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DEPARTMENT OF CHEMICAL ENGINEERING JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY, A.B. ROAD, RAGHOGARH, DIST. GUNA -473226, M.P., INDIA 2011-2012
CERTIFICATE This is to certify that the work titled "PRODUCTION OF BISPHENOL A submitted by Rahul Agrawal (ER. No. 08431G) and Aakash Suman (ER. No. 08401G) in partial fulfillment for the award of degree of B. Tech of Jaypee University of Engineering & Technology, Guna has been carried out under my supervision. This work has not been submitted partly or wholly to any other university or institute for the award of this or any other degree or diploma.
ACKNOWLEDGEMENTS
We wish to express deep sense of gratitude and sincere thanks to our project supervisor Dr. Ashish S. Chaurasia Assistant Professor, Department of Chemical Engineering & Chemical Technology for his valuable guidance, encouragement, suggestions, and moral support throughout the period of this project work. We express our thanks to Professor N. J. Rao Vice Chancellor of Jaypee University for his valuable suggestions. We would like to thank Professor K. K. Tiwari, who is associated with JUET after his retirement from ICT Mumbai for his guidance and suggestions during this project work. We would like to thank Dr. G. K. Agrawal for his suggestions during this work. Our special thank to Dr. Hari Mahalingam Head of Chemical Engineering Department for providing all the necessary facilities to complete this work. We would like to thank all other faculty members of Chemical Engineering Department for their support during this work. We would also like to extend our thanks to Library staff for their continuous support and all the information providers on the internet. Finally we would like to thank our batch mates and family for the motivation and support they have provided us.
EXECUTIVE SUMMARY
The project deals with the production of BisphenolA (BPA). It is an organic compound with the chemical formula (CH3)2C(C6H4OH)2. It is a colorless solid that is soluble in organic solvents but poorly soluble in water. The process technologies used for the production of Bisphenol A is given below. The condensation of phenol with acetone using resin catalyst is selected in the present study. The uses, manufacturers, physico-chemical properties, and health effects are also given below. Process technologies: (1) Condensation of phenol with acetone using acid as a catalyst. (2) Condensation of phenol with acetone using ion exchange resin catalyst. Ion exchange resin catalyzed condensation of phenol with acetone is the new improved process for the production of Bisphenol A. Ion exchange resin is todays preferred catalyst system for Bisphenol A manufacturer. It replaces older acid based technologies by doing away with acid based environment. All of the problems associated with handling acids, including corrosion and disposal of acid waste are eliminated. This advanced technology maximizes yield and conversion using an environmentally preferred ion exchange resin catalyst. The new reaction system promotes the BPA condensation reaction under highly favorable reaction condition while simultaneously removing the water of reaction. Raw material consumption (per 1000 kg of Bisphenol A) Process selectivity Phenol Acetone Steam (energy) consumption BPA product obtained is 99.93%- 99.98% Catalyst: Ion exchange resin catalyst Process Selected: Condensation of phenol with acetone using ion exchange resin catalyst in presence of HCl as catalyst and methyl mercaptan as promoter. Process Description: Acetone and excess phenol are reacted at a temperature of 750C and pressure is kept around 4.4 bar by condensation in an ion exchange resin-catalyzed reactor system to produce BPA, water and various byproducts. The crude distillation column having the temperature of 1700C and pressure of 560 torr helps in removing water and unreacted acetone from the reactor effluent. Acetone and lights are sent to second distillation column operating at 950C and then acetone is sent to the lights adsorber to produce a recycle 98.5% 835 265 6GJ/Ton
ii
acetone stream and water is sent for the waste water treatment via recovery column. The bottoms of the crude column having the temperature of 700C is sent to the crystallization feed pre-concentrator after it is passed from a heat exchanger where inside temperature is 510C and it is cooled to 540C, which distills phenol and concentrates BPA to a level suitable for crystallization. BPA is separated from byproducts in a proprietary solvent crystallization and recovery system where it is cooled from 540C to 410C to produce the adduct of BPA and phenol. Mother liquor from the purification system is distilled in the solvent recovery column to recover dissolved solvent which comes in this system through pump. The solvent free mother liquor stream is recycled to the recovery system. A purge from the mother liquor is sent to the purge recovery system along with the recovered process water to recover phenol. The recovered purified adduct is processed and fed at a temperature of 410C and pressure is kept around 25 torr in a BPA finishing system to remove phenol from product, and the resulting molten BPA of temperature 1750C is solidified in the flaker followed by a pump to produce product prills which comes out at a temperature of 900C and is suitable for the BPA market.
iii
TABLE OF CONTENTS
CHAPTER 1: HISTORICAL PROFILE 1.1 1.2 1.2.1 1.3 1.3.1 1.4 NATURAL OCCURRENCE TRADITIONAL APPLICATIONS/USES... USES. MANUFACTURERS.. EARLIER INDUSTRIAL APPLICATIONS.. HISTORY OF PRODUCT IN INDIA. 1 1 2 2 2 3
CHAPTER 2: APPLICATIONS 2.1 2.1.1 2.1.2 2.2 2.3 2.4 CURRENT APPLICATION.. COMMON APPLICATIONS OF BPA-PC PLASTICS... COMMON APPLICATIONS OF BPA-EPOXY RESIN PLASTIC VARIOUS GRADES SPECIFICATIONS OF BPA PRODUCT.. STANDARDS OF BPA PRODUCT 5 5 6 6 6 6
CHAPTER 3: ECONOMIC SCENARIO 3.1 3.2 3.3 3.3.1 3.3.2 3.4 3.5 GLOBAL SUPPLY SCENARIO GLOBAL DEMAND AND SUPPLY GLOBAL DEMAND SCENARIO. PC MARKET. EPOXY RESINS... PRICE AND PRICE VARIATIONS GROWTH ASPECTS... 7 8 8 9 9 10 10
CHAPTER 4: PROPERTIES 4.1 4.1.1 4.1.2 4.2 PHYSIO-CHEMICAL PROPERTIES PHYSICAL PROPERTIES. CHEMICAL PROPERTIES BIO-ENVIRONMENTAL CHARACTERISTICS 13 13 14 14
iv
4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6 4.3 4.4 4.5 4.6
ENVIRONMENTAL FATE AND IMPACTS IMPACTS HUMAN METABOLISM FATE HEALTH EFFECTS ON HUMAN BEING AND OTHER.. OBESITY BREAST CANCER HANDLING CONSIDERATIONS.. PACKAGING CONSIDERATIONS STORAGE CONSIDERATIONS. SAFETY CONSIDERATIONS
14 14 15 16 16 17 17 17 18 18
CHAPTER 5: MANUFACTURING PROCESSES 5.1 5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 PROCESS TECHNOLOGIES RAW MATERIAL REQUIREMENT CATALYST TECHNOLOGY PROVIDERS. TYPICAL FEASIBLE PLANT CAPACITY COMPARISON. 19 20 20 20 20 23
CHAPTER 6: PROCESS SELECTED 6.1 6.2 6.2.1 6.3 6.3.1 6.3.2 6.3.3 6.3.4 6.3.5 6.3.6 6.3.7 6.4 6.5 PROCESS SELECTED. PROCESS DESCRIPTION EQUIPMENTS USED.. CONTROL STRATEGY.. DESCRIPTION. COMPONENTS OF CONTROL SYSTEM. CONTROLLING SYSTEM USED.. TEMPERATURE CONTROLLER.. PRESSURE CONTROLLER FLOW CONTROLLER LEVEL CONTROLLER.. PLANT LOCATION PLANT LAYOUT 24 24 26 27 27 27 27 28 28 28 28 28 29
CHAPTER 7: MATERIAL AND ENERGY BALANCE 7.1 7.1.1 7.1.2 7.1.3 7.2 7.3 7.4 7.5 7.5.1 7.5.2 7.6 7.7 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15 7.16 7.17 7.18 BASIS.. FEED PRODUCT... REACTION INVOLVED MATERIAL BALANCE AROUND REACTOR ENERGY BALANCE AROUND REACTOR MATERIAL BALANCE AROUND DISTILLATION COLUMN I. ENERGY BALANCE AROUND DISTILLATION COLUMN I. ENERGY BALANCE AROUND CONDENSER. ENERGY BALANCE AROUND REBOILER. MATERIAL BALANCE AROUND DISTILLATION COLUMN II. MATERIAL BALANCE AROUND CRYSTALLIZER FEED SYSTEM ENERGY BALANCE AROUND CRYSTALLIZER FEED SYSTEM MATERIAL BALANCE AROUND SOLVENT CRYS AND RECOV. SYS ENERGY BALANCE AROUND SOLVENT CRYS AND RECOV. FEED SYS MATERIAL BALANCE AROUND BPA FINISHING SYSTEM ENERGY BALANCE AROUND BPA FINISHING SYSTEM MATERIAL BALANCE AROUND FLAKER. ENERGY BALANCE AROUND FLAKER. MATERIAL BALANCE AROUD LIGHT ABSORBER. MATERIAL BALANCE AROUND PURGE RECOVERY SYSTEM MATERIAL BALANCE AROUND RECOVERY SYSTEM.. OVERALL MATERIAL BALANCE 30 30 30 30 31 31 33 34 34 34 35 35 36 36 37 38 38 39 39 40 40 41 42
CHAPTER 8: DETAILED EQUIPMENT DESIGN 8.1 8.1.1 8.1.2 8.2 8.2.1 8.3 REACTOR. PROCESS DESIGN.. MECHANICAL DESIGN. HEAT EXCHANGER.. PROCESS DESIGN. DISTILLATION COLUMN 43 43 44 46 46 48
CHAPTER 9: CAPITAL COST ESTIMATION 9.1.1 9.1.2 9.1.3 COST OF REACTOR. COST OF HEAT EXCHANGER COST OF DISTILLATION COLUMN I 52 53 53
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9.1.4 9.1.5 9.1.6 9.1.7 9.1.8 9.1.9 9.1.10 9.1.11 9.1.12 9.2 9.2.1 9.2.2 9.2.3 9.2.4 9.2.5 9.2.6 9.2.7 9.3.8 9.3.9
COST OF DISTILLATION COLUMN II.. COST OF ABSORPTION COLUMN. COST OF PUMP.. COST OF CRYSTALLIZERS. COST OF THE BPA FINISHING SYSTEM.. COST OF THE RECOVERY COLUMN COST OF THE PURGE RECOVERY COLUMN COST OF THE PHENOL STORAGE TANK COST OF THE FLAKER ESTIMATION OF CAPITAL INVESTMENT ESTIMATION OF TOTAL PRODUCT COST.. COST OF RAW MATERIAL. DIRECT PRODUCTION COST. FIXED CHARGES.. PLANT OVERHEAD COST.. GENERAL EXPENSES.. TOTAL PRODUCT COST.. TOTAL REVENUE. PROFITABILITY ANAYSIS..
53 53 54 54 54 55 55 55 55 56 56 57 57 57 58 58 58 58 58
59
REFERENCE..
60
63 68 73
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LIST OF TABLES
TABLE 2.1 TABLE 2.2 TABLE 3.1 TABLE 3.2 TABLE 4.1 TABLE 5.1 TABLE 5.2 TABLE 5.3
SPECIFICATIONS OF BISPHENOL A............. STANDARDS OF BISPHENOL A GLOBAL/ INDIAN SUPPLY AND DEMAND FOR BPA GLOBAL COMPANY WISE CAPACITY. PHYSICAL PROPERTIES OF INDUSTRIALLY IMP BPA................... RAW MATERIAL REQUIREMENT RAW MATERIAL CONSUMPTION... COMPARISON OF DIFFERENT PROCESSES AVAILABLE.. FOR PRODUCTION OF BISPHENOL A
6 6 8 11 13 20 21 23
STREAM WISE PRODUCT DISTRIBUTION TOTAL CAPITAL INVESTMENT OF THE PROJECT.. COST OF RAW MATERIAL....
