Production and Analysis of Acrylonitrile

I CONTENTS LIST OF TABLE vi LIST OF FIGURES vii ABBREVIATION LIST viii 1 GENERAL INFORMATION 2 11 Physical Properties 3 12 Chemical Properties 4 13 Use of Acrylonitrile 4 14 Occurrence 5 141 Natural occurrence 5 Acrylonitrile is not known to occur as a native product 5 142 Occupational exposure 5 15 Production of Acrylonitrile 5 151 Sohio process 6 152 Production from ethylene cyanohydrin 6 153 Production from acetylene and hydrocyanic acid 6 16 Toxicology of Acrylonitrile 7 17 Reactions of Acrylonitrile 9 171 Reactions with nitrile class 9 172 Reactions with olefins and alcohols 9 173 Reactions with aldehydes and methylol compounds 9 174 Reaction of the double bond 9 175 Reactions of both functional classses 10 2 SITUATION IN THE WORLD AND TURKEY 12 21 Acrylonitrile Marketing in theWorld 12 II 22 Acrylonitrile Marketing InTurkey 14 3PROCESS SELECTION AND CAPACITY 16 31 Process Selection 16 311 Cost estimation for all production methods 16 32 Production of Acrylonitrile from SOHIO Process 20 321 Catalysts 23 33 Capacity of the Process 23 4ACRYLONITRILE PRODUCTION FLOW DIAGRAMS I 25 41 Block Flow Diagram 25 42 Explain the Related Equipments 26 421 Used equipments 26 43 Explain the Raw Materials 30 431 Propylene 30 432 Air 31 433 Ammonia 31 44 Explain the Byproduct Materials 32 441 Hydrocyanic acid 32 442 Acetonitrile 32 443Carbon monoxides 34 45 Evaluation and Examination of By Products 34 5 PROCESS FLOW DIAGRAM II 37 51 Acrylonitrile Production in Chemcad Simulation 37 52 Chemcad Equipment Values 38 521 Reactor 38 522 Quencher 39 III 523 Absorber 40 524 Recovery column 41 525 Acetonitrile column 41 526 HCN column 42 527 ACN column 42 6 MATERIAL AND ENERGY BALANCE 44 61 MATERIAL BALANCE 44 611 Material Balance for Reactor 44 612 Quench column 54 613 Absorber 55 614 Recovery column and decanter 56 615 Aceto column 57 616 HCN column 57 62 ENERGY BALANCE 58 621 Preheating of reactor 58 622 Energy Balance Around Reactor 59 623 Energy Balance Over Product Gas Cooler 61 624 Energy Balance Around Quench Column 63 625 Energy Balance Around After Cooler 65 626 Energy Balance Around Absorber and Heat Exchanges 67 627 Energy Balance Around Recovery Column 68 7 DESIGN OF EQUIPMENT 71 71 Fluidized Bed Reactor FBR 71 711 Mechanical design of the reactor 72 712 Checking tower height for various external and internalloads 73 IV 713 To design the skirt support 76 72 Distillation Column Design 77 721 To find the diameter of the distillation column 80 722 Provisional Plate Design 83 723 To check weeping rate 83 724 To check plate pressure drop 84 725 Plate layout 85 73 Heat Exchanger Calculation 85 74 Pump Pipesizes Design 86 75 Compressor Design 89 8 PLANT PLAN AND SITE SELECTION 92 81 Marketing Area 92 82 Raw Material Supply 92 83 Transport Facilities 92 84 Availability of Labor 93 85 Availability of Utilities 94 86 Availability of Suitable Land 94 87 Environmental Impact and Effluent Disposal 95 88 Local Community Considerations 95 89 Climate 95 810 Political Strategic Considerations 96 811 Raw Material Source 97 812 Number of Working Staff 97 813 Storage Tanks 99 814 Raw Materials Purchased From Domestic And Abroad 99 V 815 Domestic and Distributed Products 100 816 Plan Layout 101 REFERENCES 104 VI LIST OF TABLE Table 11 Some physical properties of acrylonitrile 3 Table 12 The primarily toxic effects in humans of acrylonitrile 8 Table 21 The biggest manufacturers of Acrylonitrile in the World 13 Table 21 The amount of acrylonitrile produced by PETKIM over the years 14 Table 31 Cost of each component 16 Table 32 Reaction and cost of component 16 Table 33 Cost of each component 17 Table 34 Reaction and cost of component 17 Table 35 Cost of each component 18 Table 36 Reaction and cost of component 18 Table 41 Physical properties of propylene 30 Table 42Propylene Values of thermophysical properties of the saturated liquid and vapor 30 Table 43 Thermodynamic properties of air 31 Table 44 Physical and chemical properties of ammonia 31 Table 45 Commercial acetonitrile specifications 33 Table 46 Properties of carbonmonoxides 34 Table 61 Conversion percentages 45 Table 62 Molecular weight in kg kgmole 45 Table 64 Material balance over quench column 55 Table 63 Energy required for preheat the reactants 58 Table 64 Components and its properties 59 Table 65 Energy required 60 Table 66 Energy required 62 Table 67 Enthalpy out with gases 63 Table 68 Enthalpy out with the mixture 66 Table 69 Enthalpy out with unabsorbed gases from top 67 Table 610 Enthalpy out with bottom stream 68 Table 611 Enthalpy out with Distillate 69 Table 71 XY composition 77 VII LIST OF FIGURES Figure11 Structure of acrylonitrile 2 Figure 21 World acrylonitrile capacity 12 Figure 22 Historical prices in USA Belgium and China 14 Figure 31 SOHIO Process 20 Figure 41 Block Flow Diagram of Acrylonitrile in SOHIO Process 25 Figure 42Block diagram for fluidized bed reactor 27 Figure 43 Chemical formula of acetonitrile 32 Figure 51 Process Flow Diagram on Chemcad Simulation 37 Figure 71 McCabe thiele chart 79 Figure 81 Labor productivity growth of different countries 94 Figure 82 Average temperatures and precipitation in Gebze 2017 96 Figure 83 Pathways of deciding plant layout 101 Figure 84 The site location of the company 102 Figure 85 Plant layout 103 VIII ABBREVIATION LIST SOHIO Standard Oil of Ohio ACN Acrylonitrile ABS Acrylonitrilebutadienestyrene PAM Polyacrylamide VOC Volatile organic compound 1 SECTION I GENERAL INFORMATION 2 1 GENERAL INFORMATION Figure11 Structure of acrylonitrile1 Acrilonitrile also called acrylic acid nitrile propylene nitrile vinylcyanide propenoic acid nitrile is a multidirectional and reactive monomer which can be polymerized under a wide variety of conditions and copolymerized with wide range of other vinyl monomers It was first prepared in 1893 by the French chemist Charles Chemical formula C3H3N1 Acrylonitrile is a clear colorless liquid with a slightly sharp odor Considering that acrylonitrile is produced in such huge amounts due to its varied uses and that it is a toxic chemical with stringent regulations on its environmental impacts the process is viable for modification 33 If there is no leakage during storage and transportation was not found However in cigarette smoke and motor vehicle exhaust acrylonitrile it increases its importance in terms of human health In addition exposure can create a potential risk Acrylonitrile on health and environment researches and evaluations were carried out that examine the effects in a multifaceted way 34 3 11 Physical Properties Acrylonitrile C3H3Nmolwt 53064 is an unsaturated molecule having a carboncarbon double bond combinated with a nitrile group It is a uncolored liquid With the faintly pungent odourof peach pits Its properties are summerized in Table 1 Acrylonitrile is misciple with most organic solvents including aceton benzene carbontetrachloride ether ethanol ethyl acetate ethylene cyanohydrin liquid carbon dioxide methanol petroleumether toluene xylene and some kerosene The water solubility of acrylonitrile at a number of temperatures is shown in Table1 1 Table 11 Some physical properties of acrylonitrile 2 Molecular formula C3H3N Molar mass 5306 Density 08060 gcm320oC Freezing point 8355 005 oC Boiling point 760mmHg 773oC Flash point 5oC Critical temperature 2460 oC Criticalpressure 3535 x 103kPa Ignition temperature 4810oC Vıscosity at 25oC 034 4 12 Chemical Properties The presence of both the olefinic carboncarbon double bond group and the nitrile group in acrylonitrile gives the molecule its matchless and varied reactivity This reactivity leads to the great versatility of acrylonitrile as a raw material The olefinic group can undergo polimerization and copolymerization hydrogenation oxidation addition and cyclization The nitrile group can undergo hydrogenation hydrolysis hydration esterification cyclization and reduction 3 13 Use of Acrylonitrile Acrylonitrile is used as A pure material for the production of synthetic fibres plastics and synthetic rubber One of the causes for the versatility of acrylonitrile is that it can form copolymers with other unsaturated compounds such as styrene and butadiene 1 Acrylonitrile is commercially produced by propylene ammoxidation in which propylene ammonia and air react with the catalyst in the fluidized bed Acrylonitrile is primarily used as a comonomer in the production of acrylic and modacrylic fibers It includes plastic surface coatings nitrile elastomers barrier resins and adhesives In addition various antioxidants are used as a chemical intermediate in the synthesis of pharmaceuticals dyes and surfactants 4 In the synthesis of compounds used for the production of adhesives antioxidants binders for dyestuffs and emulsifiers 1 5 14 Occurrence 141 Natural occurrence Acrylonitrile is not known to occur as a native product 142 Occupational exposure Occupational emptying to acrylonitrile have been measured in monomer production and in the production of staples resins polymers and other chemical intermediates from acrylonitrile 5 a Monomer production b Fibre production c Resin production d Rubber and polymer production e Organic chemical synthesis f Miscellaneous 15 Production of Acrylonitrile Today almost all acrylonitrile is produced by ammoxidation of propene Although the first report of the preparation of acrylonitrile from propene occurred in a patent by the Allied Chemical and Dye Corporation in 1947 it was a decade later when Standard Oil of OhioSohio developed the first commercially feasible catalyst for this process Nowadays all of the United States capacity and approximately 90 of the world capacity for acrylonitrile is based on the Sohio process 1 There are various methods for the production of acrylonitrile The main ones 2 Sohio process Production from ethylene cyanohydrin Production from acetylene and hydrocyanicacid 6 151 Sohio process Approximately 90 of total ACN production follows the Standard Oil of Ohio SOHIO process which is based on propylene ammoxidation Reaction is too high selective fast ACN production without the need for excessive recycling efforts 3 The cost of ACN production where more than 70 of propylene is produced has increased in recent times For this reason ACN is produced as a result of the work because it is necessary to find alternative more economical solutions In particular propane ammoxidation is seen as the brightest alternative process 3 In this process propene oxygen as air and ammonia are catalytically converted directly to acrylonitrile using a fluidizedbed reactor operated at temperatures of 400 500 C and gauge pressures of 30 200 kPa 03 2 bar 1 2CH2CHCH3 2NH3 3O2 2CH2CHCN 6H2O 152 Production from ethylene cyanohydrin Germany IG Farben Leverkusen and the United States American Cyanamid earliest produced acrylonitrile on an industrial scale in the early 1940s These operations were based on the catalytic dehydration of ethylene