safeguard Facilities that help to reduce the occurrence frequency of the deviation or to

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mitigate its consequences.

HAZOP analysis objectives are to identify potential operating scenarios/parameter that could:

Present danger to personnel. Result in a fire and /or an explosion and toxic release. Have an adverse effect on the community and the environment. Have adverse effect on asset. Make recommendations to eliminate or minimize the consequences of any potential hazards identified.

5.3.2 Guidewords, Selection of Parameters and Deviations

The HAZOP process creates deviations from the process design intent by combining guide words such as no, more, less and others with process parameters which result in a possible deviation from design intent. For example when the guide word "No" is combined with the parameter "flow" the deviation will result in "no flow" results. The team should then list all probable causes that will result in a no flow condition for the node. A sample list of guide words and parameters are given below.

Table 5.2: List of guide words and parameters used in HAZOP Studies Guidewords Parameters

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No More Less Reverse Other Than Part of Sooner Than Later Than

Specific Parameters Corrosion/Erosion Flow Services/Utilities Temperature Maintenance Pressure Composition

Phase Reaction Level Inserting /Purging Contamination Instrumentation Sampling Safety

5.3.3 Screening for Causes of Deviations There are three basic types of causes:

1. Human error The acts of omission or commission by an operator, designer, constructor or other person creating a hazard that could possibly result in a release of hazardous or flammable material.

2. Equipment failure Mechanical, structural or operating failure results in the release of hazardous or flammable material.

3. External Events Items outside the unit being reviewed affect the operation of the unit to the extent that the release of hazardous or flammable material is possible. External events include upsets on adjacent units affecting the safe operation of the unit (or node) being studied, loss of utilities, and exposure from weather and seismic activity.

5.3.4 Consequences and Safeguards

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HAZOP is important as its primary purpose is to identify scenarios that would lead to the release of hazardous or flammable material into the atmosphere, consequently exposing workers to injury. Therefore it is necessary to determine, as exactly as possible, all consequences of any possible causes of a release that are identified by the group. This will help to determine a risk ranking in HAZOPs where multiple hazards are uncovered so that priority of the hazard can be established, and also it will help to determine whether a particular deviation results in an operability problem or hazard.

If the consequences for a particular cause of a deviation cause an operability problem only, then the discussion should end and move on to the next cause, deviation or node. If the cause will result in the release of hazardous or flammable material, then safeguards should be identified. Safeguards should be included when a combination of cause and consequence presents a credible process hazard. Safeguard is summarized based on the following general criteria: 1. Systems, engineered designs and written procedures that are designed to prevent a catastrophic release of hazardous or flammable material. 2. Systems that are designed to detect and give early warning following the initiating cause of a release of hazardous or flammable material. 3. Systems or written procedures that mitigate the consequences of a release of hazardous or flammable material.

5.3.5 Selected Node

In our case, three HAZOP nodes selected, which are from the first distillation column to the reactor, reactor to the absorber and absorber to the second distillation column. These nodes are selected due to the fact that they are very essential to the process in the production of maleic anhydride. The first node is selected due to transfer process gas to the reactor. Meanwhile for second nodes is to transfer converted gas to the absorber. Lastly for the third node is to transfer air into the reactor . Due to these fact, those node are selected.

98

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HAZOP ANALYSIS FOR NODE 1 - Inlet to Reactor (R-201) INTENTION: To transfer process gas to the reactor PARAMETER: FLOW Figure 5.1: Study Note 1- Reactor N o 1 GUIDE WORD NO DEVIATIO N No flow POSSIBLE CAUSE Control valve failto- close. Line wrecked. Line blockage, isolation valve closed. Exchanger blockage. Vaporizer heater failure CONSEQUENCE Process stop. Loss of feed to reactor and no output. N-butane released to atmosphere Release of flammable mixture to environmen t. Exchanger failure No n-butane from vaporizer Less feed to reactor, reduce rate of reaction, lead to less yield of production Release of flammable mixture to environmen t. Less nbutane from vaporizer SAFEGUARDS Install low flow alarm to alert operator. Install control valve that fail-toopen. Regular patrolling & inspection of transfer line. Install backup heater at vaporizer No action required. Install bypass valve. Regular patrolling & inspection of transfer line. Install backup heat exchanger

LESS

Less flow

Reduced feed rate. Control valve failed in partially open position. Leakage in piping system. Leaking flange. Less efficient of heat transferred . Less

exchanger efficiency at vaporizer

MORE

More flow

Control valve fails to responds. Instrument failure. Overheate d vaporizer.

More feed to reactor, low product yield and more byproducts. Runaway reaction in reactor. Overpressur e reactor and possible explosion.

Install bypass valve and high flow alarm. Frequent calibration on instrument. Follow preventive maintenanc e. Install high and trip flow alarm to alert operator. Install high temperature alarm at vaporizer. Install the check valve. Install pressure indicator. Emergency venting/pur ging.

REVERS E

Reverse flow

No check valve. High pressure from downstrea m. Pressure controller fails


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Desired flow could not be achieved Loss product yield from the reactor effluent. Failure of Reactor.

PARAMETER: TEMPERATURE

No GUIDE DEVIATION WORD 1 Less LESS temperature

POSSIBLE CAUSE Feed at low temperatur e. Exchanger less efficient. Vaporizer less efficient. Ambient condition change Feed at high temperatur e. Vaporizer overheatin g. Ambient condition change Defective control

CONSEQUENCE Less product yield. Lower rate of reaction

SAFEGUARDS Install low temperature alarm. Install backup heater. Install temperature indicator and flow control valve Install high temperature alarm Install temperature indicator and flow control valve Install trip alarm for very high temperature.

