TABLE OF CONTENTS. Chapter No & Title

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1 SUMMARY Today, Turkey is not the one of the countries that produces styrene and the need for this monomer is met only through imports. In this project, the design and establishment of a new styrene plant, located in Izmir, Aliağa with the capacity of 300,000 tons/year was aimed. To carry out the production of styrene, vapor phase adiabatic dehydrogenation of ethylbenzene is selected from among several processes. In the selected process; vapor phase adiabatic dehydrogenation of ethylbenzene, ethylbenzene and low pressure steam are used as the raw materials; styrene is the main product while benzene, toluene and light gases mainly forms from carbon dioxide and hydrogen are the byproducts. Based on the basis of design, the overall reaction is an endothermic reaction in which the total conversion is 0.76 and styrene is obtained with 99.7% purity as designated by ASTM. Depending on the economic analysis, the cost of one kilogram of ethylbenzene is 1.25 dollars and one kilogram of styrene could be sold from 2 dollars. Therefore, based on these researches, the cost of fixed capital investment could be paid back. The process is seen as profitable. i

2 TABLE OF CONTENTS Chapter No & Title ii Page SUMMARY... i TABLE OF CONTENTS... ii LIST OF TABLES... iv LIST OF FIGURES... v LIST OF SYMBOLS... vi 1. INTRODUCTION PROCESS OPTIONS AND SELECTION Dehydrogenation of Ethylbenzene Adiabatic dehydrogenation Oxidative dehydrogenation Styrene via Benzene and Ethane Styrene via Toluene and Methanol Styrene via Butadiene BASIS OF DESIGN Design Specifications Feasible Process Conditions Process Structure PROCESS FLOW-SHEET DIAGRAM (PFD) WITH MASS AND ENERGY BALANCES Process Flow Diagram Mass and Energy Balances EQUIPMENT DESIGN Basis for the Design of Storage Tanks Basis for the Design of Reactors Basis for the Design of Heat Exchangers Basis for the Design of Phase Separators Basis for the Design of Distillation Columns REFERENCES APPENDIX A.1. CALCULATIONS OF EQUIPMENT DESIGN A.1.1 TK-101 Ethylbenzene Storage Tank Design A.1.2 TK-102 Styrene Storage Tank Design... 30

3 A.1.3 R-101 Reactor Design A.1.4 R-102 Reactor Design APPENDIX A.2 CHEMCAD SIMULATIONS A.2.1 H-101 Fired Heater A.2.2 H-102 Fired Heater A.2.3 R-101 Kinetic Reactor A.2.4 R-102 Kinetic Reactor A.2.5 E-101/E-102 Heat Exchanger A.2.6 E-103/E-104/E-105 Heat Exchangers A.2.7 E-106 Heat Exchanger A.2.8 E-107/E-108/E-109 Heat Exchangers A.2.9 E-110 Heat Exchanger A.2.10 E-111 Heat Exchanger A.2.11 V-101 Dynamic Vessel A.2.12 V-102 Dynamic Vessel A.2.13 T-101/T-102/T-103 Distillation Columns A.2.14 T-104 Distillation Column A.2.15 All Stream Compositions A.2.16 Overall Mass and Energy Balance iii

4 LIST OF TABLES Page Table 2.1: Comparison of styrene production processes... 9 Table 3.1: Design Specifications Table 3.2: Reaction kinetics of ethylbenzene [13] Table 3.3: Physical properties of reactants and products Table 4.1: Operating conditions for each equipment Table 4.2: Flow summary table Table 4.3: Utility summary table Table 4.4: Mass balance for each equipment Table 4.5: Heat balance for each equipment Table 5.1: Equipment summary for storage tanks Table 5.2: Equipment summary for reactors Table 5.3: Equipment summary for heat exchangers Table 5.4: Equipment summary for phase separators Table 5.5: Equipment summary for distillation columns iv

5 LIST OF FIGURES Page Figure 1.1: Structure of styrene [2] Figure 1.2: Styrene consumption in 2006 [4]... 2 Figure 1.3: The global styrene capacity in 2006 [4]... 2 Figure 2.1: Block diagram of adiabatic dehydrogenation of ethylbenzene [1] Figure 2.2: Flow sheet of adiabatic dehydrogenation of ethylbenzene [1] Figure 2.3: Flow sheet of crude styrene distillation [1] Figure 2.4: Block diagram of oxidation of ethylbenzene [9] Figure 2.5: Flow sheet of styrene production from benzene and ethane [9] Figure 2.6: Block diagram of styrene production from toluene and methanol [11]... 7 Figure 2.7: Block diagram of styrene production from toluene and methanol [11]... 8 Figure 3.1: Styrene demand in Turkey at Figure 3.2: Ethylbenzene/styrene system at 10 kpa Figure 3.3: Ethylbenzene/styrene system at 120 kpa Figure 3.4: Ternary diagram for EB/styrene/water at 10 kpa Figure 3.5: Process block diagram Figure 4.1: Process flow diagram Figure 4.2: Overall mass balance Figure 4.3: Overall heat balance Figure A.2.1: Model tank v

6 LIST OF SYMBOLS A ABS Al2O3 atm C1 C2 cm Cp cw D Di E EPS g g H H h hps K kg kj kmol kpa LLE lps m mm MOC MPa mps : Area : Acrylonitrile-Butadiene Styrene Polymer : Aluminum Oxide : Atmosphere : Corrosion Factor : Second Factor : Centimeter : Heat Capacity : Cooling Water : Diameter : Internal Diameter : Activation Energy : Polystyrene : Acceleration of Gravity : Gram : Enthalpy : Height : Hour : High Pressure Steam : Kelvin : Kilogram : Kilojoule : Kilomole : Kilopascal : Liquid-Liquid Equilibria : Low Pressure Steam : Meter : Millimeter : Material of Construction : Megapascal : Medium Pressure Steam vi

7 N : Newton P : Pressure PFR : Plug Flow Reactor PO : Propylene Oxide R : Gas constant s0 SBL SBR T TBC U V V W C : Centigrade : Wall Thickness : Styrene-Butadiene Latex : Styrene-Butadiene Synthetic Rubber : Temperature : 4-tert-Butylcatechol : Overall Heat Transfer Coefficient : Volume : Volume : Watt ν ρ ϭ : Stitching Factor : Density : Maximum Allowable Stress vii

8 1. INTRODUCTION Styrene, also called as vinylbenzene, phenylethylene, styrol and cinamene, found in some foods and plants, is one of the most significant industrial aromatic monomer in petrochemical industry (Figure 1.1) [1]. Figure 1.1: Structure of styrene [2]. Styrene is an aromatic, colorless liquid which is slightly soluble in water while its solubility is high in alcohol and ether. Styrene can undergo many different types of reactions because of its aromatic ring and unsaturated side chains. It can polymerize to polystyrene or can copolymerize with monomers like butadiene and acrylonitrile to significant industrial materials. Styrene can also be oxidized to benzoic acid, benzaldehyde and styrene oxide which is a material that used in perfumes, cosmetics, biological and agricultural chemicals [2]. Small-scale commercial production of styrene was achieved in 1930s and since that time the demand for styrene-based polymers has increased substantially [1]. The global consumption of styrene in 2006 was 25 million metric tons. Figure 1.2 shows the distribution of styrene consumption by products. Nearly 47% of styrene is used to generate polystyrene, a material found in many products like toys, plastic cups, household appliances, and insulation. In addition to polystyrene, styrene is used to produce expandable polystyrene (EPS), acrylonitrile-butadiene styrene polymer (ABS), styrene-butadiene synthetic rubber (SBR), styrene-butadiene latex (SBL), UPR and others [3,4,5]. 1