26 56 57
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LIST OF FIGURES
FIG 3.1 FIG 3.2 FIG 3.3 FIG 3.4 FIG 3.5 FIG 5.1
BISPHENOL A CONSUMPTION PATTERN WORLD CONSUMPTION OF BISPHENOL A..... GLOBAL PC PRODUCTION VOLUME. GLOBAL EPOXY RESINS PRODUCTION VOLUME. BISPHENOL A WORLD CAPACITY.. SCHEMATIC FLOW DIAGRAM SHOWING BPA PRODUCTION BY ACID CATALYZED PHENOL ACETONE CONDENSATION
7 8 9 10 12 20
FIG 5.2
SCHEMATIC FLOW DIAGRAM OF BISPHENOL A PROD BY ION EXCHANGE RESIN CATALYZED PHENOL ACETONE CONDENSATION
22
FIG 6.1
PROCESS FLOW DIAGRAM OF ION EXCHANGE RESIN CATALYZED PROCESS FOR PRODUCTION OF BPA
25
FIG 6.2 FIG 6.3 FIG 7.1 FIG 7.2 FIG 7.3 FIG7.4 FIG 7.5
CONTROL STRATEGY OF THE REACTOR. PLANT LAYOUT.. MATERIAL BALANCE AROUND REACTOR. MATERIAL BALANCE AROUND DISTILLATION COLUMN I.. MATERIAL BALANCE AROUND DISTILLATION COLUMN II. MATERIAL BALANCE AROUND CRYSTALLIZER FEED SYS.. MATERIAL BALANCE AROUND SOLVENT .. CRYSTALLIZATION AND RECOVERY SYSTEM
27 29 31 33 35 35 36
FIG 7.6 FIG 7.7 FIG 7.8 FIG 7.9 FIG 7.10 FIG 7.11
MATERIAL BALANCE AROUND BPA FINISHING SYSTEM. MATERIAL BALANCE AROUND FLAKER. MATERIAL BALANCE AROUND LIGHT ABSORBER. MATERIAL BALANCE AROUND PURGE RECOVERY CLM. MATERIAL BALANCE AROUND RECOVERY COLUMN... MATERIAL BALANCE AROUND THE WHOLE PLANT
38 39 40 40 41 42
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LIST OF SYMBOLS
Cp Jf A,B,C T P R H 0 298 f
H
Cao
Specific heat Joint factor Antoines Constants Temperature,K Pressure,torr Universal gas constant,J/mol.K Standard heat of formation, kJ/kmol Heat of reaction, J kg-1 Density, 0 at initial condition, kg m-3 Viscosity, kg m-1 s-1 Initial Concentration Pressure drop
Dimensionless numbers Bi Le Pr Re Sh
Biot number Lewis number Prandtl number Reynolds number Sherwood number
CHAPTER
1
HISTORICAL PROFILE
1.1 Natural occurrence [1] Bisphenol A (abbreviated BPA) does not occur as such in nature. It is a man-made molecule and was invented in 1891. It is a relatively small synthetic, organic compound with a molecular weight of 228. It is a white powder and is an estrogen mimicker, and can cause hormone disrupting effects. Bisphenol A is mainly used as a bifunctional monomer in the manufacture of polycarbonate plastic and epoxy resins and as an antioxidant in PVC.
1.2 Traditional applications [2] BPA is a monomer used to make polycarbonate resins for applications such as construction, electronics and food containers. Some 63% of BPA is used to make polycarbonates. A further 27% goes into epoxy resin production, and the remaining 10% is used for other products including speciality resins and flame retardants. Bisphenol A is used primarily to make plastics, and products containing bisphenol A-based plastics have been in commerce use since 1957. At least 8 billion pounds of BPA are used by manufacturers yearly. It is a key monomer in production of epoxy resins and in the most common form of polycarbonate plastic. Polycarbonate plastic, which is clear and nearly shatter-proof, is used to make a variety of common products including baby and water bottles, sports equipment, medical and dental devices, dental fillings and sealants, eyeglass lenses, CDs and DVDs, and household electronics. BPA is also used in the synthesis of polysulfones and polyether ketones, as an antioxidant in some plasticizers, and as
a polymerization inhibitor in PVC. Epoxy resins containing bisphenol A are used as coatings on the inside of almost all food and beverage cans, however, due to BPA health concerns, in Japan epoxy coating was mostly replaced by PET film. Bisphenol A is also a precursor to the flame retardant
tetrabromobisphenol A, and was formerly used as a fungicide. Bisphenol A is a preferred color developer in carbonless copy paper and thermal paper, with the most common public exposure coming from some thermal point of sale receipt paper. BPA-based products are also used in foundry castings and for lining water pipes.
1.2.1 Uses [3,4] Plastics and resins made using BPA are found in many of the products you use every day to make your life more convenient - products like canned foods to eyeglasses to vital medical equipment and food and beverage containers. Some other Uses of Bisphenol A are: baby bottles and nursing products dental sealants and orthodontic products water bottles and other food and beverage containers the liners of food cans CDs and DVDs eyeglasses water pipes sports safety equipment medical equipment and tubing consumer electronics PVC
1.3 Manufacturers [4 Jingjiang Concord Plastics Technology Co., Ltd china Shanghai Righton Co., Ltd. China Bayer Polymers Baytown, Texas Dow Chemical Freeport, Texas Sabic Innovative Plastics Burkeville, Alabama Sabic Innovative Plastics Mount Vernon, Indiana Hexion Specialty Chemicals Deer Park, Texas Sunoco Chemicals Haverhill, Ohio Kesar Loteparhuram, India. Idemitsu chemicals pvt.ltd. Kesar petroproducts pvt. Ltd. India Mitsubishi chemicals Ltd.
1.3.1 Earlier Industrial applications The main market for bisphenol-A (BPA) is in the production of polycarbonate (PC) with the second largest outlet being epoxy resins. Other uses include flame retardants (mainly tetrabromobisphenol-A), unsaturated polyester resins and polyacrylate, polyetherimide, polysulphone resins, other polysters, the
halogenated form is used as flame retardants, the alkylated form is used as stblizer and antioxidants for rubber and other plastics.
In India, Bisphenol A is primarily used in manufacturing of epoxy resins, phenolic resins and processing of polyvinyl chloride. Epoxy resins are thermosetting resins chiefly used for coating and adhesives. The glass fibre reinforced laminates of epoxy resins are light in weight and have the highest tensile strength for any reinforced plastics. High quality higher grade polycarbonates is needed to produce consumer goods such as glazing, electrical parts, compact disc and automotive parts.
1.4 History of Bisphenol A in India [5] Bisphenol A was first developed in 1891 but saw little use until the 1930s when it was used as a synthetic estrogen product. The first reported synthesis of BPA was from Thomas Zincke of the University of Marburg, Germany. The Uses came into notice in 1930s when it was used as a synthetic estrogen product. Use of Bisphenol A slowed with the discovery of DES, a more potent artificial estrogen, later found to cause reproductive cancer in the children of mothers who took it. In the 1940s and 1950s, scientists discovered that Bisphenol A, when combined with the gas phosgene, helped create a clear, hard plastic called polycarbonate. This material was used in eyeglasses, baby bottles, shatter-resistant lights and many other applications. The commercial production of bisphenol a started in india in 1970s.
Bisphenol A on Timeline 1891: Bisphenol A, or BPA, is developed. 1930s: The chemical is used as a synthetic estrogen. 1960s: Food manufacturers begin to use BPA to make hard, clear plastic for items such as baby bottles and the lining of metal food cans, including liquid baby formula. 1968: The first Phenol producing plant was installed in india in 1968 with the commissioning of unit of Herdillia Chemicals Ltd at Thane, Maharashtra with an installed capacity of 10,000 tonne per annum. 1998: Patricia Hunt, a geneticist at Washington State University, notices that control mice had many more defective eggs when stored in polycarbonate cages. 2000-present: More than 1,000 studies are published showing harm to lab animals from BPA, including cancer, obesity, diabetes, reproductive failures and neurological disorders. 2008: Annual sales of BPA exceed $6 billion. April 2008: Canadian health officials begin steps to declare BPA a toxin and to have it banned from use in baby bottles and tableware for children. Several manufacturers - including Nalgene, Wal-Mart, Toys "R" Us and CVS pharmacies - announce plans to phase out use of the chemical in children's products.
August 2008: The Food and Drug Administration declares BPA to be safe. September 2008: The National Toxicology Program, an advisory board to the FDA and Environmental
Protection Agency, releases its report expressing some concern for how BPA affects the prostate and neural development of fetuses , infants and children. It also expressed concern about the chemical's effect on breast tissue and early puberty. A study published in the Journal of the American Medical Association in September tied BPA to heart disease in humans. Lawmakers start to call for a ban of the chemical in children's products. October 2008: The FDA's Science Board finds that the FDA ignored hundreds of studies on BPA and advises the agency to reopen its investigation of the chemical. A study finds that even low levels of BPA can interfere with chemotherapy for breast cancer patients.
CHAPTER
2
APPLICATIONS
2.1 Current Applications [2]
2.1.1 Some of the common applications of Bisphenol A-polycarbonate plastic include: [2] CDs, DVDs, Blu-Ray and other discs Roof lights Covers for solar panels Security glazing, e.g. transparent cabins for ski lifts Roof modules in cars Safety goggles and protective visors Helmets Sunglasses Reusable water bottles Roofs of sport stadiums Safety hats Medical equipment (blood oxygenators, respirators, dialysers, single-use operating instruments) Housings for electronic equipment (cell phones, cameras, hairdryers, computers, TVs, coffee makers) Electrical kettles Plug connectors Electrical equipment, such as plug connections or switches Headlamps and bumpers in cars Conservatory or green house glazing
2.1.2 Some of the common applications of Bisphenol A-epoxy resins include coatings for: [2] Underwater ship hulls Cargo tank linings Steel bridges Storage tanks(metal and concrete) Electric motors, engines, machinery Construction panels(cladding, roofing, ceilings, garage doors) Gardening tools and equipment Automotive parts and coatings Steel furniture Printed circuit boards 2.2 Various Grades of Bisphenol A [6] Bisphenol A has following grades: A,B,C,D,E. Grade A, B are intended for production of optical polycarbonate; Grade A is used for production of molding and extrusion polycarbonates, as well as extra grade polysulfones Grade C is employed in processes of production of epoxy resins and lacquers; Grade D sort for production of epoxy resins, lacquers, adhesives and other products; Grade B sort for production of epoxy resins, adhesives and other products. 2.3 Specifications for Bisphenol A [7] Table 2.1 specifications of Bisphenol Aa meter Value Molecular Formula Mol Wt CAS # Description Assay Crystallization Point in deg cel Free phenol in ppm Isomers (%) Moisture (%) 2.4 Standards for Bisphenol A [8] Table 2.2 Standards of Bisphenol A BISPHENOL A-STANDARD PRODUCT SPECIFICATIONS PARAMETER PURITY(asp,p-isomer,dry state), min. MELTING point, min. o,p-isomer,max. Phenol,by GC,max Iron,max. Ash,max. Color25g/35cm3 MeOH,max. Value Unit Flooring (industrial/public buildings, food/catering industry, chemical plants, pharmaceutical industry, hospitals) Food and drink cans/can ends General lined cans(oil, hairspray) Collapsible tubes Coil coatings for household appliances Composites used for rackets, surfboards, helmets, pipes, windmill blades, aviation Adhesives Printing inks
metal
C15H16O2 228.29 [80-05-7] White powder or flakes 99.6 % min 156 min 300 max 0.1 max 0.1 max
CHAPTER
3
ECONOMIC SCENARIO
Global BPA capacity in 2008 was around at 5.16-mtpa, and demand about 4.38-mt. Asia is the largest producing region, with 45% of total capacity, followed by Europe (28%) and America (24%) Within Asia, 68% of total capacity is in three countries Japan, Korea and Taiwan. Taiwan alone accounts for 27% of total Asian capacity, followed closely by Japan (26%) and Korea (15%). China has only 11% of Asian capacity for BPA, but accounts for 28% of total Asian demand. Japan ranks second in terms of demand in Asia, with an 18% share, followed by Korea and Taiwan (15% each). While BPA was in oversupply in 2005 and 2006, the market became relatively tight from mid-2007 due to a shortage of its raw material, phenol, and increased demand from PC and epoxy resins. However, much new phenol capacity has started coming on stream from 2008, while new BPA capacity has also been added in Asia, pushing the market back into over supply. Indian scenario:- is totally opposite and shows a tight supply of the product
3.2 Global/ Indian supply and demand for BPA [2009](KPA) [10] Table 3.1 Global/ Indian supply and demand for BPA
Region America Europe Asia China Japan Korea Taiwan Other Asian(including India) Total Asia Others Total
3.3 Global/Indian demand scenario [11] The main market for BPA, globally, is in production of PC resins, followed by use for manufacture of epoxy resins. Other uses include flame retardants (mainly tetrabromobisphenolA), unsaturated polyester resins and polyacrylate, polyetherimide and polysulphone resins.