MORE

More temperature

Temperature increase in heat exchanger and reactor. Overpressure reactor Catalyst deactivation. Runaway reaction Explosion

PARAMETER: PRESSURE

No GUIDE DEVIATION WORD 1 Less pressure LESS

POSSIBLE CAUSE Vaporizer failure Pipe leakage

CONSEQUENCE Reverse flow Less n-

SAFEGUARDS Install pressure indicator

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butane

Install low pressure alarm

MORE

More Pressure

Partial blockage of line (possibly due to partially closed valve). Vaporizer failure

Increase pressure in reactor. Transfer line subjected to full delivery or surge pressure. Build up pressure in feed stream.

Install pressure indicator at inlet or reactor. Clear blockage or open valve.

HAZOP ANALYSIS FOR NODE 2 - From Reactor Outlet to Absorber INTENTION: To transfer converted gas to the absorber PARAMETER: FLOW Figure 5.2: Study Node 2-Reactor to Absorber N o 1 GUIDE WORD NO DEVIATI ON No flow POSSIBLE CAUSE Control valve failto-close. Line fracture. Line blockage, isolation valve closed.
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CONSEQUENCE Release of flammable mixture to environment . Heat exchanger failure. Compressor damage due

SAFEGUARDS Install low flow alarm to alert operator. Install control valve that fail-toopen. Regular

LESS

Less flow

Blockage in cyclone Saturated filter (F201. No reactor effluent to the pump. Compressor failure. Reduced feed rate. Control valve failed in partially open position. Leakage in piping system. Leaking flange. Less efficiency of heat exchanger. Control valve fails to responds. Air pressure to drive valve fails. Instrument failure. Increase of compressor capacity

to no inlet. Loss of production.

patrolling & inspection of transfer line. Frequent replacing of filter.

Drop in the rate of reaction that lead to lesser yield of production from the reactor effluent Release of flammable mixture to environment . Overflow amount of reactor effluent Less absorption efficiency due to high load. Instrument damage.

Install low flow alarm to alert operator Install bypass valve. Regular patrolling & inspection of transfer line.

MORE

More flow

REVERS Reverse E flow

No check valve. Pressure controller


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Desired flow could not be achieved

Install bypass valve Follow preventive maintenanc e. Install high and trip flow alarm to alert operator. Install speed controller Installed the check valve. Emergency

fails

Loss product yield from the reactor effluent Failure of Reactor

venting/pur ging

PARAMETER: TEMPERATURE

No GUIDE DEVIATION WORD 1 Less LESS temperature

MORE

More temperature

POSSIBLE CAUSE Reactor effluent at low temperature . Catalyst deactivation Less reaction in reactor Ambient condition change. Reactor effluent at high temperature . Overheating reactor. Ambient condition change.

CONSEQUENCE Lower product conversion and yield

SAFEGUARDS Install low temperature alarm.

Temperature increase in heat exchanger. Temperature increase in F-201 thus less acid is removed.

Install high temperature alarm. Install backup heat exchanger. Install temperature indicator

PARAMETER: PRESSURE

105

N o

GUID E WOR D LESS

DEVIATIO N

POSSIBLE CAUSE

CONSEQUENCE

SAFEGUARDS

Less pressure

Low compressor efficiency. Fugitive emissions (Undetected leakage that allowed the gas to release). Partial blockage of line (possibly due to partially closed valve). Isolation valve closed in error. Relieve valve does not function

Reverse flow. Loss of materials for the undetected leakage.

Install pressure indicator and flow control valve. Install check valve. Install pressure indicator at inlet absorber. Clear blockage or open valve. Proper installati on of relieve valve and run through the test.

MORE More Pressure

Increase pressure downstream. Transfer line subjected to full delivery or surge pressure. Pipe vibration due to high pressure. Excess load to absorber.

106

HAZOP ANALYSIS FOR NODE 3 - From Air Compressor into Reactor INTENTION: To transfer air into the Reactor PARAMETER: FLOW

Figure 5.3: Study Node 3-Air Compressor N o 1 GUIDE WORD NO DEVIATIO N No flow POSSIBLE CAUSE Valve opening failure of stream 5 before entering reactor Line blockage of S5 Pipe fracture and large leakage of S5 Control valve of S5 failed in partially open position Leakage in pipeline at S5 Pressure control system failure at S5 accomplish ed Valve closing of partially open valve of S5 failed Check valve of S5
107

CONSEQUENCE Decrease pressurepressure increment not accomplished Decrease temperature desired pressure not accomplished

SAFEGUARD S Install flow indicator at S5 Install low flow alarm at S5

LESS

Less flow

Decrease pressure desired pressure increment not Increase temperaturepossible compressor overheated

Install flow indicator at S5 Install low flow alarm at S5

MORE

More flow

Compressor overload possible compressor overheated Increase pressure-

Install flow indicator Install high flow

defect Pressure controller system failure of S5 Backflow due to back pressure from downstream

REVERS E

Reverse flow

possible compressor overpressure Increase temperaturepossible compressor overheated Breakdown or leakage in compressor

Install flow indicator

PARAMETER: TEMPERATURE

No GUIDE DEVIATION WORD 1 LESS Less temperature

POSSIBLE CAUSE Failure of heat exchanger E107(more cooling air flow)