9 Figure 1.2: Styrene consumption in 2006 [4]. Figure 1.3 displays the distribution of styrene capacity. The largest styrene production is carried out in Asia/Pacific region which is followed by Europe, North America, Middle East and South America. Figure 1.3: The global styrene capacity in 2006 [4]. In Turkey, styrene production was begun in 1975 by Petkim; however, the production was stopped in 1991, because the factory has lagged behind in terms of capacity, technology and economy. Nowadays, Turkey is not one of the countries that produces styrene. Therefore, the need for styrene is met only through imports [6]. Today, about 28.7 million metric tons of styrene is produced globally [4]. In this project, the design and establishment of a new styrene plant that can also compete in today s conditions with the capacity of 300,000 tons/year is aimed. Various methods have been developed for the production of styrene. Those methods can be listed as dehydrogenation of ethylbenzene which could also be separated as adiabatic and oxidative, styrene via benzene and ethane, styrene via toluene and methanol and styrene via 2

10 butadiene. The method of adiabatic dehydrogenation of ethylbenzene is selected to produce styrene commercially among these options. 2. PROCESS OPTIONS AND SELECTION There are various methods to produce styrene commercially. Those methods can be listed as dehydrogenation of ethylbenzene which could also be separated as adiabatic and oxidative, styrene via benzene and ethane, styrene via toluene and methanol and styrene via butadiene. 2.1 Dehydrogenation of Ethylbenzene About 85% of the commercial styrene production is carried out by dehydrogenation of ethylbenzene reaction. The reaction is performed with steam in vapor phase over a catalyst, primarily iron oxide. In addition, dehydrogenation of ethylbenzene can be either adiabatic and oxidative [1]. As mentioned before, dehydrogenation of ethylbenzene is carried out in the existence of steam. The role of the steam in this reaction is to lower the partial pressure of ethylbenzene; therefore, to shift equilibrium toward styrene, to supply the required heat of reaction and to clean catalyst by carrying out a reaction with carbon in which hydrogen and carbon dioxide are released as products. In addition, reaction is carried out over a catalyst. Several catalysts such as iron oxide, chromium or potassium could be used for this type of reaction. Generally, iron is used as the catalyst, because physical properties and activity of iron is better and it gives higher yields than the other types of catalysts [1] Adiabatic dehydrogenation Figure 2.1 shows the block diagram of adiabatic dehydrogenation of ethylbenzene. In this process, ethylbenzene and steam are the raw materials; benzene, toluene, residue to fuel and styrene are obtained as products. Figure 2.1: Block diagram of adiabatic dehydrogenation of ethylbenzene [1]. 3

11 Adiabatic dehydrogenation process is usually carried out in multiple reactors in series (Figure 2.2). The required heat of reaction is injected with superheated steam or by indirect heat transfer. Ethylbenzene feed is mixed with recycled ethylbenzene and steam to prevent the coke forming. This steam is heated by using a heat exchanger and the superheated steam helps to bring reaction temperature to the required value, around 640 C. In the first reactor, the stream is passed through a catalyst. Because of the adiabatic reaction, temperature decreases in outlet stream. Therefore, outlet stream is heated again and is passed through a second reactor. The conversion of ethylbenzene in the first reactor is 35 % and 65 % overall. The reactors are operated at lowest pressure which is applicable and safe. Ethylbenzene feed ratio is determined as giving the optimum yield with minimum cost. From the second reactor effluent, heat is recovered to minimize the energy consumption. Then, the effluent is condensed and separated into vent gas, crude styrene and steam condensate streams. The vent gas which is mainly form from hydrogen and carbon dioxide is used in the recovery of aromatics. After the recover stage, the vent gas could be used as a fuel or feed stream to produce hydrogen. The crude styrene stream is fed into a distillation column in which the stream condensates and is reused [1,7]. Figure 2.2: Flowsheet of adiabatic dehydrogenation of ethylbenzene [1]. 4

12 Figure 2.2 displays the flowsheet of adiabatic dehydrogenation of ethylbenzene. In this figure, a represents the steam super-heater, b represents the reactor, c is the high pressure steam, d is the low pressure steam, e represents the condenser and f is a heat exchanger. Figure 2.3 shows the flowsheet of crude styrene distillation. Crude styrene contains benzene (1%), toluene (2%), ethylbenzene (32%), styrene (64%) and other materials (1%). Mainly, three steps are required to separate crude styrene into components. From the first distillation column, benzene and toluene are separated and sent to another plant to distinguish benzene and toluene from each other. From the second distillation column, ethylbenzene is separated and recycled to the dehydrogenation reactors. Finally, from the third column, styrene and a residue that can be used as fuel are obtained. The boiling points of ethylbenzene and styrene are very close to each other. Therefore, at least trays column are required for their separation. Besides, an inhibitor is necessary in distillation column. Generally, aromatic compounds with hydroxyl, amino and nitro groups are used. Inhibitor should be colored and that color could not be seen in final product. On the other hand, finished monomer is usually inhibited with TBC during the transportation and storage [1]. Figure 2.3: Flow sheet of crude styrene distillation [1] Oxidative dehydrogenation Another method to produce styrene commercially uses ethylbenzene as the starting material where it consists of coproduction of propylene oxide additionally (Figure 2.4). As the first step, ethylbenzene is oxidized to ethylbenzene hydroperoxide with air at 130 C and 0.2 MPa in liquid phase and catalyst is not required. The propylene epoxidation is an exothermic 5

13 reaction operated in fixed bed catalytic reactor under isothermal conditions. The reaction between the ethylbenzene hydroperoxide and propylene occurs in the existence of excess ethylbenzene and metallic catalysts like titanium or molybdenum at 110 C, 4 MPa. Ethylbenzene hydroperoxide and propylene is converted to propylene oxide. In distillation column, as a first step, unreacted propylene is recycled to the propylene epoxidation. The bottom product propylene oxide needs additional operations. By the help of propylene oxide purification step, product is obtained with a high purity. In addition, α-phenylethanol is separated and dehydrated to styrene over an appropriate metal oxide like Al2O3 at low pressure and 250 C. The conversion of ethylbenzene hydroperoxide is almost complete and the selectivity of propylene oxide producing reaction is more than 70%. Oxidation of ethylbenzene method is another route except from adiabatic dehydrogenation of ethylbenzene to produce styrene commercially [1,8,9]. Figure 2.4: Block diagram of oxidation of ethylbenzene [9]. 2.2 Styrene via Benzene and Ethane This is a developing method in which styrene is produced from benzene and ethane monomers. In this method, ethane and ethylbenzene from alkylation unit are fed to the reactor over a catalyst that is able to produce ethylene and styrene (Figure 2.5). From the dehydrogenation reactor, effluent is taken, cooled and separated to ethylene which is recycled to alkylation unit back. This method has some constraints that the recovery of aromatics; hydrogen and ethane separation are inefficient and heavies are produced at high levels. Therefore, the development of the process is ongoing [10]. 6