cyanohydrin Ethylene cyanohydrin was produced from ethylene oxide and aqueous hydrocyanic acid at 60C in the presence of a basic catalyst The intermediate was so dehydrated in the liquid phase at 200C in the presence of magnesium carbonate and alkaline or alkaline earth salts of formic acid 1 HOCH2CH2CN CH2CHC N H2O An advantage of this process was that it generated few impurities but it was not economically competitive American Cyanamid and Union Carbide closed plants based on this technology in the mid1960s 1 153 Production from acetylene and hydrocyanic acid Before the improving of the propene ammoxidation process a major industrial route to acrylonitrile involved the catalytic addition of hydrocyanic acid to acetylene 1 HCCH HCN CH2CHCN 7 Though a vapour phase reaction has been reported the commercial reaction usually was carried out at 80 C in dilute hydrochloric acid containing cuprous chloride Unreacted acetylene was recycled The yield from this reaction was good however the raw materials were relatively costly some undesirable impurities divinylacetylene and methyl vinyl ketone were difficult to remove and the catalyst required frequent regeneration Du Pont American Cyanamid and Monsanto employed this method until about 1970 1 16 Toxicology of Acrylonitrile Acrylonitrile is toxic if inhaled or ingesting or in touch with the skin Skin touch causes blistering the eyes and mucous membranes are particularly at risk Symptoms of acute exposure are headache nausea dizziness and vomiting After substantial exposure the symptoms are unconsciousness spasms and cessation of breathing These symptoms can be delayed a few hours after exposure Acrylonitrile must be regarded as if it is potentially carcinogenic to man If any contact with Acrylonitrile has taken place or is suspected immediate advice of medical service is strongly recommended 6 If somebody breathe in these gases these gases can generate serious sharp toxicity loss of consciousness also death However antidotes can prevent from serious harm 7 Violent body soreness and allergic dermatitis occurs when contacting with acrylonitrile directly Death of users of acrylonitrile can happens Because of death industries of pharmaceutical developed fumigants 8 Acrylonitrile is a carcinogen chemical and it is depending proof carcinogenicity from studies in experimental animals Oral exposure to acrylonitrile caused cancer of the fore stomach and increased benign tumors in mice 8 9 Acrylonitrile must be stayed away from effective oxidizers principally bromine and strong bases strong acids copper copper alloys ammonia and amines Bromine is reactive with these chemicals Contacting with these chemicals could cause chemical reaction which could consequently of a fire or explosion Before acrylonitrile comes in contact via any other chemical chemical suitability should be determined 10 8 Table 12 The primarily toxic effects in humans of acrylonitrile 2 Toxidity Routes of Exposure Dose Time Headache tremor convulsions Inhalation Acute Nausea vomiting headache dizziness Inhalation 35220 mgkg Acute Dizziness fever nausea vomiting Dermal inhalation Acute Erythema Dermal Acute Skin swelling skin burning Dermal Acute Headache sleep disorder chest pain Inhalation For months Headache weakness tiredness nausea vomiting nosebleedinsomnia Inhalation For years Decreasing of hemoglabin Inhalation 255 mgkg Chronic Headache tiredness swelter Inhalation Chronic 9 17 Reactions of Acrylonitrile 171 Reactions with nitrile class Hydration and Hydrolysis Hydrolysis of the nitrile class in part manufactures acrylamide sulfate which upon neutralization yields acrylamide this is the principle for acrylamides traditional produced in concentrated 85 sulfuric acid In dilute acid or alkali finalized hydrolysis occurs to yield acrylic acid 3536 172 Reactions with olefins and alcohols Compounds like olefins and secondary and tertiary alcohols which form carbonium ions in acid and Nsubstituted acrylamides are created via The Ritter reaction 36 173 Reactions with aldehydes and methylol compounds When sulphuric acid catalyzed formaldehyde and acrylonitrile reactive to form any of NN methylene bisacrylamide or 135triacrylylhexahydrostriazine based on the conditions Such Nmethylol benzamide reactive along with yield mixed bisamides in the presence of sulfuric acid NMethylol phthalimide reactive long with occur Nphthalimido methylacrylamide35 174 Reaction of the double bond Hydrogenation The excellent yield of propionitrile is achieved along with the catalysts of metal This propionitrile can be more easier hydrogenated to propylamine 36 Halogenation For generationing of 23dihalopropionitriles at low temperatures halogenation yields going quietly If there is pyridine addition of chlorine constitutes 23dichloropropionitrile 223 trihalopropionitrile is admitted when there is no UV light in risen temperatures with UV light both 223 and 233isomers are formed For giving 23dichloropropionic acid esters chlorination and alcoholysis occur 36 10 Hydroformylation The other name of this process is the oxosynthesis For giving βcyanopropionaldehyde acrylonitrile in contact with a blend of hydrogen and carbon monoxide cobalt octacarbonyl has been catalyzed This reacts via HCN and ammonia after that hydrolysis produces glutamic acid on a huge traditional measure3536 Hydrodimerization Adiponitrile have been done for consisting the induce of acrylonitriles dimerization electrochemically and chemically Hydrodimerization with its derivatives happens 36 175 Reactions of both functional classses For fabricating 3chloropropionic acid hydrolysis of acrylonitrile have been catalyzed by hydrochloric acid Alcoholysis and chlorination happens in the presence of sulfuric acid and alcoholysis and hydrochlorination also happens Glycidamide is consisted by intervention of acrylonitrile with hydrogen peroxide Such forms bis 2carboxamidoethyl sulfide or poly β alanine treatment with water a weak base sulfide or containing ammonium 36 11 SECTIONII SITUATION IN THE WORLD AND TURKEY 12 2 SITUATION IN THE WORLD AND TURKEY 21 Acrylonitrile Marketing in the World Its worldwide production is approximately 5 million tons per year and besides being used in the manufacture of acrylic fibers responding for almost 50 of consumption 19 Acrylonitrile profitability will remain low because capacity is expanding faster than demand is growing However very little acrylonitrile is consumed carbon fibre production is growing rapidly 11 Demand for acrylonitrile is broadly tied to the general economy and is therefore cyclical Most of acrylonitriles major end marketsABS resins acrylic fiber and adiponitrile for instanceare cyclical and impacted by economic downturns when consumer spending contracts In 2016 China alone accounted for 32 of the global acrylonitrile market Further growth is forecast for acrylonitrile through 2021 Northeast Asia is forecast to account for about 55 of the global incremental demand over the next five years The acrylonitrile markets dependence on the state of the economy was evidenced during the global recession in 200809 when it dropped by 12 in just a year12 Figure 21 World acrylonitrile capacity11 Production of acrylonitrilebutadiene acrylonitrile globally accounting for 34 of the overall demand ABS is the largest thermoplastic engineering resin in the market because of its unique properties rigidity heat resistance and toughness which make it a prime copolymer for diverse technical and demanding applications The composition of ABS resins can vary widely allowing the production of many different grades that can be tailored Acrylic fiber was once the single largest outlet for acrylonitrile accounting for more than half of the market in 2000 Over the past decade the acrylonitrile volumes used to produce acrylic fiber have contracted at an average rate of 33 annually and now account for ab acrylonitrile demand 12 Acrylamide is the worlds third for acrylonitrile More than 90 of acrylamide is used for polya PAMs are organic flocculants and their dominant use is as wastewater treatment agents They are used primarily as conditioning and dewatering aids for sludges thickening of waste sludges in municipal sewage treatment and in in Over the next five years acrylonitrile demand is expected to increase 32 Overall 55 of the global demand growth is expected to come from Northeast Asia followed by the Middle East and North America Acrylamide and ABS resin applications will account for most acrylonitrile demand growth through 2021 12 Table 21 The biggest manufacturers of Acrylonitrile in the World Ineos DSM and Asahi Kasei are leader 13 butadienestyrene ABS resins is the primary end use for acrylonitrile globally accounting for 34 of the overall demand ABS is the largest thermoplastic engineering resin in the market because of its unique properties rigidity heat resistance and toughness which make it a prime copolymer for diverse technical and demanding applications The composition of ABS resins can vary widely allowing the production of many different grades that can be tailored for different enduse applications 12 Acrylic fiber was once the single largest outlet for acrylonitrile accounting for more than half of the market in 2000 Over the past decade the acrylonitrile volumes used to produce acrylic fiber t an average rate of 33 annually and now account for ab largest acrylonitrile end use accounting for 13 of the market for acrylonitrile More than 90 of acrylamide is used for polyacrylamide PAM production PAMs are organic flocculants and their dominant use is as wastewater treatment agents They are used primarily as conditioning and dewatering aids for sludges thickening of waste sludges in municipal sewage treatment and in industrial operations such as pulp and paper plants Over the next five years acrylonitrile demand is expected to increase at an average annual rate of 2 Overall 55 of the global demand growth is expected to come from Northeast Asia the Middle East and North America Acrylamide and ABS resin applications will account for most acrylonitrile demand growth through 2021 12 Table 21 The biggest manufacturers of Acrylonitrile in the World26 Ineos DSM and Asahi Kasei are leader companies in the world26 styrene ABS resins is the primary end use for acrylonitrile globally accounting for 34 of the overall demand ABS is the largestvolume thermoplastic engineering resin in the market because of its unique properties of strength rigidity heat resistance and toughness which make it a prime copolymer for diverse technical and demanding applications The composition of ABS resins can vary widely allowing the use applications 12 Acrylic fiber was once the single largest outlet for acrylonitrile accounting for more than half of the market in 2000 Over the past decade the acrylonitrile volumes used to produce acrylic fiber t an average rate of 33 annually and now account for about 29 of largest acrylonitrile