CONSEQUENCE Desired increment in temperature is not accomplished

SAFEGUARDS Install temperature controller Install pressure controller Install low pressure alarm Install low temperature alarm Install temperature controller Install pressure controller Install low pressure alarm Install low temperature alarm

MORE

More temperature

Failure of heat exchanger E-107(less cooling air flow)

Desired increment in temperature is not accomplished

108

PARAMETER: PRESSURE

N o

GUID E WOR D LESS

DEVIATIO N

POSSIBLE CAUSE

CONSEQUENCE

SAFEGUARD S Install temperat ure controlle r Install pressure controlle r Install low pressure alarm Install low temperat ure alarm Install temperat ure controlle r Install pressure controlle r

Less pressure

Undetectable leakage in pipeline (low flow) in S5 Valve opening failure of S5

Decrease temperaturedesired increment is not accomplished Reverse flowpossibly compressor vibrating

MOR E

More Pressure

Control valve opening failure of S5 (fail-toclose) High feed S5 temperature entering the compressor
109

High temperaturecompressor overheated Compressor ruptured

Install high pressure alarm Install low temperat ure alarm

110

CHAPTER 6: WASTE TREATMENT

There are 3 types of waste produced by our plant. There are: -liquid waste -gaseous waste -solid waste

6.1 Liquid waste The liquid waste contains acidic discharge from T-102 and lean dibutyl phthalate discharge from T-101. Non-acidic waste is from the drainage system in the plant area. Oil and grease from equipment during the sampling also will be routed into the wastewater system. Table 6.1: Waste Streams Properties Parameter Waste Type of waste Type of treatment Stream 28 wastewater Liquid Wastewater treatment Stream 19 DPA Liquid Wastewater treatment

The cooler should be installed at stream 19 & stream 28 so that it can occupy the standard B.

There are two standards for effluent discharge specified in the Environmental Quality Act (EQA) 1974: 1. Standard A for discharge upstream of any raw water intake. 2. Standard B for discharge downstream of any raw water intake.
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The standards are listed in the Third Schedule of the Environmental Quality Act 1974, under the Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979 , regulations 8 (1), 8 (2) and 8 (3). An extract of the standards is given below: Table 6.2: Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979 (extract) Parameters Temperature pH value BOD5 COD Phenol Sulphide Oil and Grease Standard A 40C 6.0-9.00 20mg/l 50mg/l 0.001mg/l 0.50mg/l Not Detectable Standard B 40C 5.5-9 50mg/l 100mg/l 1.0mg/l 0.50mg/l 10mg/l

Table 6.3: Plant Wastewater and Standard B Values of EQA Parameter Temperature PH value BOD5 at 20C COD ppm ppm Unit C Standard B 40 5.5-9.0 20 50 Plant wastewater 40 5.0-9.0 10000 5000

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Phenol Oil

mg/l mg/l

1.0 10

>1.0 >10

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6.1.1 Waste Water Treatment Process

wastewater

Screening

To remove big particles & minimize blockages in sludge handling facility

pH stabilizer
To protect downstream process and equipment from high acidity water that is corrosive in nature.

Equalizing

Reduce hydraulic loading into the downstream process&reduce potential overflow

Coagulating

Remove suspended, phosphorus, coloured & colloidal solid which cannot be removed by sedimentation.

Clarifier

Separate wastewater into sludge and spent water to be treated separately.

Disinfection

Sludge dewatering

Remove the water content in the sludge for the sludge treatment.

114

Release to the sea

115

Sludge thickening

To thicken the sludge from 1% dry solid to about 6% dry solid content.

Sludge storage

Disposal to Kualiti Alam

For further treatment

6.1.1.1 PRIMARY TREATMENT

This is the first stage of waste treatment which is the primary treatment stage. The wastewater is undergoes screening process to will move to a tank.

6.1.1.2 SECONDARY TREATMENT

The secondary treatment starts with pH stabilizer. This is chemical treatment stage consists of multiple mixers to facilitate the mixing of acid and base in order to stabilize the pH inside the equipment. Then, the wastewater will move to equalization and coagulation tank. The coagulation tank is one of the biological treatments.

116

6.1.1.3 TERTIERY TREATMENT

The third treatment starts with the clarifier facility. The clarifier will reduce the velocity of wastewater that enables the suspended solid to settle out. This process will increase the efficiency of the wastewater treatment.

Next, the sludge is produced containing inert and non biodegrable organic matter. This type of waste must be disposed by remove the amount of water first by dewatering process.

After the dewatering process, it will move to the thickening of the sludge. This will decrease the volume of the sludge as well as to reduce the cost of sludge to be treated.

Then,the sludge will be sent to Kualiti Alam for further treatment. Before that, the sludge will be stored for 30 days to allow enough accumulation.

On the other side, some of the sludge after dewatering process will undergo disinfection process to allow the wastewater to be released to the open water system. This disinfection use calcium hypoclorite.

The last biological treatment is biopond facility before being released to the sea. The wastewater will be exposed to the microorganism that will dissolve in remaining organic substances. The ratio of wastewater from disinfection must be very low to the wastewater contained biopond to prevent toxicity to microorganism. The process takes one or two weeks before released to the sea.