14 Figure 2.5: Flowsheet of styrene production from benzene and ethane [9]. 2.3 Styrene via Toluene and Methanol Figure 2.6 shows the block diagram of styrene from toluene and methanol. In this process, toluene and methanol are the raw materials; styrene, hydrogen, ethylbenzene and waste water are obtained as products. Figure 2.6: Block diagram of styrene production from toluene and methanol [11]. To produce styrene from toluene and methanol in commercial scale would have a significant effect on the market of styrene. In this process, styrene is produced from toluene and methanol by the side-chain alkylation reaction at C and atmospheric pressure over a zeolite catalyst. The advantage of this method is the usage of cheaper raw materials. Therefore, the cost of styrene production can be decreased significantly. In addition, by using a new catalytic technology, the selectivity of this process can be increased. However, this process is not carried out in commercial scale yet [10]. Figure 2.7 shows the flowsheet of styrene production from toluene and methanol. First of all, toluene and methanol at 25 C and 1 atm are compressed and heated to saturated vapors. Toluene and methanol vapor streams are mixed with toluene and methanol recycles, fed to the furnace and superheated to between 465 C and 540 C. Then, this superheated stream is fed into the reactor which operates adiabatically. The stream leaving the reactor is cooled to 38 C and vapor, organic and aqueous phases are obtained from decanter. The vapor stream mainly 7

15 consists of hydrogen that can be used as a fuel. The organic phase involves toluene, ethylbenzene and styrene. The organic phase is fed to distillation column. The top product containing toluene and methanol found in small quantity is recycled. The bottom product taken from distillation column contains ethylbenzene and styrene. Therefore, this stream is fed into a second distillation column in which ethylbenzene is obtained as a top and styrene is obtained as a bottom product. The aqueous stream contains methanol and water generally. This stream is fed into another distillation column in which waste water and methanol are separated from each other and the obtained methanol is recycled to the furnace back [11]. Figure 2.7: Block diagram of styrene production from toluene and methanol [11]. 2.4 Styrene via Butadiene Conversion of butadiene to styrene consists of a two-step process. In the first step, butadiene is converted to 4-vinylcyclohexene. The reaction is carried out over a copper containing zeolite catalyst or iron dinitrosyl chloride catalyst complex and this reaction is exothermic. Higher conversion of butadiene is achieved in liquid phase reaction. In the second step, oxidative dehydrogenation of 4-vinylcyclohexene is carried out to form styrene. By the help of catalysts, 90% conversion and 92% selectivity could be obtained. Table 2.1 shows the comparison of different styrene production processes where + represents advantageous, ++ means more advantageous and represents disadvantageous. 8

16 Table 2.1: Comparison of styrene production processes Process Conversion Cost Energy 1. Dehydrogenation of Ethylbenzene recovery Safety issues Commercial 1.1 Adiabatic Dehydrogenation Oxidative Dehydrogenation Styrene via Benzene and Ethane Styrene via Toluene and Methanol Styrene via Butadiene scale Among these methods, adiabatic dehydrogenation of ethylbenzene has been selected. Oxidative dehydrogenation of ethylbenzene, styrene via benzene and ethane, styrene via toluene and methanol, styrene via butadiene have been eliminated due to safety issues, conversion and commercial problems as listed in Table BASIS OF DESIGN 3.1 Design Specifications Considering the information obtained from the Turkish Statistical Institute, the styrene requirement in Turkey has been predicted as 1,000,000 tons/year at 2030 (Figure 3.1). The aim in this project is to establish a new styrene plant that supplies 30% of the styrene requirement in Turkey in which nearly 300,000 tons/year styrene is produced. Figure 3.1: Styrene demand in Turkey at

17 Based on the investigations from different resources, it was seen that one kilogramme of ethylbenzene could be bought from 1.25 dollars and one kilogramme of styrene could be sold from 2 dollars. The selected process; vapor phase adiabatic dehydrogenation of ethylbenzene is carried out in two successive PFRs. The overall reaction is endothermic which requires low pressure and high temperature. The operating range of pressure is between 1.4 and 2.4 bar (Table 3.1). The control of temperature is very significant and the operating range of temperature should be between 600 and 655 C. As a catalyst, potassium promoted iron oxide is used and the total conversion is Besides, styrene is obtained with 99.7% purity. Peng Robinson was chosen as the equation of state due to its reliability for predicting the properties of hydrocarbons in styrene production process [7]. Additionally, as a process mode, continuous process is selected because it reduces cost and waste, saves money and increases productivity. By changing the run time, the output can be altered; therefore, flexibility is higher in continuous reactors than the batch reactor [12]. Table 3.1: Design Specifications Process Reaction Type Catalyst Endothermic Potassium promoted iron oxide Operation Temperature ( C) Operation Pressure (bar) Total Conversion (%) 76 Product Purity (%) 99.7 Thermodynamic Model Process Mode Peng Robinson Continuous In styrene production plant, ethylbenzene and low pressure steam are used as raw materials. Because ethylbenzene will be supplied to this process from the plant belongs to Professor Ahmet Sirkecioğlu s team found in Aliağa, the location of styrene plant is also decided as Aliağa. Therefore, the transport of the raw material ethylbenzene into styrene plant will be easier. 10

18 3.2 Feasible Process Conditions In the adiabatic dehydrogenation of ethylbenzene, two consecutive PFRs are used. In this type of reactors, six different reactions take place and they can be listed as styrene, benzene and ethylene, toluene and methane, carbon monoxide and carbon dioxide reactions. From these reactions, only the styrene synthesis reaction is reversible while the other ones are irreversible [13]. Styrene Reaction: C6H5CH2CH3 C6H5CHCH2 + H2 (1) r 1F = p EB k 1F e E 1F/RT (2) r 1R = p S p H2 k 1R e E 1R/RT (3) Benzene/Ethylene Reaction: C6H5CH2CH3 C6H6 + C2H4 (4) r 2 = p EB k 2 e E 2/RT (5) Toluene/Methane Reaction: C6H5CH2CH3 + H2 C6H5CH3 + CH4 (6) r 3 = p EB p H2 k 3 e E 3/RT (7) Carbon Monoxide Reactions: 2H2O + C2H4 2CO + 4H2 (8) r 4 = p w p 0.5 E k 4 e E 4/RT (9) H2O + CH4 CO + 3H2 (10) r 5 = p W p M k 5 e E 5/RT (11) Carbon Dioxide Reaction: H2O + CO CO2 + H2 (12) r 6 = p W p CO k 6 e E 6/RT (13) Table 3.2 shows the reaction kinetics of styrene process. The table of reaction kinetics instantly express that higher temperature is favorable for the first reaction because the activation energy of the forward reaction is greater than the activation energy of the reverse reaction due to endothermic reaction. In addition, low pressure and high ethylbenzene concentrations are preferable for the styrene production. However, reaction rates of side reactions also increase with temperature. Therefore, in order to reduce the production of byproducts, temperature should be kept at low. However, there is a conflict come out between conversion and selectivity. At this point, low pressure is a significant parameter to reduce the production of byproducts [13]. 11