end use accounting for 13 of the market crylamide PAM production PAMs are organic flocculants and their dominant use is as wastewater treatment agents They are used primarily as conditioning and dewatering aids for sludges thickening of waste sludges in dustrial operations such as pulp and paper plants 12 at an average annual rate of 2 Overall 55 of the global demand growth is expected to come from Northeast Asia the Middle East and North America Acrylamide and ABS resin applications will 26 14 Figure 22 Historical prices in USA Belgium and China14 22 Acrylonitrile Marketing InTurkey 30 of ACN locally sourced from PETKIM the rest is heavily imported from Europe 15 AKSA imports more Acrylonitrile than any other fiber producer in the world 15 In 1985 Petkim began producing 70000 tons of acrylonitrile Petkim currently produces 90000 tons year of acrylonitrile 16 Table 21 The amount of acrylonitrile produced by PETKIM over the years 20 2007 2008 2009 2010 2011 Acrylonitrile 91538 ton 90367 ton 93552 ton 94045 ton 98072 ton 15 SECTIONIII PROCESS SELECTION AND CAPACITY 16 3PROCESS SELECTION AND CAPACITY 31 Process Selection 311 Cost estimation for all production methods Production from ethylene cyanohydrin Main reaction HOCH2CH2CN CH2CHC N H2O Table 31 Cost of each component37 Table 32 Reaction and cost of component37 CH2CH2O HCN CH2CHCN H2O Mol 1 1 1 3 MW gmol 42 27 53 18 Molmol of Propylene 0792 0509 1 0339 Dollarsmol 715 637 425 05 Gross profit 425x1050339715x0792637x05094486dollarskg of acrylonitrile This method is not suitable for producing AN Chemical Costdollarkg CH2CH2O ethyleneoxide 715 HCN hydrocyanicacid 637 C3H3Nacrylonitrile 45 H2Owater 05 17 Production from acetylene and hydrocyanic acid Main reaction HCCH HCN CH2CHCN Table 33 Cost of each component37 Chemical Costdollarkg C2H4 acetylene 1625 HCN 637 C3H3Nacrylonitrile 45 H2Owater 05 Table 34 Reaction and cost of component37 Gross profit 425x11625x0490637x0509 02114 dollarskg of acrylonitrile 02114x06001268 dollars per kg of AN this method is not profitable HCCH HCN CH2CHCN Mol 1 1 1 MW gmol 26 27 53 Molmol of Propylene 0490 0509 1 Dollarsmol 1625 637 425 18 Sohio process ammoxidation of propylene Main reaction CH2CHCH3 NH3 32 O2C3H3N 3 H2O Table 35 Cost of each component37 Chemical Costdollarkg C3H6propylene 09 NH3ammonia 03 O2oxygen C3H3Nacrylonitrile 45 H2Owater 05 Table 36 Reaction and cost of component37 C3H6 NH3 32O2 C3H3N 3 H2O Mol 1 1 32 1 3 MW gmol 42 17 48 53 54 Molmol of Propylene 0792 0320 0905 1 1019 Dollarsmol 090 030 425 05 Gross profit is 425x105101909x079203x032039507 dollarskg of acrylonitrile Propylene conversion is higher than 95 also a selective yield in AN close to 80 39507x08 31605 dollars per kg of acrylonitrile Cost is cheaper than other production methods 1 It is the most commonly used procedure in the production of acrylonitrile 1 19 Propylene conversion can be higher than 95 3 The resulting byproducts can be used for other processes 3 SOHIO process is selected for the production of acrylonitrile Today approximately 90 of total ACN production follows the Standard Oil of Ohio SOHIO process which is based on propylene amoxidation Reaction is too high selective fast ACN production without the need for excessive recycling efforts 21 The cost of ACN production where more than 70 of propylene is produced has increased in recent times For this reason ACN is produced as a result of the work because it is necessary to find alternative more economical solutions In particular propane ammoxidation is seen as the brightest alternative process 21 The ammoxidation reaction is formed by catalytic oxidation of hydrocarbons in the presence of mixed metal oxides or organic nitriles used as catalysts and ammonia in order to produce water Typical reagents are alkenes The reaction consists of three main processes the oxidation of hydrocarbons to the introduction of intermediates in active sites the introduction of nitrogen and the oxidative dehydrogenation of Nlinked species One of the most innovative ways of producing ACN is the traditional SOHIO process 21 All the reaction takes place in the vapour phase in the presence of a catalyst The primary byproducts of the process are hydrogen cyanide acetonitrile and carbon oxide The recuperation of these by products depends on influences such as market conditions plant location and energy costs Hydrogen cyanide and acetonitrile although they carry a market value are usually specified specifying that the production of these byproducts has little effect on the economics of producing ACN 1 Variations within the SOHIO process may provide for purification storage and loading facilities for these recoverable byproducts Other diversities of the SOHIO process contain the recovery of ammonium sulfate from the reactor effluent to allow for biological processing of a waste water stream and variations in catalysts and reactor situations 1 20 32 Production of Acrylonitrile from SOHIO Process In the standard SOHIO process as given air ammonia and propylene are introduced into a fluid bed catalytic reactor operating at 032 bar pressure and 400510 C Ammonia and air are fed to the reactor in slight extra of stoichiometric proportions because extra ammonia drives the reaction closer to integration and air continually regenerates the catalyst An important feature of the process is the high conversion of reactants on a oncethrough basis with only just a few seconds habitation time The heat generated from the exothermic reaction is recovered via a wasteheatrecovery boiler 1 Figure 31 SOHIO Process Air Ammonia Propylene 2 3 4 5 6 1 2 3 4 5 6 7 8 9 8 Sulfuric acid 10 12 13 1 12 9 7 11 10 20 Exhaust Gas 14 22 16 23 17 18 28 29 Acrylonitrile Impurities 14 Water 15 16 11 17 18 19 21 24 25 Acetonitrile HCN Water Ammonium Sulfate 22 Catalyst 49 which represents the fourth major level of improvement is currently recommended in the process Emissions of ACN during startup are radically higher than during normal operation During startup the reactor is heated to operating temperature before the reactants propylene and ammonia are introduced Effluent from the reactor during startup begins as oxygenrich then passes through the explosive range before reaching the fuelrich zone that is maintained during normal plant operation To prevent explosions in the line to the absorber the reactor effluent is vented to the atmosphere until the fuelrich effluent mixture can be achieved The absorber vent gas contains nitrogen and unconverted oxygen from the air fed to the reactor propane and unconverted propylene from the propylene feed product ACN byproduct hydrogen cyanide and acetonitrile other organics not recovered from the absorber and some water vapour 1 The ACN content of the combined column purge vent gases is slightly high about 50 of the total VOCs emitted from the recovery acetonitrile light ends and product columns The rest of the vent gases occur noncondensibles that are dissolved in the feed to the columns the VOCs that are not condensed and for the columns operating under vacuum the air that leakages into the column and is removed by the vacuum jet systems 1 For the ACN process byproduct hydrogen cyanide and acetonitrile are incinerated along with product column bottoms The primary impurity problem related to the incinerator stack is the formation of NOx from the fuel nitrogen of the acetonitrile stream and hydrogen cyanide Carbon dioxide and fewer amounts of CO are emitted from the incinerator stack gas Other emission sources contain the volatilization of hydrocarbons through process leaks fugitive emissions and from the deep well ponds breathing and working losses from product storage tanks and losses during product loading operations The fugitive and deep wellpond emissions consist primarily of propane and propylene while the storage tank and product loading emissions comprise primarily of ACN 1 23 321 Catalysts Numerous catalyst formulations have been proposed to counterpoise the lower yield coming about because of the improvement of side responses and their execution has reliably enhanced with time They are on the whole utilizing blended oxides relies upon antimony arsenic bismuth cobalt tin iron molybdenum nickel phosphorus tellurium uranium vanadium with or without help 17 33 Capacity of the Process When determining capacity for acrylonitrile production plant to be established in Turkey the domestic market in Turkey is necessary to take into consideration PETKIM is known to produce about 90000 tons of acrylonitrile annually 16 Likewise AKSA which has become the worlds largest producer of acrylic fibers when it turns its inner market meets a part of the production of acrylonitrile by taking the full amount produced by PETKIM However AKSA 315000 tons year with the largest capacity in the world because it is the only acrylic fiber manufacturer in Turkey meets the needs of the remaining acrylonitrile from abroad Therefore all the needs of acrylonitrile in Turkey which also aims at establishing a facility is providedAs is known about 90 acrylonitrile raw material is present in the production of acrylic fibers According to AKSA producing 315000 tons of fiber per year the amount of ACN is 283500 tons15 90000 tons of acrylonitrile PETKIM per year 16The remaining amount of acrylonitrile will be 193500 tons The acrylonitrile capacities produced in different parts of the world are shown in table 21 and table 22 Inos DSM and Asahi Kasei are world leaders in the production of acrylonitrile2526 These include Turkey which we determine by looking at the needs of 193500 tonnes of acrylonitrile as a target of generating 75 of capacity the facility will have an annual production capacity of approximately 146000 tons of acrylonitrile 1516 24 SECTIONIV PRODUCTION FLOW DIAGRAMS 25 4ACRYLONITRILE PRODUCTION FLOW DIAGRAMS I 41 Block Flow Diagram Figure 41 Block Flow Diagram of Acrylonitrile in SOHIO Process45 26 42 Explain the Related Equipments 421Usedequipments Fluidized Bed Reactor Quencher Recovery Ammonium sulphate unit Purification In the standard SOHIO process as given air ammonia and propylene are introduced into a fluid bed catalytic reactor operating at 032 atm and 4005100C Ammonia and air are fed to the reactor in slight excess of stoichiometric proportions because excess ammonia drives the reaction closer to completionand air continually regenerates the catalyst An important feature of the process is the high conversion of reactants on a oncethrough basis with only a few seconds residence time The heat generated from the exothermic reaction is recovered via a wasteheat recovery boiler 1 4211Fluidized bed reactor Flowing of small solid particles usually in a cylindrical bed into the process of moving these solid particles in a suspended manner by sending them through the plate at a rate as low as the fluid by means of a field distributor plate on the lower side of the bed Here the velocity of the particles