117

6.2 Gaseous waste Gaseous waste which emits from absorber mainly consists of nitrogen, carbon dioxide, carbon monoxide and other hydrocarbon. These pollutants can be removed from airstreams either through flaring, absorption, adsorption, condensation or incineration. Each specific instance is carefully analyzed before commitment is made to any type of approach. This is to ensure that the technique is economically feasible under certain condition. Table 4.1 summarizes the limitation for each treatment method. Table 6.4: Summary of limitations for each treatment method Treatment method Flaring Limitation Flaring functioned as to recover as much as possible usable material from collected gas, to remove entrained liquids from the gases and to completely burn the remaining hydrocarbon gases. Flare system is an environmentally sound way to remove hydrocarbons from process system The flare gas recovery systems make recovery and re-use more economical. Condensation Condensation method is generally not utilized as method for removing a solvent vapor from air unless the concentration of solvent in gas is high and the solvent is worth recovery. Condensation cannot remove all the solvent but it can only be used to reduce the solvent concentration in the carrier gas Absorption Require good liquid-gas contact and proper equipment selection Optimization of absorber is important

118

The power consumption of a modern, high-energy scrubber can be significant because of the high pressure drop involved Adsorption Dry absorbents such as activated carbon and molecular sieves can be used to remove final traces of gaseous pollutants Generally carried out in large, horizontal fixed bed and often equipped with blower, condenser, separator and control Typically, installation consists of two bed; one is on stream while the other is being generated. Incineration Two methods in common use : direct flame and catalytic oxidation Direct flame has lower capital cost requirement but higher operating cost particularly if auxiliary fuel is required Provides clean, odorless effluent if the exit-gas temperature is sufficiently high

Considering all the options, flare system has been chosen for treating the gaseous waste as it is more economical and it fulfills the requirement to treat the gaseous waste discharged. The advantages of using flare system are: Emission are kept at minimum Most units have safety relief valves venting to the flare system Gaseous discharged from startup and shutdown can be sent to the flare system

6.2.1 Flare system process flow The flare system consists of the following components: a) Gas collection header and piping for collecting gases from processing units b) Knock-out drum to remove and store condensable and entrained liquids c) Seal drum d) A flare stack e) Pilots and steam injection systems
119

The flare system has a continuous pilot flame and necessary steam is added to provide the complete combustion of gases ignited by pilot flames. Waste gaseous discharged at the off line gas will be collected at the collection line. The collection line will transfer gases from valves to the flare header. The design of collection line will prevent the air from entering the flare gas collection system. The collected gaseous will then be transferred to the knockout drum through flare header. Gases and condensable and entrained liquids received will then be separated in knockout drum in which both the liquids for disposal and gases for flare will be transferred seal drum. Seal drum will discharge liquids for disposal and gases to the flare. Apart from that, seal drum also will prevents the flame from backing down to the flare system and water will be heated to vaporize residual hydrocarbon. Gaseous discharged will be send to the flare stack. Gaseous will flow to the flare top and steam ring will inject steam into the flare tip to improve air and gas mixture and also to ensure the complete combustion. The overall process is summarized in figure 4.2.

Gases

Relief valves and collection lines

Flare header

Knockout Drum

Seal drum

Flare

Figure 4.1: Overall flare system

120

Figure 6.1: Flare system process flow diagram The stack is designed in order to allow smokeless operation and ensure that a minimal amount of smoke is released. The flare stacks has the height of approximately 80 meters to eliminate the risk of exposure to flame and heat radiation. Steam is piped to the flare burner tip in order to control the flame. This will ensure that the gaseous are completely burned and protects burner tip from flame heat. In order to comply with the regulations, filter is installed at the stack gas tip and gas quality monitoring is used to monitor the level of gas release so that it is within the permissible limit. As according to Environment Quality Act (clean air) regulation 1978, the result of all tests conducted shall be expressed on the basis of flue gas containing 12% by volume of carbon dioxide. Therefore, in this process, the carbon dioxide gas released must be below 12 % by volume.

121

6.3 Solid Waste Handling Solid wastes are categorized into two which are hazardous and non-hazardous. The hazardous solid waste falls under schedule waste in which proper treatment method is required to dispose the waste. This is because its effects can last very long and can cause a significant hazard to human health if it is left exposed. There are several means of disposal available for solid wastes handling since these wastes will remain at the point of origin until decision is made to dispose them. The method includes recycling, chemical conversion, incineration, pyrolysis and landfill (Peter, Timmerhaus and West, 2003). Environmental regulations, overall economics and local condition are generally are taken in account in order to select the most acceptable one.

Solid waste Spend catalyst

Characteristics Hazardous waste (scheduled waste) May contain toxic and reactive substances

122

Fouling Sludge Construction waste (metal, brick, steel etc.)

Categorized under hazardous waste May contain toxic substance Can be recycled Large size waste need to be grinded first to convert it into small pieces

Solid wastes for this process mainly consist of spent catalyst and sludge from wastewater treatment plant. Table 4.2 shows the type of solid waste disposed from this process. Table 6.5: Solid wastes and their characteristics

6.3.1 Spent catalyst: The catalyst used in this process is vanadium phosphorus oxide catalyst. This spent catalyst is categorized under scheduled waste due to its nature which flammable and reactive. Therefore, proper handling need to be implemented as this waste is hazardous to public health and environment. For this process, the spend catalyst is handled by store in metallic drum and send to the approved recovery plant.

6.3.2 Sludge: Sludge is generated from the wastewater treatment plant. The sludge will be de-watered using belt pressing to turn it into dry, lighter sludge cake before disposal. The sludge which contained also toxic waste is sent to Kualiti Alam for further treatment and disposal.

6.3.3 Construction waste: Construction wastes which consist of metals, drums, steels, unused machine falls under recycled waste. These types of wastes are not simply thrown away, but will be recycled. Some of the valuable waste such as metals will be sold to the contractors.