19 Table 3.2: Reaction kinetics of ethylbenzene [13]. Reaction Kinetics Arrhenius Activation Energy, Concentration (Pascals) Constant E (kj/kmol) 1 st Reaction (Forward) ,981 p EB 1 st Reaction (Reverse) 6x ,127 p S p H 2 nd Reaction 27, ,989 p EB 3 rd Reaction 6.5x ,515 p EB p H 4 th Reaction 4.5x ,997 p 2 W p E 5 th Reaction 2.6x p W p M 6 th Reaction ,638 p W p CO Table 3.3 shows the physical properties of reactants and products that are taken from CHEMCAD component databank. The boiling points of ethylbenzene and styrene are very close to each other; therefore, large number of stages, typically 70 to 100, is required in distillation columns to distinguish them effectively [7]. Table 3.3: Physical properties of reactants and products Formula Molecular Weight (g/mol) Melting Point ( C) Boiling Point ( C) Critical Pressure (bar) Styrene C8H Ethylbenzene C8H Toluene C7H Benzene C6H Methane CH Critical Temperature ( C) Carbon Monoxide CO Carbon Dioxide CO Ethylene C2H Hydrogen H Water H2O The styrene process consists of liquid-liquid-vapor equilibrium in decanter and involves vapor-liquid equilibrium in distillation columns. Figure 3.2 is the Txy diagram of ethylbenzene/styrene system at 10 kpa which is the top pressure of the first distillation column. Because the separation is difficult, many trays and high reflux ratio is needed in these columns. Figure 3.3 shows the Txy diagram of ethylbenzene/styrene system at 120 kpa. 12

20 Separation at that pressure is easier, so fewer trays and reflux ratio is sufficient. Figure 3.2 and Figure 3.3 are taken from CHEMCAD component databank based on the Peng Robinson thermodynamic model. Figure 3.2: Ethylbenzene/styrene system at 10 kpa. Figure 3.3: Ethylbenzene/styrene system at 120 kpa. 13

21 In decanter, the mixture is separated into three phase; aqueous, organic and inorganic. Major components in this separation are water, styrene, ethylbenzene, hydrogen, benzene and toluene. Figure 3.4 displays the ternary diagram for ethylbenzene/styrene/water system at 10 kpa. 10 kpa pressure gives a temperature which is close to 40 C and shows LLE equilibrium. In addition, the organic phase involves small amount of water while the aqueous phase is composed of pure water. Figure 3.4: Ternary diagram for EB/styrene/water at 10 kpa. 3.3 Process Structure From among styrene production methods, adiabatic dehydrogenation of ethylbenzene was selected. As seen in the Figure 3.5, first of all, low pressure steam is preheated in a furnace, then mixed with ethylbenzene and fed to two successive, adiabatic PFRs in order to produce styrene. The six main reactions occur in two reactors. Later, the reactor effluent is cooled and sent to the three-phase separator. By the help of this separator, light gases and water are removed as light products and heavy product, respectively. On the other hand, the intermediate layer, organic phase, is sent to the distillation columns in order to separate styrene from other components. The first three parallel columns operate under vacuum to prevent the polymerization of styrene. From those three columns, styrene is obtained as bottom product and the top products are fed into two-phase separator. The top product of separator is compressed and released as vent gas. The bottom product is fed into another column to separate unreacted ethylbenzene from byproducts; toluene and benzene. The separated unreacted ethylbenzene is then recycled back. For this process the battery limit includes receipt of styrene. The byproducts; benzene and toluene; will be sold to the plant in which ethylbenzene is produced and will be donated to Chemical Engineering Laboratory of ITU while the rest of it will be sold to manufacturers, respectively. 14

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23 4. PROCESS FLOW-SHEET DIAGRAM (PFD) WITH MASS AND ENERGY BALANCES 4.1 Process Flow Diagram Fresh ethylbenzene having temperature of 200 o C and pressure of 4 bar, (stream 1), and recycled ethylbenzene, (stream 2), are combined with low pressure and superheated steam at 868 o C and 5 bar, and the obtained stream 3 is heated in the furnace, H-101. The process has two plug flow reactors in series. The first reactor, R-101, has 1.8 bar operation pressure, 42% conversion and the second reactor, R-102, is operated under 1.5 bar pressure, has 40% conversion. Mixture of ethylbenzene and steam, (stream 6), having 650 o C and 3 bar is feed to the first plug flow reactor then products are preheated up to 650 o C at furnace, H-102, to feed them into the second reactor. After second reactor, the products which have temperature of 620 o C are cooled to 40 o C by using heat exchangers, E-101 and E-102. Cooled mixture, (stream 12), is fed to a vessel, V-101, which operates under 1 bar and at 40 o C. The vessel separates the mixture into three phase which are vapor phase, (stream 13), leaving from top of the vessel, organic phase, (stream 14), having high concentration of organic compound especially hydrocarbons, and stream 15, pure water phase. The organic phase is divided into three arms, (stream ), to be fed to distillation columns. The process has three identical distillation column, T-101, T-102 and T-103, in parallels. Each distillation column has 0.1 bar top pressure and 0.3 bar bottom pressure and purifies heavy component styrene which is taken apart from bottom of the distillation column with 0.3 bar and about 71 o C. Obtained styrene, (stream 30, 38 and 40), is pumped, P-101, P-102 and P-103, to styrene storage tanks. On the other hand, in the distillate streams, (stream 17, 36 and 39), there exist 76% ethylbenzene as a mole fraction. Three distillate flows are combined with each other and unit flow, stream 41, is fed to a two phase separator, V-102, to separate organic phase and remove vent gas after precooling operation. The vessel operates under 0.1 bar and at 41 o C. The next step is that the mixture having high concentration of ethylbenzene, (stream 33), is fed to another distillation column, T-104, operating under 1.2 bar top pressure. The heavy component in this distillation column is ethylbenzene and major light components are benzene and toluene. The heavier component, ethylbenzene, is taken from bottom of column, (stream 23), to be recycled, (stream 2), the system by using a pump, P-106. Benzene and toluene remained in the distillate stream, (stream 18). Process Flow Diagram is given in Figure 4.1 on the following page. 16

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25 Table 4.1 shows the operating conditions for each equipment. Table 4.1: Operating conditions for each equipment Equipment Name Operation Temperature ( C) Operation Pressure (bar) TK-101/ TK R R V V T-101/ T-102/ T T Mass and Energy Balances The flow summary of the process is given in Table 4.2. The stream numbers in Table 4.2. are indicated on process flow diagram. Table 4.2: Flow summary table Stream Name Temperature ( C) Pressure (bar) Vapor mole fraction Total flow (Tonne/year ) Total flow (kmol/h) Flowrates kmol/h Ethylbenzen e Water Toluene Benzene Hydrogen Styrene Ethylene Methane Carbon Dioxide Carbon Monoxide Stream Name

26 Temperature ( C) Pressure (bar) Vapor mole fraction Total flow (kmol/h) Total flow (Tonne/year ) Flowrates kmol/h Ethylbenzen e Water Toluene Benzene Hydrogen Styrene Ethylene Methane Carbon Dioxide Carbon Monoxide Stream Name Temperature ( C) Pressure (bar) Vapor mole fraction Total flow (kmol/h) Total flow (Tonne/year ) Flow rates kmol/h Ethylbenzen e Water Toluene Benzene Hydrogen Styrene Ethylene Methane Carbon Dioxide Carbon Monoxide

