CHAPTER 1 TO 4

0CHAPTER 1 INTRODUCTION 1.1 1.1.1 Process Background Chemical Background of Ethyl Acetate Ethyl acetate (ETAC or EA) is the organic compound that is an ester derive from the reaction of ethanol and acetic acid. Its chemical formula can be written as CH3COOCH2CH3 or can be simplified as C 4H8O2. It is a colourless liquid and has a smell that is slightly sweet and fruity. According to Gaspar [1], ethyl acetate has been largely used as a solvent in paints, coatings, inks and adhesives. Besides, it also has been used as a solvent in many chemical process replacing aromatic compound which generate serious damage to the environmental and human beings. Other than that, its physiologic harmlessness in combination with its oleophilic characters has made it especially suitable for extraction processes in the food industry and for the preparation of cosmetics. Its low boiling point is the basis for its application as a high grade defatting agent. Therefore, because there is no ETAC supply in Malaysia as well as increase in demand globally, ethyl acetate has been chosen as a product for this study 2 1.2 Chemical and Physical Properties of Ethyl Acetate Table 1.1: Physical and Chemical Properties of Ethyl Acetate [2] Properties Formula Molecular weight Melting point Boiling point Flash point Critical temperature Vapour density Vapour pressure Values C4H8O2 88.11g/mol -83.6 ℃ 77.1 ℃ -3 ℃ 250 ℃ Viscosity 3.04 (Air=1) 12.4kPa (@20 ℃ ¿ 0.46mPa.s (@20 ℃ ¿ Specific gravity Appearance Odour Odour threshold Solubility 0.902 Colourless liquid Ether-like, fruity 3.9ppm Soluble in cold water, hot water, diethyl Heat of combustion Heat of vaporization Suface tension ether, acetone, alcohol, benzene 2238.1 kJ/mol 35.60kJ/mol 24dynes/cm (@20 ℃ ¿ 1.3 Manufacturing Process of Ethyl Acetate Ethyl acetate is synthesized in industry via classic Fisher esterification. This method is the first method that has been commercializes in industry. The process of the reaction is between ethanol and acetic acid. According to Katikaneni and Cheryan [3],these mixtures will converts to the ester in about 65- 75 % of theoretical. The reaction of this mixture can be accelerated by adding acid catalyst. 3 Besides, Tishchenko Reaction is one of the method to produce ethyl acetate. From the research of Seki et al [4], this method was first discovered by Claisen. This method used the catalytic dimerization of aldehydes that will produce the corresponding ester. In view of synthetic organic chemistry, the Tishchenko Reaction is one of the most ideals methods for preparing ester because no toxic reagent require for the reaction to occur[4]. Ethyl acetate also can be produced by dehydrogenation process of ethanol. Ethanol is dehydrogenated to acetaldehyde which further reacts to form ethyl acetate. Since it is only one feedstock, it will reduce the production and investment costs. This process was developed by Davy Process Technology Limited. This process has been industrially employed and used copper as the catalyst. The alkylation of acetic acid and ethylene is one of the manufacturing process to produce ethyl acetate. According to Yamamoto et al [5], this method has attracted much attention because it is ideally has no by-product is produced with this reaction. This method has been commercialized named Avada technologies. 1.4 Application and Uses of Ethyl Acetate Ethyl acetate can be used in a wide variety of industries including; food production, beverage, pharmaceutical, cosmetics and various other industries. Table 1.2: Uses of ethyl acetate in various industry [6] Some example of the flavour is in essence manufacturing of pineapple.5. Others industries It is widely used as industrial solvent in various other industries such as in coatings.1 Toxicology Information of Ethyl Acetate The toxicity data were extracted from Material Safety Data Sheet (MSDS). intermediate in the pharmaceutical. Other than that. Table 1. adhesives and rayon to dissolve material. lacquers.4 Food Production Ethyl acetate is commonly used as a flavour enhancer in food production. inhalation. eye contact. ethyl acetate is used as a solvent for varnishes. 1. Beverage It is usually used as a flavour enhancer in beverage. dry cleaning and may also present in wines. Beside. bananas. These data were used to indicate the toxic level of the chemical and it is needed as references when deciding the design of the plant. cream. Cosmetics Ethyl acetate is often used as aroma enhancer in cosmetic especially in perfumes.5 Process Safety of Ethyl Acetate 1. ingestion Acute oral toxicity (LD50): 4100mg/kg (mouse) Acute toxicity of the vapour (LC50): 45000mg/m 3 -3 hours . it is used in nail polisher and nail polisher remover. Pharmaceutical Ethyl acetate is widely used as extraction gent. strawberries and other fruit flavours and whiskey.3: Toxicity information of ethyl acetate [2] Entry routes Toxicity to animals Absorbed through skin. it is suggested that it need to be away from the source of ignition and must be store in a tightly closed container. inhalation. talkativeness. it is recommended a safe chemical storage building that meets specific regulations for storing the ethyl acetate. store it in a cool.5. Chronic Effects on Ay cause reproductive effects( based on animal test data) Humans Special remarks on Acute potential health effects: other toxic effects in humans 1.5 Chronic effect (mouse) on Cause damage to the following organs: mucous membrane. May affect gastrointestinal tract(nausea. Skin: May cause skin irritation 2. It must be keep separated from incompatibles substances such as oxidizers. central nervous system (CNS). slowed reaction time. vomiting) 5. etc) 1. which is used in spectrophotometry and environmental testing. May affect behavioural/ central nervous system(mild central nervous depression-exhilaration. May cause damage to the following organs: blood.2 Storage and Handling of Ethyl Acetate Ethyl acetate is a flammable clear liquid. humans upper respiratory tract. Other than that. kidneys. permeator) Special remarks on May effect genetic material (mutagenic). . May cause irritation of conjunctiva 3. dry and well-ventilated area. dizziness. May cause respiratory tract and mucous membrane irritation 4. Other toxic effects on Hazardous in case of ingestion. Since it is flammables. Besides. Eyes: May cause eye irritation. Slightly hazardous humans in case of skin contact( irritant. liver. use proper personal protective equipment and wash thoroughly after handling.g. . If spilled. Avoid contact with eyes. sand) and then place in container. skin. vermiculite. and clothing and avoid breathing vapour or mist. absorb it with inert material (e. Provide ventilation and remove all sources of ignition.6 As for handling. The combined ETAC supply volume was more than 2.5 million tonnes in 2013 [7].1: Global Ethyl Acetate (ETAC) Production in 2013 [8] . It is followed by India. Asia-Pacific captured the biggest share of the global production volume and China is an unrivalled leader of the world ETAC market.7 1. accounting for over half of the global ETAC production.6. the UK.2).57 million tonnes in 2013 (Figure 1.1 Market Demand The global production of ethyl acetate (ETAC) grew by over 80% from 2004 to 2011 and exceeded 2. Japan and Brazil. Figure 1.6 Market Survey and Outlook 1. 2: Production rate of ethyl acetate from 2005 to 2013 [9] Figure 1.3: Ethyl acetate market price from 2004 to 2013 [10] A) North American [11] .8 Figure 1. two by Solutia.000-tonne annual capacity to the US according on Mexico’s export to the US. Europe still relies on imports to meet demand. soared in 2011. US imports in the first 11 months of 2011 totaled 37. According to US retail research firm NPD Group. a 10% increase over 34. The high demand of ETAC come from inks and coatings which represents 60%. sends about 20% of its 92. Mexico.totals around 102. there are five ETAC plants capacity that serve the US market . and one by Celanese in Mexico .9 According to ICIC Business Chemical. and 10% comes from adhesives and cosmetics. .892 tonnes.4: The capacity of ethyl acetate in North America [11] B) Europe [12] Burridge (2011) from ICIS Business Chemical reported that.two owned by Eastman.500 tonnes. Celanese's ETAC plant in La Cangrejera. a popular downstream use. with material sourced mainly from Eastern Europe. Figure 1. Sales of nail polish. India.585 tonnes in the same period of 2010. The increase partly is due to cracker outages and increases in market demand. Players are concerned that the current uncertainty and slower demand will push prices down.10 China and Brazil.000 tonne annual capacity. Figure 1. Large import volumes arrived in Europe from India and China in 2011.5 shows the list of company in Europe that serve the Europe market totals around 441. Figure 1.5: Prices of Ethyl Acetate from 2009 to 2011[12] . The price of ETAC keep rising. prices dropped heavily in August to €976/tonne. however. However. Figure 1.6. Asia ETAC capacity per year is shown in Figure 1. Demand in China has been estimated by market participants at 1m tonnes/year. Singapore.12. several of these countries purchase volumes from China due to the price competitiveness of Chinese material so as to meet local demand.6. South Korea and Taiwan.14] .2 Market Outlook [11. with an estimated capacity of 3m tonnes/year as of May 2013. Japan.6: Asia ETAC capacity tonnes per year [15] 1. Japan. China is the largest ETAC producer and exporter in the world. South Korea and Taiwan were China's three largest markets by volume in 2012. Indonesia. Other countries in Asia that produce ETAC are India.11 A) Asia [14] According to ICIS Business Chemical. 12 A study done by ICIS Chemical Business generally agrees that ETAC in Asia is in oversupply due to capacity expansion in China and India in recent years. This results in supply overhang in which has prevented several Asian producers from to utilize their plant in full capacity since 2012. Despite China’s overcapacity in ETAC, Kamel (2010) believe that it was not a threat to the world market especially Europe as the European market requires a certain quality and realibility of products. He added that Chinese are definitely not a competitior as Chinese continuing to supply China. New venture of ETAC expansion in Middle East happen for the first time In May 2013. Saudi Arabia's Saudi International Petrochemical (Sipchem) started up a 100,000 tonne per year of ETAC plant in Al-Jubail. Large part of ETAC is likely to be market in Europe. The technology is provided by Rhodia and the feedstock of ethanol will obtained from Brazil. The US will continue to depend on imports to satisfy demand, because this niche product is a mature market with growth tracking GDP. Moreover, Zeachem attempts to start up and produce ETAC from biomass as they received a $232.5 million grant from the US Department of Agriculture. Making ETAC from biomass is cost effective. This could be affect the plant capacity in that region. Moreover, China's Taixing Jinjiang has started its new 200,000 mt/year ethyl acetate plant in June 2015 [16]. Overall, Southeast Asia is set to become the most important region globally for ethyl acetate production and consumption, where demand is growing rapidly by 5 to 6% per year [17]. For Southeast Asia outlook, ETAC imports from China by volume were led by Indonesia and Vietnam, Thailand, the Philippines, Malaysia and Singapore. 