123

Overall, although there are several methods available in handling solid wastes, suitable method is chosen for the specified type of waste based on the economic consideration and their effects to environment. Landfill, incineration and chemical conversion is not proposed in this treatment method due to high cost.

CHAPTER 7: PROCESS ECONOMICS AND COST ESTIMATION

Our plant has targeted to produce 35000 TPA of Maleic Anhydride. Besides being physically realizable, a thorough economic analysis must be conducted to ensure the plant is economically viable. For the cost estimation, two types of main cost that need to be considered: Total Capital Investment (TCI)

124

The total capital investment cost is our initial investment into the plant and involves a large sum of money. It covers a wide range of cost to kick-start the project. Despite its high cost, the total capital investment is an one-time expenditure. Breakdown of the TCI will be elaborated further. Total Production Cost (TPC) The total production cost is specific to our process to produce maleic anhydride and it is a annually recurring cost that involves the raw material, labour cost, maintenance, and other miscellaneous cost.

7.1 COST ESTIMATION FOR TOTAL CAPITAL INVESTMENT The most important part of the total capital investment cost estimation is the estimation of the cost of equipment required, also known as the Purchased Equipment Cost (PEC). The other components in the capital investment are usually a percentage or factor of the PEC. The PEC of our plant is shown in table 7.1. Detailed equipment design for both major and minor equipment are done beforehand to give the most accurate PEC cost. Our plant consists of a packed bed reactor, 4 storage tanks, absorber, 2 mixers, 9 Heat Exchangers, 2 air compressors, 3 distillation column, and one pump. The total accumulated cost is around RM 10.3 million.

Purchased equipment cost /unit


Packed bed reactor Tank(storage) Absorber

unit 1 4 1 2 9 2 3 1

total cost(RM) 861,497.00


2519734

Mixer
Heat exchanger air Compressor Distillation clomun Pump total

631,125 8614.4 373,623 810,324.00 5,094,871.00 11,326.00 10,311,114.40

Table 7.1 Purchased Equipment Cost (PCE)


125

The PEC is the direct cost. Other direct cost to be considered are: i. ii. iii. iv. v. vi. vii. Installation cost Instrumentation and controls cost Piping installation cost Electrical cost Building,process and auxilary cost Service facilities and yard improvement Land

They are estimated based on a percentage of PEC. Table 7.2 below summarizes each of the direct cost:
% estimate range 25-55% of PEC 8-50% of PEC 10-80% of PEC 10-40% of PEC 10-70% of PEC 40-100% of PEC 4-8% of PEC % estimated total cost (RM) 40% 4124445.76 40% 60% 35% 50% 70% 6% 4124445.76 6186668.64 3608890.04 5155557.2 7217780.08 618666.864 RM41,347,568.74

Installation cost Instrumentation and controls cost Piping installation cost Electrical cost Building,process and auxilary cost service facilities and yard improvement Land TOTAL DIRECT COST

Table 7.2: Total Direct Cost

Adding the PEC to the sum of the cost, the total direct cost is RM41,347,568.74 The indirect costs known as the non-manufacturing fixed capital investments, involve cost that are not immediately visible or quantifiable. They are classified as: i. ii. iii. iv. v. The calculated indirect cost is shown in Table 7.3:
126

Engineering and supervision Legal Expenses Construction Expense Contingency

\
Indirect cost Engineering and supervision Legal Expenses Construction Expenese Contingency TOTAL INDIRECT COST % estimate range 5-30% of DC 1-3% of FCI 10-20% of FCI 5-15% of FCI % estimated 25% 2% 15% 10% total cost (RM) RM10,336,892.19 RM1,416,012.63 10620094.71 7080063.141 RM29,453,062.67

Table 7.3: Total Indirect Cost

The fixed capital investment = Total direct costs + Total indirect costs = RM41,347,568.74 + RM29,453,062.67= RM70,800,631.41 Lastly, working capital must also be included because it is the additional cost needed to maintain and operate the plant when revenue is generated. Sinott (2005) recommends the working capital to be 15% of the fixed capital for a petrochemical plant.

Fixed-capital investment working capital Total capital investment = FCI +WC

RM70,800,631.41 15% of TCI RM83,294,860.48

Table 7.4: Total Capital Investment

The total capital investment Fixed Capital Investment + Working Capital = RM83,294,860.48

7.2 COST ESTIMATION FOR TOTAL PRODUCTION COST The Total Production Cost (TPC) can be classified into: 1. Fixed Operating Costs: Costs that are fixed and do not changes with production rate. 2. Variable Operating Costs: Costs that are dependent on the amount of product produced.
127

In our case, the product is maleic anhydride. 3. General expenses. This includes: administrative costs, distribution and marketing, as well as research and development. Because our production capacity is fixed at 35000 TPA, our variable costs only need to be calculated once and it will maintain the same annually. The yearly total production cost is shown below:

Raw material: The main raw material used is mixed butane. To produce 35000 TPA (44.7 kmol/hr) of maleic anhydride, the amount of mixed butane feed rate needed is 140 kmol/hr according to material balance calculation. The annual cost for raw material is calculated in Table 7.5:
Raw material mixed butane Cost (RM) per ton 600 Quantity (kmol/hr) 140 Molecular Weight (kg/kmol) 58.12 Quantity (kg/hr) 8136.8 Quantity Cost (RM) (TPA) 65,094 39,056,640.00