27 Stream Name Temperature ( C) Pressure (bar) Vapor mole fraction Total flow (kmol/h) Total flow (Tonne/year ) Flow rates kmol/h Ethylbenzen e Water Toluene Benzene Hydrogen Styrene Ethylene Methane Carbon Dioxide Carbon Monoxide Stream Name Temperature ( C) Pressure (bar) Vapor mole fraction Total flow (kmol/h) Total flow (Tonne/year ) Flow rates kmol/h Ethylbenzen e Water Toluene Benzene Hydrogen Styrene Ethylene Methane Carbon Dioxide Carbon Monoxide

28 Utility types used for heating and cooling, their flow rates are given in Table 4.3. REASONITY!!!! Table 4.3: Utility summary table Equipment R101 R102 TK101 TK102 H101 H102 P101A/B P102A/B Utility type lps lps lps lps mps lps lps lps Utility flow rate (kg/h) Equipment P103A/B P104A/B P105A/B P106A/B E101 E102 E103 E104 Utility type lps lps lps lps cw cw lps lps Utility flow rate (kg/h) Equipment E105 E106 E107 E108 E109 E110 E111 Utility type lps lps lps lps lps lps cw Utility flow rate (kg/h) ,1 Mass and energy balances are carried out by using CHEMCAD simulation program. Table 4.4 and 4.5 shows the mass and energy balances for each equipment, respectively. Table 4.4: Mass balance for each equipment MASS BALANCE Equipment Name Stream kg/h Stream kg/h Equipment No (In) No No (Out) H-101 Fire Heater R-101 PFR H-102 Fire Heater R-102 PFR E-101 Heat Exchanger E-102 Heat Exchanger Dynamic Vessel V T-101 Distillation Column

29 T-102 Distillation Column T-103 Distillation Column E-111 Heat Exchanger V-102 Dynamic Vessel P-104 A/B Pump T-104 Distillation Column P-106 A/B Pump Table 4.5: Heat balance for each equipment HEAT BALANCE Equipment Name Stream No kj/h Stream No kj/h (In) (Out) H-101 Fire Heater 3-2,29x ,04x10 15 R-101 PFR 6-2,01x ,01x10 15 H-102 Fire Heater 8-2,01x ,97x10 15 R-102 PFR 10-1,97x ,97x10 15 E-101 Heat Exchanger 9-1,97x ,04x10 15 E-102 Heat Exchanger 11-2,04x ,71x10 15 V-101 Dynamic Vessel 12-2,71x ,18x10 13 Equipment No 14 3,75x ,73x10 15 T-101 Distillation Column 29 3,75x ,05x ,32x10 12 T-102 Distillation Column 31 3,75x ,07x ,32x10 13 T-103 Distillation Column 37 3,75x ,05x ,32x10 13 E-111 Heat Exchanger 41 1,22x ,82x10 5 V-102 Dynamic Vessel 34 2,82x ,95x ,78x10 5 P-104 A/B Pump 33 4,78x ,81x10 5 T-104 Distillation Column 35 4,81x ,54x ,89x10 5 P-106 A/B Pump 23 2,89x ,90x10 6 Total EKLENECEK EN ALTA TABLO

30 As a result, overall mass balance and heat balance can be shown as in Figure 4.2 and Figure 4.3. Figure 4.2: Overall mass balance Figure 4.3: Overall heat balance 5. EQUIPMENT DESIGN Vinylbenzene production process consists of two storage tanks, two furnaces, two plug flow reactors, three heat exchangers, two vessels, four condensers, four reboilers and four distillation columns. 5.1 Basis for the Design of Storage Tanks The design calculations of storage tanks are in Appendix A.1. Table 5.1 shows the properties of storage tanks. Table 5.1: Equipment summary for storage tanks 23

31 Equipment TK-101 TK-102 Material Ethylbenzene Styrene Operation Conditions 25 C - 1 bar 25 C - 1 bar Waiting Time 1 week 1 week MOC Stainless Steel 316 Stainless Steel 316 Volume (m 3 ) 11,165 8,367 Inside Diameter (m) Wall Thickness (m) Height (m) Inhibitor - TBC Tank Base Klopper Klopper Tank Cover Flat Flat 5.2 Basis for the Design of Reactors In the process, two series consecutive plug flow reactors are found. The design properties of those reactors can be seen in Table 5.2. Table 5.2: Equipment summary for reactors Equipment R-101 R-102 Type of reactor Plug flow Plug flow MOC Stainless steel 316 Stainless steel 316 Conversion Operation Condition Adiabatic Adiabatic Catalyst Potassium promoted iron oxide Potassium promoted iron oxide Operation Pressure (bar) Operation Temperature ( C) Reactor Volume (m 3 ) Outer Diameter (m) Thickness (m) Length (m)

32 5.3 Basis for the Design of Heat Exchangers Sizing for all heat exchangers are carried out by using CHEMCAD. The reports are introduced in Appendix A.2. Equipment summary for heat exchangers is given in Table 5.3. Table 5.3: Equipment summary for heat exchangers Equipment E-101 E-102 E-103 E-104 MOC Carbon Steel Carbon Steel Carbon Steel Carbon Steel Total Area (m 2 ) Tube Length (m) Tube Number Overall Heat Transfer Coefficient (W/m 2 K) Water Amount (kg/h) 289, , , ,677 Heat Duty (kj/h) 1.2x x x x10 7 Equipment E-105 E-106 E-107 E-108 MOC Carbon Steel Carbon Steel Carbon Steel Carbon Steel Total Area (m 2 ) Tube Length (m) Tube Number Overall Heat Transfer Coefficient (W/m 2 K) Water Amount (kg/h) 814, , , ,434 Heat Duty (kj/h) -5.8x x x x10 7 Equipment E-109 E-110 E-111 MOC Carbon Steel Carbon Steel Carbon Steel Total Area (m 2 ) Tube Length (m) Tube Number Overall Heat Transfer Coefficient (W/m 2 K) Water Amount (kg/h) 178,434 59,600 88,720 Heat Duty (kj/h) 6.3x x x

33 5.4 Basis for the Design of Phase Separators Sizing for all phase separators are carried out by using CHEMCAD. The reports are introduced in Appendix A.2. Equipment summary for phase separators is given in Table 5.4. Table 5.4: Equipment summary for phase separators Equipment V-101 V-102 Operation Temperature ( C) Operation Pressure (bar) Orientation Horizontal Horizontal MOC Carbon Steel Carbon Steel Length (m) Diameter (m) Basis for the Design of Distillation Columns Sizing for all distillation columns are carried out by using CHEMCAD. The reports are introduced in Appendix A.2. Equipment summary for distillation columns is given in Table 5.5. Table 5.5: Equipment summary for distillation columns Equipment T-101 T-102 T-103 T-104 MOC Stainless Steel Stainless Steel Stainless Steel Stainless Steel Diameter (m) Height (m) Orientation Vertical Vertical Vertical Vertical Operation Temperature ( C) Operation Pressure (bar) Number of Stage Feed Stage Reflux Ratio