1.6.3 Market Price of Raw Materials 13 In the process to produce ETAC, ethanol, acetic acid and ethylene are the major feedstocks to be used in industries. In the recent years, ethanol production from renewable sources as an alternative for a low –cost ethanol availability has shown interest among industries. This scenario has favored many to study the production of different chemical for instance, ethyl acetate from bio-ethanol due to low cost and environmental friendly. Many believe that, ethanol represents a promising alternative source of feedstocks over ethylene, acetic acid and acetaldehyde as raw materials for manufacturing ethyl acetate. According to Platts Financial (2015), Philippines is one of the country that produce bioethanol recently (Figure 1.7), thus, this would be an advantages for industries to market ETAC in Southeast Asia especially Malaysia, due to lower price of feedstock. Figures below show the price of the major feedstock to manufacture and process ETAC. Asian acetic acid output was estimated to be 8 million to 9 million tonnes per year in 2015 with below 500 usd dollar per tonne while , global ethylene prices tumbled 15% in January 2015 to $834 per metric ton from $977 per metric tonne in December. Figure 1.7: Ethanol market price on December 2015 [18] 14 Figure 1.8: Acetic acid market price on December 2015 [19] Figure 1.9: Ethylene market price on December 2015 [17] 1.6.4 Market Price of Ethyl Acetate jumped 29% mostly because of increases in raw materials such as industrial ethanol (+8%) and ethylene (+29%). the price of ETAC was dropped an average of $ 957. (2012). While in recent report study by ICIS shows that in January 2014.7 Process Selection . In European market. Figure 1.50 per tonne FOB China and it is expected to increase annually for over years. the prices of ETAC range.082. according to Kelly et al. (2012) [20].40 per tonnes contrary with the previous expectation by the distributors due to China’s economic slowdown and low price of feedstocks and crude oil globally.15 In 2011.918/tonne).10: Ethy acetate market price in US Gulf on January 2012 [20] 1.852-1. consistent with Kelly et al.126 per tonne in midOctober 2011 studied by ICIS Business Chemical. In October 2012. To market ETAC globally was still promising as the distributor spot prices rose to 84 to 87 cent per pound ($1. the price of ETAC is an average of $1. the price of ETAC increase to an average of $927.27 to $1. and alcohol at the distillate while pure ethyl acetate is obtained as the bottom product. C2 H 5 OH +C H 3 COOH →C H 3 COO C2 H 5 + H 2 O (1) The technology for this route was described by Hoechst A. .16 Ethyl acetate is an important environmental friendly solvent. water. a) Fisher esterification b) Tischenko reaction A) c) d) The akylation of acetic acid with ethylene The dehydrogenation of ethanol Fisher esterification A conventional method of producing ethyl acetate is by esterification of ethanol with acetic acid (reaction 1) which is synthesized mainly in industry in the presence of catalyst. The reaction can obtain 90% acetic acid conversion and 100% ethyl acetate selectivity [21]. The reaction is expressed as follow. flavors and essence and pharmaceuticals. Dehydration and the azeotropic distillation of ethyl acetate and water take place in the first column. surface coating. The pilot plant uses three distillation columns (Figure 1.1). The third column to give waste water at the base while at the top is recycled to the reaction column. Acetic acid and ethanol are fed into the bottom of the column. industrially used in a wide range of applications including printing inks. Ethyl acetate can be synthesized into four possible processes. At the second column consist of ester.G. 11: Pilot plant of ETAC from acetic acid and ethanol by Hoechst A.17 Figure 1. ethyl acetate is produced by dimerization of acetaldehyde in the presence of catalyst such as aluminum alkoxide.1. This technology took place mainly in europe during the first half of this century and the overview of the process for production of ethyl acetate was described by Hoechst as shown in Figure 1.The reaction is expressed by 2C H 3 CHO →C H 3 COO C2 H 5 (2) . The conversion can be achieved to 61% yield of the ester by adding aluminum ethoxide at -20˚C [24]. sodium alkoxide or solid bases like alkaline earths oxides [23].G [22] B) Tischenko reaction In this route. This technology (Avada) has been commercialized.12: Tishchenko process for ethyl acetate. Ethyl acetate is respectively the addition of ethylene to acetic acid. This process is preferable at locations where competitive ethanol is not available.13 shows a process flow diagram of AVADA technology for production of ethyl acetate.G. [22] C) The akylation of acetic acid with ethylene The process to produce ethyl acetate in this route involving the alkylation of acetic acid with ethylene is shown below in reaction 3.18 Figure 1. Hoechst A.by INEOS (formerly as BP) for this process at its plant in Hull based on ethylene and acetic acid as a feedstock with a solid catalyst [13]. Figure 1. C2 H 4 +C H 3 COOH → C H 3 COO C 2 H 5 (3) . . in a competitive way with respect to the before mentioned processes.19 Figure 1. This method is cost effective than esterification. this process has become very attractive as ethanol is the only feedstock needed for the process as well as the growing production of bio-ethanol.13: Addition of ethylene to acetic acid for production of ethyl acetate by AVADA team in 2001 [13] D) Dehydrogenation of ethanol Ethyl acetate can also be obtained by dehydrogenation of ethanol. however. A conversion of 65% with selectivity to ethyl acetate of 99% can be obtained at 240˚C and 20 bar [26]. In particular. it results in surplus of ethanol feedstock in the plant. The ethanol is dehydrogenated to acetaldehyde. The schematic diagram of the flowsheet is described in Figure 1.3.4.20 The side reaction may be obtained as shown in Figure 1. is used by South Africa's Sasol in a 50.000 tonne/year plant in Secunda. which only uses ethanol feedstock. This method. Figure 1. The Davy dehydrogenation system applies a simple reaction vessel containing multiple catalyst beds and the reactants continue downward through the catalyst beds for dehydrogenation process and being re-heated along the way. according to the following reaction: 2C 2 H 5 OH → C H 3 COO C 2 H 5 +2 H 2 (3) This technology has developed by Davy Process Technology from UK.14: Davy Process flowsheet of ethyl acetate production [25] . The overall reaction of direct conversion of ethanol to ethyl acetate. which further reacts to form ethyl acetate. 16: A simplified scheme of the process based on the use of copper/copper chromite commercial catalyst by Santacesaria et al. (2012) [26] 1.1 Economic Potential (EP) .21 Figure 1.7.15: Ethyl acetate process dehydrogenates ethanol in a two-stage reaction [25] Figure 1. 834 Platts McGraw Hill financial 88.05 3. the profit excluding the cost of equipments and operating costs) pathway.e. Ethylene C (¿ ¿ 2 H 4 ) ¿ 28.11 0. The gross profit is computed as the income derived from the sales of products and byproducts less the costs of feedstock as a mass basis.07 0.05 0.93 Technon Orbichem 2 7 www.5 Orchid Chemical Supplies Ltd.4 Tecnon Orbichem Acetaldehyde (C H 3 CHO) 44.com Ethyl acetate (C H 3 COOC 2 H 5 ) Hydrogen ( H2 ) . The average price of raw materials and products based on year 2015 and 2016 are shown in Table 1.3: The average price of raw materials and products Chemicals C ¿ Ethanol ¿ ) ¿ Molecular Cost Weight (g/mol) (US dollar/kg) 46..626 References Platts McGraw Hill financial Acetic acid (C H 3 COOH ) 60.3. Table 1. The gross profit is used as a vehicle for screening out the process path that cannot be profitable.cleancaroptions.05 0. The EP is calculated based on the gross profit (i.22 Economic considerations are obviously major constraints on any engineering design. 332 H2O 1 18 18 0.59 Products C H 3 COO C 2 H 5 1 1 60.20 0 Tischenko reaction Reactants Overall Chemical Equation 2C H 3 CHO Kmole Molecular Weight (kg/kmol) Weight Weight / Weight EA Price of Component ($/kg) Gross profits ($/kg EA) Products C H 3 COO C 2 H 5 2 44.93 – 3.5 1 88.05 1 88.52) = 0.11 0.68) – 0.05 88.05 1 60.52 0.11 .4 0.57 The akylation of acetic acid with ethylene Reactants Overall Chemical Equation C2 H 4 C H 3 COOH Products C H 3 COO C 2 H 5 Kmole Molecular Weight (kg/kmol) 1 28.07 0.626(0.11 60.11 1 0.05 88.93(1) – 0.11 1 3.23 Fisher esterification Overall Chemical Equation Kmole Molecular Weight (kg/kmol) Weight Weight / Weight EA Price of Component ($/kg) Gross profits ($/kg EA) Reactants C2 H 5 OH C H 3 COOH 1 46.68 1 0.4(0.11 88.93 0.93 0.07 46.05 88.5 = -2. 834 60.07 92.11 1 0. sodium Ethylene.05 0.32 0.4 1(0.93(1) – 0.2 Detailed Analysis of Process Selection Detailed analysis on Fisher esterification and Tischenko reaction Aspect Overall Reaction Path Raw Material Catalyst Fisher esterification Tischenko reaction The akylation of acetic Dehydrogenation of acid with ethylene ethanol C2 H 5 OH +C H 3 COOH →C 2CHH33COO CHOC→C +H 2C 2 C H25 H OH 2 H 5H 3 COO 2 O C 2 HC 5 2 H 4 +C H 3 COOH → C H 3 COO 5 → C H 3 COO C 2 H 5 +2 H 2 Ethanol and acetic acid acid catalysts (sulfuric Acetaldehyde aluminum alkoxide.24 Weight Weight / Weight EA Price of Component ($/kg) Gross profits ($/kg EA) 28.05 0.93) – 0.68(0.11 1 0.14 1.834) = 0. .045 0.591 2 2 4 0.7.045 7 1.626(1.045) = 0.629 C H 3 COO C 2 H 5 Products 2 H2 1 88. Acetic acid sulfuric acid or solid acid Ethanol Copper Oxide.68 0.4) – 0.11 88.391 88.045(7) + 0.93 Dehydrogenation of ethanol Overall Chemical Equation Reactants 2C 2 H 5 OH Kmole Molecular Weight (kg/kmol) Weight Weight / Weight EA Price of Component ($/kg) Gross profits ($/kg EA) 2 46.93 0.32(0. G hydroxide Hoechst A.G Avada by INEOS. Zinc Oxide.25 acid. 0.391 0. ion-exchange resins). toluenesulfonic acid or Gross Profit ($/kg) Advantages -High product yield rate -High product yield and alternative -low corrosiveness -Simple Technique. maintenance fee for -Not environment friendly equipment as it may -Catalyst is expensive build with ethylene unit which result in high capital cost producealuminium Technology available Hoechst A.332 -2.591 -Technique is advance. Davy technology . para- alkoxide catalyst (Avada process). quality of ethyl acetate water relatively low investment. -Reaction without loss of -Feedstock is quite a small molecules.57 0. -Able to produce high -producing low acid waste Producing cost -Low corrosiveness. energy -Relatively friendly to consumption and pollution Disadvantages -High corrosiveness environment -Only competitive when the -Ethyl acetae unit should which cause high raw material cost is low. few. 26 . it will leads to poor performance of the project and cause losses and damage in various aspect.8. minimize cost of production and distribution as well as for the future expansion of the plant. we have listed three main industrial estates that located at east and south of Peninsular Malaysia. safety. it is also must be taken into consideration in order to maximize profitability of the project.8 It is Project Feasibility and Site Study important to conduct feasibility study before starting plant construction to determine whether our plant is feasible to be built in term of economic aspect. However. For the construction of the ethyl acetate.2 Factors in Selecting Site . 1. Besides.8. Terngganu. 1. The industrial estates are: Teluk Kalong. other factors such as room of expansion and safe living conditions for plant operation as well as surrounding community are also need to be considered. Pahang Pengerang.Johor.1 Site Study Location for the chemical plant plays very important role because it can effect on the plant operation and its success. environmental impact controllability and the flexibility for our plant. Gebeng Industrial Area. Otherwise.27 1. 8. it have to be exported in such a distance. Therefore. the plant site can consequence capital cost.28 A suitable site must be found for a new project. sea and air). 1. The distance between the site and source of supply should be given attention because if the raw material is far from the site. source of this raw material need to be identify and considered. the site and equipment layout planned because for long term period. Here the factors of the final site are choose based on a complete survey of raw material availability and price. the site must be located near to port which has excellent infrastructures and good transportation network.8. the advantages of various geographical areas and last but not least facility and infrastructure of the site. source of power and water. Therefore. good transportation network (via land.4 Land Price Sufficient land must be available for the purposed of plant and future expansion. 