equals the velocity of the fluid Such fluidized workout makes the solid particles move quickly in the bed creating a perfect mixing between them 22 The air is introduced below the bottom grid whereas mixed propene and ammonia are introduced through the spiders above the grid Residence time in the reactor is between 2 to 20 seconds There is almost complete transformation of propene and the selectivity of acrylonitrile is around 80910 The main reactions and side reactions of the process in reactor are as follows The gaseous phase product stream is remove in liquid phase through counter current water absorber to remove inert gases and recover reaction products Mixture of acrylonitrile acetonitrile carbon oxides and hydrogen cyanide are formed Product surge is sent to fractionator to remove hydrogen cyanide 27 Acrylonitrile is separated from acetonitrile by extractive distillation Acrylonitrile obtained after extractive distillation is subjected for drying The acrylonitrile obtained after drying is 99 pure Acetonitrile and hydrogen cyanide which are the primary byproducts of the process are subjected to incineration Incineration leads to the formation of nitrogen oxides carbon oxides which are the primary pollutants Other emission resource involve the volatilization of hydrocarbons through process leaks and from the deep well ponds breathing and the working losses from the product storage tanks and losses during product loading operations Primarily propene and propane are emitted in the fugitive and deep well or pond emissions whereas storage tank and product loading emissions consists of acrylonitrile 23 Figure 42Block diagram for fluidized bed reactor23 The equipment of the following table fluidized bed reactors is summarized23 28 4212 Quencher The reactor offgas must be quenched to the condensation temperature and the excess ammonia removed Due to the presence of impurities it is impossible to recycle the ammonia and it needs be removed with sulfuric acid The two others for the quench system are quench and acid treatment in one step acidic quench quench and acid treatment in two separate steps basic quench In the acidic quench reactor offgas is touched with a circulating solution of sulfuric acid and ammonium sulfate in water Fresh sulfuric acid is added to keep the system acidic and to avoid ammonia breakthrough Water or preferably recycle streams from the plant are added to balance the evaporative losses come by quenching hot reactor offgas A purge is taken to avoid oversaturation of ammonium sulfate The quench also removes the catalyst which then is removed from the purge by settling or filtration 24 Advantages Higher recovery efficiency of acrylonitrile due to low pH Lower polymer production in the quench section Opportunity to reuse waste water streams Disadvantages Lower recovery of acrylonitrile due to high pH in the quench Higher polymer formation in the quench In the first step of the basic quench reactor offgas is quenched with water Water losses are made up by adding fresh water or recycling plant waste water streams Mainly the catalyst fines are removed from the reactor offgas However the addition of water causes the reaction of highboiling oligomeric compounds and organic ammonium salts which must be purged from the system in common with organic acids In the second step the gas is treated isothermally with sulfuric acid to remove excess ammonia Fresh acid has to be added to maintain the acidity but no additional water is required 24 29 4213 Recovery Having change to the quench section organics are typically recovered from the reactor off gases by absorption scrubbing with chilled water The remaining waste gas is sent to treatment The scrubber liquor is passed to an extractive distillation column recovery column where the acrylonitrile and hydrogen cyanide products are separated in the overheads from the acetonitrile The acetonitrile is rather refined for sale as a product but it may be stripped and incinerated with energy recovery The recovery column bottoms contain highboiling organic compounds for incineration and some ammonium andor sodium salts of organic acids which are sent as an aqueous stream to waste water treatment 24 4214 Ammonium sulfate unit The ammonium sulfate in the quench purge is recovered by crystallisation to produce a saleable byproduct The crystallisation stage generates a waste liquor stream The effluent streams from the crystallisation process that include some ammonium sulfate organics and possibly catalyst fines are incinerated or routed to the final waste water treatment 24 4215 Purification The overheads from the recovery column containing acrylonitrile hydrogen cyanide and a small amount of water are distilled to produce acrylonitrile and hydrogen cyanide products In some plant designs the heads column to refine the hydrogen cyanide and the drying column to remove the water are sectional to reduce energy consumption The hydrogen cyanide may be incinerated or transformed into other products on site or sold if a market is available 24 If stored it has to be maintained at a low temperature and kept acidic by the addition of acetic acid phosphoric acid sulfuric acid and sulphur dioxide to prevent polymerisation Due to the reactive and toxic nature of hydrogen cyanide it is not stored for longer than a few days If the material cannot be sold or used then it is incinerated All sites must therefore have the capability to overthrow all of the hydrogen cyanide produced The final step is the purification of the acrylonitrile by rectification in the acrylonitrile column The drying column and the acrylonitrile column may be operated at low pressure to reduce the distillation temperature and to reduce acrylonitrile polymer creation In order to protect the final product against possible polymerisation reactions during storage small quantities of inhibitors such as MEHQ monomethyl ether of hydroquinone are added to the acrylonitrile 30 The ruins from the bottom of the acrylonitrile column contains some high boilingpoint nitriles 24 43 Explain the Raw Materials 431 Propylene Propylene C3H6 is a colorless gas It is occured by thermal cracking of ethylene At low concentration it forms an explosive and flammable mixture with air while at high concentrations it can reason asphyxiation and skin burns It is used in the petrochemical industry for the production of polypropylene isopropyl alcohol propylene oxide and other chemicals 25 Table 41 Physical properties of propylene 25 Table 42Propylene Values of thermo physical properties of the saturated liquid and vapor 26 31 432 Air Air is a consist of gases 78 nitrogen and 21 oxygen with traces of water vapor carbon dioxide argon and various other components 27 Table 43 Thermodynamic properties of air 28 433 Ammonia Ammonia is also commercially and commonly available as an aquaeous solution the must common commercial formulation is 2830 NH3 29 Table 44 Physical and chemical properties of ammonia30 Property Value Molecular weight 1703 Color Colorless Physical state Gas at room temperature Melting point 7770C Boiling point 33350C Density gas 07710 gl Odor Sharp 32 44 Explain the Byproduct Materials 441 Hydrocyanic acid 4411 Chemical properties of hydrocyanic acid Hydrocyanic acid has a density of 0688 gcm3 at 20C a boiling point of 257C and a freezing point of 14C It burns in air to yield H2O CO2 and N2 a mixture of hydrocyanic acid vapors and air explodes when ignited Hydrocyanic acid a very weak acid distilleted upon storage especially in the presence of impurities Its salts are called cyanides and its organic derivatives nitriles Hydrocyanic acid is created upon hydrolysis of amygdalin present in bitter almonds and apricots An aqueous hydrocyanic acid solution can be provided by the distillation of potassium ferrocyanide K4FeCN6 with dilute sulfuric acid H2SO4 31 4412 The uses of hydrocyanic acid The greater part of the hydrocyanic acid manufactured in this way is spended in the manufacture of acrylonitrile either by condensation with ethylene oxide to form ethylene cyanhydrin or directly by liquid phase catalytic combination with acetylene Acrylonitrile is polymerised with butadiene to form specialpurpose synthetic rubbers These nitrile rubbers are used for mechanical rubber pads textile and paper sizings and for petrol and oil resistant goods They are marketed in the United States under brand names Hycar Paracril Butaprene and Chemigum Hycar will shortly be produced in this country by British Geon Ltd 32 442Acetonitrile Acetonitrile CH3CN is a byproduct of acrylonitrile manufacture 38 Figure 43 Chemical formula of acetonitrile38 33 4421Physical and chemical properties Physical properties Acetonitrile is a volatile colourless liquid with a sweet etherlike odour 38 It is extremely soluble in water and easily miscible with ethanol ether acetone chloroform carbon tetrachloride and ethylene chloride 39It is immiscible with many saturated hydrocarbons petroleum fractions40 Table 45 Commercial acetonitrile specifications 38 Chemical properties Although acetonitrile is one of the most stable nitriles it under goes typical nitrile reactions and is used to produce many types of nitrogencontaining compounds It can be trimerized to S trimethyltriazine and has been telomerized with ethylene an copolymerized with alphaepoxides 38 Acetonitrile produces hydrogen cyanide when heated to decomposition or when reacted with acids or oxidizing agents41 4421 Use of acetonitrile It is used as a solvent for spinning synthetic fibres and in casting and moulding plastics In laboratories it is commonly used in highperformance liquid chromatographic HPLC analysis and as a solvent for DNA synthesis and peptide sequencing 42 34 443 Carbon monoxides Carbon monoxide is a colorless odorless gas Prolonged exposure to carbon monoxide rich atmospheres may be fatal It is easily fired It is just lighter than air and a fire can flash back to the source of leak very easily Under prolonged exposure to fire or intense heat the containers may strongly rupture and rocket 43 Table46Properties of carbon monoxides 44 Main Reaction 2C3H6 2NH3 3O2 2C3H3N 6H2O Side Reaction 4C3H6 6NH3 302 6 C2H3N 6H2O C3H6 3NH3 3O2 3HCN 6H2O 2C3H6 3O2 6CO2 6H2O 45 Evaluation and Examination of By Products Nearly all of the acrylonitrile ACN produced in the world today is produced using the SOHIO process for ammoxidation of propylene and ammonia The all reaction happen in the vapour phase in the presence of a catalyst The primary byproducts of the process are hydrogen cyanide acetonitrile and carbon oxides The save of these byproducts depends on factors such as market conditions plant location and energy costs 35 Hydrogen cyanide and acetonitrile although they carry a market value are usually incinerated indicating that the production of these byproducts has little effect on the economics of producing ACN Variations within the SOHIO process may ensure for purification