3.3.1 PC Markets [12] The market for BPA had been growing strongly at an average rate of 10% per year over the last few years, driven primarily by increasing demand for PC resins. Optical media, including audio compact discs (CDs), CD-ROMs, recordable CDs and digital versatile disks (DVDs), had been driving growth in BPA demand via PC. However, the growth in this application is slowing significantly, due to the downloading of music and films from the Internet and other competing technologies becoming more popular. PC resins are also used in the place of traditional materials, such as metal and glass, in automotive components while glazing and sheet products can be used in architectural, security and transportation applications. Automotive glazing offers potentially strong growth opportunities for BPA/PC producers. While PC is being used in rear body parts, roof modules and fixed side windows, there has been strong resistance from automobile manufacturers in the more general replacement of glass. The higher cost, compared to glass, could be a limiting factor, although PC does offer weight savings, broader design options and easier handling that could bring efficiencies on the automotive production line. Over the next few years, applications are expected to widen into back lights and rear windows in truck cabins, moveable side windows and vehicle top applications.
Fig 3.3 Global PC Production volume 3.3.2 Epoxy resins [11] The second largest end use of BPA is epoxy resins. There are several types of epoxy resins, but those based on BPA and epichlorohydrin account for the majority. High performance coatings are one of the primary applications, followed by electrical/electronic laminates, adhesives, flooring and paving applications, mainly in the automotive, construction and aerospace industries. BPA will grow at an average annual rate of 5.5% during 20092014, as the industry tries to recover
volume lost during the recessionary years. Bisphenol A consumption for epoxy resins production will experience the fastest growth in Asia.
Fig 3.4 Global Epoxy resins Production volume 3.4 Price and Price variations [13] Bayer Shanghai chemicals ltd- USD 2661.11 per ton/Rs.122916/ ton Shanghai Sinopec Mitsui Chemicals co. ltd- USD 2629.81 per ton/ Rs.121470.92/ ton There is no significant price change seen in past 2-3 years.
3.5 Growth prospects [13,14] Global BPA consumption has increased at an average rate of almost 10% per year from 2007 to 2010, driven by PC demand and improved epoxy resin markets. However, growth has slowed considerably. In Europe, growth is expected to be flat, while the strongest growth will be in Asia, mainly China. Up to 2010, growth in the Chinese market was mainly due to epoxy resins. However, with the start-up of PC capacity in China by Teijin and Bayer and several projects planned, BPA demand in China will be driven in the future by PC. Another driver behind BPA demand is the strong growth in Asia, as a whole. In 2005-207, Asian BPA markets grew at an average of 13% per year with PC pushing it at 19% year. Future growth will be much lower, as the global economic downturn hits markets. The US market is expected to grow at 4.2% per year up to 2012, with PC and epoxy resins growing at 4.5% per year and 3.5% per year respectively. US demand is expected to increase from 1.06- mt in 2006 to reach 1.25-mt tons in 2011. In 2007, BPA imports were 4,810-tons, while exports were 34,500-tons. In short, PC will continue to be the main driver for BPA, with global growth forecast at 5-6% per year.
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Table 3.2 : Global Company wise capacity GLOBAL BISPHENOL A CAPACITY, '000 TONNE/YEAR Capacity Company Location West Europe Bayer
Dow GE Plastics
Shell
Antwerp, Belgium Krefeld-Uerdingen, Germany Stade, Germany Bergen op Zoom, Netherlands Cartagena, Spain Pernis, Netherlands
East Europe Petro Borzesti ZC North America Aristech Bayer Dow GE Plastics Shell
10 10
Haverhill, Ohio Baytown, Texas Freeport, Texas Burkville, Alabama Mount Vernon, In Deer Park, Texas
Wuxi, China 10 Lote parshuram, India 7.5 Chiba, Japan 70 Kashima, Japan 80 Nagoya, Japan 80 Osaka, Japan 60 Shin Nihon* Kyushu, Japan 95 Mitsui Pulau Sakra, Singapore 70 Kumho P&B Yeochon, S Korea 30 Nan Ya Mailiao, Taiwan 72 Chang Chun Mailiao, Taiwan 20 Taiwan Prosperity Linyuan, Taiwan 25
11
In India there is a demand of 40000 MTPA of Bisphenol A (2009) and the installed capacity within India is 28000 MTPA rest of the product is been imported from the outside market. The manufacturers presumed to increase their manufacturing capacities with level of demand they see in future. As the global market is already over supplied, most of them dont see any further growth in manufacturing capacities except some of the Asian countries like India and China, because the market in the asian countries is very tight and the consumption and demand gap is still not covered by the Domestic production units.
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CHAPTER
4
PROPERTIES
4.1 Physio-chemical Properties [15] Bisphenol are colorless, odourless substances and most of them are solid at room temperature. The melting point of most of the important Bisphenols are between 100-200C. Bisphenols are virtually insoluble in water. Their solubility in organic solvent is determined by their substituents. Whereas bisphenol A is the only readily soluble in polar media such as ethers and alcohols, bisphenols with large aliphatic groups in the molecule are soluble in araliphatic and aliphatic hydrocarbons. The alkali salts of bisphenol are water soluble. However their solubility decreases drastically with increasing substitution. The boiling points of bisphenols are very high because of the size of the molecules and its polarity. For this reason and because of the decomposition frequently observed during boiling. Bisphenols are rarely distilled. Some important physical properties of bisphenols are summarized below.
4.1.1
Physical properties of industrially important Bisphenol A are Table 4.1 Physical properties of industrially important Bisphenol A Density at 20oC 160oC Bulk density Bp at 101.3kPa 1.4 kPa 0.4 kPa Heat of vaporization at 101.3 kPa Flash point Ignition temperature Solubility of water at 83oC Solubility in acetone, alcohols Solubility in methylene chloride 1.04g/cm3 1.065g/cm3 0.492g/cm3 360oC 240oC 222oC 404J/g 227oC 510oC 0.344 wt% good ca 1 wt%
13
The chemical properties of Bisphenols are determines by Phenolic OH groups, the aromatic rings and the alkyl bridge. They therefore undergo the same reactions as the corresponding substituted monophenols. They are also suitable as building block for higher molecular mass linears polyesters are polyethers because of their bifuctionality. Bisphenols which are alkylated ortho to the OH group readily trap radicals and are therefore suitable as stabilizers. Under hydrogenation condition of Bisphenol a is cleaved to give 4-isopropylphenol, alkali catalyzed cleavage gives 4isopropylphenol in good yields. Both compounds are good to obtain by other methods. The alkali catalyzed cleavage of various Bisphenols has been investigated . the cleavage can also be catalyzed by acid to form indans and spirobisindans.The purely thermal cleavage is generally less straight forward. 4.2 Bioenvironmental Characteristics [17]
The vast majority of BPA produced, greater than 99.9%, is consumed at manufacturing sites to make products such as polycarbonate plastic or epoxy resins .Low levels may be released to the environment in the effluent.
water from biological wastewater treatment plants. Bisphenol A dust (particulates) is controlled by workplace practices and engineering design and is not a significant contributor to
environmental exposures. The relatively small amount of vapor released to the atmosphere is rapidly degraded by sunlight. The distribution of BPA in the environment can be predicted by its physical properties (Staples et al, 1998). Bisphenol A is a solid with low volatility at ambient temperature conditions, water solubility of 120-300 milligrams per liter and a greater solubility at alkaline pH values. Based on these properties, a simple equilibrium model predicts that about 50% of BPA in the environment has the potential to bind to sediments or soils with the rest remaining in the water column. Biodegradation plays a major role in the removal of BPA from the environment. Rapid and
extensive breakdown of BPA has been demonstrated in a variety of laboratory biodegradation tests. Recent studies demonstrate that BPA degrades
The trace amounts of BPA remaining in treated wastewater will continue to biodegrade in receiving waters and downstream of treatment plants. Studies using real world surface water
14
samples taken from various geographies demonstrate rapid degradation with a half- life in the range of 1 to 4 days (i.e., time for 50% degradation). Numerous publications have reported measured concentrations of BPA in streams and rivers in Japan, Europe and the United States. The median reported water concentrations from 21
European and 13 United States studies are 0.016 and 0.5 micrograms/L respectively. Aquatic tests performed on a fresh water and salt water algae, invertebrates and fish , suggest that bisphenol A is only moderately toxic to aquatic animals. Bio-concentration and metabolism studies have shown that bisphenol A has no significant bioaccumulation potential.
4.2.3 Human Metabolism Fate [18] Following the four-step procedure recommended by the United States National Academy of Sciences (NRC, 1983), a safety assessment of BPA concludes that the potential human exposure to BPA from food contact with polycarbonate plastic and epoxy resin is minimal and poses no known risk to human health. This conclusion is based on the following key points: BPA is not carcinogenic and does not selectively affect reproduction or development. The NoObserved-Adverse- Effect-Level (NOAEL) for BPA, confirmed in multiple laboratory animal tests, is 50 mg/kg body weight per day; The estimated dietary intake of BPA from food contact with polycarbonate plastic and epoxy resin, based on the results of multiple migration studies with consistent results, is less than 0.000118 mg/kg body weight/day; and This potential human exposure to BPA is more than 400 times lower than the maximum acceptable or "reference" dose for BPA of 0.05 mg/kg body weight per day established by the U.S. Environmental Protection Agency, which is derived from the No-Observed-Adverse- EffectLevel. An independent analysis by the European Commission's Scientific Committee on Food (SCF), using a similar methodology, has confirmed the safety of polycarbonate plastic and epoxy resin food contact applications. The SCF estimated total dietary intake of BPA from all food contact sources to be in the range of 0.00048 to 0.0016 mg/kg body weight per day, which is below the Tolerable Daily Intake set by the SCF of 0.01 mg/kg body weight per day. The use of polycarbonate plastic and epoxy resins for food contact applications has been and continues to be recognized as safe by the U.S. Food and Drug Administration, the European Commission's Scientific Committee on Food, the United Kingdom Food Standards Agency, the Japanese Ministry for Health, Labor and Welfare, and other regulatory authorities worldwide.
15
Bisphenol A is an endocrine disruptor, which can mimic the body's own hormones and may lead to negative health effects. Early development appears to be the period of greatest sensitivity to its effects, and some studies have linked prenatal exposure to later neurological difficulties. Regulatory bodies have determined safety levels for humans, but those safety levels are currently being questioned or under review as a result of new scientific studies. A 2011 study that investigated the number of chemicals to which pregnant women in the U.S. are exposed found BPA in 96% of women. In 2007, a consensus statement by 38 experts on bisphenol A concluded that average levels in people are above those that cause harm to many animals in laboratory experiments. However, they noted that while BPA is not persistent in the environment or in humans, biomonitoring surveys indicate that exposure is continuous, which is problematic because acute animal exposure studies are used to estimate daily human exposure to BPA, and no studies that had examined BPA pharmacokinetics in animal models had followed continuous low level exposures. They added that measurement of BPA levels in serum and other body fluids suggests that either BPA intake is much higher than accounted for, or that BPA can bioaccumulate in some conditions such as pregnancy, or both. A 2011 study. A 2008 report by the U.S. National Toxicology Program (NTP) later agreed with the panel, expressing "some concern for effects on the brain, behavior, and prostate gland in fetuses, infants, and children at current human exposures to bisphenol A," and "minimal concern for effects on the mammary gland and an earlier age for puberty for females in fetuses, infants, and children at current human exposures to bisphenol A." The NTP had "negligible concern that exposure of pregnant women to bisphenol A will result in fetal or neonatal mortality, birth defects, or reduced birth weight and growth in their offspring."