1. This is crucial if large volumes of raw material are required for production. operational cost and market price. reasonable land price. The cost of the land and premise also need to be included in .3 Raw Material Availability The production of ethyl acetate uses ethanol and acetic acid as the main raw material. it is essential to consider many factors in selecting site. Thus. this two utilities are very important and their source should be available near to site location to minimize the cost. Table 1. The cost of the land depends on the location and it should be economical as possible to reduce the total investment and construction cost.1 shows industrial tariff by TNB. suitable load-bearing characteristics. Meanwhile. 1. For water supply.8. wells or purchased from a local authority.5 Electric and Water Supply In chemical industrial plant. the geographical of the land should be ideally be flat.29 the site selection because it will affect the final cost of the project. Besides. . Thus. the power supply is easily available and obtained from Tenaga Nasional Berhad (TNB) in Peninsular Malaysia. large quantities of water and electric supply are required for plant operation. process water can be drawn from a river. well drained and contour structure of the land. 00 sen/kWh For the next kWh (201 kWh onwards) per month 44.60 sen/kWh The minimum monthly charge is RM600.LOW VOLTAGE INDUSTRIAL TARIFF For the first 200 kWh (1 -200 kWh) per month 38.20 TARIFF E1 .70 RM/kWh For all kWh 33.MEDIUM VOLTAGE GENERAL INDUSTRIAL TARIFF For each kilowatt of maximum demand per month 29.1 : Industrial Tariff by TNB Table 1.20 TARIFF DS – SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO QUALIFY ONLY) For all kWh 42.00 .60 RM/kW For all kWh 33.30 Table 1.70 sen/kWh The minimum monthly charge is RM600.1 (continued) TARIFF CATEGORY CURRENT RATE (1 JAN 2014) TARIFF D .10 sen/kWh The minimum monthly charge is RM7.70 sen/kWh The minimum monthly charge is RM7.00 TARIFF E1S – SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO QUALIFY ONLY) For each kilowatt of maximum demand per month 23. 31 TARIFF E2 .00 .70 sen/kWh For all kWh during the off-peak period 20.HIGH VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF For each kilowatt of maximum demand per month during the peak period 35.20 sen/kWh The minimum monthly charge is RM600.00 RM/kW For all kWh during the peak period 35.90 sen/kWh The minimum monthly charge is RM600.50 RM/kW For all kWh during the peak period 33.00 TARIFF E3 .50 sen/kWh The minimum monthly charge is RM600.00 RM/kW For all kWh during the peak period 31.50 sen/kWh For all kWh during the off-peak period 21.90 RM/kW For all kWh during the peak period 33.10 sen/kWh The minimum monthly charge is RM600.70 sen/kWh For all kWh during the off-peak period 17.60 sen/kWh For all kWh during the off-peak period 19.00 TARIFF E2S – SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO QUALIFY ONLY) For each kilowatt of maximum demand per month during the peak period 32.MEDIUM VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF For each kilowatt of maximum demand per month during the peak period 37.00 TARIFF E3S – SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO QUALIFY ONLY) For each kilowatt of maximum demand per month during the peak period 29. water transportation (through river. If more incentives are offered. canals or sea) and air transport is considered and accordingly plant location is decided. Important consideration should be that the cost of transportation should remain fairly small in comparison to the total cost of production. a suitable method of transportation like rail.6 Transport Facilities Since freight charges of raw materials and finished goods enter into the cost of production. In fact. therefore transportation facilities are becoming the governing factor in economic location of the plant. 1.8. respectively. The establishment of such factory will have a foreign exchange saving effect to the country by substituting the current imports. this project will generate tax revenue and income for the government in terms of payroll tax.8.32 1. other than creating employment opportunities. it can influence foreign and local investors to invest in the specific area. . Depending upon the volume of the raw materials and finished products. then these incentives will give more feasibility for the plant to be built. The project will also create backward and forward linkage with the chemical production sub sector and the manufacturing sector. In terms of government incentives. storage and shipping are considerable important if the raw material supply and the product distributions are dealing with important and exportation. road.7 Politics and Economics Since new chemical plant is to be build. solids. Besides that. The site selected should have satisfactory and efficient disposal system for plant wastes or effluents such as drainage system and dumping 1. chemicals and other waste products likely to be produced during the production process. Available manpower from local technical institutes will give a beneficial contribution to run the plant smoothly. a favourable cooperative and friendly attitude towards the industry and favourable living conditions and standards keeping in view the availability of medical and educational facilities.9 Availability and Stability of Labour and Services .8 Other Facilities Despite electric and water supply.8. waste and disposal facilities should be taken into consideration. housing. Thorough study should be made regarding disposal of water like effluents. competitive wage rates of workers.33 1. and transport facilities. The few factors to be considered regarding availability of labours and services are: availability of men power of requisite skill. other enterprises which are complementary or supplementary regarding raw materials. other input. labour and skill required. The plant should be placed in an area where sufficient labour supply is available.8. . fire service. inexpensive manpower from the surrounding area will contribute in reducing the cost of operation. recreational facilities. cost of living etc. moderate taxes and the absence of restricting laws. It is one of the most crucial part in plant design as improper design and ways of dumping will resulted in environmental and society problem. Kertih . Bhd..6km from Kuantan Town. Kertih.34 Overview and Comparison of Site Location Table 1. • Chemical plastic • 1011. Johor Bahru Kemaman Town • 5km from •116km from Senai International Kuantan Port. Pahang. RM 14 – 16/ft² Natural Gas from Petronas Gas Sdn.093 hectareshectares • Petrochemical 1500 hectares planned RM 12 .72 hectares 8. Pengerang.15/ft² Natural Gas from RM 8/ft² Natural Gas 4800 hectares. Teluk Kalong. from Petronas Petronas Gas Sdn. Terengganu Kuantan. Airport •407km from KLIA Type of Industries Area Available Land Price Feedstock Sources • Petrochemical •120km from JB • Refinery • Heavy Industries • Chemical and • Petrochemica. • 40km from • 42km from • 9.Johor. Bhd...5: Site location characteristics comparison Selection Criteria Location Gebeng. Gas Sdn. Bhd. Airport •147km to Changi Int. Has capacity of 50 mgd.22GW of TNB 900 Mw (800Mw) electricity and supplies power to • Paka IPP Station YTL the entire PIC complex.3 mgd.35 Water Supply (PGU III pipe line) Kertih. . Energy Sources TNB Tanjung •Pengerang co-generation plant • Kenyir Dam • Paka Power Station Gelang. Kuantan. (PGU III • Semambu Water pipe line) • 77km of pipes from the Sungai • Terengganu Treatment Plant Seluyut Dam to PIPC Waterworks Department capacity of some 75.480t an TNB 400 Mw hour for plants within the complex. 600 MW •It also produced continuous Kenyir Hydro Station supply of steam up to 1. • Industrial Water Production plant upstream Paka River under construction. (PCP) generates 1. • Kuantan Port • Kuala Terengganu •East coast Highway airport • Kertih airport Labour •University Technology MARA •University Technology Malaysia • Kemaman Port •University Technology MARA • Islamic International University (UTM) •Terengganu Advance Institute Malaysia (IIUM) •Polytechnic (TATI) •Polytechnic •Johore Skills Development •Terengganu Safety Training Center (JSDEC) Centre (TSTC) • Expected to employ 70. and recycling plan.000 •Terengganu Plastic Technology workers during construction and Training Center (TPTTC) generate 4.000 new jobs upon Other Facilities •Environment Technology Park completion. Singapore. Incorporating a training centre. waste collection and C4 and C5 olefins . jetty facility with water dept of to coastline traversing Johor Bahru and 24 metres.36 Transport Facilities Main road to •The construction of a deepwater • Trunk roads parallel Kuala Lumpur. handling Very Large Crude • Kuala Terengganu – • Railway Carriers (VLCCs) Kuala Lumpur new • Kuantan Airport highway. •naphtha cracker complex with a Toxic waste treatment - capacity of 3Mtpa of propylene. would facilitate from North to South. 000t of (PBT) • 1-butene.37 processing centre as well as raw •petrochemical and polymer material management and storage complex to produce C4 and C5 facilities. servicing facilities. Ethylene Glycol Ethylene Derivatives Low Density Polyethylene . T MTBE • Polypropylene Ethylene Polyethylene Vinyl Chloride Monomer Polyvinyl Chloride (PVC) Ammonia/ Syngas Acetic Acid Aromatics Olefins Ethylene Oxide. • Propylene • The chemical plants will • Ethanol produce up to 250.000t/y of • Polypropylene hydrogen peroxide. Chemicals Produced • • East coast Highway Acrylic Acid and Esters • Gasoline • Syngas • Diesel • Butyl Acrylate • Polyisobutylene • Oxo-alcohols • Isononanol • Phathalic Anhydride and • non-ionic surfactants Plasticizers • methanesulfonic acid • Butanediol • hydrogen peroxide • Tetrahydrafurane • C4 co-monomer • Gamma-butyrolactone • oxo-products.000t of • Polybutane Terepthalate isononanol (INA) and 110. maintenance and derivates. 220. 38 . gas and petrochemical hub. .000 MTA of ethyl acetate plant at the newly open industrial land.39 1. would facilitate handling Very Large Crude Carriers (VLCCs) and very few Environmentally Sensitive Areas (ESAs) which are easily preserved are affected. Besides that. Figure : Map of Industrial Area in Pengerang Figure shows the map of Pengerang industrial area. Pengerang's Strategic location to international sea lanes and natural attributes such as sheltered harbour and deepwater makes it an ideal location to serve as an oil.8.Singapore – China and its natural attributes such as sheltered harbour and deepwater makes it an ideal location to serve as an oil. gas and petrochemical hub.11 Site Selection After considering the three locations on the basis of several factors. Pengerang. The construction of a deepwater jetty facility with water dept of 24 metres. Strategically located open to the access to existing major international shipping lanes: Middle East . we have decided to build the proposed 50. Johor Bahru based on its competitive advantages for our plant setup and production. Other than that. respectively makes it an promising choice besides having low negative socioeconomic impact as it is relatively unpopulated thus leads to minimal population relocation. . easy access of water and energy supply from 77km of pipes from Sungai Seluyut Dam to PIPC to supply raw water to the complex and Pengerang co-generation plant (PCP) generates 1. new products as well as create countless job opportunities as several of these petrochemical projects take off in the near future. arising from the Economic Transformation Programme.40 Pengerang is one of the largest pieces of investments in the Pengerang district and located on a single plot measuring about 20. The project will house oil refineries. petrochemical plants as well as a liquefied natural gas (LNG) import terminals and a regasification plant. naphtha crackers. will create a more dynamic and progressive oil and gas industry in Malaysia. Malaysia companies will be able to partake with local and foreign investors to invest in new technologies.22GW of electricity and supplies power to the entire PIC complex. The focus on oil and gas projects.000 acres. there were several process routes have been identified in order to produce Ethyl Acetate such as Fisher esterification. After doing the economic potential analysis and considering the advantages. dehydrogenation process of ethanol has been chosen as the process route. Next. step is to determine the suitable process flow diagram from a several PFD exists. safety factor and the raw material availability. disadvantages.2 Process Database Table 2. dehydrogenation process of ethanol. . and alkylation of acetic acid and ethylene. Tishchenko reaction. The database is needed to proceed this step.41 CHAPTER 2 PROCESS SYNTHESIS 2. 