storage and loading facilities for these retrievable byproducts Other variations of the SOHIO process added the recovery of ammonium sulfate from the reactor effluent to allow for biological treatment of a waste water stream and variations in catalysts and reactor conditions 44 36 SECTIONV PRODUCTION FLOW DIAGRAMSII 37 5 PROCESS FLOW DIAGRAM II 51 Acrylonitrile Production in Chemcad Simulation Figure 51 Process Flow Diagram on Chemcad Simulation Air Ammonia Propylene 2 3 4 5 6 1 2 3 4 5 6 7 8 9 8 Sulfuric acid 10 12 13 1 12 9 7 11 10 20 Exhaust Gas 14 22 16 23 17 18 28 29 Acrylonitrile Impurities 14 Water 15 16 11 17 18 19 21 24 25 Acetonitrile HCN Water Ammonium Sulfate 38 52 Chemcad Equipment Values 521 Reactor In kgh Out kgh Ammonia 700503 Propylene 1644363 Air 11258095 ACN 1667866 HCN 189714 Acetonitrile 56158 Acrolein 15563 Acrylic Acid 4287 Acetic Acid 7145 Carbon Dioxide 267204 Carbon Monoxide 62143 Water 20769946 7 8 9 8 7 10 39 522 Quencher In kgh Out kgh Ammonia Propylene Air ACN 1667866 1667866 HCN 189714 189714 Acetonitrile 56158 56158 Acrolein 15563 15563 Acrylic Acid 4287 4287 Acetic Acid 7145 7145 Carbon Dioxide 267204 267204 Carbon Monoxide 62143 62143 Water 208770547 208770547 Sulfuric Acid 5248331 5248331 Ammonium Sulfate 7071408waste 12 11 14 15 25 40 523 Absorber In kgh Out kgh Ammonia 181934waste Propylene Air ACN 1667866 1667866 HCN 189714 189714 Acetonitrile 56158 56158 Acrolein 15563 15563waste Acrylic Acid 4287 4287waste Acetic Acid 7145 7145waste Carbon Dioxide 267204 267204waste Carbon Monoxide 62143 62143waste Water 208770547 208770547 9 41 524 Recovery column In kgh Out kgh ACN 1667866 1667866distillate HCN 189714 189714distillate Acetonitrile 56158 56158bottom Water 208770547 208770547bottom 525 Acetonitrile column In kgh Out kgh Acetonitrile 56158 56158distillate Water 208770547 208770547bottom 11 17 18 19 16 23 16 42 526 HCN column In kgh Out kgh ACN 1667866 1667866bottom HCN 189714 189714distillate 527 ACN column In kgh Out kgh ACN 1667866 1667866distillate 17 21 24 18 28 29 43 SECTIONVI MATERIAL AND ENERGY BALANCE 44 6 MATERIAL AND ENERGY BALANCE 61 MATERIAL BALANCE Material balances are the basis of process design A material balance taken over complete processs will determine the quantities of raw materials required and products produced Balances over Individual process until set the process stream flows and compositions The general conservation equation for any process can be written as Material out material in generation consumption accumulation For a steady state process the accumulation term is zero If a chemical reaction is taking place a particular chemical species may be formed or consumed But if there is no chemical reaction the steady state balance reducesto Material out Material in A balance equation can be written for each separately identifiable species present elements compounds and for total material 611 Material Balance for Reactor Basis Plant capacity 146000 tonsannum Consider 365 working daysannum Therefore outputday 146000 tons 365days 400 tonsday Capacity 400 tons day x 1day24 hours x 1000kg 1tons 1666667 kgh 1666667 kgh 5303kmolkg 31428 kmolh 45 Catalyst Performance AsusingcatalystBiMogivenbySohiotheconversionofC3H6istakenas 76 Table 61 Conversion percentages Molecular Weight Table 62 Molecular weight in kg kgmole 80 to ACN 23 to Aceto 59 to HCN 15 to Acrylic acid 07 to Acrolein 02 to Aceticacid 51 to CO2 29 to CO 14 to UnconvertedC3H6 Acrylonitrile C2H3CN 5303 Acetonitrile CH3CN 4102 Hydrogen cyanide HCN 2701 Propylene C3H6 4203 46 Acrylonitrile formation reaction C3H6 32 O2 NH3CH2 CHCN 3H2O Assume there is 1 loss of ACN as in any outlet stream or which may polymerized 1666667 099 1683502 kgh 31428 099 31745 kmolh So actual capacity of plants are1683502 kghand 31745 kmolh But only 80 is being converted to acrylonitrile Therefore actual C3H6 supplied 31745 08 39681 kmolh Propyleneammoniaair 11295 Mole ratio76 Ammonia NH3 17 Oxygen O2 32 Nitrogen N2 28 Acrolein CH2CHCHO 5603 Carbon monoxide CO 2801 Water H2O 18 Carbon dioxide CO2 4401 Acrylic acid CH2CHCOOH 7203 Acetic acid CH3COOH 6002 47 Acrylonitrile 2C3H6 3O2 2NH32CH2 CHCN 6H2O rC3H6 kC3H6 x C2 C3H6xC2 NH3 x C3 O2 C3H6 32O2 NH3CH2 CHCN H2O 4203 48 17 5303 54 Propylene required for 80 conversion to ACN 1683502x 4203 5303 1334293 kgh for 80 conversion Actual C3H6used 1334293 080 1667866kgh Hydrogen Syanide C3H6 3NH3 3O2 3HCN 6H2O rC3H6 kC3H6 x C C3H6 xC3 NH3 x C3 O2 C3H6 3NH3 3O2 3HCN 6H2O 4203 51 96 8103 108 Hydrogen Cyanide produced 059 x 1667866x 8103 4203 189714 kgh Acetonitrile 2C3H6 3NH33O23CH3CN 6H2O rC3H6 kC3H6 x C2 C3H6 xC3 NH3 x C3 O2 C3H6 32NH3 32O232CH3CN 3H2O 4203 48 255 6153 54 Acetonitrile produced 0023x1667866 x 6153 4203 56158 kgh 48 Acrolein C3H6 O2 CH2 CHCOOH H2O rC3H6 kC3H6 x C C3H6 x C O2 C3H6 O2CH2CHCHO H2O 4203 32 5603 18 Acrolein produced 0007 x 1667866 x 5603 4203 15563 kgh Acrylic Acid 2C3H6 3O22 CH2 CHCOOH 2H2O rC3H6 kC3H6 x C2 C3H6 x C3 O2 C3H6 32O2CH2 CHCOOH H2O 4203 48 7203 18 Acrylic acid produced 0015x1667866 x 7203 4203 4287 kgh Acetic Acid 2C3H6 3O23CH3COOH rC3H6 kC3H6 x C2 C3H6 x C3 O2 C3H6 32O232CH3COOH 4203 48 9003 Acetic Acid produced 0002 x 1667866 x 9003 4203 7145 kgh 49 CarbonDioxide 2C3H6 9O26CO2 6H2O rC3H6 kC3H6 x C2 C3H6 x C9 O2 C3H6 92O23CO2 3H2O 4203 144 13203 54 Carbon Dioxide produced 0051 x 1667866 x 13203 4203 267204 kgh Carbon Monoxide C3H6 3O23CO 3H2O rC3H6 kC3H6 x C C3H6 x C3 O2 C3H6 3O23CO 3H2O 4203 96 8403 54 Carbon Monoxide produced 0029x1667866 x 54 4203 62143 kgh Ammonia a 2C3H6 3O2 2NH3 2CH2 CHCN 6H2O Reactants C3H6 39681x080 317448 kmol NH3 1 x 317448 317448 kmol O215 x 317448 476172 kmol Products C3H3N 1 317448 317448 kmol H2O 3 x 317448 952344 kmol 50 bC3H6 3NH3 3O2 3HCN 6H2O Hydrogen Syanide Reactans C3H6 39681 x 0059 2341 kmol NH3 3 x 2341 7023 kmol O2 3 x 2341 7023 kmol Products HCN 3 x 2341 7023 kmol H2O 3 x 2341 7023 kmol c C3H6 32NH3 32O232CH3CN 3H2O Reactans C3H6 39681 x 0023 912 kmol NH3 15 x 912 1368 kmol O2 15 x 912 1368 kmol Products CH3CN 15 x 912 1368 kmol H2O 3 x 912 2736 kmol Total Ammonia a b c 317448 7023 1368 401358 kmol 401358 kmolh x 17 kgkmol 6823086 kgh NH3 C3H6 042 1667866 x 042 700503 NH3 consumed NH3excess unreacted 700503 6823086 181944 kgh 51 Water a C3H6 32O2 NH3CH2 CHCN H2O Acrylonitrile Reactans C3H6 39681 x 080 317448 kmol NH3 1 x 317448 317448 kmol O2 15 x 317448 476172 kmol Products CH3CN 15 x 317448 476172 kmol H2O 3 x 317448 952344 kmol bC3H6 3NH3 3O2 3HCN 6H2O Hydrogen Syanide Reactans C3H6 39681 x 0059 2341 kmol NH3 3 x 2341 7023 kmol O2 3 x 2341 7023 kmol Products HCN 3 x 2341 7023 kmol H2O 3 x 2341 7023 kmol cC3H6 32NH3 32O232CH3CN 3H2O Acetonitile Reactans C3H6 39681 x 0023 912 kmol NH3 15 x 912 1368 kmol O2 15 x 912 1368 kmol 52 Products CH3CN 15 x 912 1368 kmol H2O 3 x 912 2736 kmol d C3H6 O2CH2CHCHO H2O Acrolein Reactans C3H6 0007 x 39681 277 O2 1 x 277 277 Products C3H4O 1 x 277 277 H2O 1x 277 277 eC3H6 32O2CH2CHCOOH H2O Acrylic Acid Reactans C3H6 0015 x 39681 595 kmolh O2 15 x 595 8925 kmolh Products C3H4O2 1 x 595 595 kmolh H2O 1x 595 595 kmolh fC3H6 92O23CO2 3H2O Carbon Dioxide Reactans C3H6 0051 x 39681 20237 kmolh O2 15 x 20237 3035 kmolh 53 Products CO2 3 x 20237 60711 kmolh H2O 3 x 20237 60711 kmolh g C3H6 3O23CO 3H2O Carbon Monoxide Reactans C3H6 0029 x 39681 11507 kmolh O2 3 x 11507 34521 kmolh Products CO 3 x 11507 34521 kmolh H2O 3 x 11507 34521 kmolh Total Water a b c d e f g 1153886 kmolh x 18 kgkmol 20769946 kgh Air h C3H6 32O232CH3COOH Acetic Acid Reactans C3H6 0002 x 39681 07936 kmolh O2 15 x 07936 119 kmolh Products CH3COOH 15 x 07936 119 kmolh Total O2 a b c d e f g h Total 637838 kmolh x 32 kg kmol 20410816 kgh 54 Air contains 2095 O2and 7807 N2 20410816 02095 97426329 Air C3H6 675 Air in 1667866 x 675 11258095 O2in 11258095 x 02095 2358571 N2 in 11258095 x 07807 8789194 O2 excess 2358571 20410816 3174894 kgh N2 out 8789194 kgh ACN 1683502 kgh 2NH3 H2SO4 NH42SO4 NH3 present in gas unconverted 181944 kgh 17kgkgmol 10702 kmol h H2SO4 required 1070258 2 535129 kmol h 535129 98076 5248331kgh But 98 H2SO4 includes 2 water 002098 5248331 1071087kgh NH42SO4 formed 1070258 2 535129 x 132144 70714086 kgh For 33 NH42SO4 solution the amount of water added 70714086 03370714086 21428510970714086 14357 kgh 612 Quench column Input stream Effluent from Reaction via effluent cooler Two section provided in Quench column Water is circulated over both section from stripper ie water in Water from Aceto stripper 1548016 Excess NH3 1859264 kgh 55 NH3react with H2SO4 Reaction 2NH3H2SO4NH42SO4 34029806 13808 H2SO4required 1859264 x 98063402 5359 kgh Table 64 Material balance over quench column 613 Absorber Assumption Offgases containing CO CO2 N2 unreacted O2 unreacted C3H6 Not absorbed in water and are remove from top of column Also HCN of 05 in is removed in it ie Component Material in kgh Material out kgh Acrylonitrile 16833266 16833266 Acetonitrile 56152 56152 HCN 189694 189694 CO2 26717 26717 CO 62136 62136 Water 17750882 as feed 1548016 as Lean Water 13572492 at top 1965855at bottom Total 5581582 5581582 56 0005 189694 94847 kgh ACN out at top as off gases 54 kgh Off gases contains some entrained water 10859 kgh and all CO2 CO N2 Unconverted C3H6 data Solubility of Acrylonitrile in water wt Top of absorber have temperature 40 o C and at 40 o C water added at top Feed at bottom also 40 o C and feed enter at bottom is also at 40 o C But about 25 o C maintain in column using side stream cooling So take solubility of Acrylonitrile around 77 wt in water Therefore for 892766 kgh ACN is Water required for absorb ACN 16833266 x 923 77 20178057 kgh Acetonitrile HCN have infinite solubility in water for absorption 614 Recovery column and decanter Recovery Column We have Separation of Acetonitrile as bottom and Acrylonitrile as overhead using extractive distillation using water as solvent All Acrylonitrile and all HCN feed separated as overhead Also separation such as total Aceto 98 to bottom and 2 as overhead At 40oC 79 At 30oC 75 At 20oC 73 57 Aceto at bottom 56152 x098 55028kgh Aceto attop 56152x002 1123kgh Now bottom has 17 dilute solution of Aceto of water with Aceto at bottom 56152x 100 17 3303058 kgh Water as overhead 1619731 kgh Decanter Now consider top stream have is separated out in decanter in aqueous water phase and organic ACN phase Separate out 95 of aqueous phase as water in decanter Water goes with organic phase 5 of top stream 005 x 1619731 80986 kgh Water removed 1619731 809861538744 kgh 615 Aceto column Total Acetonitrile in feed separated as overhead Acetonitrile is overhead55028kgh In Acetostripper the total Acetonitrile go as overhead with water and get 70 acetonitrile as overhead Acetonitrile is over head 55028 kgh 70 Water with Acetonitrile as over head 23583 kgh 30 Water out a bottom 3303058 23583 3279475 kgh 616 HCN column The feed of HCN column is generally ACN HCN with little amount of H2O and Acetonitrile Hence it can be treated as binary