A 2008 review has concluded that obesity may be increased as a function of BPA exposure, which "merits concern among scientists and public health officials ".A 2009 review of available studies has concluded that "perinatal BPA exposure acts to exert persistent effects on body weight and adiposity". Another 2009 review has concluded that "Eliminating exposures to (BPA) and improving nutrition during development offer the potential for reducing obesity and associated diseases". Other reviews have come with similar conclusions. A later study on rats has suggested that perinatal exposure to drinking water containing 1 mg/L of BPA increased adipogenesis in females at weaning.
16
development and increases breast cancer risk". Another 2008 review concluded that "animal experiments and epidemiological data strengthen the hypothesis that fetal exposure to xeno estrogens may be an underlying cause of the increased incidence of breast cancer observed over the last 50 years". BPA may be similar to diethylstilbestrol caused birth defects and cancers in young women whose mothers were given the drug during pregnancy. A 2011 study using the rhesus monkey, a species that is very similar to humans in regard to pregnancy and fetal development, found that prenatal exposure to BPA causes changes in female primates' uterus development. A 2011 rodent study found that male rats exposed to BPA had lower sperm counts and testosterone levels than those of unexposed males. A 2011 mice study found that male mice exposed to BPA became demasculinized and behaved more like females in their spatial navigational abilities. They were also less desirable to female mice.
4.3 Handling[5]
Minimize exposure to product dust resulting to open transfer operations ,mechanical handling and fabrication. Good housekeeping and controlling of dust is necessary to minimize dust ignition hazard.
Following are the controls for sacks, bulk sacks, hopper trucks and cars that may help increase plant safety. Sacks 25 kg Sacks are commonly used for Bisphenol A packaging. Sacks should be stored in a clean, well ventilated area. Before a sack is lifted , it should be inspected for snags and punctures.
Bulk Sacks 500-1000kgs Bulk sacks are commonly used for Bisphenol A packaging. Lifting straps are attached to the bulk sack to allow the sack to be lifted by a tow motor or hoist. Bulk sacks are typically made of Ultraviolet (UV) resistant woven ,Polypropylene or similar material.
17
Hopper trucks and Hopper cars Both hopper trucks and hopper cars are sealed containers that are loaded through roof hatches and gravity or pneumatically unloaded through bottom outlet nozzles. Containers should be inserted using inert gas containing less than 9.3% by volume oxygen. Gravity unloading can be fascilitated with the use of a mechanical vibrator.
Storage bins and silos are usually made of one of the following. Concrete Alumunium Stainless steel Epoxy resin coated carbon steel Most bins and silos have a cone shaped bottom with a slope of about 6o degrees or greater to minimise the tendency towards hanging up or plugging of material. Storage bins and silos should be grounded and padded with an inert gas such as nitrogen to reduce the risk of electric spark, dust explosion and moisture gain. Storage bins should be equipped with properly designed explosion relief devices.
It would be wise to limit your exposure, not easily done since BPA is found in so many household products alone, but here are a few steps you can take to reduce your contact. Don't use plastic containers in microwaves. Use glass or ceramic. Use non- polycarbonate plastics such as polypropylene and polyethylene. Most major plastic consumer goods manufacturers now offer non-polycarbonate alternatives for drinking bottles, microwave bowls, and plastic liners.
Cut down on canned foods. To keep food from reacting with the metal of the can, a plastic coating made from bisphenol A is commonly applied to the inside of the can. This coating appears as a solid color on the inside of the can, and can leach into the food stored inside.
Avoid eating or drinking from polycarbonate plastics used in such products as hard plastic baby bottles, 5 gallon water cooler bottles, hard plastic water bottles, plastic silverware, and Lexan products. You can check for the type of plastic on the bottom of the bottle polycarbonate bottles may be labeled with recycling number 7 ("Other" type of plastic) or may contain the letters "PC" below the recycling symbol.
18
CHAPTER
5
MANUFACTURING PROCESSES
5.1 Process technologies [21, 22, 23, 24, 25, 26] available for the manufacture of Bisphenol A on commercial level are Condensation of phenol with acetone using acid as a catalyst Condensation of phenol with acetone using ion exchange resin catalyst
Acid catalyzed condensation of phenol and acetone is one of the commercial route commonly used for bisphenol a production. In this process phenol and acetone in 3:1 molar ratio are reacted in four glass lined stirred reactor at 50C and 1 atm pressure using anhydrous hydrochloride catalyst and methyl mercaptan as promoter. The residence time is around 3hr in this process in all four reactors. The reaction is exothermic, cooling water is passes through the reactor jacket for cooling. Around 99% of the acetone is converted into bisphenol a. phenol is used in the excess to ensure predominance of the forward reaction. The most important controlling parameter is temperature. Higher temperature causes the isomerism of bisphenol a. further with increase in temperature, viscosity of reaction mixture keeps on increasing. HCl is stripped off from the crude product of the reactor which is recovered and recycled. The product is further purified in the next distillation column where water is separated. During distillation, some stabilizers are added to prevent isomerism of bisphenol to o- and p- isomers. The reaction product is then distilled under reduced pressure in phenol- bisphenol a column. Further the purification of bisphenol a for removal of o- and p- isomers takes place. The product is further purified by crystallization.
19
Table 5.1 Raw material requirement Process selectivity Phenol Acetone Steam (Energy) requirement 95% 860kg 275kg 12.5GJ/Ton
HCl recycled
Phenol Acetone
water
Phenol
MeSH
Reactor
Hyrogen Chloride
Purification Dryer
Evaporator Crystallizer
Bisphenol A
Fig 5.1 Schematic flow diagram showing Bisphenol A production by Acid catalyzed phenol acetone condensation
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Phenol column
Water column
HCl column
Ion exchange resin catalyzed condensation of phenol with acetone is the new improved process for the production of Bisphenol a. ion exchange resin is todays preferred catalyst system for bisphenol a manufacturer. It replaces older acid based technologies by doing away with acid based environment. All of the problems associated with handling acids, including corrosion and disposal of acid waste are eliminated. Its a fully continues process that incorporates catalytic stripping, a novel reactor technology for the condensation of phenol and acetone. This advanced technology maximizes yield and conversion using an environmentally preferred ion exchange resin catalyst. The new reaction system promotes the BPA condensation reaction under highly favorable reaction condition while simultaneously removing the water of reaction. The catalytic stripping reactor provides a very high effective phenol to acetone ratio that, together with an improved high activity and high selectivity catalyst, results in complete conversion of acetone and max phenol conversion, with low by product formation. Much higher conversion and better selectivity are achieved than with other ion exchange catalyst system. This reduces recycles and utility consumption thereby reducing operating and capital costs. High phenol conversion permits a simple 1 stage crystallization system.
Table 5.2 Raw material consumption Process selectivity Phenol Acetone Steam (energy) consumption BPA product obtained is 99.93%- 99.98% 98.5% 835 265 6GJ/Ton
Technology suppliers:
The Sinopec/ Lummus Technology, China Badger Technologies, NY Mitsubishi Technologies, Japan Mitsui-toatsu ltd, Japan Chemwik sp. Technologies Ltd, Dow chemicals, Midland, Mighigan USA
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Acetone Phenol
Condensation Unit
Adduct
Dephenolation
Product handling
Mother liquor Concentration and phenol recovery unit Secondary Crystallization unit Rearrangement product Waste water PROCESS FLOW DIAGRAM
Fig 5.2 Schematic flow diagram :Bisphenol A production by ion exchange resin catalyzed phenol acetone condensation
22
Due to the above mentioned points of comparison we concluded that The new technology i.e. Condensation of Phenol and Acetone with Ion exchange resin catalyst in the most economical, less polluting, and most advanced technique for the Bisphenol a production. So we will select the New process for the production.
23
CHAPTER
6
PROCESS SELECTION
6.1 Process Selected
Condensation of phenol with acetone using ion exchange resin catalyst in presence of HCl as catalyst and methyl mercaptan as promoter.
6.2 Process Description Acetone and excess phenol are reacted at a temperature of 750C and pressure is kept around 4.4 bar by condensation in an ion exchange resin-catalyzed reactor system to produce p,p BPA,water and various byproducts. The crude distillation column having the temperature of 1700C and pressure of 560 torr which helps in removing water and unreacted acetone from the reactor effluent. Acetone and lights are sent to second distillation column operating at 950C and then acetone is sent to the lights adsorber to produce a recycle acetone stream and water is sent for the waste water treatment via recovery column. The bottoms of the crude column
0
having the
temperature of 70 C is sent to the crystallization feed pre-concentrator after it is passed from a heat exchanger where inside temperature is 510C and it is cooled to 540C, which distills phenol and concentrates BPA to a level suitable for crystallization. BPA is separated from byproducts in a proprietary solvent crystallization and recovery system where it is cooled from 540C to 410C to produce the adduct of p,p BPA and phenol. Mother liquor from the purification system is distilled in the solvent recovery column to recover dissolved solvent which comes in this system through pump. The solvent free mother liquor stream is recycled to the recovery system. A purge from the mother liquor is sent to the purge recovery system along with the recovered process water to recover phenol. The recovered purified adduct is processed and fed at a temperature of 410C and pressure is kept around 25 torr in a BPA finishing system to remove phenol from product, and the resulting molten BPA of temperature 1750C is solidified in the flaker followed by a pump to produce product prills which comes out at a temperature of 900C and is suitable for the BPA market.
24
25
Fig 6.1 Process Flow diagram of Ion Exchange resin catalyzed Process for production of Bisphenol A
Table 6.1 Stream wise product distribution STREAM.NO. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 PHENOL (kg/hr) 693.13 146.05 146.05 3.723 138.75 7.30 2.482 1.095 3.723 1.095 3.723 693.13 547.08 ACETONE (kg/hr) 168.78 5.22 5.22 5.22 5.22 5.22 BPA (kg/hr) 663.48 663.48 663.48 33.174 663.48 33.174 663.48 662.81 WATER (kg/hr) 52.38 52.38 52.38 0.67 52.38 52.38 -
6.2.1 Equipments used REACTOR DISTILLATION COLUMN I DISTILLATION COLUMN II CRYSTALLIZER FEED SYSTEM SOLVENT CRYSTALLIZATION AND RECOVERY SYSTEM BPA FINISHING SYSTEM FLAKER LIGHT ABSORBER RECOVERY COLUMN
26
Fig 6.2 Control Strategy Of the Reactor 6.3.1 Description 6.3.2 Components of a Control System [42] The system is divided into the following components: Process Measuring element Controller Final Control Element
27
It is desired to maintain the temperature in the reactor by means of the controller. If the measured temperature differs from the desired temperature, the controller senses the difference or error and changes the flow of Jacketed water.
Pressure in the reactor is maintained by means of controller. If pressure in the reactor is increased then the reactor stream is purge out to blow down vessel.
A flow controller is a device used to measure and control the flow of fluids and gases. A mass flow controller is designed and calibrated to control a specific type of fluid or gas at a particular range of flow rates. The FC can be given a setpoint from 0 to 100% of its full scale range but is typically operated in the 10 to 90% of full scale where the best accuracy is achieved. The device will then control the rate of flow to the given setpoint. FCs can be either analog or digital, a digital flow controller is usually able to control more than one type of fluid or gas whereas an analog controller is limited to the fluid (or gas) for which it was calibrated.
Level in the tank or the reservoir is maintained by means of controllers. If level in the tank of reservoir is increased or decreased the effluent is added or drained out automatically using the level control elements etc.