Table 7.5: Raw Material Cost


The raw material cost per annum = RM 39,056,640.00

Meanwhile, other miscellaneous raw material costs such as Dibutyl Phalate solvent and Vanadium Phosphate Oxide (VPO) can be regarded as a % of the total production cost. The total production cost comprising of all components are shown in Table 7.6:

Production costs a) Direct production cost f1 Maintenance & repair f2 Operating supply f1+f2 f3 Raw material (DPA, catalyst) f4 Operating labor f5 Utilities f6 laboratory charges f7 Patent and royalties f8 Direct supervisoy b) f9 Fixed charges c) f10 Plant Overhead cost general expenses, f11

% estimate range 2-10% FCI 0.5-1% FCI

% estimated 5% 1% 6% 30% 10% 15% 1.00% 4% 3.00% 10% 5% 18%

total cost (RM) RM3,540,031.57 RM708,006.31

10-80% TPC 10-20% TPC 10-20% TPC 1-4% TPC 0-6% TPC 1-4% TPC 10-20% TPC 5-15% TPC 15-25% TPC

RM31,860,284.13 RM10,620,094.71 RM15,930,142.07 RM1,062,009.47 RM4,248,037.88 RM3,186,028.41 RM10,620,094.71 RM5,310,047.36 RM19,116,170.48

128

f3+f4++f10 Total production cost

96.00% RM106,200,947.12 RM106,200,947.12

Table 7.6: Total Production Cost

The total production cost is therefore: RM 39,056,640.00 + RM106,200,947.12 = RM145,257,587.12

7.3

PROFITABILITY ANALYSIS

The profit of a plant can be determined through various methods. The established methods to estimate the profitability of a plant are shown below: 1. 2. 3. 4. After Tax Cash Flow (ATCF) Pay Back Period (PBP) Rate of Return (ROR) Net Present Worth (NPW)

The economic assumptions used in our calculation are: i. ii. The plant has a project plant life of 20 years. The plant construction period is 4 years before commencing production. Hence, the total investment cost is distributed between the 4 years. iii. The operating cost, income and raw material cost is assumed to maintain throughout the lifetime of the project. iv. v. Local Taxes is 25% according to Malaysias tax system. Interest Rate is 10% per year

7.3.1 Revenue The total revenue generated from our sales of products and by products. Main product sold is maleic anhydride while by product is iso-butane that is obtained from treatment of mixed butane.

129

Production MA Iso-Butane

(kmol/hr) Molecular Weight (kg/kmol) 44.7 36.9 98 58.12

Quantity (kg/hr)

Quantity (TPA)

Market price of MA (RM/T)

Revenue RM/year

4380.6 35044.8 2144.628 17157.024 total

RM 4500 157,701,600.00 570 9779503.68 RM 167,481,103.68

Table 7.7: Total Revenue The annual revenue generated from our sales of products and by products = RM 167,481,103.68 7.3.2 Gross Earnings Gross earning is the profit deduced from the difference of revenue and total production cost. It is the simplest way to give a quick measure of how profitable our plant can be. From earlier calculation, our total production cost = RM145,257,587.12 The gross earning is RM 167,481,103.68 - RM145,257,587.12= RM 22,223,516.56 It must be noted that the gross earning is just a crude estimation. Other profitability methods shown in the subsequent section will take into account more detailed costing. 7.3.3 After Tax Cash Flow (ATCF) The table below shows the after tax flow diagram. The plant will start up in year 3, and the Total Capital Investment calculated earlier is RM83,294,860.48. This amount of cost is needed to kickstart the plant project. The weightage of the cost are distributed among the 3 years as follows: Year 1: the design cost: It involves the designing the plant on paper and requires skilled human capital who are professionals in the field design. Requires moderate TCI Year 2 Construction cost

130

Both years are the most resource intensive years because much human labor is needed to partake in the construction of the plant. It is also the year where construction materials are being purchased, hence the high cost. Requires most TCI Year 3: Working capital Operators and management are needed to start up the newly constructed plant, as well as maintaining the plant in a reliable and functional state. Requires moderate TCI

131

Year An -3 -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 20

Annual Capital Investment A(I) 16,658,972 49,976,916 16,658,972

Sales Income A(SI)

Operating costs A(OI)

Depreciation A(BD)

Income Before Tax A(IBT)

Income Tax (30%)

Income After Tax A(IAT)

167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 167,481,104 -24,988,458

145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587 145,257,587

7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063 7,080,063

22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517 22,223,517

6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055 6,667,055

15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462 15,556,462

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

22

Table 7.8: After Tax Cash Flow Diagram

132

Figure 1: Cash Flow Diagram After Tax

133

7.3.4 Depreciation Depreciation is 10% of the capital investment and is calculated by: RM70,800,631 x 10% = RM 7,080,063

7.3.5 Payback Period The payback period, which is the year when all the capital investment is recovered, is 3 years as seen from the graph. At the end of the 20 years, the plant is decommissioned and sold off, thus generated a salvage value of 30% of the Total Capital Investment = RM 24,988,458

7.3.6 Rate of Return (ROR) The rate of return is an index used to gauge the performance of the money invested. It is the ratio of annual profit to investment, and can be calculated by the following equation:

ROR

Cumulative net cash flow at en d of proje ct 100 per cent Life of pr oject original investment 417,060,617 100% 25.04% 20 83,294,860.48

Expected ROR (Rate of Return) should meet the MARR (Minimum Attractive Rate of Return), which is the minimum rate of return accepted to start a project. A general guide of MARR= 15% is used. Our rate of return is 25.04%, which greatly exceeds 15%, thus our maleic anhydride plant project is worth investing.