2.1 Introduction As discussed in Chapter 1.1 is the summary of all the database for each chemical that involved in this process. ppm STEL.3 Five Key Shynthesis . mg/mm3 Heat of 0 3 0 2 4 2 0 4 0 40 °C 1 3 0 1000 1000 38.1: Relevant Database for chemicals involved Molecular Formula MW. 5.5 -40. °C Solubility in water Viscosity.15(20°C) psig Physical form Boiling point. °C Flash point. -249.42 Table 2.5285 mPa·s at 0 °C) 20 °C).06 1833 Hydrogen H2 2. °C Melting point. 5.21 mPa s at 20 Colourless gas -253 -259 -38.95 kPa (at 20 101 kPa at 20°C - 0.1 Acetaldehyde C2H4O 44.37 -114 16 241 miscible 0.4 kJ/mol 2.6 50 238 377 0.0 334 miscible 0.10 901 kg/m3 Vapour Pressure. g/mol Density (liquid) Ethanol C2H6O 46.1 -84 -4. kJ/mol Heat of fusion. °C Critical point.3668 mPa·s at NFPA Rating (0- HR FR RR 4) TWA.0084 (15°C) Colourless liquid 77.46 15 25 36.117 - 2850 -286 -3239.07 785. cP (25 °C Colourless liquid 78.7 kJ/mol Heat of combustion.123.0012 Pa s (at Colourless liquid 20.02 70.4546 mPa·s at (at 25 °C 20 °C 0.0 260 Soluble 0.7 kJ/mol Heat of formation.99 Ethyl Acetate C4H8O2 88.0 -240 Not soluble 0. deg C °C 0.3 - 0 - vaporization. -1785.001074 Pa s 0.32 - 0.8 . 43 2.2. a maximum of 98–99% of selectivity has been obtained for 60–65% of ethanol conversion. 2. Dehydrogenation of ethnanol was choosen because the reaction can achieved high product yield.1 Step1: Elimination of Differences in Molecular Type For the manufacture of ETAC.2 Step2: Distributions of the chemicals Figure 2. The advantages and disadvantages of each route has been discussed in chapter 1. environmental factor and safety factor.1: Distribution of chemical By using copper chromite catalyst.3. low corrosiveness and produce low acid waste water. never obtained . data from the chemical involving reaction shown in Table 2. This performance. Selection of process being done based on the economic potential.3. 3 Step 3: Elimination on Differences in Composition Figure 2. 10 bars and an ethanol residence time of 97.44 before. elimination of different composition by using pressure swing distillation (PSD) . in one step reaction. Elimination of chemcial is based on decreasing relative volatility so that the most difficult splits are made in the absence of other components (ethanol and ethyl acetate) rather than remove early sequence .000 MTA. those components of greatest molar percentage in the feed.5 g h/mol. ethanol dehydrogenation to ethyl acetate. has been achieved by operating at 220–240 ◦C.3.2: Flowsheet 1. 2. In this project. valuable chemical like pure hydrogen (exempt of CO) and acetaldehyde are produced in mild conditions as by product[1]. has been studied by using the low-cost ethanol availability with copper chromite catalyst to produce ETAC in large scale 50. In this process. extractive distillation has been proposed in the prior art for separating ethyl acetate from ethanol and water. ethanol and water form a ternary azeotrope whose boiling point is also close to that of ethyl acetate. or triethylene glycol for this purpose has been described in US-A-4569726. elimination of different composition by using extractive distillation It is difficult to separate a mixture comprising ethyl acetate. ethanol and water so as to recover substantially pure ethyl acetate therefrom because the boiling points of ethyl acetate and ethanol lie close to one another and both compounds form a binary azeotrope with ethyl acetate whose boiling points are close to that of ethyl acetate. The comparison between two technques is summarized in Table 2. diethylene glycol. while use of an extractive agent comprising dimethyl sulphoxide for the same purpose has been suggested in US-A-4379028. In addition ethyl acetate. PSD technique is selected due to high purity of product can be obtained. .2. PSD technique to break the azeotrope of ethyl acetate-ethanol-water mixtures has been published by European patent EP 1117629 B1. using of an extraction agent comprising polyethylene glycol. In order to overcome this problem. While. pressure swing distillation (PSD) and extractive distillation can be alternatives to break the azeotrope.3: Flowsheet 2.45 Figure 2. 46 Table 2.2: Comparison between PSD and extractive distillation Pressure Swing Distillation More easier to gain high purities Avoid the potential problem of product Extractive Distillation Difficult to attain higher purities May have impurities ( as it involves contamination Higher total annual cost Does not need separating agent High energy consumption Heat integration is straightforward solvent) Lower total annual cost Require solvent for the separation process Lower energy consumption Need temperature differential driving force . 4: Flowsheet with temperature.4 Step 4: Eliminate Differences in Temperature.47 2. and phase change operations in the ETAC process . and Phase Figure2.3. pressure. Pressure. 3 shows possible flowsheet and the process undergoes the following operation: 1. ethanol and water is separated by using pressure swing from moderate pressure of 15 bar to low pressure 1 bar at bubble point temperature according to pattern EP 1 117 629 B1. the product sinks. Light component. hydrogen is removed from flash drum 5. the states are assumed to be fixed and operations are inserted to eliminate the temperature. The azeotrope mixtures of ethyl acetate. reaction at high pressure ( 20 bar to 30 bar) or low pressure (10bar). The pressure of liquid effluent from flash drum is lowered to 1 bar and the temperature is raised to 40˚C 6. however. Its temperature is raised and the dry ethanol vaporize to the reactor temperature. . The hot vapor effluent from the reactor is cooled to -10˚C to condensed the heavy products. pressure. low pressure is chosen as the operating cost could be minimized. 260˚C 3. and the reaction and separation operations. and phase differences between the feed sources. 4. For the reaction. Its pressure is increased to 10 bar to a reactor pressure 2. In this project.48 In this synthesis step. Figure 2. there are two alternatives. 3.5: Flowsheet showing task integration for the ETAC process .49 2.5 Step 5: Task Integration Figure 2. ethanol and ethyl acetate form a minimum binary azoetrope mixture (Pattern EP-A. The other product. The bioethanol is dried first in order to eliminate the water in the ethanol. The separation occur at temperature.50 The production of EA in this plant is based on the dehydrogenation of ethanol process. The distillate from the second distillation column become the feed for the third distillation column. 1 bar and 68. The purpose of this distillation column is to separate ethanol from the remaining ethyl acetate to be recycle back to the reactor. 15 bar. However. According to the distillation theory. The unseparated ethanol and ethyl acetate which is the distillate product of the third distillation column is recycle back to the first distillation column. which are ethyl acetate.0 151 886). unreacted ethanol and water is separated after that. the ethanol is heated up to the desired temperature which is 260oC. 170 oC and pressure. This process involves the catalytic reaction which the catalyst will be placed in the packed bed reactor. The reaction occur at temperature and pressure. Hydrogen is separated based on different phase.. The reactor label as R-101. Then. The second distillation column which labelled as D-102 is used to separate ethyl acetate from ethanol.4 oC respectively. Acetaldehyde is separate after the hydrogen by using the distillation column which label D-101 at pressure and temperature. Hydrogen can be seperated by using two alternatives. Acetaldehyde will become the distillate product and ethyl acetate and ethanol will be separate in the next distillation column. acetaldehyde. water and unseparated ethyl acetate will be the distillate. The product then is separated according to the specific characteristic. not all of the ethanol can be separated. flash drum or phase seperator. . Ethyl acetate will become the bottom product and the ethanol. pressure swing distillation is introduce to the plant as it can break the azeotropes. Phase separator is chosen as there would be no pressure drop during the process compare to flash drum. 260 oC and 10 bar respectively. Therefore. Hydrogen is separate first as it is easier and has large amount. 51 2. operation and maintenance.4. packed bed reactor is effective in high temperature and pressure. The lifespan of the catalyst in the process can last until 3-5 years.5). . The reaction is the dehydrogenation of ethanol in a gas phase. There are several type of reactor which are Continuous Stirred Reactor (CSTR). which at 2600C and at pressure 10 bar. it can produce high yield of ethyl acetate with the present of suitable catalyst. Every reactor have their own characteristic. Catalyst being used in the dehydrogenation process of ethanol is BASF Cu-1234 or known as Copper Chromite.4 Equipment Selection 2. Besides. The average price for the catalyst would be in the range of US $5-30/ kilogram. For the EA plant. there only one reactor due to only one reaction happened.1 Reactor (Packed Bed Reactor) Reactor are vessels designed to contain chemical reaction. Packed Bed Reactor (PBR) has been chosen as it is allowing continuous process (Figure 2. Table 2. Chemical engineer design the reactor to ensure the reaction proceed with the highest efficiency towards the desired product and then producing high yield of the product while requiring least amount of money to build and operates. In addition. This reactor also is easy to build and has low cost of construction.3 shows the characteristic of the catalyst. the characteristic of the reactor which allow the catalytic process made it become chosen as the dehydrogenation process need catalyst. Plug Flow Reactor (PFR) and Packed Bed Reactor (PBR). Other than that. For producing ethyl acetate. The hydrogen then is sell in order to get the benefit.97 21 0. which is vapour-liquid separation.) Sud-Chemie TCuO/CuCr2O 4466 CuO/Cr2O3 =53/45) Basf Cu-1234 CuCr2O4-CuO-CuBaCrO4-Al2O3 45-1-1311-30% b.48 127 0.22 Figure 2.29 1.3: The characteristic of catalyst for dehydrogenation of ethanol Sample Composition given by the companies BASF K-310 CuO-ZnO-Al2O3 40-402-% b.41 1.52 Table 2. hydrogen is produce as by product and flash drum is used to separate the hydrogen from the product which is EA.4. It is used specifically to separate different phase of matter.11 1.2 Flash Separator Flash drum is one of the separation unit in the industrial sector. In this plant.6: Schematic diagram of Peck Bed Reactor (PBR) 2.w.) Surface area (m2/g) Pores volume (cm3/g) Copper dispersion (%) 106 0. .w. Pressure Phase Justification R01 T (°C) 260 .53 2.4. Table 2.5 Process Operating Condition . the unreacted ethanol is recycled back to the feed and it need to be mixed in order to make it become more homogeneous with the incoming feed.4. There are three distillation column used in this plant which label as D-101. The heat causes components with lower boiling and higher volatility to be vaporized.4 Mixer Mixer is a unit operation that involve manipulation of a heterogeneous physical system with the intent to make it more homogeneous. leaving less volatile components as liquids.3 Distillation column Distillation column is the most common separation unit that has been used in any chemical industries. P (bar) 10 Vapour This reactor operates (Dehydrogenation depending on the type of Reactor) – catalyst used.4. 