6.4 Plant Location: [42] We have decided to locate our plant in Navi Mumbai(Maharastra).The raw materials for the production of Bisphenol A are phenol and acetone which we can get from the petrochemical companies which is already been there and are producing these petrochemical products. Mumbai is located in coastal areas and due to this the transportation cost will be low when it is shipped from other coastal areas ,either it is in india or china,japan ,Taiwan etc. in the other neighbouring countries like
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150 m
100 m
Fig 6.3 Plant Layout
29
CHAPTER
7
MATERIAL AND ENERGY BALANCE
7.1 Basis
Total plant capacity is 5250 TPA= 662.81 kg/hr of 99.9% purity There is 97% conversion in the reactor There is 95% and 85% conversion in crystallizer feed concentrator and solvent crystallization system respectively . There is a theoretical requirement of phenol: Acetone ratio of 2:1 but practically 4:1 ratio is used to obtain desired conversion in the reactor.
7.1.1 Feed
174.00 kg/hr of Acetone 691.38 kg/hr of Phenol MeSH as promoter HCl as catalyst
7.1.2 Product
662.81 kg/hr of p-p bisphenol a of 99.9% purity. 52.38 kg/hr of water which is sent for treatment in waste water treatment plant.
7.1.3 Reaction involved 2 C6H5OH Phenol + CH3COCH3 Acetone C15H16O2 + H2O Bisphenol A water
30
[Material Balance and Energy Balance Uses data from ref. 29, 30, 31, 32, 33, 34]
Stream 1
REACTOR @ 97%CONVERSION
Stream 3
Stream 2
Fig 7.1 Material balance around reactor Stream 1 Acetone (fresh feed): 168.78 kg/hr
Stream 2 Phenol from Light absorber and fresh feed stream: 693.13 kg/hr Acetone from Light absorber: 5.22 kg/hr
Stream 3 BPA: 663.48 kg/hr (after 97% conersion) Unconverted Phenol: 146.05 kg/hr (Due to excess feed) Unconverted Acetone: 5.22 kg/hr Water: 52.38 kg/hr
7.3 Energy balance around reactor [35] Reaction in the reactor is Exothermic. Cp= a+bT+CT2 Inlet For phenol a= 207.48 b= -103.75 x 10-3 c= 274 x 10-6 molar flow rate of phenol= 7.57 kmol/hr so inlet heat of phenol and acetone are as follows Qphenol = 7.57 [207.48 (348-301) - ((103.75x10-3)/2(3482-3012 ) + ((274 x 10-6)/3(3483-3013)] = 72124.23 kJ/hr
31
molar rate of acetone= 3 kmol/hr Qacetone = 3[(71.96(348-301))+ ((20.1x 10-2)/2(3482-3012) ((12.78x 10-5)/3(3483-3013)] = 17442.2kJ/hr
Outlet
Molar flowrate of phenol= 1.57 kmol/hr Qphenol= 1.57[207.48 (313-348)-((103.75x10-3)/2(3132-3482)+((274 x 10-6)/3(3133-3483)] = -11163.15 kJ/hr
Molar flowrate of acetone= 0.09 kmol/hr Qacetone= 0.09[(71.96(313-348))+ ((20.1x 10-2)/2(3132-3482) ((12.78x 10-5)/3(3133-3483)] = -391.86 kJ/hr
Molar flowrate of BPA= 2.91 kmol/hr QBPA = 2.91 x 1.2(313-348) = 122.22 kJ/hr
Molar flow rate of water= 2.91 kmol/hr Qwater= 2.91[50.84(313-348)+((213.08x10-3)/2(3132-3482)-((631.39x10-6)/3(3133-3483)] = -5320 kJ/hr
Q=Heat of product -Heat of reactant +Heat of reaction Heat of reaction: Heat of formation of BPA= -369 kJ/mol Heat of formation of Acetone= -226 kJ/mol Heat of formation of Water= -285.8 kJ/mol Heat of formation of Phenol= -165.64 kJ/mol
32
=( -369-285.8) ( (2*-165.640)-226) = - 97.52 kJ/hr Therefore, Q=- 89566.43-13170.38- 97.52 kJ = -102834.33 kJ/hr Utility(Cooling water) added to decrease the temperature from 750 C to 400 C. Q = m Cp (T2-T1) -102834.33 = m*4.2*(313-348) So, mass of cooling water(m)=700 kg/hr. 7.4 Material balance around distillation column I: Stream 4
To DSII
Stream 3
DISTILLATION COLUMN I
To crystal feed system Stream 5 Fig 7.2 Material balance around distillation column I Stream 3 BPA: 663.48 kg/hr (after 97% conersion) Unconverted Phenol: 146.05 kg/hr (Due to excess feed) Unconverted Acetone: 5.22 kg/hr Water: 52.38 kg/hr
33
7.5 Energy Balance around the distillation column I [35] Feed temperature=443 K Top temperature of the distillation column=453K Bottom temperature of the distillation column=473K Heat capacity with varying temperature Cp= a+bT+CT2 7.5.1 Energy balance around the condenser [35] Molar flow rate of BPA= 2.91 kmol/hr Molar flow rate of phenol= 1.58 kmol/hr Molar flow rate of acetone= 0.09 kmol/hr Inlet temperature of the feed= 313K Outlet temperature of the product at condenser= 298K QAcetone= 0.09[(71.96(453-443))+ ((20.1x 10-2)/2(4532-4432) ((12.78x 10-5)/3(4533-4433)] = 122.72kJ/hr Qwater = 2.91[50.84(453-443)+((213.08x10-3)/2(4532-4432)-((631.39x10-6)/3(4533-4433)] = 569.54kJ/hr
7.5.2 Energy balance around the reboiler [35] Molar flow rate of BPA= 2.91 kmol/hr Molar flow rate of phenol= 1.54 kmol/hr Latent heat of phenol = 122 kJ/kg QBPA= 2.91x 1.2x (473-443) = 104.76 kJ/hr Qphenol= 1.54 [207.48 (473-443)-((103.75x10-3)/2(4732-4432)+((274 x 10-6)/3(4733-4433)] + 1.54*94*122 = 10046.57 + 17660 kJ = 27707.57 kJ/hr Qout2= QBPA+ Qphenol = 27812.33 kJ/hr
34
7.6 Material balance around distillation column II: Stream 6 To light absorber
Stream 4
DISTILLATION COLUMN II
Stream 4
Stream 7 Water 52.38 kg/hr 7.7 Material balance around crystallizer feed system: Stream 8
Stream 5
Stream 9 Fig 7.4 Material balance around crystallizer feed system Stream 5 BPA 663.48 kg/hr Phenol 146.05 kg/hr
35
7.8 Energy balance around crystallizer feed system [35] Qin=Qbpa+Qphenol =(663.48*1.2+146.94*1.43)(343-333) =10048.7 kJ /hr Qout 1=Qphenol = (138.2*1.43)(327-343) = -3162.02 kJ /hr Qout 2=Qbpa+Qphenol = (663.48*1.2+7.3*1.43)(327-343) = -12905.84 kJ /hr 7.9 Material balance around solvent crystallizer and recovery system:
Stream 11
Stream 13 Fig 7.5 Material balance around solvent crystallization and recovery system
36
7.10 Energy balance around solvent crystallizer and recovery system [35] Here we have 2 inputs and 3 outputs . The temperature inside the equipment is maintained at 750 C. Inlet temperature of the feed =400 C Qin 1= Qbpa+Qphenol =(663.48*1.2+7.3*1.43)( 348-327) =16938.59 kJ /hr Qin 2=Qbpa =(33.17*1.2)( 348-327) =835.88 kJ /hr Qout 1=Qphenol =(2.48*1.43)( 348-327 ) =74.47 kJ /hr Qout 2=Qphenol+Qbpa =(1.095*1.43+663.48*1.2)(314-343) = -23134.5.14 kJ /hr Qout 3=Qphenol+ Qbpa =(3.723*1.43+33.174*1.2)(333-348) = -676.9 kJ /hr
37
Stream 14
Stream 12
Stream 15
Stream 12
7.12 Energy balance around BPA finishing system FEED TEMPERATURE= 1700 C PRODUCT TEMPERATURE=175 0C TEMPERATURE INSIDE THE SYSTEM=200 0C Qin= Qbpa+Qphenol =(663.48*1.2+1.095*1.43)(473-443) =23932.25 kJ /hr Qout 1=Qbpa=(663.48*1.2)(448-473) = -19904.4 kJ /hr Qout 2=Qphenol=(1.095*1.43)(343-443) = -156.58 kJ /hr
38
Stream 15
FLAKER
Stream 16 Fig 7.7 Material balance around Flaker Stream 15 BPA: 663.48 kg/hr
7.14 Energy balance around Flaker FEED TEMPERATURE= 1650 C TEMPERATURE INSIDE THE TOWER=2000 C PRODUCT TEMPERATURE=1000 C Qin=Qbpa = (663.48*1.2)(453-438) =11942.64 kJ /hr Qout= Qbpa+Qmoisture =(662.81*1.2+0.61*4.2)(373-453) =-63834.72 kJ /hr
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LIGHT ABSORBER
stream 20 \
Fig 7.8 Material balance around light absorber Stream 20 Phenol: 693.13 kg/hr
Stream 2 Phenol: 693.13 kg/hr Acetone: 5.22 kg/hr 7.16 Material balance around Purge recovery system: Stream 17
Stream 18 Stream 7
(for recycle)
Stream 19
40
Stream 10
RECOVERY COLUMN
41
OVERALL OVERALL PROCE[Type a quote MATERIAL from the document or the BALANCE summary of an
(acetone as fresh feed+ acetone from recycle stream+ phenol from the light absorber+
phenol from recycle stream+ catalyst consumed) = = (168.78+ 5.22+ 146.05+ 547.08) 867.13 kg/hr
Total mass out= (BPA produced+ moisture removed in the process+ waste water removed+ acetone recycled+ phenol recycled+ catalyst regenerated) = (662.81+ 0.67+ 52.38+ 5.22+ 146.05) = 867.13 kg/hr
42
CHAPTER
8
DETAILED EQUIPMENT DESIGN
8.1.1 Process Design of Reactor [27,43] Continuous Stirred Tank Reactor Conversion 97% First order reaction Rate constant, k 24.8 min-1. Performance Equation: V/FAo = XA/-rA -rA = k CAo(1-XA) CAo= molar flow rate /volumetric flow rate Volumetric flow rate = mass flow rate/ density. = 174/792 = 0.22 m3/hr. CAo = 174/(58*0.22) = 13.63 kmol/m3. V=
. . . ( .
)
V = 1.2846 m3 = 1284.6 ltr. Taking L/D ratio = 1.5 V= 1.2846= D3 = 1.08 So, D = 0.57 m L = 3.85 m.
.
43
8.1.2 Mechanical design of Reactor [27,43] Design pressure Operating temperature MOC Type of head Joint efficiency Design stress DS factor DS at 70oc So, DS = 1.4*60 = Corrosion allowance Shell thickness, Ths = Pi Di / (2f j- p ) + C Let di = 1.1 m Ths = (4.5*105*1.1)/[(2*90*106*0.98)-(4.5*105)] + 0.003 Ths = 0.005813m Head thickness, Thh = Pi Rc Cs / [( 2fj + Pi (Cs 0.2))] Cs = [ 3 + (Rc / Rk)1/2 ] Head thickness including corrosion allowance = 1.1 * 0.06 = 0.066 Cs = [ 3 + (1.1 / 0.066 )1/2 ] = 1.77 Thh = ( 4.5*105 * 1.1 * 1.77 ) / [(2*90*106*0.98) + (4.5*106 (1.77 0.2 ))] Thh = 0.00494m Let head thickness including corrosion allowance is 6.2 mm Longitudinal stress, L = P di / 4t = (4.5 * 105 * 1.1)/ (4 * 6.2 * 10-3 ) 6 2 L = 19.95 * 10 N/m Circumferential stress, h = P di / 2t = (4.5 * 105 * 1.1) / (2 * 6.2 * 10-3) = 39.91 * 106 N/m2 Assume bed height 1.5 times the top and bottom head i.e. 1.1 * 1.5 = 1.65 m Height of reactor, = 1.1 + 1.65 + 1.1 = 3.85 m Weight of cylindrical plate for shell W1 = di h Ths = 8000 kg/ m3 = 3.14 * 1.1 * 3.85 * 0.005813 * 8000 = 618.71 kg W1 = 618.71 * 9.8067 N W1 = 6067.59 N 4.5x105 70oc 8%Cr, 12% Ni alloy steel Torrispherical 0.98 90x106 1.4 60 84 0.003m
44
Weight of head, W2 = 2 (di/2)2 Thh = 2 * 3.14 * (1.1/2)2 * 0.00494 * 8000 = 75.11 kg = 75.11 * 9.8067 N W2 = 736.63 N Weight of vessel fitting, internal and external fitting etc., W3 = 15% of ( W1 + W2) W3 = 0.15 * (6067.59 + 736.63) N W3 = 1020.63 N Weight of the content, Volume of the reactor = 0.5 m3 = volume * density of BPA = 0.5 * 1040 = 520 kg = 520 * 9.8067 = 5099.48 N Total weight of vessel = W1 + W2 + W3 + W4 = 6067.59 + 736.52 + 1020.63 + 5099.48 = 12924.32 N Direct stress due to weight of vessel and its content and attachment, Now, w = W / [ (di + t) t] = 12924.32 / ( * (1.1 + 0.0062) * 0.0062)) = 5.99 * 106 N/m2 As vessel height is limited wind load can be neglected.