distillation considerably HCN ACN alone From feed all ACN and 99 pure HCN is recovered from top F D W 1029515 D W Where F related to feed D related to distillate overhead products W related to bottom products 58 For HCN Balance F XF D XD W XW 100103 D 099 W001 Solving above two equations for D W D 100102kgh 62 ENERGY BALANCE The reference temperature 25ᴼC 621 Preheating of reactor Preheating is required to initiate the exothermic reaction Preheating is also carried out at 425ᴼC Table 63 Energy required for preheat the reactants Component Kgh Molewt Kg molh Cpat 425ᴼC nicpi C3H6 166769 4203 39678 283 1122887 Ammonia 700430 17 41202 1005 414080 Air 1125692 29 388170 721 2798706 Σ ni Cpi 4335673 ΔT 42525 400 ᴼC Energy Supplied to preheat reactant Σ ni Cpi x ΔT 173427 kcal energy supplied by the heater 59 622 Energy Balance Around Reactor Reactants in at 425ᴼ C Products out at 425ᴼC At 25ᴼ C At 25ᴼ C a Energy supplied by the heater 173427 Kcal b Total heat of reaction Formation of Acrolein Acetic acid Acrylic acid is small So neglected 1 C3H6 NH3 15O2 CH2CHCN 3H2O 2 23C3H6 NH3 O2 CH3CN 2H2O 3 13C3H6 NH3 O2HCN 2H2O 4 C3H6 45O23CO2 3H2O 5 C3H6 3O2 3CO 3H2O Table 64 Components and its properties Compound Kcalgmol Propylene 488 Ammonia 110 Water 578 Acrylonitrile 4537 Dioxide 9405 Carbon Oxide 3281 Hydrogen Cyanide 311 Acetonitrile 1980 60 Heat of reaction Σ heat of product formation Σ heat of reactants formation Acrylonitrile 4537 3578 488 110 13291 Kcalgmol 132910 Kcalkgmol Hydrogen Cyanide 3311 6578 488 3110 29138 Kcalgmol 291380 Kcalkgmole Acetonitrile 151980 3578 48815110 16507 Kcalgmol 165070 Kcalkgmole Carbon Dioxide 3 9405 3578 488 46043 Kcalgmol 460430 Kcalkgmole Carbon Monoxide 33281 3578 488 27671 Kcalgmol 276710 Kcalkgmole Total ΔH Σni ΔHR 5713067623 Kcal Table 65 Energy required Compo nent Kgh Mol Wt K Molh Cpi at 4250C nicpi ACN 16833266 5303 317429 2488 789763 Aceto 56152 4102 13363 17631986 11862 HCN 189694 2701 70231 995 69879 CO2 26717 4401 60706 1005 61009 CO 62136 2801 22183 744 16504 H2O 17129923 18 951662 845725 110917 61 C3H6 34973 4203 8249 283 23344 NH3 1859264 17 10936 928 10148 O2 98981276 32 309316 745 230440 N2 863405 28 30836 71 30765 Σ ni Cpi 1593840 ΔT 42525 400 oC Σ ni Cpi x ΔT 6375360 kcal Enthalpy of the cooler Enthalpy of Reactant at 25ᴼC Heat of reactions Enthalpy of product 425ᴼC 173427 5713067623 6375360 507379735 Kcal Coolant required This heat is removed using steam at 110ᴼC which is superheated up to 370ᴼC Msteam x Cpsteam x ΔT 507379735 Kcal Msteam x 1 x 370110 507379735 Kcal Msteam 195146052 kgh This is the amount of steam required to removed the heat at evolved in the reactor 623 Energy Balance Over Product Gas Cooler Inlet temperature of gases 425C Outlet temperature of gases 230C Enthalpy in with gases 6375360 Kcal Enthalpy out with gases 62 Table 66 Energy required Compon ent Kgh Mol Wt K Molh Cpi at 230C nicpi ACN 16833266 5303 317429 2191 695486 Aceto 56152 4102 13363 1743 23291 HCN 189694 2701 70231 935 65665 CO2 26717 4401 60706 1003 60888 CO 62136 2801 22183 713 15816 H2O 17129923 18 951662 747 710891 C3H6 34973 4203 8249 227 18725 NH3 1859264 17 10936 928 101486 O2 98981276 32 309316 727 224872 N2 863405764 28 30836 70 215852 Σ ni Cpi 39843026 ΔT 23025 205C Σ ni Cpi x ΔT 816782033 kcal Coolant Required Steam required to cool the effluent at temperature 110C which is heated upto heated up to 200C temperature Msteam x Cpsteam x ΔT Enthalpy out with gases Enthalpy out with gases 6375360 816782033 179245833 Kcal Msteam x 1 x 200110 179245833Kcal 63 Msteam 1991620 kgh 624 Energy Balance Around Quench Column 1 Enthalpy in with product gases 816782033 Kcal 2Enthalpy due to heat of reaction In the Quench column the neutralization of ammonia using Sulphuric acid take place 2NH3 H2SO4 NH42SO4 3402 9606 13808 ΔHR 76662 Kcal Kmol Ammonium Sulphate Amount of NH42SO4 formed 39072 kghfrom Material Balance Total heat liberated due to reaction 76662 x 3907213808 2169277 Kcal 3 Enthalpy out with gases at top Table 67 Enthalpy out with gases Compo nent Kgh Mol Wt K Molh Cpi at 850C nicpi ACN 16833266 5303 317429 1978 627874 Aceto 56152 4102 13363 1721 22997 HCN 189694 2701 70231 888 62365 CO2 26717 4401 60706 922 55970 CO 62136 2801 22183 698 15483 H2O 17129923 18 951662 473 450136 C3H6 34973 4203 8249 176 14518 64 O2 98981276 32 309316 702 217139 N2 8634057 28 30836 696 2146185 Σ ni Cpi 3612667 ΔT 8525 60 0C Σ ni Cpi x ΔT 21676002 kcal d Enthalpy out with bottom stream Σ ni Cpi ΔT 65 x 39072 1 x 1762 Cp of NH42SO4 65 Kcal kg 25810080 Kcal Heat carried away by H2SO4 polymer neglected in bottom stream as it is very very small e Heat required liquefying the water vapor which out from bottom and cool from 230 to 85 ᴼC to cool water vapor to 230 to 100ᴼC Exchange of latent heat of vaporization cool liquid water from 100 to 85ᴼC 1965855x 1 x 130 1965855 x 550 1965855x 1 x 15 111266093 kcal Enthalpy removed So water added a b c d e 516756227 Kcal Msteam x Cpsteam x ΔT 516756227 Kcal Msteam x 1 x 23 516756227Kcal Msteam 22467662 kgh 65 This is water added to quench column 625 Energy Balance Around After Cooler Inlet temperature of gases 85oC Outlet temperature for gases 40oC Boiling point of ACN 78oC Boiling point of Aceto 82oC Therefore at 400C temperature ACN and Aceto will get condensed a Heat in with gases 21676002 Kcal b Heat required to condense ACN MACN x ZACN 168332665303 x 780 24759471 Kcal c Heat required to condesese Aceto MACETO x Z ACETO 561524102 X 711 973283 Kcal d Enthalpy out with the mixture 66 Table 68 Enthalpy out with the mixture Component Kgh Mol Wt K Molh Cpi at 40ᴼC nicpi ACNL 16833266 5303 317429 2687 852931 AcetoL 56152 4102 13363 2106 28142 HCN 189694 2701 70231 866 60820 CO2 26717 4401 60706 89 54028 CO 62136 2801 22183 697 15461 C3H6 34973 4203 8249 1585 13074 O2 98981276 32 309316 70 216521 N2 863405764 28 30836 696 2146185 H2OL 17129923 18 951662 18 1712991 Σ ni Cpi 5100153 ΔT 4025 15 0C Σ ni Cpi x ΔT 76502295 kcal e Enthalpy absorbed by the water added a b c d 114524971 Kcal Mwater Cpwater ΔT Cooling water temperature is 30ᴼC is added and out let temperature is 40ᴼC Mwater x 1 x 10 114524971 Mwater 114524971 67 114524971 kg cooling water required 626 Energy Balance Around Absorber and Heat Exchanges Inlet temperature of Absorber 40ᴼC Outlet temperature of Absorber 40ᴼC at top Maintain temperature in absorber 25ᴼC a Enthalpy in with feed mixture 76502295 kcal b Enthalpy out with unabsorbed gases from top Table 69 Enthalpy out with unabsorbed gases from top Component Kgh Mol Wt K Molh Cpi at 40oC nicpi CO2 26717 4401 60706 89 54028 CO 62136 2801 22183 697 15461 O2 989812 32 309316 70 2165212 N2 8634057 28 30836 69 2127684 C3H6 34973 4203 8249 1585 13074 H2OG 1712992 18 951662 162 1541692 HCN 189694 2701 70231 866 60820 Σ ni Cpi 402928 ΔT 4025 15oC Σ ni Cpi x ΔT 604392 kcal cEnthalpy out with bottom stream 68 Table 610 Enthalpy out with bottom stream Compone nt Kgh Mol Wt K Molh Cpi at 300C nicpi ACN L 16833266 5303 317429 2657 843408 Aceto L 56152 4102 13363 2134 28516 HCN 189694 2701 70231 806 56606 H2O L 17129923 18 951662 18 1712991 Σ ni Cpi 2641521 ΔT 3025 5 oC Σ ni Cpi x ΔT 13207605 kcal d Enthalpy in with lean water Mlean water x Cp x ΔT 210633 x 1 x 40 25 31595091 Kcal e Enthalpy removed by cooling system Heat evolved Heat in with feed Heat with lean water heat out with gases Heat out with bottom product a d b c 16581083 Kcal 627 Energy Balance Around Recovery Column a Heat in with feed 31595091 Kcal F HF Temperature of column 85ᴼC at top b Load on reboiler Qb 69 Feed at 80ᴼC It is Saturated liquid Load on reboiler Qb for vaporization of ACN Aceto H2O as distillate HT in Remaining comp coming from bottom Σm x Z Σ ni Cpi x ΔT 887366 x 147 596 x 17368 847639 x 550 17781735839x 11080 6518895503 Kcal Let stream is used in reboiler at 1 atm having Z stream 550 K calkg Steam required in reboiler Mstream x Zstream 6518895503 Mstream 1185254 kgh cEnthalpy out with Distillate DHD Table 611 Enthalpy out with Distillate DHD Component Kgh Mol wt Kmolh Cpi at 85ᴼC nicpi ACN 16833266 5303 317429 1677 532328 Aceto 56152 4102 1368 135 18468 HCN 189694 2701 70231 92 64612 H2O 17129923 18 951662 619 589078 Σni Cpi 1204486 ΔT 8525 60ᴼC Entalpy out with distillate Σni Cpi ΔT 7226916 Kcal D HD 70 SECTIONVII DESIGN OF PROCESS EQUIPMENTS 73 238 mm Take carrosion alowance 3mm t 238 mm Taking standart value t 6mm 2 To find the thickness of coil ensured to circulate the cooling water Internal coils are provided inside the reactor attached with the reactor wall Water is fed at 40kgfcmand 250 o C Designing for half coil jacket p 40 kgcm2 pd 40 x 105 kgcm2 fa 980 Kgcm2 di 550 mm tc pdi 2 fa Ca 15 mm standard uo 05 ms lm 1 m 05 1422 s Checking for total circum ferential shear fps ptDi 2ts p2di 4tc25ts 61011kgcm2 712 Checking tower height for various external and internalloads Data Height of the reactor 138 2 158 Internal diameter of the reactor 46m Thicknessofshell 6mm Designpressure 082Kgfcm2 75 3 Stresses due to the wind load Wind pressure pw 006 Vw2 Where Vw Maximum windvelocity 70 kmh Pw 294 Nm2 2937Kgfcm2 Windlow pw 07 pw x Do xx 07 x 294 x 46 x x 94668 x N Bending moment due towind pw x2J 39445 x2J Stressfwx Mw Z Mwπ4 Do2tsc x 106 MNm2 00079 x2MN m2 00805 x2kgm2 4 Resultant axialstress a Upwind size fJ ftmax fwx fap fdx 980 x 085 00805 x2 31433 00641 x 352 X 8094 m b Downwind size ftmax comp fwx fap fdx 0125E tDo fwx fap fdx 76 0125 x 203 x 106 000646 00805 x2 31433 00641 x 352 X 8889 m 713 To design the skirt support Since column height is large 14m skirt assistance is used the crosssection of the skirt is uniformly deployed at a enough distance from the axis This gives a large value of the section modulus and helps to rise the resistance to bending action Data Diameter of vessel D 46m Height of the vessel n138 m Weight of vessel attachments etcW 12600 kg Wind pressure 1285 kgm2 Skirt height 5 m Diameter of skirt 4500 nm Various stresses are 1 Stresses due to dead load FdW π Dsk tsk 12600 π x 460 x tsk 87 tsk kgcm2 2 Stress due to wind load Fwb 07 x ρ1 x h1 Do h12 π x 460 x tsk 350296 tsk kgcm2 77 Maximum sensile stress Fdfwhfallowable 87tsk350296tssk980 Take Tsk 738 mm 72 Distillation Column Design To estimate relative volatility av At top T280C PHCN sat 7943 mmHg PACN sat 11601 mmHg 1 7097 mmHg At bottom T 820C PHCN sat 464623 PACN sat 5029 av 12 589 Equilibrium data is given by y x H 1x Table 71 XY composition X 01 02 03 04 05 06 07 08 09 1 Y 04 06 072 08 085 09 093 096 098 1 78 Equilibrium curve is plotted using the above data Here xF021 xD0999 xW0008 Since feed is at its temperature online is verical From the graph xD 052 Rm1 Rm 088 Rop 12 x Rm 106 The number of theoretical stages131 12 Taking all efficiency 06 Number of actual stages 1206 20 79 Figure 71 McCabe thiele chart 81 Bottom temperature 82OC At top of the density ρHCN697 kgm3 ρv Density of HCN vapor PM RT 1099 kgm3 P Pc PH PN 90156176 422 ρL Density of ACNliquid of saturation