34 REFERENCES [1] Behr, A. (n.d). Styrene Production from Ethylbenzene. Technical University of Dortmund, Faculty of Biochemical and Chemical Engineering, Germany. [2] Url-1 < date retrieved [3] Woodle, G. B. (2006). Styrene. Encyclopedia of Chemical Processing, , doi: [4] Url-2 < / /0506S3_abs.pdf > date retrieved [5] Url-3 < date retrieved [6] T.C. Milli Eğitim Bakanlığı, MEGEP (Mesleki Eğitim ve Öğretim Sisteminin Güçlendirilmesi Projesi).(2007). Benzen ve Türevleri Prosesi, Turkey. [7] Vasudevan, S., Rangaiah, G. P., Konda, M., Tay, W. H. (2009). Application and Evaluation of Three Methodologies for Plantwide Control of the Styrene Monomer Plant. Ind. Eng. Chem. Res., 48, [8] Url-4 < date retrieved [9] Clerici, M. G. (2013). Liquid Phase Oxidation via Heterogenous Catalysis. In Kholdeeva, O. A. (Ed.), Organic Synthesis and Industrial Applications, New Jersey. [10] Nexant, Styrene/Ethylbenzene Process Technology, Production Costs and Regional Supply/Demand Forecasts, California. [11] Url-5 < date retrieved [12] Url-6 < > date retrieved [13] Luyben, W. L. (2011). Design and Control of the Styrene Process. Ind. Eng. Chem. Res., 50,

35 APPENDIX A.1. CALCULATIONS OF EQUIPMENT DESIGN A.1.1 TK-101 Ethylbenzene Storage Tank Design Figure A.2.1: Model tank Mass flow rate = kg/h Retention time = 7 days Feed = kg Vdesign = kg/866 kg/m 3 Vdesign = m 3 (Assuming that the tank is %80 full.) Hliquid/cylinder/Di = 2 (Assumption) V = (πdi 3 /4)*2Di Di = m = 1784 cm Hliquid/cylinder = 35.7 m The tank is closed and at atmospheric pressure, so the design pressure is happened by hydraulic pressure. Therefore, the tank operates at inner pressure. 25 o C = 866 kg/m 3 Phydrostatic = hϼ Phydrostatic = 35.7 m*866 kg/m 3 = kg/m 2 Pinternal = 1 bar Tdesign = 25 o C + 25 o C = 50 o C Pdesign = 1.1 Pinternal + Phydrostatic Pdesign = 4.13 bar = 4.21 kg/cm 2 Tank material of construction is selected as Stainless Steel 316. The maximum allowable stress (ϭ) = 175 N/mm 2 = 1700 kg/cm 2 Stitching factor (ν) =

36 For cylindrical part: s0 = = 2.46 cm = 24.6 mm C1 (Corrosion Tolerance) is chosen as 4 mm. s = s0 + C1 + C2 s = C2 C2 = 1.1 mm s = mm sstandard = 35 mm For bottom part: Klopper bottom is chosen. Cs = 1 4 R/r = 10 Cs = 1.54 s0 = PDiCs 2νσ (3+ R/r ) = s = s0 + C1 + C2 = C2 C2 = 1.8 mm s = 43.6 mm sstandard = 45 mm Vbottom = 0.1(Di-2s) 3 Vbottom = m 3 hi = Di s hi = 3.43 m For head part: Flat head is chosen. = 3.78 cm = 37.8 mm Do = Di + 2s = mm + 2*35 mm = mm Area = πd2 4 A = mm 2 = m 2 It is assumed that a 100 kg person stays on the cover. F = 100 kg* 9.81 m/s 2 = 981 kg.m/ s 2 P = F A = 3.92 N/m2 = 3.92*10-6 N/mm 2 s0 = CDo P/σ C =

37 s0 = (0.55)(1784) /175 = 1.46 mm sstandard = 7 mm Vtotal = m 3 / 0.8 = m 3 Vtotal = Vcylinder + Vbottom Vcylinder = m 3 Lcylinder = V A = π = m Htank = Lcylinder+ sbottom + hi + shead Htank = m + 45(10-3 ) m m + 7(10-3 ) m Htank = m A.1.2 TK-102 Styrene Storage Tank Design Mass flow rate = kg/h Retention time = 7 days Feed = kg Mass flow rate = kg/h Retention time = 7 days Feed = kg Vdesign= kg/909 kg/m 3 Vdesign= m 3 (Assuming that the tank is %80 full.) Hliquid/cylinder/Di = 2 (Assumption) V = (πdi 3 /4)*2Di Di= m = cm Hliquid/cylinder = m The tank is closed and at atmospheric pressure, so the design pressure is happened by hydraulic pressure. Therefore, the tank operates at inner pressure. 25 o C = 909 kg/m 3 Phydrostatic = hϼ Phydrostatic = m*909 kg/m 3 = kg/m 2 Pinternal = 1 bar Tdesign = 25 o C + 25 o C = 50 o C Pdesign=1.1 Pinternal + Phydrostatic Pdesign = 4 bar = 4.06 kg/cm 2 The maximum allowable stress = 175 N/mm 2 = 1700 kg/cm 2 Stitching factor (ν) =

38 For cylindrical part: s0 = PDi = = 2.15 cm = mm 2νσ P C1 (Corrosion Tolerance) is chosen 4 mm. s = s0 + C1 + C2 s = C2 C2 = 1.1 mm S = mm sstandard = 28 mm For bottom part: Klopper bottom is chosen. Cs = 1 4 R/r = 10 Cs = 1.54 s0 = PDiCs 2νσ (3+ R/r ) = s = s0 + C1 + C2 = C2 C2 = 1.6 mm s = 41.6 mm s = 45 mm Vbottom = 0.1(Di-2s) 3 Vbottom = m 3 hi = Di-0.445s hi = 3.11 m For head part: Flat head is chosen. = 3.32 cm = 33.2 mm Do = Di + 2s = mm + 2*28 mm = mm Area = πd2 4 A = mm 2 = m 2 It is assumed that a 100 kg person stays on the cover. F = mg F=100 kg* 9.81 m/s 2 = 981 kgm/ s 2 P = F A = 4.71 N/m2 = 4.71(10-6 ) N/mm 2 s0 = CDo P/σ C = 0.55 (it is certain for this formula) 31

39 s0 = (0.55)( ) /175 =1.46 mm sstandard = 7 mm Vtotal = m 3 / 0.8 = m 3 Vtotal = Vcylinder + Vbottom Vcylinder = m 3 Lcylinder = V A = π = 38.5 m Htank = Lcylinder+ sbottom + hi + shead Htank = 38.5 m + 45(10-3 ) m m + 7(10-3 ) m Htank = m A.1.3 R-101 Reactor Design This reactor includes 94% water and 6% ethylbenzene. So, the reactor is designed as torispherical bottom and head with stainless steel. In the reactor, temperature is 650 C, pressure is 3 bar. Mass flow rate = kg/h Tdesign = = 675 C Patm = 1 bar Pdesign= (1.1)*3 = 3.3 bar Pdesign>Patm So, the reactor operates at internal pressure. The maximum allowable stress = 77.5 N/mm 2 Stitching factor (ν) = 0.95 Vreactor = Vbottom + Vhead + Vcyl = 46 m 3 L/Di = 4 Vreactor = 2*0.1*Di 3 + ((π*di 2 )*L)/4 = 46 m 3 (By neglecting the s values in the equation) Di = 2.39 m L = 9.56 m Cylindrical section: s0 = ((3.06 kg/cm 2 )*(2390mm))/(2*0.95* kg/cm kg/cm 2 ) = 4.88 mm s = (s0/ν)+c1+c2 C1 = 2 mm (Corrosion Tolerance) (s0/ν)+c1 = 7.14 mm C2 = 0.29 mm s = (s0/ν)+c1+c2 =