Stress due to offset piping s = 2T/[ t di (di + t)] Torque due to offset piping, T = 562 N = 2 * 562/[ * 0.0062 * 1.1 (1.1 + 0.0062)] = 47.42 * 103 N/m2 Eq. stress, = ( h2 - h a + a2 + 3 s2)1/2 a = l+ w a = (19.95 * 106) + (5.99 * 106) = 25.94 N/m2 2 6 6 6 2 3 2 1/2 r = [(39.91 * 106) - (35.91 * 10 * 25.94 * 10 ) + (25.94 * 10 ) + 3(47.42 * 10 ) ] 2 r = 36.52 * 106 N/m
r
For satisfactory design, r should be less than i.e. 36.52 * 106 < 90 *106 That shows our design is satisfactory.
45
Support, Bracket support Taking width of base plate = 18 mm Thickness of plate = 6.2 mm Load with steel bracket, Ibs = 60 Lc Lc = 60 * 18 * 6.2 = 6696 N No. of brackets = 12924.32 / 6696 = 1.93 = 2 Nos. 8.2.1 Process Designing of Heat exchanger [28] Ms = 867.13 kg/ hr Tc1 = 40oC Tc2 = 170oC Viscosity = 25 cp = 25 * 10-3 kg/ ms Cps = 2184 J /kg Mw = 1000 kg/hr Th1 = 220oC Th2 = 166.8oC Viscosity = 0.355 cp = 0.355 * 10 -3 kg/ ms Cpw at 220oC = 4630 J/ kg Q = 867.13/3600 * 2184 * (170 40) = 68380 W 68380 = 1000/3600 * 4630 * (220 Th2) Th2 = 166.8 oC Assume it to be a counter current heat exchanger, T1 = 50oC T2 = 126.8oC TLMTD = T1 T2/(ln(T1/T2)) TLMTD = 76.8oC R = Th1 Th2/(Tc2 Tc1) = 0.374 S = Tc2 Tc1/(Th1 Tc1) = 1.86 For the calculated values of R and S the value to temp. correction factor from fig.6.11 of pg no. 162 of B I BHATT [53]. F = 0.95 TLMTD = 0.95 * 76.8 oC = 72.96oC Value of U taken from table 6.7 of page no.163 of B I BHATT and trial values of do and L after trial and error [53], Tube length = 10 ft = 3.048 m Tube outer dia = 0.015875 m U = 500 W/m2oC Apro = Q/U T = 68380 / (500 * 72.96) = 1.87 m2
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Apro = do l Nt Number of tubes, Nt = Apro/( do l) = 1.87/( * 0.015875 * 3.048) = 12.32 = 16 Nos. Let no. of tube passes be 4, For 4 pass and triangular pitch, Pt/do = 1.25 from table 6.2 of pg no 145 of BI BHATT K1 = 0.175 n1 = 2.285 now, tube bundle i.e. Db = do(Nt/k1)1/n1 = 15.875 * (16/0.175)1/2.285 = 114.54 mm = 115 mm Shell ID Ds = 115 + C C = 15 mm i.e. clearance Ds = 115 + 15 = 130 mm Evaluation of hi, Tube side flow area, at = (Nt/4) * (/4) * (di)2 = (16/4) * (/4)* (0.0133858)2 = 5.62 * 10-4 m2 Tube side mass velocity = Gt = (1000/3600)/(5.62 * 10-4) = 132.27/m2 s Density of water at 80oc = 971.8 kg/m3 Tube side fluid velocity, ut = Gt/ density = 132.27/971.8 = 0.136 m/s Reynolds number, Re = di Gt/ = (0.0133858 * 132.27)/ 0.355 * 10-3 = 4987 > 4000 Thermal conductivity of water at 80oc = 0.628 w/ m2oc Pr = cp/ k = (0.355 * 10-3 * 4186)/ 0.628 = 2.36 Using Dittus- Bolter equation, Nu = hi di / kf = 0.023 * Re 0.8 * Pr 0.33 (/ w)-0.14 hi = (0.023 * 0.628/0.0133858) * (4987)0.8 * (2.37)0.33 * 1 = 1301.29 W/m2oC Evaluation of BPA side HT coeff, ho Shell side flow area, As As = (Pt do / Pt) * Ds * Bs Pt/ do = 1.25, Ds = 220 mm, Bs = Ds/5 = 44 mm As = (1.25do do/1.25do) * 0.220 * 0.044 As = 1.94 * 10-3 m2 Shell side mass velocity, Gs = ms/As =(867.13/3600)/ 1.94 * 10-3 Gs = 124.16 kg/m2s
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Us = Gs/density = 124.16/1200 = 0.103 m/s Shell side eq.dia for triangular pitch, de = 1.1/do(Pt2- 0.907 do2) = (1.1/15.875) * (19.8437 2 (0.907*(15.875)2)) = 11.4465 mm Shell side Reynolds number, Re = de Gs/ = 0.0114465 * 124.16/25*10-3 = 568.4 Pr = Cp/k = 25*10-3 * 2184/ 0.19 = 287.36 For Re = 568.4 and 25% baffle spacing read Jf from the graph 6.14 of BI BHATT [53] Jf = 1.95 * 10-2 Nu = hs de/ kf = Jh Re Pr 1/3 (/ w)-0.14 hs = 1.95 *10-2 * 0.19/0.0114465 * 568.4 * 287.36 1/3 * 1 hs = 1211.78 W/m2oC Overall heat transfer coefficient, (1/Uo) = (1/ho) + (1/hod) + (do ln (do/di)/2kw + (do/di)(1/hid) + (do/di)(1/hi) hod = 2000 W/ m2oC from table 6.9 of pg no 175 of BI BHATT [53] hid = 5000 W/m2oC Kw = 50 Uo = 193.29 W/m2oC Heat transfer area required, Ar = Q/Uo T = 68380/(193.29*72.69) = 4.86 m2 Shell side pressure drop, Ps = 8 Jf (Ds/dl)(L/Bs) s. Vs2/2(/w)-0.14 Ds = 0.220, dl = 0.01144, L = 3.048 Bs = 0.044, Vs = 0.103 m/s, s = 1200 kg/m3 For Res = 568.4, Jn from fig 6.15 = 8*10-2 Ps = 8*8*10-2(0.72/0.01144)(3.048/0.044){1200*(0.1032)/2} = 5423.97 Pa Ps = 5.42 kPa Tube side pressure drop Pt=Np[ 8 Jf(L/di)( /w)-0.14+2.5]* .Vt2/2 Np=4, L= 3.048m, di=0.01338 Ut = 0.136 m/s, = 971.8 kg/m3, /w =1 Ret = 4087, Jf from 6.13 fig.= 5.5*10-3 Pt= 4[8* 5.5*10-3*(3.048/0.0133858)*1 +2.5]* (971.8* 0.1362)/2 = 450.9 Pa Pt = 0.45 KPa
8.3 Process design of distillation column [36] Design of sieve tray Column by using:Fenskey-Underwood Gillilands method Fenskey equation Nm = log [(XLK/XHK)d/ (XHK/XLK)b]/logLk Nm = Minimum no. of trays, Lk = Average volatility of light key with respect to heavy key
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Heavy key component= phenol Light key component= acetone Lk = 25.30 (XHK)d = mole fraction of heavy key component in distillate = 1.06*10-3 (XLK)d= mole fraction of light key component in distillate = 0.998 (XLK)b= mole fraction of light key component in bottom = 1.87*10-3 (XHK)b = mole fraction of heavy key component in bottom = 0.998 Nm = log[(0.998/1.06*10-3)*(0.998/1.87*10-3)]/log 25.30 = 4.06 Gillilands Co-relation:N Nm/N +1 = 1 exp[(1+54.4 )/(11+117.2)])[(-1)/*0.5)] = (R-Rm)/(R+1) R = 1.5 Rmin R = 3(by using underwood method in energy balance) = (3 2)/(3+1) = 0.25 N Nm/N +1 = 1 exp[(1+(54.4*0.25))/(11+117.2*0.25)])((0.25-1/0.250.5)) N = 7.68 N = No. of the theoretical stages required for distillation Assume tray efficiency = 0.75 Actual no of stages required for distillation Column =9 V =57.6 kg/hr L =809.53 kg/hr L/V = Lw/Vw = 809.53/57.6 = 14.05 P = 0.73 atm(Pressure at the top of the column) Mavg =XiMi T = 60.4 0C(dew point) v = PMavg/RT = (153.31*0.73)/(8.314*333.4) = 1.08 kg/m3 Density of liquid at the top L = 1/[(wt. fraction/ acetone)+(wt. fraction/ phenol)] = 805.191 kg/m3 FLv = Lw/Vw*(V/L)0.5 = 0.10281 Assuming tray space = 0.45m From the fig 8.16 page no-444 (Bhatt and Thakore) [54] Cf = 0.055 Vf = Flooding velocity Vf = (Cf)*((L V)/V)0.5 = 1.501 m/s Let actual velocity throughout tower = 0.85*Vf = 0.85*1.501 =1.275 m/s Volumetric flow rate of vapour at the top Qv = (V )/( V) = (57.6)/(1.08*3600) = 1.148*10-3 m3/sec An =Net area required at the top An = Qv / V = 1.48*10-3/1.276 = 1.196 m2 Let down comer area Ad = 0.12 Ac An = Ac Ad = Ac 0.12 Ac = 0.88 Ac Ac = inside cross sectional area of tower 0.88 Ac = 1.16*10-3 Ac = 1.359 m2
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Inside diameter of column required at the top Di = 1.29 m at the top Volumetric flow of liquids QL = L/ L = 0.000576 m3/sec Check for weeping, Vhmin = K 0.9*(25.4 - dh)/v Vhmin =Minimum velocity of vapours through holes Assume Weir height hw = 50 mm(for both section) Hole diameter dh = 5 mm(for both section) Plate thickness t = 5 mm(for both section) Height of liquid crest over the weir how = 750*(Lm/ (L*lw))2/3 Lm = (0.7) L = 0.7*809.53 = 566.671/3600= 0.1574kg/s (minimum) L = 805.161 kg/m3 From table 8.34 page no-449 (Bhatt and Thakore) [54] For Ao / Ac = 0.12 , lw/Di = 0.770 lw = length of weir = 0.77*1.79= 1.0164 m Minimum how = 750*(.1574/(805.191*0.9933))^(2/3) = 2.53 mm At minimum rate hw + how = 50+2.53 = 52.53 mm From fig 8.19 page no-449 , k = 30.10 Vhmin = 30.10 0.9*(25.4 - 5)/(1.08).5 = 9.63 m/s Vha = Actual vapour velocity through holes at minimum vapour flow rate, Ah = hole area Aa = actual area Ad = downcomer area=0.12*Ac Assume hole area is 8% of active area Aa=Ac-2*Ad Aa=(1.32*10-3)-(2*0.12*1.32*10-3) m2 Aa=0.0010032 m2 Ah=8 % of Aa =8.02*10-5 m2 Vha = (0.7*1.48*10-3)/.0010032 = 10.32 m/s Vha > Vmin Tray pressure drop:Dry plate pressure drop hd = 51*( V h/C0)^2 *( V / L) Vh =Maximum velocity of vapors through hole Vh = Q V/A h (maximum) V = 2.16 kg/m3 , L = 804.85 kg/m3 From fig 8.20 pg no-450 ( Bhatt and Thakore) For plate thickness/ hole diameter = 1 Ah / Ap = Ah/Aa =(8.02*10-5/0.0010032)*100= 0.08 C0 = 0.8422 Ap = perforated area hd =34.64mm hw = 50 mm Lc Maximum height of liquid crest over the weir Lmax= Lm/.7 =0.1574/7 = 0.224kg/sec
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lw=0.0315 m Maximum how = 750*(Lmax/( L * lw))(2/3) = 32.05 mm Residual pressure drop hr = (12.5*103)/805.191 = 15.52 mm Total pressure drop per plate ht = hd + ( hw + how) + hr = 132.03 mm Pressure drop = 9.8*10-3* L* ht Pressure drop = 9.8 * 10-3 *100.30*805.191 =1043.35 N/m2 Checking of downcomer design hdc = 166(Lmd/L Am)2 Lmd = liquid flow rate through down comer Lmd = L = (805.53 )/(3600) = 0.2248kg/s L = 805.191 kg/m3 Am = Ad or Aap whichever is smaller Aap= Perforated area Ad = 0.12 Ac = 0.12*1.32*10-3 = 1.584*10-4m2 hap = hw 10 = 50-10 = 40 mm = 0.04m Aap = 0.04*lw = 0.04*0.0315 Aap = 1.26*10-3 m2 Ad > Aap Therefore take Am = Aap Am = Aap = 1.26*10-3 m2 hdc=166{L/(Am* L)} hdc = 166{0.2248/(1.26*10-3*805.191)}2 = 8.15 mm hb = Liquid back up in down comer hb = hw+ how + ht + hdc = 50+32.05+132.223+8.15 = 222.42 mm 222.42 < (Lt + hw) /2 Lt=Tray spacing=450mm Residence time in down comer Tr = Ad x hb x L/(Lmd) Lmd= 0.2248 kg/sec Tr = 126.19 seconds Tr > 3 sec Hence,downcomer area and tray spacing are acceptable Checking of entrainment Vapour velocity based on net area,Vn=Q/An Vn = 1.48*10-3/1.16*10-3 = 1.26 m/s % of flooding = Vn/Vf = 1.26/1.5101= 0.843*100 = 85% FLv =0.10281 , =.51 (from fig 8.18 pg no 447 B I Bhatt) % entrainment = 51 % which is greater then 10%
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CHAPTER
9
ECONOMIC EVALUATION
9.1 CAPITAL COST ESTIMATION [27] 9.1.1 Cost of reactor Type Stirred Tank Reactor Volume of reactor 1.284 m3 Material of construction Carbon steel On basis of capacity of reactor The total weight of the reactor (Wv) = 12924.32 N = 1318 kg Cost of Stirred Tank reactor in 2002 = 1*73*(Wv)-0.34 * Wv (From chapter-12, Eq.12-50 from Plant design and economics for chemical engineers, and Timmerhaus) = $ 19240 (as in 2002) = ` 9,94,000
Peters
Using CHEMICAL ENGINEERING PLANT COST INDEX (CEPCI) [41] Value in present time
Where, C = present cost Co = cost in the base year (in our case its 2002) Ci = Plant cost index of the present year = 785 Cio = Plant cost index in base year = 426 Total Cost of reactor = $ 35453 = ` 18,32,211 (The present rate of US Dollar is ` 51.68 as on 08.04.2012) And material of construction is carbon steel
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9.1.2 Cost of Heat Exchanger Heat Exchanger for surface area of 5m2 (Plant design and economics for chemical engineers,Peters and Timmerhaus,ch 14, fig.-14-15) Cost of Heat Exchanger in 2002 = $ 1250 Total Cost = $ 1250 Present Cost = $ 20700 (using CEPCI) = ` 1,19,000 (The present rate of US Dollar is ` 51.68 as on 08.04.2012) And material of construction is carbon steel