ρsat ρv Density of ACN vapor PMRT 218 kgm3 ρsat is estimated bySpencer and Danner equation ρsat PcRTC Zc 11Tc27 where Pc Vc1389m3g Tc520K ZcPcVc RTc 0045 Therefore ρsatρL 10354 Surface tension of ACN 224 x 103NM dyncm Step4 To estimate column diameter from flooding consideration i At bottom FLV L ρG05 30 21805 0042 ρL10354 CS67 flood Unf 2002 21805 σ ρLρG 82 CS67 flood Unf 2002 21805 224 1035218 Unf 1873 fts057 ms ii At top FLV LρG05 05 1098 0198 G ρL 697 Csb flood Unf 2002ρG05 032 σ ρL ρG05 Unf 475 fts 144 ms Designing for 85 flooding flow rate Bottom Unf 057 x 085 0485 ms Top Unf 144 x085 122 ms Maximum volumetric flow rate of vapour At bottom Q1 27819 218 x 3600 035 m3s At top Q1 834591098 x 3600 211 m3s Net area requıred Bottom 0350485 072 m2 Top 211122 172 m2 Top greater value An 072 m2 Providing 15 for downcomer An 015 At 83 At 48 Therefore π 4 dc 0456 Hence dc 078 08 m Area At π 4 dc2 0505 m2 722 Provisional Plate Design 1 Down comer area Ad 015 x 0503 0075 m2 2 Net area An At Ad 043 m2 3 Active area Aa At 2Ad 03m2 Assume hole area An 01 x Aa 003m2 Hole diameter dh 5 mm Weiz height 55 mm Plate thickness 5 mm Weiz length 076 Dc 0608 m Single cross flow pattern is used 723 To check weeping rate hw Height of weiz 55 mm how height of crest over weiz equivalent clear liquid mm Equation 1812a how 664 q Lw 23 Maximum liquid rate 75 turn down 84 q 075 x 123 092 kgs 092 1025 897 x 103 m3s Lw Weir length 06 m how 664 897 x 10323 0608 4714 mm hw how 10214 mm hd 508 Cv 2 pgplun2 Cv 075 Here Uh linear gas velocity trough perforation 27819 3600 x 218 x 1 00353 1004 ms Hence hd 10279 h σ 409σ ρ1dh 409 224 1025 x 5 1787 hd h σ 12067 724 To check plate pressure drop Total pressure drop plate ht hd h1 103 mm h1 hw howmax hr hr 125 x 103 ρl 1215 mm hw 50 mm howmax 482 mm ht 220 mm of liquid 952 mm of water 85 725 Plate layout Lw Dc 077 Qc 1050C Assuming width of calming zone 50 mm Width of stiffening ring 50 mm Angle subtended at plate edge by unperforated strip 180 105 750C Mean length unperforated edge strips λdc 50 x 103 75 180 1058 m Area of unperforated edge strips 50 x 103 x 1058 00529 m2 Area of claming zone 2 x 50 x 10306372 x 50 x 103 0537 m2 Area of perforations Ap Aa aue Acz 03026 m2 Ah Ap 00353 03026 0117 lp dh 265 lp 265 x 5 1325 mm No of holes hole area Area of one hole 00353 π4 00052 1800 73 Heat Exchanger Calculation Total ΔH Σni ΔHR 5713067623 kcal6633506 kjs Heat exchangervertical tubes 015 m 87 Cross sectional area of pipe ᴨ480x1032 503x103 m2 Design flow rate70043 kgh 700433600x600 324x103m3s Pipe velocity 324x103 314x008024 064 ms Re ρ x V x d µ 600 x 064 x 0080 1862x104 16498388 Absolute roughness 0046 mm steel pipe47 Relative roughness absolute roughness pipe inside diameter 0046 80 575x104 Friction factor 0003747 Length including misscellaneous losses 158 600 x 80x 103 638 m Equivalent length of pipe use values İnlet line 158 m Elbows 4x40 160 Gate valves 7547 Total 1833 m L 1581833 x 0080 1592 m Pf 8f x Ld x ρ x V22 Pf 8x00037x1580080x600x06422 718356 N m2 718356 600x98 122 m liquid Total head 158122 1702m 88 Pump 2 Density propylene 5144 kgm349 Viscosity propylene 000009 Nsm250 Design flow rate1519317 kgh 15193173600x5144 82x103m3s Pipe velocity 82x103 314x008024 163 ms Re ρ x V x d µ 5144 x 163 x 0080 000009 74530844 Absolute roughness 0046 mm steel pipe47 Relative roughness absolute roughness pipe inside diameter 0046 80 575x104 Friction factor 0002547 Length including misscellaneous losses 158 600x 80x 103 638 m Equivalent length of pipe use values İnlet line 158 m Elbows 4x40 160 Gate valves 7547 Total 1833 m L 1581833 x 0080 1592 m Pf 8f Ldx ρ x V22 Pf 8x00025x1580080x5144x16322 269921 N m2 269921 5144x 98 053 89 Total head 158 053 1633 m 75 Compressor Design W P1x V1x nn1 x P2P1n1n 1 51 P nxRxT V Vhava1125692 kgh x 11226 m3kg 9181827m3h n 388170 mol h P2 388170molh x 0082LatmmolK x 425273K 9181827x 103 L h 241x 103 atm P1 388170 molh x 0082LatmmolK x25273 K 9181827x103 L h 103x 103atm Compressor ratio P1 P2 103x 103241x 103 042 ƐP 86 Ɣ CPCV 1451 m Ɣ 1 ƔxƐP 51 14 1 14 x 086 033 n 11m 1 1033 149 W nxRxTxnn1 x P2P1n1n 1 First section work inlet 250C W1 388170 moleh x 8314 JmoleK 25273K x 1491491x241x103 103x103149 11491 W19418106818 Jh x 1h3600s 2616140 watt 90 Second section work inlet 4250C W2 388170 moleh x 8314 JmoleK 25425K x 1491491x241x103 103x10 314911491 W2 221x1011 Jh x 1h3600s 61424585 watt Total work W1 W2 6404072581 watt 64040 k 91 SECTIONVIII PLANT LOCATION AND SITE SELECTION 92 8 PLANT PLAN AND SITE SELECTION 81 Marketing Area Acrylonitrile is a very important raw material in the production of large number of chemical products It can be used as a raw material in the manufacture of acrylonitrile and many other chemical with many different applications Demand for acrylonitrile is broadly tied to the general economy and is therefore cyclical Most of acrylonitriles major end markets ABS resins acrylic fiber and adiponitrile for instance are cyclical and impacted by economic downturns when consumer spending contracts In 2016 China alone accounted for 32 of the global acrylonitrile market Further growth is forecast for acrylonitrile through 2021 Northeast Asia is forecast to account for about 55 of the global incremental demand over the next five years 12 82 Raw Material Supply Another most important factor for the site selection is availability and price of favorable raw material If the costs of shipping the product are not major than the cost of shipping feed plants that produce bulk chemicals are best located close to the source of the major raw material The main raw materials for the manufacture of acrylonitrile have been amonia air and propylene fractions The choice between these has varied from country to country and has been strongly influenced by economic and affected factors 52 83 Transport Facilities In order to move personnel equipment raw materials and products to the desired plant site a good transportation substructure is needed In this case a site should be determined by considering at least two great forms of transport road rail waterway canal or river or a seaport Especially three things are considered related to transportation while selecting site Firstly it is considered that since the yields will be delivered from abroad suppliers and transportation will be needed there must be more than one transport facility The other one is that transportation facilities are important when cost and delivery time are considered Site location is convenient more than one transportation option By this way raw material can be obtained with lower transportation cost and less delivery time 52 93 The last one is availability of airports It is important because during the startup stage and when the factory is running it will be required to provide technical and management support from the headoffice to the factory If airport is close to factory as much as probable total travel time and cost will be reduced 84 Availability of Labor Availability of labor especially skilled labor is considered as one of the most important factors while making site selection studies Nowadays companies require much more than just a dense labor pool they want to reach the labor that has the right skills in order to meet the specific needs of the industry Over the past five to six years availability of skilled labor has become even more important in business relocation and expansion decisions In order to have qualified labor governments are also playing critical roles over the last few years States and group across the country have become more proactive in working with companies and industries in order to provide that they have access to skilled labor In fact training programs and training grants have become a standard part of encouraging packages However there are some challenges that countries may have to face in terms of labor force53 One of the challenges facing manufacturing companies across the country is a growing population of veteran workers that are approaching retirement age Although this may be a very important problem for some countries Turkey has great labor potential with its young and dynamic population all over the country However quality and education of this young population also carry great importance 45 of Turkeys population is under 25 years old and unemployment is striking high amongst those aged 1524 18 Turkeys economy has been undergoing a structural shift from agriculture to industry and services For instance GDP composition of industry increased from 7 to 34 between 1990 and 2010 40 But this structural shift has not been paralleled by a shift in the skills of the labor force to the ones needed for the new sectors causing imbalances in the Turkish labor market All in all Turkey has better labor potential compare to the countries which Turkey is in competition with With proper education and help of the state big companies will make more and more investment by trusting that strong labor force 53 94 Figure 81 Labor productivity growth of different countries 53 85 Availability of Utilities Availability of utilities including electrical power natural gas water and sewer carrygreat importance in order to make investment for a specific area In order to construct a new facility to a new area that place should either have the enough natural sources that are needed for utility studies or the industry where electrical power water and fuel can be purchased from Utilities are needed for the maintenance of chemical processes For example electricity is needed in the electrochemical processes motors lightings and general uses Steams required for the process are generated by using the most economic fuel Most importantly water is used in almost each part of the process By looking the current industry areas and the natural resources of Turkey it can be seen that most of the heavy industry areas are located in the seaside or close to the water resources The reason behind this situation is that a company should have located within maximum of one mile of founded power lines natural gas supplies or other fuel supplies In terms of the water a water main should be located at or adjacent to the site or within the maximum distance of one mile of major base line The acceptable minimum diameter for a water line to a site is known as eight inches 54 86 Availability of Suitable Land It is considered that the soil is resistant to slip is robust is ideal for cargo handling is flat for proper factory landing and is used for expansion that may be needed in the future It is an important detail to choose the land far from the earthquake zone In this case the danger of flooding and erosion is an important factor in determining appropriate land When these 95 factors are evaluated the land cost is also optimized 52 87 Environmental Impact and Effluent Disposal Facilities should be designed without any public anxiety for proper disposal of wastes When choosing an installation site the