40 sstd = 12mm Torispherical Bottom: Cs = 1/4*(3+(R/r) 0.5 )) = 1.54 s0 = ((3.06 kg/cm 2 )*(2414mm)*1.54)/( 2*0.95* kg/cm 2 ) = 7.58 mm (s0/ν)+c1 = 9.79 C2 = 0.33 s = (s0/ν)+c1+c2 = sstandard =14 mm Torispherical Head: Cs = 1/4*(3+(R/r) 0.5 )) = 1.54 s0 = ((3.06 kg/cm 2 )*(2414mm)*1.54)/( 2*0.95* kg/cm 2 ) = 7.58 mm (s0/ν)+c1 = 9.79 C2 = 0.33 s = (s0/ν)+c1+c2 = sstandard = 14 mm A.1.4 R-102 Reactor Design This reactor includes 91% water, 3.5% ethylbenzene, 2.2% styrene and other byproducts. So, the reactor is designed as torispherical bottom and head with stainless steel. In the reactor, temperature is 650 C, pressure is 3 bar. Mass flow rate = kg/h Vreactor = Vbottom + Vhead + Vcyl = 56 m 3 L/Di = 4 Vreactor = 2*0.1*Di 3 + ((π*di 2 )*L)/4 = 56 (By neglecting the s values in the equation) Di = 2.56 m L = m Cylindrical section: s0 = ((3.06 kg/cm 2 )*(2560mm))/(2*0.95* kg/cm kg/cm 2 ) = 5.23 mm s = (s0/ν)+c1+c2 C1 = 2 mm (Corrosion Tolerance) (s0/ν)+c1 = 7.5 mm C2 = 0.29 mm s = (s0/ν)+c1+c2 = mm sstandard = 12mm 33

41 Torispherical Bottom: Cs = 1/4*(3+(R/r) 0.5 )) = 1.54 s0 = ((3.06 kg/cm 2 )*(2584mm)*1.54)/( 2*0.95* kg/cm 2 ) = 8.1 mm (s0/ν)+c1 = mm C2 = 0.36 s = (s0/ν)+c1+c2 = mm sstandard = 15 mm Torispherical Head: Cs = 1/4*(3+(R/r) 0.5 )) = 1.54 s0 = ((3.06 kg/cm 2 )*(2584mm)*1.54)/( 2*0.95* kg/cm 2 ) = 8.1 mm (s0/ν)+c1 = mm C2 = 0.36 s = (s0/ν)+c1+c2 = mm sstandard = 15 mm 34

42 APPENDIX A.2 CHEMCAD SIMULATIONS Stream numbers are the same with flow summary table. A.2.1 H-101 Fired Heater CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 21:59:48 Fired Heater Summary Equip. No. 2 Name Temperature Out C Heat Absorbed kj/h e+008 Fuel Usage(SCF) A.2.2 H-102 Fired Heater CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:12:01 Fired Heater Summary Equip. No. 7 Name Temperature Out C Heat Absorbed kj/h e+007 Fuel Usage(SCF)

43 A.2.3 R-101 Kinetic Reactor CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:09:57 Kinetic Reactor Summary Equip. No. 8 Name Reactor type 2 Reaction phase 1 Thermal mode 2 Pressure In kpa Tout C Reactor volume m Concentration Flag 1 Specify calc. mode 1 Conversion Key 1 No. of Reactions 7 Molar Flow Unit 1 Activ. E/H of Rxn Unit 4 Volume Unit 1 Time Unit 2 Overall IG Ht of Rxn e+007 (kj/h) Mass unit 1 Partial P unit 8 A.2.4 R-102 Kinetic Reactor CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:15:28 Kinetic Reactor Summary 36

44 Equip. No. 6 Name Reactor type 2 Reaction phase 1 Thermal mode 2 Pressure In kpa Tout C Reactor volume m Concentration Flag 1 Specify calc. mode 1 Conversion Key 1 No. of Reactions 7 Molar Flow Unit 1 Activ. E/H of Rxn Unit 4 Volume Unit 1 Time Unit 2 Overall IG Ht of Rxn e+007 (kj/h) Mass unit 1 Partial P unit 8 A.2.5 E-101/E-102 Heat Exchanger CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:18:21 Heat Exchanger Summary Equip. No. 5 Name 1st Stream dp kpa st Stream T Out C Calc Ht Duty kj/h e+007 LMTD Corr Factor st Stream Pout kpa TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 5 Service of Unit Item 6 Size 1.0m x 6.1m Type AEL (Hor/Vert) H Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) 509.3/500.8 m2; Shell/Unit Surf/Shell 509.3/500.8 m2 8 PERFORMANCE OF ONE UNIT 9 Type of Process Sensible Sensible 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 37

45 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 0.00/995.92/ 0.00/ /0.00 / 0.53/0.00 kg/m3 19 Conductivity 0.00/0.61 / 0.00/ /0.00 / 0.07/0.00 W/m-K 20 Specific Heat 0.00/75.42 / 0.00/ /0.00 / 51.14/0.00 kj/kmol-k 21 Viscosity 0.00/0.87 / 0.00/ /0.00 / 0.03/0.00 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / / kpa 28 Heat Exchanged 6.924e+007 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: 76.8 Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No OD m;thk m;length m;pit m; Ptn Tube Type Bare Material 1 Carbon Steel 41 Shell A-285-C 1.02 ID 1.04 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 32 Spacing C/C 0.68 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 55 Remarks: 56 A.2.6 E-103/E-104/E-105 Heat Exchangers TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 5 Service of Unit Item 6 Size 2.4m x 2.4m Type AEL (Hor/Vert) V Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) / m2; Shell/Unit Surf/Shell / m2 8 PERFORMANCE OF ONE UNIT 9 Type of Process Sensible Vert Cond 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name Utility in Process in 38

46 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 0.00/995.92/ 0.00/ /827.79/ 0.36/ kg/m3 19 Conductivity 0.00/0.61 / 0.00/ /0.12 / 0.01/0.12 W/m-K 20 Specific Heat 0.00/75.42 / 0.00/ /193.95/134.12/ kj/kmol-k 21 Viscosity 0.00/0.86 / 0.00/ /0.41 / 0.01/0.42 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / /2.442 kpa 28 Heat Exchanged 5.799e+007 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No OD m;thk m;length m;pit m; Ptn Tube Type Bare Material 1 Carbon Steel 41 Shell A-285-C 2.44 ID 2.46 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 15 Spacing C/C 0.49 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 55 Remarks: 56 A.2.7 E-106 Heat Exchanger TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 5 Service of Unit Item 6 Size 0.3m x 3.7m Type AEL (Hor/Vert) V Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) 32.0/31.1 m2; Shell/Unit Surf/Shell 32.0/31.1 m2 39