2. Distillation works by the application and removal of heat to exploit differences in relative volatility. In this plant. 2. The remaining acetaldehyde is recycle back to the second distillation column.4: Operating Process Condition Equipment Temperature.D-102 and D-103. Mixture with high relative volatility are easier to separate. For commerical Packed Bed copper/copper chromite . 5%). Table 2. supported on alumina (PBR) and containing barium chromite as promoter.4 (Continued) D-101 68. the products such as EA. From bottom stream of distillation Distillation column 1. The column 1 acetaldehyde is separated as overhead in this distillation column. it is preferable to operate the reactor at high temperature and pressure in order to reach a high ethanol conversion (65%) and high selectivity of EA (ethyl acetate) (93% . Since the reactor temperature is high. EA and other products will be separated at bottom stream and D-102 170 15 Mixture flows to next distillation column. Meanwhile. the reactor should be design well with suitable PS-01 34 10 Phase Separator Mixtur materials for construction. and water are then sent to second distillation column C-101 for separation between EA (bottom .4 1 Liquid Distillation column 1 was functioned Distillation as acetaldehyde flash drum.54 Tubular Reactor catalyst. column 2 ethanol. Acetaldehyde and other e products are separated as liquid bottoms stream in flash drum and then sent to next distillation column while hydrogen will be removed as vapour distillate stream.98. EA will be separate at overhead stream to be recycled to E-0 1 260 10 Liquid distillation column 1.4 (Continued) H-02 170 15 Liquid Heater 2 Product from bottom stream of distillation column 1 will be heated to 170oC before C-01 34 10 Vapor cooled to 34oC and then will be Cooler 1 C-02 76 15 Liquid Cooler 2 C-03 entering distillation column 3. Besides. Before recycled to distillation Cooler 3 column 1. Product from reactor will be sent to flash drum. However. Product from overhead stream of Liquid Distillation distillation 2 will enter distillation column 3 column 3 in order to recover large amount of ethanol to be recycled to reactor. overhead stream will C-04 Liquid be cooled to 40. there are still EA component D-103 76 1 flow to overhead stream. Overhead product produced from distillation 2 are cooled in 25 15 Liquid E-104.4 25 25 1 1 1 . Ethanol feed and recycled ethanol are Evaporator mixed and then sent to E-100 for H-01 heating to 260oC. Mixture is cooled from 72.4 1 Liquid will be heated to 68.oC.55 product) and other heavy key components (overhead product).4oC. The bottom product from flash drum 68.4 to Liquid 68 oC Mixture is cooled from 78 oC to Liquid 25 oC This mixer comprises stream Cooler 4 C-05 Cooler 5 M-01 68. Heater 1 Table 2. Liquid stream from mixer 1 25 1 to 10 Liquid Pump 1 will be pump to 10 bar and will P-02 enter evaporator directly. Pump 3 poduct from pump 2 will be V-01 pump to 15 bar. 71. External heater to ensure that the temperature in reactor is maintained at 260 oC .. This 2 valve are required to reduced a pressure product from distillation 2 from 15 bar to 1 bar and stored to storage XC-01 260 Liquid tank.6 8 to 15 Liquid bar.6 1 to 8 Liquid Pump 2 bottom poduct from distillation column 1 will be pump to 8 P-03 71. This 2 valve are required to reduced a pressure product from distillation 2 from 15 bar to 1 bar and then will be sent to V-04 25 15 to 7 Liquid Valve 4 V-05Valve 5 25 7 to 1 Liquid distillation column 3. Before entering Distillation 2.4 1 Liquid feed. Overhead stream of distillation Mixer 2 column 3 and bottom stream of P-01 phase separator will be mixed. Before entering Distillation 2.56 Mixer 1 from bottom product of distillation column 3 and fresh M-02 68. Valve 1 will reduced a pressure 34 10 to 1 Liquid Valve 1 bottom flash drum from 10 bar to 1 bar before entering V-02 & V-03 74 15 Liquid Valve 2 & 3 distiilation 1. ethanol and water) from product stream in order to get high purity of desired product which is ethyl acetate. liquid-liquid extraction. azeotropic. while the last column is used to separate the unreacted ethanol to be recycled to reactor.. reactive) distillation. stripping.5 Heuristics Applied for PFD Heuristics 4: Introduce purge streams to provide exits for species that enter the process as impurities in the feed or are formed in irreversible side reactions. add separators to recover valuable species or add reactors to eliminate toxic and hazardous species. A large amount of hydrogen need to be removed before entering distillation column because it will increase energy required and make a separation process difficult. The first column is used to separate acetaldehyde from product stream. The unconverted ethanol are recycled and in kept of safe handling before being treated or sold. Heuristic 9: Separate liquid mixtures using distillation.57 2. In step 4 of choosing the Process Flow Diagram (PFD) to eliminate the differences of temperature. PFD 1 is chosen because it attempt to eliminate the . Heuristic 43: To increase pressure of a stream. pressure and phase. unless refrigeration is needed. The flash drum column is used to separate hydrogen from acetaldehyde and other products. pump a liquid rather than compress a gas. enhanced (extractive. even in small concentrations. Heuristic 5: Do not purge valuable species or species that are toxic and hazardous. flash drum and distillation column is used to recover byproducts produced such as hydrogen. The second column is used to separate azeotrope mixture (ethyl acetate. acetaldehyde. Meanwhile. There are one flash drum and three distillation column that is used to separate the chemical components. and others. when these species are in trace quantities and/or are difficult to separate from other chemicals. crystallization and/or adsorption. This result in the capability of using a pump to compress a liquid rather than using a compressor to increase .58 differences in pressure first before attempting to eliminate the differences in temperature and phase. Below are the guidance followed when performing material balance calculation.1. highest yield of ethyl acetate can be obtained.000 MTA of Ethyl Acetate with molecular weight of 88 kg/kmole.1 Procedure for Material Balance Calculation There are several rules of thumb to be followed. . 3.1 Material Mass Balance The plant is designed to produce 50. By feeding dry ethanol to reactor at optimum condition.59 CHAPTER 3 MATERIAL AND ENERGY BALANCES 3. This production plant is mainly to produce ethyl acetate by reaction of dehydrogenation of ethanol. (a) Flowchart is constructed and all given variable values are filled in. If one such quantity is given.60 (b)A basis of calculation need to be done in order to know the amount or flowrate for each stream. it is usually most . if not. If no reactions occur and there are N species present.. they needed to be converted to one basis or the other method. a total mass flow rate and component mole fractions or conversely). either the problems is underspecified or a relationship between the variables not yet put in consideration. When the value of an unknown has been calculated. all subsequently calculated quantities will then be correctly scaled. normally it assumes the amount of a stream with a known composition. lie out the problem solution.61 convenient to use it as basis of the calculation. Unknown and relations among them are identified. the value should be . there are still more information to be gathered (the flow chart may not consist the all required information). (d)Problems are being book kept.g. (e) Known stream volumes or volumetric flow rates will be converted to mass or molar quantities using tabulated densities or gas laws. (h)Material balance equations are written. (i) Equations derived in step (g) and (h) are solved for the unknown quantities. particularly mass and molar flow rates and mass or mole fractions of the stream components are labeled. if not. either on each component or on total mass or moles and all but one species. Balances are written in order such that those involve the fewest unknowns. Relationship between unknown quantities in the labeling should be incorporated as well. (f) For given mixed mass and mole units for a stream (e. they are translated into equations in the variables defined in step (c). If no amounts or flow rate is specified. (c) All unknown stream variables on the chart. (g) For information that is given in the problem but has not been used in labeling the flowchart. If the number are equal. there will be the most N balances. This value then will be put in the flowchart. Input = total mass enters through system boundary Generation = total mass-produced within the system Output = total mass leaves though system boundary.1.Consumption = Accumulation Where.2 Assumption of Material Balance Calculation Mass balance is the basis factor needs to be considered for designing a chemical plant. They are: . Consumption = total mass consumed within the system Accumulation = total mass build up within the system In this manual calculation. they must be scaled 3. Unit operation Min (kh/hr) Mout(kh/hr) The general mass balance equation is: Input + Generation . there are a few assumptions made and needed to be highlighted.Output . (j) If a stream quantity or flow rates was given in the problem statement and another value Q was either taken as a basis or calculated for this stream. mass balance is consists of two parts: calculated manually and carried out by using simulation program.62 written down in the flowchart immediately. During our design. This value will then be substituted for calculation of unknowns in any equations. The basic concept that is applied for manual calculation is based on the general balance equation. the initial setting of the material balance parameter is given as following. . Thus. 3. expander.1.3 Manual Material Balance Target production of Ethyl Acetate is 50.64 kmol/hr EA The summary of the result of manual calculations regarding the material balance is given in the table below from table to table. The total input of any substance either to pump.000 MTA. mixer. The system is steady state. Operating days for the plant is 350 days. valve.63 This plant design is based on a basis of 50. Catalyst used in reactor do not contribute in mass. No leakage in pipes and vessel in the system. or heat exchanger is assumed equal to the total output of the substance where no reaction occur in that devices. The entire components in the system behave as ideal gas. 24 hours a day.000MTA of Ethyl Acetate production. the desired production of Ethyl Acetate is. ¿ 50000 MT 1000 kg 1 year 1 day 1 kmol × × × × year 1 MT 350 days 24 hr 88 kg = 67. For the production of 50000 MTA Ethyl Acetate. 761 8 3438.1.00 Mass Balance for Reactor.008 10343 0 0 150.000 0.000 0.000 6904.000 0.000 224.3.1 10343 0 4 74.000 0.0 0.000 0.000 0 88.000 0 46.0 0.09 0.1 74.008 3438.9 0.000 0.000 0.1 Compone nt H2 Acetaldehy de EA Ethanol 3. R-01 .3.1 0.761 9 1 .0 0. M-01 Stream 1 Stream 29 Stream 2 (Freshfeed) kmole/ kg/hr hr (Recycle) kmole/ kg/hr hr (Outlet) kmole/ kg/hr hr 0 44.09 4 6904.2 Mass Balance for Mixer 1.000 0.85 0.64 3.000 0.000 150.000 0.000 0.1 MW 2.9 1 224.85 .1. 1365 5 5 Acetaldeh yde EA Ethanol 3.0000 0. FS-01 .3.152 kmole/hr kg/hr 2 0. EA = 93% Acetaldehyde = 7% Compone nt H2 Stream 4 (Inlet) MW Stream 5 (Outlet) kmole/h kg/hr r 146.8506 0.3 Mass Balance for Phase Separator.1.0077 10343.2307 67.0000 0.8507 10343.042 450.136 224.0951 10343.0000 9 292.3058 44 88 46 0.1510 5980.1288 10.6977 303.0000 0.65 1) Reaction path: C2H5OH ↔ C2H4O + H2 C2H5OH + C2H4O ↔ C4H8O2 + H2 2C2H5OH ↔ C4H8O2 + 2H2 (Overall Equation) 2) Conversion = 65% (Ethanol) 3) Selectivity.9612 78.5846 3620.0001 224. 