7.3.7 Net Present Value/Worth (NPV) Money earned at the moment of time can be re-invested to generate extra income. Hence, money is worth more in the early period of the project compared to when later.
134

Therefore we are

interested to know the present worth of each years net cash flow. This is calculated by the formula below:

NPW

n t

NFW n n 1 ( 1 r )

where, NFW estimated net cash flow in year n r discounted rate (interest rate) per cent/100 t life of projects, years

The plant life of the project is 20 years while the interest rate is 10%. A sample calculation for the NPW at year 5 is shown. 52,524,288 = RM 32,613,450

Table 7.9 shows the calculated NPW. The cumulative net present worth can also be determined.
Year of Completion 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Net Cash Flow A (NCF) -60658335.75 -38,021,811 -15,385,286 7,251,238 29,887,763 52,524,288 75,160,813 97,797,337 120,433,862 143,070,387 165,706,912 188,343,436 210,979,961 233,616,486 256,253,011 278,889,535 301,526,060 324,162,585 346,799,109 Discount Factor, fd (i = 10%) 0 0.9091 0.8264 0.7513 0.6830 0.6209 0.5645 0.5132 0.4665 0.4241 0.3855 0.3505 0.3186 0.2897 0.2633 0.2394 0.2176 0.1978 0.1799 Discounted Cash Flow for 10% [A(NCF)*fd] 0 -34,565,283 -12,715,113 5,447,963 20,413,744 32,613,450 42,426,319 50,185,498 56,183,286 60,675,810 63,887,188 66,013,225 67,224,718 67,670,374 67,479,427 66,763,937 65,620,856 64,133,839 62,374,868 Discounted Cash Flow for 10% Cumulative 0 -38,021,811 -50,736,924 -45,288,961 -24,875,216 7,738,234 50,164,553 100,350,051 156,533,336 217,209,147 281,096,334 347,109,560 414,334,277 482,004,652 549,484,079 616,248,016 681,868,872 746,002,711 808,377,579

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19 20 20

369,435,634 392,072,159 417,060,617

0.1635 0.1486 0.1486

60,405,678 58,279,028 61,993,403

868,783,258 927,062,286 989,055,689

Table 7.9: Net Present Worth The cumulative present net worth is RM 989,055,689 It can be seen that at every subsequent year, the present net worth decreases, hence proving correct that money invested later will worth less.

7.3.6 Discounted cash-flow Rate of Return (DCFRR) The discounted cash flow Rate of Return is a measure of the maximum interest rate that the maleic anhydride project could generate revenue but break even by the end of project life. This means the cumulative net present worth of the project is 0. The DCFRR is dependent on the interest rate. By calculating the cumulative NPW at various interest rate, we can extrapolate a point that gives us an interest rate that will yield 0 cumulative NPW. This is shown in the equation:

(1 r )
n 1

n t

NFW

' n

where, NFW estimated net cash flow in year n r' discounted cash flow rate of return per cent/100 t life of projects, years
Cumulative NPW at interest rate of 0 to 30% are calculated:
i 0 10 20 30 Cumulative NPW 417060617.1 140271457.5 41561161.12 -8291589.507

Table 7.10: Cumulative NPW at various interest rate, i

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A graph of Cumulative NPW is plotted against the interest rate. From the graph at Figure 2, it can be seen that NPW becomes 0 between i=20% and i=30%. A close up look on the graph shows that the line intersects x-axis at i=28%. Hence, the discounted cash-flow rate of return is 28%. At this interest rate, the cumulative NPW of the project will become zero.

Figure 2: Cumulative NPW versus interest rate

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7.4 DISCUSSION From our economic analysis, it can be seen that the plant will need a Total Capital Investment of RM83,294,860.48. The Total Production is RM145,257,587.12, which is higher than the TCI because a bulk of it comprises of the cost of mixed butane, our raw material. Nevertheless, our annual revenue generated from the sales of maleic anhydride and side-product iso-butane is a total of RM167,481,103.68. A plot of the cash flow diagram indicates that our investment is recovered at year 3, the break-even point. After factoring in the taxes, the plant is calculated to be able to earn a total of RM 417,060,617 in cumulative profit after 20 years in operation. Therefore, our plant is economically feasible and attractive. The profitability analysis using various methods and its significance is described in the Table 7.11. Methods Investment Value RM 83.3 million Significance Indicates financial resources needed Shows yearly income and cumulative RM 417 million worth Shows how fast the capital investment can be recovered Shows time value of money at the present year Measures performance of capital by the ratio of annual profit to investment. Measures performance of capital allowing for timing of cash flows

Net Future Worth

Pay-back time

3 years

Net Present Worth (10% interest rate)

RM 140.3 million

Rate of Return

25.04%

Discounted Cash Flow Rate of return

28%

Table 7.11: Profitability Analysis Comparison

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From the process economics analysis above, we can see that various profitability analysis methods have their own roles, advantages as well as weaknesses. Whether a project is viable and the methods to determine so are usually decided by the company. In our case, we have decided that the MARR should be more 15%, which we have achieved. This MARR is also in agreement with the values recommended in textbooks. We must always keep in mind that the cost estimation is only a valid for a certain time frame and can be subjected to change. This is because actual cash flow in any years can be affected by external factors, such as price changes in raw materials, or any other operating costs that are tied of our production of maleic anhydride. Therefore, a sensitivity analysis should be carried out to take into considerations uncertainties that might occur. Lastly, various scenarios that are non-quantifiable can also affect the economics of our plant, such as technology advancement, weathering and government policies. A thorough economic analysis should also have contingency plans for these factors in order for it to be truly comprehensive.