47 8 PERFORMANCE OF ONE UNIT 9 Type of Process Sensible Vert Cond 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name Utility in Process in 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 0.00/995.92/ 0.00/ /787.37/ 2.80/ kg/m3 19 Conductivity 0.00/0.61 / 0.00/ /0.11 / 0.02/0.12 W/m-K 20 Specific Heat 0.00/75.42 / 0.00/ /178.11/ 92.70/ kj/kmol-k 21 Viscosity 0.00/0.86 / 0.00/ /0.26 / 0.01/0.30 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / / kpa 28 Heat Exchanged 7.509e+006 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No. 146 OD m;thk m;length m;pit m; Ptn Tube Type Bare Material 1 Carbon Steel 41 Shell A-285-C 0.34 ID 0.36 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 33 Spacing C/C 0.53 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 55 Remarks: 56 A.2.8 E-107/E-108/E-109 Heat Exchangers TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 40

48 5 Service of Unit Item 6 Size 4.1m x 3.0m Type AKL (Hor/Vert) H Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) / m2; Shell/Unit Surf/Shell / m2 8 PERFORMANCE OF ONE UNIT 9 Type of Process Pool Evap Horiz Cond 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name Process in Utility in 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 0.37/860.47/ 0.37/ /908.25/ 3.02/ kg/m3 19 Conductivity 0.01/0.13 / 0.01/ /0.68 / 0.03/0.68 W/m-K 20 Specific Heat /181.89/139.70/ /78.64 / 43.86/78.56 kj/kmol-k 21 Viscosity 0.01/0.40 / 0.01/ /0.17 / 0.01/0.17 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / /1.305 kpa 28 Heat Exchanged 6.271e+007 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No OD m;thk m;length m;pit m; Ptn Tube Type Bare Material TP 316 & 317 Stn. Stl 41 Shell A-285-C 2.44 ID 4.09 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 15 Spacing C/C 0.49 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 55 Remarks: 56 41

49 A.2.9 E-110 Heat Exchanger TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 5 Service of Unit Item 6 Size 1.1m x 6.1m Type AKL (Hor/Vert) H Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) 237.9/234.9 m2; Shell/Unit Surf/Shell 237.9/234.9 m2 8 PERFORMANCE OF ONE UNIT 9 Type of Process Pool Evap Horiz Cond 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name Process in Utility in 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 3.83/754.02/ 3.83/ /908.25/ 3.02/ kg/m3 19 Conductivity 0.02/0.10 / 0.02/ /0.68 / 0.03/0.68 W/m-K 20 Specific Heat /230.27/178.44/ /78.64 / 43.86/78.56 kj/kmol-k 21 Viscosity 0.01/0.23 / 0.01/ /0.17 / 0.01/0.17 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / /1.964 kpa 28 Heat Exchanged 1.246e+007 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No. 652 OD m;thk m;length m;pit m; Ptn Tube Type Bare Material 1 Carbon Steel 41 Shell A-285-C 0.69 ID 1.17 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 15 Spacing C/C 0.14 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 42

50 55 Remarks: 56 A.2.10 E-111 Heat Exchanger TEMA SHEET Customer Ref No. 3 Address Prop No. 4 Plant Loc. Date Rev 5 Service of Unit Item 6 Size 1.1m x 6.1m Type AEL (Hor/Vert) H Connected in 1 Para 1 Seri 7 Surf/Unit(G/E) 675.3/657.6 m2; Shell/Unit Surf/Shell 675.3/657.6 m2 8 PERFORMANCE OF ONE UNIT 9 Type of Process Sensible Horiz Cond 10 Fluid Allocation Shell Side Tube Side 11 Fluid Name 12 Flow kg/h 13 Liquid kg/h 14 Vapor kg/h 15 NonCondensable kg/h 16 Steam kg/h 17 Evap/Cond kg/h 18 Density 0.00/995.92/ 0.00/ /831.17/ 0.25/ kg/m3 19 Conductivity 0.00/0.61 / 0.00/ /0.12 / 0.01/0.13 W/m-K 20 Specific Heat 0.00/75.42 / 0.00/ /190.35/ 81.79/ kj/kmol-k 21 Viscosity 0.00/0.86 / 0.00/ /0.42 / 0.01/0.52 cp 22 Latent Heat J/kg 23 Temperature(In/Out) / / C 24 Operating Pressure kpa 25 Fouling Factor m2-k/w 26 Velocity m/sec 27 Press Drop Allow/Calc / /3.782 kpa 28 Heat Exchanged 1.189e+007 kj/h; MTD(Corrected): C 29 Transfer Rate, Service: Calc: Clean: W/m2-K 30 CONSTRUCTION DATA/SHELL Sketch 31 Shell Side Tube Side 32 Design/Test Press kpa /Code /Code 33 Design Temperature C No. Passes per Shell Corrosion Allowance m Connections IN ID m Size & OUT ID m Rating 39 Tube No OD m;thk m;length m;pit m; Ptn Tube Type Bare Material 1 Carbon Steel 41 Shell A-285-C 1.14 ID 1.17 OD m Shell Cover 42 Channel or Bonnet A-285-C Channel Cover 43 Tubesheet Stationary A-285-C Tubesheet Floating 44 Floating Head Cover Impingement Protection: Yes 45 Baffles Cross A-285-C Type SSEG Cut(Diam) 15 Spacing C/C 0.23 m 46 Baffles Long Seal Type 47 Supports Tube C.S. U-Bend 48 Bypass Seal Arrangement Tube-Tubesheet Joint 49 Expansion Joint No. Type 43

51 50 Rho-V2-Inlet Nozzle Bundle Entrance Bundle Exit 51 Shell Side Tube Side 52 Gasket Floating Head 53 Code Requirements Tema Class R 54 Weight/Shell 55 Remarks A.2.11 V-101 Dynamic Vessel CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:50:46 Dynamic Vessel Equip. No. 10 Name Pressure kpa Three phase option Y Diameter m Cylinder length m Liq flow 1 spec Liq flow 2 spec Vent Flow Model 4 Calc temp. C Calc press. kpa CHEMCAD Page 1 Simulation: 3distConverge Date: 12/22/2016 Time: 16:32:05 Preliminary Vertical Vessel Sizing for Unit # 10 Loadings and Properties Vapor Light Heavy Flowrate kg/h kg/h kg/h Flowrate m3/h m3/h m3/h Density kg/m kg/m kg/m3 K constant m/sec 44

52 Min disengaging height m Min inlet nozzle to HLL m Mist eliminator m Design pressure kpa Allowable stress kpa Shell joint efficiency Head joint efficiency Head type Ellipsoidal Corrosion allowance m Vessel density kg/m3 Weight percent allowance Surge time min. Holdup time min. Surge height m Light outlet to baffle m Inside diameter ID m V_max m/sec Length m Length / Diameter ratio Shell thickness m Head thickness m Inlet to mist eliminator m Liq to inlet m Baffle to liq m Heavy liq to light outlet m Heavy liq height m Shell weight kg Head weight kg Total weight (empty) kg Total vessel volume m3 Total weight (full) kg Total weight (full) w/allow kg A.2.12 V-102 Dynamic Vessel CHEMCAD Page 1 Job Name: 3distConverge Date: 12/29/2016 Time: 22:55:38 Dynamic Vessel Equip. No. 23 Name Pressure kpa Three phase option Y Diameter m Cylinder length m Liq flow 1 spec Liq flow 2 spec Vap flow spec Vent Flow Model 4 Calc temp. C