1.0 67.374 8 101. M-02 .13 0.1 77.857 3 5878.4 00 78.70 00 88.698 303.06 9 489.836 57 9854.9 00 46.0 3 6 2 09 155.3.63 66.04 3620.0 3 292.44 2.155 81 39.585 1.4 Stream 6 (Inlet) MW 2.15 kg/hr Stream 7 (Overhead) kmole/ kg/hr hr 143.151 1.806 03 3580.0 10.862 147.231 450.981 27 Mass Balance for Mixer.306 1 41 60.482 4.965 389.6 8.67 287.00 kmole/h r 146.095 10343.961 5980.66 Componen t H2 Acetaldeh yde EA Ethanol Total = 3.3 Stream 9 (Bottom) kmole/h kg/hr r 0 44. 000 0 0.7 44 94 0.61 99 1086.8569 0.4823 8.9 45 9854.5 Mass Balance for Distillation 1.3.9646 (Overhead) kmole/ kg/hr hr 4.4 66 4666. D-01 Compone M nt W H2 Acetaldeh 2 44 Stream 12 Stream 13 Stream 14 (Inlet) kmole/ kg/hr hr 4.008 6 0.857 63 389.482 4. 83 66.964 2 0 0.74 63 389.80 02 5878.0419 .482 4. 44 179. 43 101.8 MW t H2 Acetaldeh yde EA Ethanol Total = 3. 60 155.4823 8.8578 2.7 0 0. 57 77.1.60 84 1085.0010 3 389.81 44 5879.762 88 66.0000 0.7 317 8.83 90 3580. 88 66 23.964 (Outlet) kmole/ kg/hr hr 2. 46 86 23.964 (Bottom) kmole/ kg/hr hr 2.5 45 1094 82 80 80 02 99 0.041 317 8.856 634 389.67 Componen Stream 27 Stream 11 Stream 12 (Recycle) kmole kg/hr /hr (Inlet) kmole/ kg/hr hr 2. 179. 88 0 99.2 Mass Balance for Distillation 2.000 64. 1 5 69. 0.69 68 total = 3.000 0.36 0.1.80 0.508 66.91 5 164.09 0 99.1 4 6 10297.6 9 7 9 8 Compone M nt W H2 2 Acetaldeh yde EA Ethanol Total = .001 64.877 8 4594.771 4524.37 46 7 164.810 8 5703.000 44 0.6 03 176.30 5 5771.37 9 4525.3.68 yde EA Ethanol 66.000 5702.000 0.5672 29 643.4 2.6 36 10297 9 98.000 (Bottom) kmole/ kg/hr hr 0. 88 .009 98.814 5 5879.81 0.6 88 4 101.000 0. 0.001 0.042 0.3 46 46 5 10940.0044 9 72. D-02 Stream 17 Stream 18 Stream 22 (Inlet) kmole/ kg/hr hr 0.042 5703.60 83 14. 1.87 27 4594.3 64.44 7 4666.000 (Overhead) kmole/ kg/hr hr 0. 1. 76 8 3438.008 0.7628 1085.9 1 74. D-03 M W EA Ethanol kmole/ hr 0.008 0.0077 3438.9 46 92 98.37 85 4525.000 0.76 0.000 kg/hr 0 0.69 3.0000 0 0.7706 4524.36 0.60 0.61 96 1086.1.0416 9 0.2 kg/hr Stream 26 2 Acetaldehy de Stream 21 (Inlet) Energy balance 3.0000 44 9 0.0416 0 0.000 0.9 89 97 82 00 07 96 total = 3.000 0.0000 0 0.2.000 (Bottom) kmole/ hr 0.9 7 23.0000 88 8 98.3.1 Energy Balance Calculation Methods .7 86 23.000 0.6 Componen t H2 Mass Balance for Distillation 3.8 06 74.000 Stream 28 (Overhead) kmole/ kg/hr hr 0. 70 In designing, it is important to determine the overall energy requirement for the process. Manual calculation for energy balance begins with the mixer and ends up with the distillation columns. A few assumptions has been made which are: The process system is a steady state Potential and kinetic energy is neglected All equipment is in steady state condition Standard reference state for enthalpy is P = 1 bar and To = 298.15 K. Adiabatic process where no heat loss to the environment. All the liquid and gas heat capacities are constant at certain temperature So, the law become Q = ΔH = ΣnoĤo - ΣniĤi Where Q = heat duty no = flow rate at outlet stream Ĥo = specific enthalpy at outlet stream ni = flow rate at inlet stream Ĥi = specific enthalpy at inlet stream Each enthalpy calculation is different depend on the phase for the stream. If the phase is in vapour phase, the specific enthalpy is calculated by using the equation; H v (T, y)  H f  H T   y k H f ,k (T1 )   y k  Cp k (T)dT T2 k k T1 If the phase is in liquid form, the specific enthalpy can be calculated by the equation; 71 H L (T, x )   x k (H f ,k   Cp k ( )d  H kvap (T)) T k T0 Where: H kvap (T )  H kvap (Tb )[ (Tck  T ) 0.38 ] (Tck  Tb ) If the stream is in the liquid-vapour mixture form, the specific enthalpy can be calculated by using Equation H(T, z )  H V (T, y)  (1  ) H L (T, x ) 3.2.2 Manual Energy Balance Calculation This section shows the example of the energy balance of certain equipment in this plant. Component Hydrogen A 27.14 Cp Constant B C D Tb (K) Tc (K) 3 9.27E-03 -1.38E-05 7.65E-09 20.35 33.2 7.716 7.235 9.014 1.82E-01 4.07E-01 2.14E-01 -1.01E-04 -2.09E-04 -8.39E-05 2.38E-08 2.85E-08 1.37E-09 293.55 350.25 156.6 461 523.2 516.2 Acetaldehyd e Ethyl Acetate Ethanol 72 Evaporator, E-01 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Flow Rate (kmol/hr) 0 0 0.053 223.6896 Inlet Temperature (°C) Outlet Flow Rate Temperature (kmol/hr) 0 0 0.053 223.6896 25 -5.96E+07 (°C) 260 -4.82E+07 (kJ/hr) 1.15E+07 Reactor, R-01 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty (kJ/hr) Phase Separator, FS-01 Inlet Flow Rate Temperature Outlet Flow (kmol/hr) 0 0 0.053 223.6896 (kmol/hr) 145.3982 10.1779 67.6632 78.2914 (°C) 260 -4.82E+07 Rate Temperature (°C) -4.50E+07 3.14E+06 260 7671 2.14E+06 Temperature Rate (°C) (kmol/hr) 0.7822 68 100.3667 1.4695 8.0000 0.73 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Inlet Flow Rate Temperatur Outlet Flow Rate Temperatur Outlet Flow Rate Temperatur (kmol/hr) 145.6632 78.4695 8.5128 77.3982 10.2914 (kmol/hr) 142.1E+07 e (°C) 30 -8.8573 (kmol/hr) 2.11E+05 (kJ/hr) Distillation 2.40E+07 -4.4341 stream(kJ/hr) Heat duty e (°C) 30 -1.9058 -3.4695 8.7703 -5.1E+07 stream(kJ/hr) Heat duty ure (°C) (kmol/hr) 2.8112 66.40E+07 Distillation Column 1.0635 47.2 1.6761 -6.9287 1.1779 67.87E+05 (kJ/hr) e (°C) 30 -5.7187 71.8112 68. D-01 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Inlet Flow Rate Temperatu Outlet 1 Outlet 2 Flow Temperat Flow (kmol/hr) Rate re (°C) 2.1504 0.7E+07 8.6 98.0441 66. D-02 Component Inlet Flow Temperat Outlet 1 Flow Tempera Rate Rate (kmol/hr) ure (°C) (kmol/hr) Outlet 2 Flow ture (°C) Rate (kmol/hr) Temperatu re (°C) . 4148 73.7187 98.0441 0.48E+06 (kmol/hr) 0 0 1.89E+07 2.2 .54E+07 (kmol/hr) 0 0.49E+07 stream(kJ/hr) Heat duty 0 0 64.2205 97.81E+05 (kJ/hr) Distillation 3.0441 2.8 -6.7703 -5.74 Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty 0.8 1.2789 -2.99E+07 -9.9319 re (°C) 188.8 -1.0441 2.8 97.0441 66.4982 188.40E+07 0 0.3469 ture (°C) 167.8057 23.2789 ure (°C) 77 -2.4914 -2.2205 167.50E+05 CHAPTER 4 SIMULATION OF MASS AND ENERGY BALANCE4. D-03 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty(kJ/hr) Inlet Flow Temperat Outlet 1 Flow Tempera Outlet 2 Flow Temperatu Rate Rate Rate (kmol/hr) 0 0.0000 170 0. This simulator we invented and developed by Aspen Technology Inc. This accurate modeling of. 4.75 4. distillation of chemically reactive compounds. The computer simulation is carried out after performing the material and energy balance manually. optimisation. The simulation results were compared with the manual calculation to get the percentage error of the calculation.1 Process Simulation ASPEN is a process simulation software package widely used in industry worldwide. ASPEN can handle very complex processes. including multiple-column separation systems.8 as our process simulator. we are using AspenOne Plus V8. Given a process design and an appropriate selection of thermodynamic models. chemical reactors. improvement. This information can then be used in an iterative fashion to optimize the design. and ASPEN has a large data bases of regressed parameters. The obtained mass and energy balances give insight into interdependencies of different process steps. thermodynamic properties is particularly important in the separation of non-ideal mixtures. Aspen Hysys. Process simulation is used to analyse every unit operations in plant as well as their combination to complex processes. and scale-up of processes. gPROMS) which are also applicable for process simulation For our study. and even electrolyte solutions. There is another Industrial standard process simulation software tools (Aspen Plus. The simulation results are valuable for design.2 Selecting Thermodynamics Model . ASPEN uses mathematical models to predict the performance of the process. The property packages available in Aspen plus allow you to predict properties of mixtures as shown in Figure 4. For this study.76 When faced with choosing a thermodynamic model.1: Selecting flowsheet of thermodynamic model . Figure 4. it is helpful to at least a logical procedure for deciding which model to try first. NRTL is chosen as the process involves with non-ideal mixtures (azeotropic mixtures) of ethanol and ethyl acetate. Elliott and Lira (1999) suggested a decision tree as shown in Figure 1-5.1. 963 3457.844 4635.9764 9753.3 Comparison between Manual Material Balance and Simulation The results obtained by manual calculation and simulation is compared to get the error deviation.18 10276.18 522.86 10311.881 3457.844 4635.28 619.012 1177.18 10276.844 5676.18 10276.963 Error % .205 9753. The formula to calculate the percentage error as below: Error % = [ Manual Calculation – Simulation Result] x 100% Simulation Result Table 4.86 10311.844 4635.2: Comparison of manual material balance and simulation results 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 Manual Calculation Simulation (kg/hr) (kg/hr) 6818.881 1177.205 9753.86 4635.86 10311.4234 10311.77 4.218 10276.205 10931.18 10276. 957 10 -5.424 2 -5.749 8 -9.40E+07 -0.45E+07 0.63E+06 -19.80E+07 -0.96E+07 -6.72E+07 0.426 7 -8.55E+07 -2.51E+07 0.53E+07 1.3: Comparison of manual equipment heat duty and simulation Stream Manual(Kj/Hr) Simulation(Kj/Hr) Percentage Error (%) 1 -4.72E+07 -5.98E+07 -6.45E+07 0.69E+07 5.588 19 -2.19E+07 3.4 Comparison between Manual Energy Balance and Simulation Table 4.50E+07 -4.735 11 -5.82E+07 -4.11E+06 19.19E+07 3.69E+07 5.71E+07 -5.253 6 -1.56E+07 80.11E+07 2.54E+07 -2.71E+07 -5.40E+07 -5.106 18 -2.895 23 -2.11E+07 -6.32E+07 -5.14E+06 -2.642 4 -4.317 22 -2.10E+07 5.11E+06 17.41E+07 -5.670 20 -2.493 21 -2.687 13 -3.284 5 -4.35E+07 0.72E+07 0.49E+07 -2.87E+07 -0.747 16 .72E+07 -5.89E+07 -2.025 9 -5.693 14 -5.462 3 -5.78 4.050 15 -5.54E+07 -2.159 17 -5.471 12 -6.17E+05 -1.69E+07 5.92E+07 -3.09E+07 -5.40E+07 -5.195 0.01E+07 -4.87E+05 -1.01E+07 -1. The simulation software used the different correlation and equations to calculate the energy balance. which is acceptable.5 24 -2.411 25 -2. several stream had shown larger errors compared to simulation results. Thus it can be concluded that the assumption made in the system are reasonable and acceptable for the calculation.10E+07 5.79 4.93E+07 -3. stream 6 give significant error due to the mixture in the stream contain 2 phase of mixture (liquid and gas) in which more detailed correlation and equation is needed .2. For the energy balance.10E+07 5.93E+07 -3. the total mass flowrate calculated by manual calculation is not significant different compare to the simulation data. which is NRTL includes the effect of temperature and pressure whereas using the data proposed. Moreover. The percentage error is not more than 5%. it was calculated based on the data from yaws' handbook of thermodynamic and physical properties of chemical compounds. we only consider the temperature different. This is due to the differences of reference points and thermodynamic properties which were applied between the data we use in manual calculation and simulation.411 Simulation Conclusion and Remarks From the table 4. icis. I.com/resources/news/2010/08/16/9385165/projects-sipchem-rhodiaplan-saudi-etac-project/ [10] Chemical market insight and foresifgt – on a single page ethyl acetate.80 REFERENCE [1] [2] [3] [4] [5] [6] [7] Overall Ethyl Acetate Supply Registered 4% YoY Increase in 2012.co.icis. A. L. Saudi Arabia.platts. (2013.com/news-feature/2015/petrochemicals/asia-petrochemicaloutlook/acetic-acid .pdf [11] Kelley. D. (2010).htm [9] Jagger.html [8] http://incolors.org/en/content/articlehtml/2003/gc/b304290c [14] http://www.club/collectionedwn-ethyl-acetate. Mirasol. Leaps of innovation. F. at Europe. US Chemical profile: Ethyl acetate Retrieved from http://www. Retrived from http://www.com/resources/news/2012/02/13/9531149/us-chemical-profileethyl-acetate/ [12] Ethyl acetate Europe prices. December 20). Retrieved from http://www.icis. Rhodia will target etac from the planned project in Al-Jubail.icis. markets & analysis.com/resources/news/2013/05/26/9672001/chemical-profile-asiaethyl-acetate/ [15] http://www. Retrieved from http://pubs.rsc.com/resources/news/2013/05/26/9672001/chemical-profile-asiaethyl-acetate/ [16] http://www. Retrieved from http://mcgroup. (2003).com/userfiles/CNF%20Samples/eac_13_11.icis. Retrived from http://orbichem.uk/news/20131220/ethyl-acetatesupply-registered-4-yoy-increase.com/chemicals/ethyl-acetate/europe/?tab=tbc-tab2 [13] Dobson. (2012). G.orbichem. 