tolerance levels for various wastewater should be considered and the requirements that may arise for additional waste treatment facilities should be taken into account While all industrial processes produce waste products they must provide the necessary precautions to the difficulties and costs of disposal Disposal of toxic and harmful wastes will be provided by local regulations and should be discussed with the authorities during the first field survey to determine if the standards are met 52 In the chemical process plant the environmental impact must be assessed As a result an environmental impact assessment study should be undertaken by the local council prior to project approval 88 Local Community Considerations The proposed facility should be accepted by the local community The local community should provide adequate facilities for facility personnel These schools banks housing entertainment and cultural facilities In order for the plant to be safe the place should be given importance and the collection should be prevented from creating additional risk ethnicity 52 89 Climate In the case of climate effects on a chemical plant it can lead to some significant consequences on the process conditions The adverse climatic conditions that the plant can suffer can increase costs Some changes or modifications may be made to the equipment The most important climate factors to consider are rain temperature changes harsh wind conditions such as hurricanes If abnormally low temperatures occur additional insulation and special heating must be provided for equipment and pipelines In addition if hard winds usually wind up in the area more robust constructions and installations are needed Climate conditions are also of great importance for facilities located around water resources such as rivers and seas Sea transport of raw materials can be badly affected 41 Production may start unexpectedly The possibility of flooding should also be investigated and necessary precautions should be taken in the field 53 96 Figure 82 Average temperatures and precipitation in Gebze 2017 59 810 Political Strategic Considerations Being established in the right place is an important component of an enterprise and its industrial success When the company chooses the wrong location it can be used for customers workers transportation materials etc it can be difficult to reach As a result the place of a companys success and general profit is a significant influence However there are some other things to consider in this process 55 Political risks and governmental regulations also play an important role in determining the stage If companies consider expanding to other countries political risk should be considered when developing a location strategy Because some countries have unstable political environments companies should be cautious about outbreaks and chaos if they plan longterm operations in such foreign countries 56 Another problem in expanding to other countries is that they may face some government obstacles and excessive restrictions and regulations For this reason government regulations should be examined in detail It should also be considered that the government can provide incentives such as tax concessions to new investment areas where the level of unemployment is high These incentives can be beneficial for companies to make their election decisions 97 811 Raw Material Source Propylene ammonia and air are important steps in determining the source of raw materials since they are identified as raw materials and then provide more costeffective options with raw materials that have strategic and economic qualification Raw material needs can be met either by domestic resources or by government regulations It is also determined by careful analysis of the raw material source cost and utility for domestic and international sources in the detailed process designs In addition to these situations it is also very important to make appropriate planning as the necessary raw materials may result in unwanted production in any process 55 812 Number of Working Staff Production units The production unit is divided into 2 sections The first unit in the reactor is the quench and absorber the second unit in which the recovery colon is located The number of staff to work here is as follows 2 units 4 shifts 4 shifts are worked in 24 hour production plants 4 workers in each shift 2 workers to work daytime 3 engineers 2 managers 1 director 2x4x42x3221 48 employees Maintenance unit 4 shifts 4 shifts are worked in 24 hour production plants 4 workers in each shift 4 workers to work daytime 3 engineers 1 manager 1 director 98 4x44311 25 employees Human resources purchasing marketing finance administrative affairs departments Human resources 7 employees Purchasing 2 employees Marketing 2 employees Finance 3 employees Administrative 6 employees 20 employees Security unit 4 shifts 4 shifts are worked in 24 hour production plants 2 workers in each shift 2 workers to work daytime 1 shift supervisor 1 shift organizer 4x2211 12 employees Stocking unit 4 shifts 4 shifts are worked in 24 hour production plants 2 workers in each shift 2 workers to work daytime 1 manager 1 director 4x2211 12 employees Subcontractors 6 employees Outsourcers catering services transport canteen service Total 123 employees 99 813 Storage Tanks Proper classification and storage of chemicals is very important Much of the workplace accidents in laboratories and factories are the result of improper storage of chemicals Chemicals should be classified and stored in such a way that they do not give a hazardous reaction in any adverse situation Products that can be chemically reacted with each other should not be stored in the immediate vicinity Storage tanks must be at ground level and open area Storages tanks should be kept away from a potential ignition source including the possibility of radiation from an adjacent adjacent fire Stainless steel or carbon steel is generally used for storage tanks Tank roofs should be fixed inside the ceiling or without roof Floating roofs reduce steam emissions These roofs can be made from aluminum for weight saving and lower costs Vertical and horizontal tanks are used to store chemicals These proceses were used for vertical storage tanks Sulfuric Acidstorage tank for acids should be 85 full The storage tank is made of carbon steel for sulfuric acid Acetonitrile and Hydrogen Cyanidestorage tank must be 90 full The storage tank is made of stainless steel for acetonitrile Acrylonitrile copper materials should not be used in the construction of the acrylonitrile storage tank Copper may induce polymerization and may color Acrylonitrile Ammonia storage tank is made of stainless steel for ammonia 7075 814 Raw Materials Purchased From Domestic And Abroad Propylene In Japan Asahi Kasei Mitsubishi Chemical Ethylene Corp and Mitsui Chemicals have cracker maintenance scheduled Their crackers combined propylene capacity are said to be around 670000 tonnesyear our company will buy 25 thousand tons from this company JXTG Nippon Oil Energy will take its Sakai the unit which has a propylene capacity of 105000 tonnesyear Our company will buy 5 thousand tons from this company In South Korea Korea Petrochemical Industry Co KPIC which has close to 240000 tonnesyear in propylene capacity Our company will buy 10 thousand tons from this company 61 Ammonia China Vietnam sign MoU for Vietnamese ammoniaurea project 14 October 2004The company currently produces 90 000 tonneyear of ammonia and 150 000 tonneyear of urea at 100 its existing plant in Ha Bac province in northern Vietnam Our company will buy 5830 thousand tons from this company 62 Sulfuric acid Eti Maden produces 55 thousand tons of sulfuric acid per year The amount of sulfuric acid we need is 4131 tons per month We take the entire sulfuric acid as Eti Maden 63 815 Domestic and Distributed Products Acrylonitrile We produce 12166 tonnes of acrylonitrile per month AKSA is buying 7425 thousand tons of acrylonitrile per month from abroad Our factory is getting 3900 tons 64 The branch of the Filofibra plant needs 10 thousand tons of acrylonitrile per month Our factory sells 8 thousand tons of acrylonitrile per month 65 We give 269 tons per month to JILIN CITY CHINA factory 66 Acetonitrile We produce 409 tonnes of asetonitrile per month We sell 409 tons per month to the Annexy Chema Pharma Industries factory in India 67 Ammonium sulfate We produce 1048 tonnes of ammonium sulfate per month The Seasexports factory in India needs 5000 tons of ammonium sulphate per month Our factory sells 1048 tons to this company 68 Hydrogen cyanide We produce 2769 tonnes of hydrogen cyanide per month Hydrogen cyanide Chi Mei Corp CMC in China where Kempro Chemical Company has purchased Methyl methacrylateStyrene Copolymer 69 101 816 Plan Layout The area to be built by Fabrikan is in the vicinity of the airport railway and other transport facilities with respect to the economical availability of the project Facility placement organizations are as important as the location of the least facilities in the economic direction and are important for creating a safe production environment In addition other factors that need to be taken into consideration when deciding on a plant layout are the minimum material transport cost flexibility and efficient use of space The figure below shows the criteria that must be taken into consideration when deciding on the layout of the facility 57 Figure 83 Pathways of deciding plant layout58 There are a number of factory order examples mentioned in the literature However the specimens may not meet the desired properties Because the dimensions of the buildings and the processes are seen to change too much For this reason changes and innovations are always made on plant settlement types that are current and widely used According to the literature there are four main facility arrangements process order product order fixed position order and group order Before examining these in detail we can refer to the relation between different production volumes and product variety and plant layout types The increase in the production volume or the variation of the final product changes the kind of facility arrangement We see in Figure 83 how the relationship between production volume and product variety affected the plant layout 102 Figure 84 The site location of the company 60 We chose Gebze because Use the road and sea port for the transportation requirements Our location is close to Yılport and Evyaport Datas show that if we consider the climate properties of Gebze the weather conditions are suitable for production of acrylonitrile The place we choose is the organized industrial zone 104 REFERENCES 1Akshay Grover Mohit Sharma Divyanshu Patel Shashwat Mitra Manufacture of Acrylonitrile April 2012 2GülinGüvendikİİpekBoşgelmez Akrilonitril2000 3Daniele Cespi 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