References
Pitches, J. (2010). ICIS pricing. Weekly Atlantic Basin Feedstocks, http://www.icispricing.com/il_shared/samples/SubPage448.asp, Retrieved Date: 9th November, 2012. McGinn, S. (2011). USGC isobutene spread over normal butane remains at six-year high, http://www.platts.com/RSSFeedDetailedNews/RSSFeed/Petrochemicals/6654166, Retrieved Date: 9th November, 2012.

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CONCLUSION
It has been proven conceptually that the most economical butane derivative product can be designed and a complete plant design product can be developed. To find the most profitable flowsheet, the team have chosen the best among all based on economic analysis. For the future process, the team have performed MEB and carry Heat Integration for optimized flowsheet. Basically, the project meets the requirement of the objectives: Maleic Anhydride production plant is designed using mixed butane as raw material. Process flowsheeting is developed. MEB for the process is performed and 99% of purity is achieve. Heat Integration for optimized flowsheet is carried with heat recovery of16.5733MW. The production rate of 35,000 metric tonne per annum is achieved.

The preparation of Maleic Anhydride uses the process of catalytic oxidizing of n-butane. Heuristic approach has been applied in identifying the appropriate design. For the process synthesis and flowsheeting, the HYSIS has been used and SPRINT is used for the Heat
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Integration calculation. A highly integrated heat exchanger network and process control system is also included to the proposed plant to ensure the profitability of the plant. For environmental responsibility, the plant has been design to achieve the target of waste minimization, cost minimization and save the Earth. The unwanted side product is being combusted and well treated to ensure the emission coming out from the plant has met the Malaysian government Environment Quality Act, 1974. A general safety study includes personal safety, emergency management, Standard Operation Procedures (SOP) and plant start-up and shut down procedures were documented in this report as well.

RECOMMENDATION
The final year design project has been useful in cultivating and enhancing the skills and knowledge at hand. As final year students, the experience gained throughout the process of this project has given the opportunity to actually design a real processing plant has increase our understanding in the chemical engineering field. Besides that, other skills were also developed in the process such as communication skills, management skill, and team work. However, we find that there few areas that needs improvements and perhaps a new approach in solving some of the problems faced. Firstly, we recommend that the PDP committee provide standardized values of key elements such as the feeds prices. We have different values of feed because taking it from different sources. So, a standardized value is appropriate to accommodate the student with a good reference. Secondly, will be the plant side location. Scope of consideration should be extended to outside of Malaysia (Middle East), because raw material availability is also high there. Thirdly, we propose that students should be provided easier access to the labs to use engineering software such as HYSYS and AutoCAD and the department should provide a proper manual as guidance.
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For our part, more justifications are needed for the chosen plant capacity because to base the plant capacity on Thirumalai Chemicals Ltd Sdn Bhd is not a really valid approach. Although the market data and demand for maleic anhydride is difficult to find and mostly kept confidential, extrapolation can be made based on the global demand. This is something that must be relooked in FYDP II. In addition to that, further research must be done on isomeric conversion technology in order to convert isomers back to its normal state. This is important to reduce the amount of by-product produced from the process. Last but not least, in our process flowsheeting we will consider to recycle unreacted n-butane, by putting more reactors if necessary to improve the yield of Maleic Anhydride. Proper economic justifications must be done beforehand though. We hope that these recommendations will be considered and useful by the PDP committee to improve the PDP project handled by the student in the future.

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REFERENCES
Barone et al,U.S. Pat. No 4,565,880 ,Maleic Anhydride Process Shyamal K.Bej and Musti S.Rac,1991 , Selective oxidation of n-butane to maleic anhydride Thirumalai Chemicals Limited, 2006 Material Safety Data Sheet Maleic anhydride, 2005 Material Safety Data Sheet Butane, 2006 Maleic Anhydride Market Research. Retrieved on Jun 2012 from http://www.alibaba.com/ Market analysis of Maleic Anhydride Retrieve on June 2012 from http://www.icis.com/ Market analysis of Maleic Anhydride Retrieve on June 2012 from http://www.ihs.com/ Application of Maleic Anhydride Retrieve on June 2012 from

http://www.thirumalaichemicals.com/images/maleicanhapplication.pdf Petrochemical & Polymer Industries Division, MIDA,June 2005,Profit from Malaysias Petrochemical Industry New York Times(1989 June 5) 500 on 2 Trains Reported Killed By Soviet Gas Pipeline Explosion, Robin, Mark L.(2000) Fire protection in telecommunication facilities, Process Safety Progress, volume 19, no. 2, pages 107-111 Freeman, Sunny; Taylor, Bill ,(2008) "Firefighter dies, thousands flee propane plant blasts" Richard Kooren,2008,Hazard of Propane Retrieve on June 2012 from

http://www.claimscanada.ca/issues/article.aspx?aid=1000224990 Environment Quality Act 1974 Occupational Safety & Health Administration (OSHA) Resource Conservation and Recovery Act (RCRA). UK HSE Acid Anhydrides Criteria Document for an Occupational Exposure Limit (1996)

Douglas, J. M., Process Synthesis for Waste Minimization. Ind. Eng. Chem. Res., 1992, 31, 238-243
Felder, R. M., & Rousseau, R. W. (2000). Elementary principles of chemical processes. John Wiley

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