9.1.3 Cost of distillation column I Diameter = 0.33m Height = 7 m No of trays = 9 Purchased cost of trays in tray column. Price includes tray deck, bubble cap, riser, downcomer and structural steel parts from ch 15, graph 15-13 (plant design and economics for chemical engineers,Peters and Timmerhaus, C= $ 300*9 = $2700 (The present rate of US Dollar is ` 51.68 as on 08.04.2012) And material of construction is carbon steel
Present year cost = $ 4975 Total cost of distillation column = $ 4975 = ` 2,58,000 9.1.4 Cost of distillation column II Diameter = 0.33m Height = 4 m No of trays = 3 Purchased cost of trays in tray column. Price includes tray deck, bubble cap, riser, downcomer and structural steel parts from graph 15-13 (plant design and economics for chemical engineers,Peters and Timmerhaus, C= $ 400*3 = $ 1200 (The present rate of US Dollar is ` 51.68 as on 08.04.2012) And material of construction is carbon steel
Present year cost = $ 2210 Total cost of distillation column = $ 2210 = ` 1,15,000
9.1.5 Cost of Absorption column Diameter = 0.5 m Height = 2 m Purchased cost of vertical column from graph 15-11 (plant design and economics for chemical engineers,Peters and Timmerhaus, Cost = $ 14000
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Purchsed cost of stacked ring, price including column internal support and distribution from graph 15-14 (plant design and economics for chemical engineers,Peters and Timmerhaus, Cost = $500 Cost of Installtion and auxillaries from graph 15-15 (plant design and economics for chemical engineers,Peters and Timmerhaus, Cost = $1500 (The present rate of US Dollar is ` 51.68 as on 08.04.2012) And material of construction is carbon steel Total cost = $ 16000 (as of 2002) Present cost = $ 29440 = ` 15,21,460
9.1.6 Cost of pump:[37] The software on www.matche.com the cost is calculated on the basis of diameter of discharge pipe. Calculate the discharge (Q) = area of pipe* velocity Where velocity is 2 m/sec Formula for calculating cost: Log10Cp = K1+K2 log10A+K3(Log10A)2 Where A = power = 0.929 kW K1, K2, K3 = constant In this case the values are, K1 = 3.3892 K2 = 0.0536 K3 = 0.1538 = ` 1,08,800 (as in 2001) CPI in the year 2001 was 397 So present year cost is ` 2,15,000 The no. of pumps used in the plant are 5, So Total cost of the pumps = ` 2,15,000 * 5 = ` 10,75,000
9.1.7 Cost of the Crystallizers:[37] From the software on www.matche.com for a crystallizer of 0.8 m3 that are used here cost around $ 40300 (in 2007) The no. of crystallizers in the process are 2, So the total cost of the crystallizers = $ 80600 (in 2007) The present day cost of the crystallizers = $ 121706 = ` 62,90,000
9.1.8 Cost of the BPA finishing system i.e. evaporator:[37] From the software on www.matche.com for a BPA finishing system of 30 ft2 that is used here cost around $ 37800 (in 2007) So the total cost of the BPA finishing system = $ 37800 (in 2007) The present day cost of the BPA finishing system = $ 57078 = ` 29,50,000
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9.1.9 Cost of the Recovery column:[37] From the software on www.matche.com for a Recovery column of 30 ft2 that is used here cost around $ 7700 (in 2007) So the total cost of the Recovery column = $ 7700 (in 2007) The present day cost of the Recovery column = $ 11627 = ` 6,63,000
9.1.10 Cost of the Purge Recovery column:[37] From the software on www.matche.com for a Purge Recovery column of 30 ft2 that is used here cost around $ 2000 (in 2007) So the total cost of the Purge Recovery column = $ 2000 (in 2007) The present day cost of the Purge Recovery column = $ 3020 = ` 1,56,000
9.1.11 Cost of the phenol storage tank:[37] From the software on www.matche.com for a phenol storage tank of 0.8 m3 that is used here cost around $ 20000 (in 2007) So the total cost of the phenol storage tank = $ 20000 (in 2007) The present day cost of the phenol storage tank = $ 30200 = ` 15,60,000
9.1.12 Cost of the Flaker:[37] From the software on www.matche.com for a Flaker of 700 kg/hr production capacity that is used here cost around $ 21300 (in 2007) So the total cost of the Flaker = $ 21300 (in 2007) The present day cost of the Flaker = $ 3216 = ` 1,66,000
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9.2 ESTIMATION OF CAPITAL INVESTMENT ITEMS BASED ON DELIVERED EQUIPMENT COST The estimation of capital investment item is based on delivered equipment cost and delivered equipment cost is calculated on the purchased equipment cost. The various percentage of delivered equipment cost are taken on the basis of type off chemical plant i.e. whether it is solid processing or solid fluid processing or fluid processing. Our type of plant is fluid processing. Thus all the values of percentages are taken into due consideration of it. Total capital investment = fixed capital investment + Working capital Fixed capital investment = Direct cost + Indirect Cost Direct cost = Onsite cost + Offsite Cost Table 9.1 Total capital Investment of the project Fraction of Delivered equipment (A) Fixed capital Investment Direct Cost Purchased equipment (a)onsite cost Land 15000 m2 (`550/ m2 ) Delivery, % of purchased Equipments Subtotal: Delivered Equipment cost Purchased equipment Installation Instrumentation and control Piping Electrical system (b)Offsite cost Building (including services) Yard improvement Service facilities Total direct cost Indirect cost Engineering and supervision Construction expenses Legal expenses Contractors fee Contingency Total Indirect cost FIXED CAPITAL INVESTMENT (A) = Direct Cost + Indirect Cost (B)Working capital TOTAL CAPITAL INVESTMENT = (A) + (B) Cost (`)
1,58,68,000 82,50,000 15,86,800 1,74,54,200 61,09,000 45,40,000 55,85,000 19,20,000 31,42,000 17,45,000 1,04,72,000 5,09,67,200 57,60,000 71,56,000 6,98,000 38,40,000 61,09,000 2,35,63,000 7,45,30,200 0.85 1,49,00,000 8,94,30,000
9.2.1 Estimation of total product cost [27] Manufacturing cost = Direct production cost + Fixed charges + Plant overhead cost
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Table 9.2 cost of raw material MATERIAL Phenol Acetone Water Hcl TOTAL QUANTITY (Kg/year) 4515000 1443700 7920821 30 UNIT PRICE Per Kg ( ` ) 87 48 0.026 150 39,28,05,000 6,93,00,000 2, 50,941 4,500 ` 46,23,15,441 COST PER YEAR ( ` )
9.2.3 Direct Production Cost : [27] (a) Raw Material Cost = ` 46,23,15,441 Since Raw Material Cost = 20-80% of Total Production Cost, for our plant we can estimate the percentage by the cost of raw material and product cost and it is roughly 60%. Therefore, Raw Material = 60% of Total Production Cost Thus, Total Production Cost (TPC) = 46,23,15,441/0.6 = ` 77,05,25,735 (b) Operating Labour = 10% of TPC = ` 7,70,52,573 (c) Direct Supervision & Clerical Labour = 10% of Operating Labour = ` 77,05,257 (d) Utilities = 10% of TPC = ` 7,70,52,573 (e) Maintenance & Repair Cost = 2% of FCI = ` 23,74,600 (f) Laboratory Charges = 5% of Operating Labour = ` 38,52,628 TOTAL DIRECT PRODUCTION COST = ` 60,03,53,076
9.2.4 Fixed Charges: [27] (a) Depreciation (Straight Line Method) Assuming Life of Equipment = 10Yrs Therefore, Depreciation Amount = Purchased Equipment Cost/ Life of Equipment = 1,74,54,000/10 = ` 17,45,400 (b) Local Taxes = 1% of FCI = ` 7,45,300 (c) Property Insurance = 0.4 % of FCI =` 2,98,000 (d) Financial Interest = 8 % of TCI = ` 71,54,400 TOTAL FIXED CHARGES = ` 99,43,100
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9.2.5 Plant Overhead Cost: [27] POC = 40% of Operating labour = ` 3,08,21,030 Total Manufacturing Cost = Direct Production Cost + Fixed Cost + POC = ` 64,11,17,000
(a) Administrative Rate = 10 % of cost for Operating Labour = ` 77,05,257 (b) Packaging, Distribution & Marketing Cost = 1 % of Total Product Cost = ` 60,03,530 (c) R & D = 1% of Total Product Cost = ` 60,03,530 TOTAL GENERAL EXPENSES = ` 1,97,12,300
Total Production = 5250 TPA = 5250 * 1000 Kg Cost of BPA = ` 132 Revenue = Total Production * Cost = ` 69,30,00,000
Profit Before Tax = Revenue Total Product Cost = ` 3,21,70,000 Depreciation = 5% of FCI = ` 37,26,000 Tax Rate = 33.9 % Profit After Tax = 0.661 (Profit before Tax Depreciation) = ` 1,88,01,484 Rate of Return = (Net Profit)/(Total Capital Investment) * 100 = 1,88,01,484/ 8,94,30,000* 100 = 21.02% Payback Period = (Total Capital Investment ) / (Profit After Tax) = 8,94,30,000/ 1,88,01,484 = 4 Yrs & 9 Months
58
CHAPTER
10
CONCLUSIONS AND RECOMMENDATIONS
Bisphenol are colorless, odorless substances and most of them are solid at room temperature. BPA is a monomer used to make polycarbonate resins for applications such as construction, electronics and food containers. Global BPA capacity in 2008 was around at 5.16-mtpa, and demand about 4.38-mt. Asia is the largest producing region, with 45% of total capacity. In India there is a demand of 40000 MTPA of Bisphenol A (2009) and the installed capacity within India is 28000 MTPA. Rest of the product is been imported from the outside market. In India, Bisphenol A is primarily used in manufacturing of epoxy resins, phenolic resins and processing of polyvinyl chloride. Ion exchange resin catalyzed condensation of phenol with acetone is the new improved process for the production of Bisphenol A. Ion exchange resin is todays preferred catalyst system for Bisphenol A manufacturer. It replaces older acid based technologies by doing away with acid based environment. All of the problems associated with handling acids, including corrosion and disposal of acid waste are eliminated. Its a fully continues process that incorporates catalytic stripping, a novel reactor technology for the condensation of phenol and acetone. This advanced technology maximizes yield and conversion using an environmentally preferred ion exchange resin catalyst. At present about 12,000 tons per annum of Bisphenol A is imported in India from various countries and only two companies are manufacturing Bisphenol A with a limited plant capacity. Therefore, it is a safe step to install the plant with a capacity of 5250 tons per annum in Navi Mumbai Maharashtra. We have designed a plant of 5,250 MTA, with techno-economic feasibility report which is stated with need, demand & supply analysis and by going through a process of mass, energy balance with detailed equipment design in the process. The payback period (4.9 years) and rate of return suggests the plant to be economic viable and a profitable venture to invest, in the interest of the stakeholders for an already existing group or a newcomer in the market.