3013 (1923) [25] http://davyprotech.com/what-we-do/licensed-processes-and-coretechnologies/licensed-processes/ethyl-acetate/specification/ [26] Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts E.icis. C. 45.com/S1003995309600487/1-s2. Russ.0-S1003995309600487-main. Santacesaria∗. Carotenuto.com/resources/news/2012/02/13/9531149/us-chemical-profileethyl-acetate/ [21] Synthesis of ethyl acetate by esterification of acetic acid with ethanol over a heteropolyacid on montmorillonite K10 http://ac. DOS 2. Child and H. plats mcgrill [19]http://www. Tishenko. J.elscdn. Am. Adkins. 38. W.. Di Serio [27] [28] [29] [30] [31] [32] [33] .pdf [20] http://www.com/resources/news/2006/07/25/2015325/chemical-profileethyl-acetate/ [18] biofuelscan.pdf? _tid=0a4d974a-ddf7-11e5-97a700000aab0f01&acdnat=1456649060_bd189dec3bd06fe929005fa7869ce504 [22] Hoechst A. R.81 [17] http://www. M.. Phys. Soc. J.545.845 (1977) [23] [24]W.icis.com/userfiles/KICHEM %202012/KICHEM2012_3_Acetyls_KW. Soc. Tesser. Chem.G. Chem. 398 (1906). 3 Process Flow Diagram with Complete Stream Table .1 Material Balance Calculation A.2 Energy Balance Calculation A.82 APPENDIX A MATERIAL AND ENERGY BALANCES A. 000 kmole/h kg/hr 0.090 0 74.008 10343.99 224.00 0.98 0.000 44.000 H2 Acetaldehyd 2.090 0 6904.851 36 EA Ethanol Pump P-01 .008 3438.1 Material Balance Calculation Mixer M-01 Stream 1 and 29 → Stream 11 Sample Calculation (Ethanol) F2 = F1+ F29 = 150.000 0.761 9 3438.1 0 150.000 6904.000 0.761 = 224.851 29 10343.000 0.14 0.000 0.14 74.000 0.761 6 224.000 0.000 0.000 0 46.83 A.000 (Recycle) Stream 2 (Outlet) kmole/hr kg/hr 0.00 e 0 88.000 0.000 0.851 kmol/hr Component MW Stream 1 Stream 29 (Freshfeed) kmole/h kg/hr r 0.00 0.09 + 74.000 0.1 150.000 r 0. 008 10343.008 10343.000 0.000 0.000 224.136 .000 0.129 10343.000 0.000 0.129 10343.000 0.000 0.136 0.000 0.129 10343.851 224.000 224.851 224.000 0.000 224.008 10343.851 0.000 0.129 10343.000 Stream 4 (Outlet) kmole/hr kg/hr 0.851 224.008 10343.84 Assuming mass in = mass out Stream 2 → Stream 3 Component MW H2 Acetaldehyd 2 e EA Ethanol 44 88 46 Stream 2 (Inlet) kmole/hr kg/hr 0.851 0.000 0.851 0.000 0.136 0.851 0.000 0.000 Stream 3 (Outlet) kmole/hr kg/hr 0.136 Evaporator E-01 Assuming mass in = mass out Stream 3 → Stream 4 Component MW H2 Acetaldehyd 2 e EA Ethanol 44 88 46 Stream 3 (Inlet) kmole/hr kg/hr 0.851 224.000 0.000 224. 65.2ζ Based on conversion of ethanol = 0.000 e EA Ethanol 44 0.2ζ = 0.000 224.65 ζ = 73. (C2H5OH)in .0765 kmol/hr Outlet 0 + 2ζ .85 Reactor R-01 Stream 4 → Stream 5 Reaction path: C2H5OH ↔ C2H4O + H2 C2H5OH + C2H4O ↔ C4H8O2 + H2 2C2H5OH ↔ C4H8O2 + 2H2 (Overall Equation) The calculation were based on overall equation.851 0+ζ (C2H5OH)in .000 0 88 46 0. Component MW H2 Acetaldehyd 2 Inlet kmole/hr 0. 153 kmol/hr Moles Ethanol left = 223.2307 67.8507 10. the product formed have the following selectivity.3058 Stream 6 (Outlet) kmole/hr kg/hr 146.6991 x 88) x 0.3058 44 88 10.5846 .6991 x 88) x 0.86 Thus.1529 292.1365 Cooler C-01 Assuming mass in = mass out Stream 5 → Stream 6 2 Stream 5 (Inlet) kmole/hr kg/hr 146.698 kmol/hr However.6991) = 146.0077 10343.0951 10343.5846 3620.1529 292.1365 450.0001 224.3058 0.5846 450.93] + 4.8266 kg/hr Component MW H2 Acetaldehyd 2 e EA Ethanol 44 88 46 Stream 4 (Inlet) kmole/hr kg/hr 0. EA = 93% of weight Acetaldehyde = 7% of weight Therefore.9612 Component MW H2 Acetaldehyd e EA 450.79 .9612 10.0000 Stream 5 (Outlet) kmole/hr kg/hr 146.2307 67.0000 0.0425 0.6977 303.1510 5980.1510 5980. according to journal.8506 224.1510 5980.664 = 5954.0000 0. Weight of EA produced = [(72.2307 67. Moles H2 produced = 0 + 2 (72.0000 0.1288 10343.2 (72.3600 kg/hr Weight of Acetaldehyde produced = (72.07 = 447.6991) = 78.1529 292.9612 78. 0951 10343.0951 10343.0425 3620.6977 303.87 Ethanol 46 78.0425 3620.1365 78.6977 303.1365 . 0356 6.6706 ) 2.9809 0.0616 66.0159 5. T in Celcius Guess 2 = 0.1024 1.2307 67.205 208.514 P°k (bar) αk/n 535.7 4. k = ξk H2 Acetaldehyd e EA Ethanol νk (kmole/hr)  k / n n 1  ( k / n  1) n lk xk × (kmole/hr yk xk 0.1183 373.1814 1070.9769 0.88 Phase Separator FS-01 Stream 6 → Stream 7 and Stream 9 Component Flowrate (kmole/hr) H2 Acetaldehyd 146.0170 0.0000 0.8057 77.0568 αk/n 0.0079 0.9830 143.8617 147.1555 0.1599 0.1343 1.1115 0.5078 C 275.4283 0.4341 0.9381 0.1529 e EA Ethanol 10.92365 1238.94928 B 67.13428401 P = 10 bar T = 30 0C = 303. k/n = P0k / P0n The recoveries of non key component.4990 0.15 1410.0478 0.0059 0.8360 155.1314 1.0093 0.0783 0.0109 total = .6977 Antoine Constant A 2.4823 0.21248 4.15 K Relative volatility.0568 1.6 236 4.46 217.8569 0. P in bar.3738 8.9612 78.0714 log P = A-B / (T+C). 89 Component H2 Stream 7 Stream 6 (Inlet) MW (Overhead) Stream 9 (Bottom) kmole/hr kg/hr kmole/hr kg/hr kmole/hr kg/hr 2.000 146.153 292.306 143.671 287.341 2.482 4.965 44.000 88.000 46.000 10.231 67.961 78.698 303.043 450.151 5980.585 3620.095 10343.136 1.374 1.155 0.862 147.062 60.448 101.681 39.639 489.109 8.857 66.806 77.836 155.981 389.703 5878.903 3580.457 9854.027 Acetaldehyd e EA Ethanol Total = Determine the pressure and temperature by bubble point calculation. Bubble point calculation:  = Pk/n / P02 = 1.64575 Pk (T )  T  =  x*k/n = 30.0014 k /nP 1x10   1.6457 6.0763  1070.6  (236)  34.0101C (4.1814  log 1.64575) Expander EX-01 Assuming mass in = mass out Stream 7 → Stream 8 90 Component MW H2 Acetaldehyd 2 44 e EA Ethanol Total = 88 46 Stream 7 (Inlet) kmole/hr kg/hr Stream 8 (Outlet) kmole/hr kg/hr 143.671 287.341 143.671 287.341 1.374 1.155 0.862 147.062 60.448 101.681 39.639 489.109 1.374 1.155 0.862 147.062 60.448 101.681 39.639 489.109 Valve CV-01 Assuming mass in = mass out Stream 9 → Stream 10 Component MW H2 Acetaldehyd 2 44 e EA Ethanol Total = 88 46 Heater H-01 Assuming mass in = mass out Stream 10 → Stream 11 Stream 9 (Inlet) kmole/hr kg/hr Stream 10 (Outlet) kmole/hr kg/hr 2.482 4.965 2.482 4.965 8.857 66.806 77.836 155.981 389.703 5878.903 3580.457 9854.027 8.857 66.806 77.836 155.981 389.703 5878.903 3580.457 9854.027 91 Component MW H2 Acetaldehyd 2 44 2.482 8.857 4.965 389.703 2.482 8.857 4.965 389.703 88 46 66.806 77.836 155.981 5878.903 3580.457 9854.027 66.806 77.836 155.981 5878.903 3580.457 9854.027 e EA Ethanol Total = Stream 10 (Inlet) kmole/hr kg/hr Stream 11 (Outlet) kmole/hr kg/hr Mixer M-02 Stream 11 and 27 → Stream 12 Sample Calculation (Ethanol) F12 = F11+ F29 = 23.609 + 77.836 =101.44 kmol/hr Stream 27 Component H2 M W Stream 12 hr 2.4823 4.9646 (Outlet) kmole/ kg/hr hr 2.4823 4.9646 kmole/ kg/hr 2 0 0.0009 0 0.0416 17 8.8568 34 389.70 17 8.8578 34 389.74 44 88 46 0.0086 4 0.7628 84 66.805 29 5878.9 3 66.814 45 5879.6 Acetaldehy de EA (Recycle) kmole/ kg/hr hr Stream 11 (Inlet) 608 47 1085. .99989 0.03 1 bar 1 bar * We choose ethyl acetate as the example for calculation i.618 96 1086.836 03 3580.59 53 10940.44 66 4666.4 62 23. Calculation of vapor pressure is base on Antoine equation.92 Ethanol 46 Total = 69 23.98 57 9854.8 01 155.0 46 179. 23 01 09 27 92 83 Distillation Column D-01 Stream 12 → Stream 13 and 14 Inlet stream 12 T feed P feed 70 °C 1 bar Specify Light key Heavy key Top P Bottom P Acetaldehyde ETAC  lk hk 0.4 39 101.9 72 77. 79698 bar 70  (217.79698  1. 1238.011 trays 0.03(1  0. and P is the column pressure 0.9998) . Use ideal Raolt's Law to calculate Kk: y P Kk  k  k xk P * where Pk is the vapor pressure.79698  0.04309)  7.9998(1  0.03) ) (ln 6.93 log PETAC  4. 0.001388 574.19481 K ETAC  iii.79698 Calculate the minimum number of stages by Frenske equation:  (1   hk ) N m  ln lk ln  lk hk  hk (1   lk ) * where α lk/hk is the relative volatility of light key to heavy key N m  (ln 0.21248  ii.0000 0.15  0.205) Relative volatility respect to key component: k / n  Kk P  k K n Pn * where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key component  ETAC / ETAC  iv. k  Calculated split fraction of each component:  kNm  hk 1  ( kNm  1) hk * where αk is the relative volatility of the component to heavy key  C2 H 4  vi. ETAC  and 64.3935 164.8144  2.03 Distillate (D) and bottom (B) flowrate: Dk  k f k and B k  (1   k )f k * where fk is the feed flowrate of the component DETAC  0.78626  1)0.03 1  (14.9109 x B .81  0.0044  0.1344 14.8144  64.6883 Results : Component Formula a k/hk xk dk bk .94 v.03 x 66. ETAC  x B  Bk /  Bi and 2.81 vii.786260. kmol/hr Distillate fraction (yD) and bottom fraction (xB): yD  D k /  D i y D .0044 kmol/hr BETAC  (1  0. 14.03)  66.03 = 0. 0005 0.000953988 EA C4H8O2 1 0.8 1.28 46 6 4666.1051 1.0044316 0.071572 99.4823 4.8144 101.5374 0. Component H2 Acetaldehyde EA Ethanol total = MW 2 44 88 46 Stream 12 (Inlet) mole 0.04198 5703.0000 0.120723 2.8569 2.6059 0.5538 0.0000 0.0077 0.5940 0.67 8.0000 0.745 5879.45 10940.01544918 1.00 mass 0.1121 1.8568759 0 de CH3CHO 9 0.0000 0.39 72.8774 4594.36 10297.69 8 Acetaldehyd e EA 164. bubble point and dew point temperature can be estimate by using mole fraction of component.00 1.2743 0.4823168 hydrogen Acetaldehy H2 4 6.9646 (Bottom) kmole/h kg/hr r 2 2.4265 1.0010 64.00 Stream 14 (Bottom) mole mass 0.1344 0.60 3 14.00 Stream 13 (Overhead) mole 0.092 0.4462 1.6 179.3935 0.15 164.00 .0493 0.5648 1.0044 3 176.8578 66.04309440 1 6 8.8100 Ethanol C2H5OH 1 720.9998923 7 2.96463 2.3720 0.03 6 0.6883037 total = Based on ASPEN PLUS.5672366 64.5672 9 99.6065 0.910861 3 M Component W Stream 12 (Inlet) kmole/h r H2 kg/hr 1 Stream 13 Ethanol Stream 14 (Overhead) kmole/h kg/hr r 4.1665 0.91 643.8774 total 3 2 14.90775455 0.8100 0.0000 0 44 88 8.00 mass 0.0356 0.444 389.0138 0.95 712.70 0.4823 3 389. 0000 0.5 Pump P-02 Assuming mass in = mass out Stream 14 → Stream 15 Stream 14 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = Pump P-03 kmole/hr kg/hr 2 0.0000 0.36 10297.96 T bubble (oC) 69.8100 99.7 Stream Stream 12 (Feed) Stream 13 (Distillate) Stream 14 (Bottom) T dew (oC) 71.4 72.1 47.8100 99.68 .69 0.36 10297.28 4594.68 Stream 15 (Outlet) kmole/h kg/hr r 0.04198 5703.8774 164.69 0.0000 44 88 46 0.0010 64.0000 0.04198 5703.4 -213.4 71.28 4594.0010 64.8774 164. 68 .0000 44 88 46 0.04198 5703.36 10297.97 Assuming mass in = mass out Stream 15 → Stream 16 Stream 15 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = kmole/hr kg/hr 2 0.0000 0.68 Heater H-02 Assuming mass in = mass out Stream 16→ Stream 17 Stream 16 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = Distillation Column D-02 kmole/hr kg/hr 2 0.69 0.69 0.0010 64.68 Stream 17 (Outlet) kmole/h kg/hr r 0.36 10297.0000 0.0000 0.0010 64.69 0.36 10297.8774 164.28 4594.8100 99.0000 0.8100 99.8774 164.8774 164.28 4594.0000 0.28 4594.36 10297.04198 5703.0010 64.69 0.0000 0.68 Stream 16 (Outlet) kmole/h kg/hr r 0.04198 5703.04198 5703.8100 99.0010 64.8774 164.8100 99.28 4594.0000 44 88 46 0. 01502 688. Calculation of vapor pressure is base on Antoine equation.21248  ii.3471 bar 170  (217.0151 15 bar 15 bar * We choose ethyl acetate as the example for calculation i.3471  0.205) Use ideal Raolt's Law to calculate Kk: y P Kk  k  k xk P K ETAC  * where Pk is the vapor pressure. 1238.9218 .992 0. log PETAC  4. and P is the column pressure 10.15  10.98 Stream 17→ Stream 18 and 22 Inlet stream 17 T feed P feed 170 °C 15 bar Specify Light key Heavy key Top P Bottom P Ethanol Ethyl Acetate  lk hk 0. 6568711.0151 1  (0.25810. Relative volatility respect to key component: k / n  Kk P  k K n Pn where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key component  ETAC / Ethanol  iv.000135 .2581 trays 0.223888)  11.99 iii. 10.6568711.992(1  0.0151(1  0.34713  0.7522 Calculate the minimum number of stages by Frenske equation:  (1   hk ) N m  ln lk ln  lk hk  hk (1   lk ) * where α lk/hk is the relative volatility of light key to heavy key N m  (ln v.6569 15.992) Calculated split fraction of each component:  kNm  hk 1  ( kNm  1) hk * where αk is the relative volatility of the component to heavy key 4  0.0151) ) (ln 2.0151 = 0.2581  1)0. k  0. 