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REFERENCS
[1] Natural occurance of BPA , At: www.bisphenol-a.org/pdf/EnvironmentDorn.pdf [2] Traditional applications of BPA, At: www.who.int/foodsafety/chem/.../2_source_and_occurrence.pdf [3] Uses of BPA, At: www.icis.com/chemicals/bisphenol-a/ [4] Uses of BPA, At: www.alibaba.com Country Search India [5] History of Bisphenol A, At: en.wikipedia.org/wiki/Bisphenol_A [6] Various Grades of BPA, At: www2.dupont.com/FluoroIntermediates/en.../BPAF_techsheet.pdf [7] Specifications for Bisphenol A ,At: monographs.iarc.fr/ENG/Monographs/vol71/mono71-71.pdf [8] Standards or BPA,At:http://www.kazanorgsintez.ru/index.php?page=catalogue&lang_id=2&aid=2625 [9] Global supply scenario, At: www.bayer.co.th/webphp/eng/production.php [10] Global/Indian supply and demand for BPA, At: http://www.slideshare.net/teviaw/ihs-webcast-greenproducts-and-supply-chain-disruption [11] Global/Indian demand scenario,At: http://www.mendeley.com/research/bisphenol-bpa-china-reviewsources-environmental-levels-potential-human-health-impacts/ [12] PC Markets, At: www.scribd.com/doc/.../Bisphenol-A-World-Market-Outlook-2011 [13]Pricevariations,At:http://www.researchandmarkets.com/reports/1554364/bisphenol_a_world_market_o utlook_2011.pdf [14] Growth prospects,At: http://www.marketresearch.com/GlobalData-v3648/North-America-BisphenolOutlook-Size-6682413/ [15]PhysiochemicalProperties,At:http://www.us.edu.pl/uniwersytet/jednostki/wydzialy/chemia/acta/ac16/zr odla/01_AC16.pdf [16] Chemical properties of Bisphenol A,At: http://www.gsi-net.com/en/publications/gsi-chemicaldatabase/single/67.html [17] Bio-environmental Characteristics,At: http://www.bisphenol-a.org/human/occsafety.html [18]HumanMetabolismFate,At:http://publications.jrc.ec.europa.eu/repository/bitstream/111111111/142211 /eur%2024389_bpa%20%20baby%20bottles_chall%20%20persp%20(2).pdf [19]Health-effects on, At: http://www.americanscientist.org/issues/feature/2010/1/assessing-risks-frombisphenol-a/1 [20] Safety Considerations ,At: http://www.bisphenol-a.org/human/herMetabolism.html [21] Process technologies, At: http://wenku.baidu.com/view/504d9a18227916888486d793.html [22] Process technologies, At: http://www.chemwik.com/EN/EN/Offer.html [23] Process technologies, At: http://www.doc88.com/p-49835442710.html [24]. Norman,P& Lieberman,(2008),Third edition. Troubleshooting Process Plant Control. [25]. Navid Naderpur ,(2008), Petrochemical production processes.
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[26]. Mall.I.D,(2007).Petrochemical Process technology. [27]. Peters.M.S and Timmerhau.K.D,(2004) Plant design and economics for chemical engineers. [28]. Sinnot.R,Towler.G,(2009),Fifth edition Chemical engineering design, Pg 1067 1089, 474-478. [29].Smith,J.M; & Van ness.H.C, Seventh edition. Introduction to Thermodynamics. Tata McGraw-Hill, New Delhi. [30]. Bhatt,B.I; & Vora,S.M,(2004), Fourth edition. Stoichiometry.Tata McGraw-Hill, New Delhi. [31]. Margaret.G wells,(1999),Second edition. Handbook of chemical process. [32] Material Balance and Energy Balance, At: http://en.wikipedia.org/wiki/Acetone as of 1st November 2011. [33] Material Balance and Energy Balance, At: http://en.wikipedia.org/wiki/Phenol as of 1st November 2011. [34] Material Balance and Energy Balance, At: http://en.wikipedia.org/wiki/BPA of 1st November 2011 [35] Energy balance around reactor Antoines Constants at: http://www.docstoc.com/docs/21918351/ANTOINE-COEFFICIENTS-FOR-VAPOR-PRESSURE [36] Bhatt,B.I; & Thakore.S.B,(2007).Introduction to Process Engineering and Design. Tata McGrawHill, New Delhi. [37] Cost of pump, At: www.matche.com/EquipCost/index.htm [38] Pricing of raw material , At: www.icis.com/v2/chemicals/9076135/phenol/pricing.html [39] Pricing of raw material , At: www.icis.com/v2/chemicals/9074857/acetone/pricing.htm [40] Total Revenue, At: www.icis.com/v2/chemicals/9074857/bisphenola/pricing.htm [41] CHEMICAL ENGINEERING PLANT COST INDEX (CEPCI), At: www.cheresources.com/invision/index.php?app=core&module=global§ion=register [42].Coughanowr,Donald.R; & LeBlanc.Steven.E,(2008),Third edition. Process Systems Analysis and Control. Tata McGraw-Hill, New Delhi. [43] Towler.Gavin; & Sinnott Ray,(2009),Fifth edition. Chemical Engineering Design.Tata McGraw-Hill, New Delhi. Chemical Engineering
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Toxicological Data on Ingredients Phenol: ORAL (LD50): Acute: 317 mg/kg [Rat]. 270 mg/kg [Mouse]. DERMAL (LD50): Acute: 630 mg/kg [Rabbit]. 669 mg/kg [Rat].
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varying degree of respiratory irritation or lung damage. Repeated exposure to a highly toxic material may produce general deterioration of health by an accumulation in one or many human organs.
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Phenol + calcium hypochlorite is an exothermic reaction producing toxic fumes which may ignite. Phenol + sodium nitrite causes explosion on heating. Peroxydisulfuric acid + phenol causes explosion.
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Molecular Weight: 94.11 g/mole Color: Colorless to light pink pH (1% soln/water): Not available. Boiling Point: 182C (359.6F) Melting Point: 42C (107.6F) Critical Temperature: 694.2 (1281.6F) Specific Gravity: 1.057 (Water = 1) Vapor Pressure: Not applicable. Vapor Density: 3.24 (Air = 1) Water/Oil Dist. Coeff.: The product is more soluble in oil; log(oil/water) = 1.5 Ionicity (in Water): Not available. Dispersion Properties: See solubility in water, methanol, diethyl ether, acetone. Solubility: Easily soluble in methanol, diethyl ether. Soluble in cold water, acetone. Solubility in water: 1g/15 ml water. Soluble in benzene. Very soluble in alcohol, chloroform, glycerol, petroleum, carbon disulfide, volatile and fixed oils, aqueous alkali hydroxides, carbon tetrachloride, acetic acid, liquid sulfur dioxide. Almost insoluble in petroleum ether. Miscible in acetone. Sparingly soluble in mineral oil.
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Toxicological Data on Ingredients: Acetone: ORAL (LD50): Acute: 5800 mg/kg [Rat]. 3000 mg/kg [Mouse]. 5340 mg/kg [Rabbit]. VAPOR (LC50): Acute: 50100 mg/m 8 hours [Rat]. 44000 mg/m 4 hours [Mouse].
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Ingestion: Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention if symptoms appear. Serious Ingestion: Not available.
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medical advice immediately and show the container or the label. Avoid contact with skin and eyes. Keep away from incompatibles such as oxidizing agents, reducing agents, acids, alkalis. Storage: Store in a segregated and approved area (flammables area) . Keep container in a cool, wellventilated area. Keep container tightly closed and sealed until ready for use. Keep away from direct sunlight and heat and avoid all possible sources of ignition (spark or flame).
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Instability Temperature: Not available. Conditions of Instability: Excess heat, ignition sources, exposure to moisture, air, or water, incompatible materials. Incompatibility with various substances: Reactive with oxidizing agents, reducing agents, acids, alkalis. Corrosivity: Non-corrosive in presence of glass. Polymerization: Will not occur.
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APPENDIX-III
MATERIAL SAFETY DATA SHEET OF BISPHENOL A
Section 1: Physical/Chemical Characteristics
Boiling Point : 400 C Vapor Pressure: < 0.1mm Hg Melting Point : 161-163 C Vapor Density(Air=1): NA Specific Gravity(H2O=1): NA Solubility in Water : Negligible Appearance and Odor: White to off-white solid .
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clothing and shoes. Seek medical help if needed. Eye: Flush eyes with plenty of water for at least 15 minutes. Get immediate medical help. Oral: If swallowed induce vomiting and get medical attention. Medical Conditions Generally Aggravated by Exposure: Unknown. Other Health Hazards: Bisphenol A, the non-fluorinated analog of Bisphenol A has caused abnormalities in the development of mouse eggs at extremely low levels (ca 20 ppb). (Reference: Current Biology, 13, 546, 2003; C&EN
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