000 5702.000 (Overhead) kmole/ kg/hr hr 0.810 5703.3789 x B .0000 64.8542 2. kmol/hr Distillate fraction (yD) and bottom fraction (xB): yD  D k /  D i y D .042 0.0009 0. ETAC  and 64.3692 98.00876  0.000 de 44 0.3094 Stream 18 Stream 22 (Bottom) kmole/ kg/hr hr 0.801 6 Component EA kg/hr .0151 dk 0.5081 66.8012 vii.00876 kmol/hr BETAC  (1  0.000 0.000 0.001 0.9920 0.276 0.3094 Results: Component hydrogen Acetaldehyde EA Ethanol total Formula H2 CH3CHO C4H8O2 C2H5OH M a k/hk 39.6569 1.0001351 x 64.00001351)  64.0001 0.81  0.8012  0.000 0.9773 66.2239 0.0000 0.50 88 64.001 0.000089 98.7349 Stream 17 (Inlet) xk 1.000 0.009 0.3789 bk 0.042 0.000 W kmole/ H2 Acetaldehy 2 hr 0.771 64.0088 98.8012 1.0000 43. Distillate (D) and bottom (B) flowrate: Dk  k f k and B k  (1   k )f k * where fk is the feed flowrate of the component DETAC  0.100 vi. ETAC  x B  Bk /  Bi and 0.81  64.0000 0.0000 0. 0000 0.877 164.508 69.9998 1.0227 1.0000 0.379 7 66.98 46 99.369 5 4525.3935 0.0000 0.360 10297.5 170.5538 0.00 0.88 Total = 8 78 98.0001 0.101 Ethanol 4524.0000 0. Component MW H2 Acetaldehyd e EA Ethanol total = 2 44 88 46 Stream Stream 17 (Feed) Stream 18 (Distillate) Stream 22 (Bottom) Cooler C-02 Assuming mass in = mass out Stream 18 → Stream 19 Stream 17 (Inlet) Stream 18 Stream 22 (Bottom) mole mass 0.0000 (Overhead) mole mass 0.00 0.9773 0.00 mole 0.9880 0.00 0.0000 0. bubble point and dew point temperature can be estimate by using mole fraction of component.375 5771.6065 1.00 T dew (oC) 172 190 190 .0000 0.0002 0.0000 0.00 T bubble (oC) 170.0000 0.6 98.0120 1.0000 0.79 1.5 189 0.68 4594.4462 1.9999 1.0000 mass 0.0000 0.309 1 Based on ASPEN PLUS. 0000 0 H2 Acetaldehy 2 hr 0.0009 0.0088 98.98 46 2 98.0009 0.77055 0.98 0.0088 98.102 Stream 18 (Inlet) Component MW kmole/ kg/hr Stream 19 (Outlet) kmole/ kg/hr hr 0.04164 0.04164 0.0088 98.797 Stream 20 (Outlet) kmole/h kg/hr r 0.0009 0.770553 4524.0088 98.79 2 98.378 5 4525.77055 88 0.04164 0.04164 0.0009 0.0000 0 44 88 46 0.797 .369 3 4524.0000 0 0.369 3 4524.3789 0.3692 98.0000 de 44 0.985 4525.79 9 7 9 7 EA Ethanol Total = 0 Valve CV-02 Assuming mass in = mass out Stream 19 → Stream 20 Stream 19 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = kmole/hr kg/hr 2 0.378 5 4525.3789 0.985 4525.770553 4524.3692 98. 04164 0.0000 0 44 88 46 0.985 4525.985 4525.797 Stream 21 (Outlet) kmole/h kg/hr r 0.797 .3692 98.3789 0.770553 4524.04164 0.0088 98.0009 0.770553 4524.3789 0.0009 0.0088 98.0000 0 0.3692 98.103 Valve CV-03 Assuming mass in = mass out Stream 20 → Stream 21 Stream 20 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = Cooler C-03 Assuming mass in = mass out Stream 22 → Stream 23 kmole/hr kg/hr 2 0. 881 .8012 1.37484 5771.3094 0.5057 69.3094 0.5081 66.0003 5702.0000 64.104 Stream 22 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = kmole/hr kg/hr 2 0.3094 0.0000 0.37484 5771.5081 66.0000 0 0.0000 0 0.506 69.3094 0.8012 1.0000 0.0000 64.0000 44 88 46 0.3748 5771.000336 5702.0000 64.5057 69.0003 5702.5081 66.506 69.0000 44 88 46 0.000336 5702.5081 66.3748 5771.8808 Stream 24 (Outlet) kmole/h kg/hr r 0.881 Valve CV-04 Assuming mass in = mass out Stream 23 → Stream 24 Stream 23 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = kmole/hr kg/hr 2 0.0000 64.8012 1.8808 Stream 23 (Outlet) kmole/h kg/hr r 0.8012 1. 0000 0.8012 1.0000 64.3094 0.37484 5771.5057 69.8808 Stream 25 (Outlet) kmole/h kg/hr r 0.5081 66.0000 0 0.8012 1.3748 5771.3094 0.0000 44 88 46 0.0003 5702.105 Valve CV-05 Assuming mass in = mass out Stream 24 → Stream 25 Stream 24 (Inlet) Component MW H2 Acetaldehyd e EA Ethanol Total = Distillation Column D-03 kmole/hr kg/hr 2 0.881 .506 69.000336 5702.0000 64.5081 66. Use ideal Raolt's Law to calculate Kk: y P Kk  k  k xk P K ETAC  iii.106 Inlet stream 21 T feed P feed 73. log PETAC  4.205) * where Pk is the vapor pressure.9042 bar 73.24 1 bar 1 bar * We choose ethyl acetate as the example for calculation i. 1238.99 0.90423  0. 0.904231  1.84297 Calculate the minimum number of stages by Frenske equation: .7 °C 1 bar Specify Light key Heavy key Ethyl Acetate Ethanol Top P Bottom P  lk hk 0.15  0.00157 577.7  (217. and P is the column pressure 0.3053 Relative volatility respect to key component: k / n  Kk P  k K n Pn * where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key component  ETAC / Ethanol  iv.21248  ii.0727 0. Calculation of vapor pressure is base on Antoine equation. 9297  1)0. kmol/hr Distillate fraction (yD) and bottom fraction (xB): yD  D k /  D i and x B  Bk /  Bi .24 = 0.0727 81.000088 vii.24(1  0. k  0.0727 81.9297 trays 0.0088  0.00867 kmol/hr B ETAC  (1  0.99) Calculated split fraction of each component:  kNm  hk 1  ( kNm  1) hk * where αk is the relative volatility of the component to heavy key 4  vi.107  (1   hk ) N m  ln lk ln  lk hk  hk (1   lk ) * where α lk/hk is the relative volatility of light key to heavy key N m  (ln v.24 1  (1.0088  0.99 Distillate (D) and bottom (B) flowrate: Dk  k f k and B k  (1   k )f k * where fk is the feed flowrate of the component DETAC  0.99 x 0.24) ) (ln 1. 1.92970.07267)  81.99(1  0.99)  0. 9888 3438.2400 684.7706 4524.00867  0.0000 0.0088 98.7606 74.0009 0.000088  0.9900 0.6182 74.3789 0.0009 0.9965 1086.0416 0.0000 0.0727 1.8478 Stream 21 (Inlet) kmole/hr kg/hr dk 0.3692 98.0000 0. Component MW Inlet Outlet .9965 Based on ASPEN PLUS.7606 23.4845 6.0001 74.7974 0.0000 1.7607 0.000 74.0416 0.7628 1085.0077 3438.0000 0.108 y D .0000 0.0000 0.9852 4525. ETAC  and 0.0001 74.6182 x B .7607 Results: Component hydrogen Acetaldehyde EA Ethanol Water total Component M W Formula H2 CH3CHO C4H8O2 C2H5OH a k/hk 676.2906 1.00037 23.0000 e EA Ethanol total = 44 88 46 0.0000 0.6182 0.0000 0.0000 xk 1.0000 0.0087 23.0000 0.0009 0.6086 bk 0.6086 23.7607 Stream 26 Stream 28 (Bottom) (Overhead) kmole/hr kg/hr kmole/hr kg/hr H2 Acetaldehyd 2 0.0000 0. ETAC  0.8009 0. bubble point and dew point temperature can be estimate by using mole fraction of component.0087 23. 0000 0 0.000 46 1.0416 0.0000 1.000 88 0.6086 7 1085.0000 e 44 0.0000 0.0000 1.0009 0.7628 1085.000 44 0.0000 1.996 0.5 75.0000 0.0000 0.0000 0 1.0000 0 Acetaldehyd e EA Ethanol Total = T bubble (oC) 77.0087 23.000 2 0.0087 23.0000 0 0.7 76.0000 0 1.0000 0.0000 0 .99 EA Ethanol Stream 27 (Outlet) kmole/h kg/hr r 0.0000 0.0000 1.0000 0.8 78 Cooler C-04 Assuming mass in = mass out Stream 26 → Stream 27 Component MW H2 Acetaldehyd 2 Stream 26 (Inlet) kmole/h kg/hr r 0.8 78 Stream Stream 17 (Feed) Stream 18 (Distillate) Stream 22 (Bottom) T dew (oC) 77.76284 88 46 0.6086 0.000 1.0000 0.0009 0.109 H2 kmole/hr kg/hr kmole/hr kg/hr 0.04164 0. 0077 0.0000 0.7606 3438.9888 74.0001 0.0001 0.989 74.9965 74.007706 74.0000 0.7607 3438.7607 3438.0000 0.0000 0 0.0000 0.110 5 1086.0000 0 0.800 Total = 23.7606 3438.6182 1 Cooler C-05 Assuming mass in = mass out Stream 28 → Stream 29 Component H2 Acetaldehyde EA Ethanol Total = MW 2 44 88 46 Stream 28 (Inlet) Stream 29 (Outlet) kmole/h kg/hr kmole/hr kg/hr r 0.6182 9 6 1086.80 23.996 . 111 . 3982 10.053 223.112 A.6896 (°C) Outlet Flow Rate Temperature (kmol/hr) 0 0 0.6896 (°C) 25 -5. M-01 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream (kJ/hr) Heat duty Inlet Flow Rate Temperature Outlet Flow (kmol/hr) 0 0 0.98E+07 Rate Temperature (°C) 25 -5.2 Energy Balance Calculation Mixer 1.35E+05 Cooler.6896 25 -5.1779 (°C) Outlet Flow Rate Temperature (kmol/hr) 145.053 223.1779 (°C) . P-01 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Flow Rate Temperature (kmol/hr) 0 0 0.053 223.053 223.96E+07 (kJ/hr) 1. C-01 Inlet Component Hydrogen Acetaldehyde Flow Rate Temperature (kmol/hr) 145.6896 (kmol/hr) 0 0 0.3982 10.98E+07 (kJ/hr) 0 Pump.98E+07 (°C) 25 -5. 4341 (°C) (kmol/hr) 2.1504 0.3667 1.41E+07 Expander.2914 -4.4695 8.113 Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty 67.8112 66.41E+07 (°C) 30 .8112 66.5128 77.3667 1.99E+04 Valve.8573 30 -8.1E+07 (kJ/hr) 3.40E+07 30 Outlet Temperature -5.50E+07 30 -1.1504 0.9287 1.87E+05 (°C) 30 -9.17E+05 (kJ/hr) -2.6632 78.8573 (°C) Outlet Flow Rate Temperature (kmol/hr) 142.2914 260 67.4695 8.5128 77.9287 1. CV-01 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Flow Rate Temperature Flow Rate (kmol/hr) 2. EX-01 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Flow Rate Temperature (kmol/hr) 142.4341 -5.6632 78. H-01 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Flow Rate Temperature (kmol/hr) (°C) 2.5128 77.24E+06 -6.4695 8.5128 77.8112 66.4341 -5.114 Heat duty (kJ/hr) -1.3E+07 8.2694 23.58E+05 2.4E+07 stream(kJ/hr) Heat duty Outlet Flow Rate Temperature (kmol/hr) (°C) 2.811 68.676 68 .242 Outlet Flow Rate Temperatu (kmol/hr) re (°C) -7.8112 30 66. M-02 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty (kJ/hr) Inlet 1 Flow Rate Temperat (kmol/hr) ure (°C) 2.4695 8.21E+05 Heater.469 8.4341 -5.32E+07 68 Inlet 2 Flow Temperatur Rate e (°C) (kmol/hr ) 0 0 68 2.4341 -5.5128 77.81E+05 (kJ/hr) Mixer.8112 68 66.782 100.11E+07 -6.4695 8. 7E+07 stream(kJ/hr) Heat duty Outlet Flow Rate Temperature (kmol/hr) 0.7703 -5.6 98.7187 71.0441 66. P-02 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Flow Rate Temperature (kmol/hr) (°C) 0. P-03 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Flow Rate Outlet Flow Rate Temperature Temperature (kmol/hr) (°C) 0.0000 0.7E+07 9.0000 0.96E+04 (kJ/hr) Pump 3. H-03 Component Inlet Flow (kmol/hr) Rate Temperature (°C) Outlet Flow (kmol/hr) Rate Temperature (°C) .0441 66.6 98.6 -5.7E+07 0 (kJ/hr) Heater 3.7187 71.7703 (°C) 71.115 Pump 2.0000 0.7187 71.0441 66.7187 98.7703 -5.0000 0.6 98.7703 -5.0441 66.7E+07 stream(kJ/hr) Heat duty (kmol/hr) (°C) 0. 29E+05 (kJ/hr) Cooler 4-C-04 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Flow Rate Temperature Flow Rate (kmol/hr) 0 0 64.2205 77 97.54E+07 -5.0441 2.03E+06 (kJ/hr) Cooler 3.4982 1.7703 -5.2205 167.0441 66.116 Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty 0.4E+07 3.0441 66.7187 98. C-03 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty Flow Rate Temperature (kmol/hr) (°C) 0 0.8 Outlet Temperature -2.4982 1.92E+07 (°C) 72.0441 2.7187 98.4 .4914 -2.0000 71.2789 -2.7703 170 -5.0000 0.7E+07 stream(kJ/hr) Heat duty 0.4914 (°C) (kmol/hr) 0 0 64.8 97.2789 -2.6 0.49E+07 stream(kJ/hr) Heat duty Outlet Flow Rate Temperature (kmol/hr) (°C) 0 0.89E+07 188. CV-02 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Inlet Flow Rate Temperature Outlet Flow (kmol/hr) 0 0.2789 (°C) 77 Outlet Flow Rate Temperature (kmol/hr) 0 0.2205 97.117 Heat duty (kJ/hr) -2.2789 -2.54E+07 -2.2789 (°C) 77 -2.54E+07 (kJ/hr) -4.2205 97.2205 97.0441 2.2205 97.0441 2.2789 (kmol/hr) 0 0.0441 2. CV-03 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty (kJ/hr) Valve 4.55E+07 -4. CV-04 Flow Rate Temperature (kmol/hr) 0 0.76E+04 (°C) 77 .54E+07 Rate Temperature (°C) 77 -2.83E+05 Valve 2.76E+04 Valve 3.0441 2. 4982 1.4 -2.4914 Inlet Temperature (°C) Outlet Flow Rate Temperature (kmol/hr) 0 0 64.04E+05 Valve 5.4982 1.4 -2.9E+07 (°C) 72.4914 -2.4982 1. C-04 Component Inlet Flow Rate Temperature Outlet Flow (kmol/hr) (kmol/hr) (°C) Rate Temperature (°C) .4982 1.118 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Flow Rate (kmol/hr) 0 0 64.9E+07 (kJ/hr) Rate Temperature (°C) 72.9E+07 (kJ/hr) -1.4 -2.4914 (°C) 72.9E+07 0 Cooler 4.4914 72. CV-05 Inlet Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty Flow Rate Temperature (kmol/hr) 0 0 64.4 Outlet Flow (kmol/hr) 0 0 64. 3469 -6.49E+05 .63E+06 -1.0441 167.4148 73.99E+07 (kJ/hr) 25 -1.5996 188. C-05 Component Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty (kJ/hr) Inlet Flow Rate Temperature (Mol/hr) (°C) 0 0.9319 0 0 0.8057 23.0E+07 Cooler 5.0441 68 0.053 73.8 0.119 Hydrogen Acetaldehyde Ethyl Acetate Ethanol Heat duty stream(kJ/hr) Heat duty 0 0 1.48E+06 Outlet Flow Rate Temperature (Mol/hr) (°C) 0 0.8057 23.97E+07 2.3469 -6.8 -1. 3 1) Manual Calculations Process Flow Diagram With Complete Stream .120 A. 121 2) Process Simulation of Process Flow Diagram Process Simulation Stream Table .