Indian Institute of Technology, Delhi

Indian Coal to Chemicals

Group 5 CHL471: Process Equipment Design and Economics
IInd Semester, 2012-13

Executive Summary
The rate at which Indian coal is used today for thermal power generation purposes is low. It is estimated to last over 200 years at the current consumption values and the reserves available. Production of industrially and commercially useful chemicals from Indian coal involves gasification of the coal to syngas as the first step. Indian coal has about 40% ash content which reduces its usefulness unless very sophisticated techniques for coal gasification and ash handling are used. Coal gasification produces 500 tonnes per day of syngas containing H2 and CO in mole ratio of 3:1 to be processed downstream for production of chemicals. Gasification of Indian coal requires extensive feed preparation operations because of the washing operations employed to reduce ash content. Feed preparation starts with crushing large chunks of coal obtained from mines using jaw crusher. With the help of washing operations, the ash content significantly reduces to about 25-30%. In the current plant, 528,000 kg of grade E Indian coal is processed per day. The feed preparation unit takes in approximately 40 kg/s of coal and delivers 19 kg/s of coal with an overall efficiency of about 50%. The prepared coal then passes through pressure feeder which injects the coal at 8atm in the gasifier. The fluidised bed reactor operates at 670 oC and 8 atm under optimum conditions. Steam from steam generator and oxygen from air separation unit is also fed to the gasifier from the bottom assembly. The syngas is purified before being sent downstream for further processing. Since Indian coal has substantial quantities of sulphur content, the syngas produced has huge acidic content. The impure syngas from the top of the reactor goes through various cleaning and cooling operations. Solid impurities are removed with the help of cyclone separators and the heat of the gas is used to preheater water for steam generation. The gas is then treated for heavy metal removal and acid gas removal. Activated carbon bed is used to get rid of mercury and other trace heavy metals. Activated MDEA solvent with a hint of piperazine is used to absorb excess CO2 and other acid and residual gases from the syngas. The treated syngas with required composition is sent to downstream operations for methanol production. The solvent is regenerated by application of heat. The flue gas from the top of regenerator is subjected to Claus Treatment reactors where sulphur is converted to elemental form eventually and extracted out of the system for other commercial purposes of economic value. Methanol production starts after the syngas is purified by removal of catalyst poisons and unwanted carbon dioxide. The incoming feed of 2600 kgmol/hour is first passed through a guard bed to reduce the poison concentration to ppb levels, this is necessary to avoid excess of deactivation of catalyst in the reactor. This feed is then compressed using reciprocating compressors to get feed at a pressure of 70 bars and a temperature of 1100 degrees Celsius. The incoming feed is mixed with recycled feed, which is at a lower temperature of 115oC to get mixed feed for the reactor at 237oC. This feed is then passed through a heat exchanger also called economizer to heat up the feed to 250oC, which is the operating temperature of the reactor. This operation ensures that additional operational costs are not incurred and heat is optimally utilized. The reactor is 2.8 meters in diameter and 23 meters in height and operates at a pressure of 70 bar and has the following zones: 1. A zone for gaseous feed to distribute properly [height = 1 m] 2. Oil zone filled with oil and catalyst this is where majority of the reaction takes place [height = 18 m] 3. A disengagement zone for the oil rising with gaseous product to settle down within the reactor [height = 4m]
i

The exit gases from the reactor are sent to a cyclone, which separates out the catalyst particles from the gaseous product. The gases are then cooled to extract out water and methanol from them by the process of condensation. The final temperature of cooled gases is 64 oC. The gaseous mixture now consists of only CO, CO2 and H2. 46% of these gases are recycled and the rest purged. The product, which is in the form of liquid, comes out of the condenser at a rate of 755 kgmol/hr. This is then sent to an atmospheric distillation column, which separated water from methanol and produces AA grade methanol at a rate of 453 MTPD. Methyl acetate is produced using a combined technique of reactive distillation column which incorporates both the reaction as well as purification in one. The reactive distillation column has a double-feed design having a total of 35 trays. The reactants, methanol and acetic acid are fed from the bottom at the 13th tray and the top at the 31st tray, respectively. Methanol flows at a rate of 1860 kg/hr and acetic acid at 3500 kg/hr in a counter current fashion. The reactive section lies between these two trays. The stripping section is at the bottom of the tower (first 13 trays) and rectifying section is from tray 32 to 35. The product, 95% pure methyl acetate, is produced at a rate of 173.5 MTPD. Presently demand of acetic acid globally is 6.5 MMTPA. In India presently there 20 companies producing acetic acid with a total installed capacity of 150,000 MTPA. Our design produces 63,000 MTPA of market grade (99% pure) acetic acid. Our plant aims to capture 15% of total Indian market of acetic acid. The mass balance on the reactor system was done using ASPENplus software. The whole process plant is divided into two parts: one is carbonylation unit and other is the purification unit. Carbonylation unit consists of the reactor, gas absorber and few ancillary units like compressor, pump and heat exchanger. Feed preparation is an important step. The pressure of carbon monoxide from the coal gasification plant is increased from 1 atm to 42 atm and is also raised for methanol depending on the reactor requirement. We are using a slurry bubble column reactor in order to carry out the heterogeneous catalytic reaction between CO and MeOH. The reactor operates at 42 atm and 180oC. The purification unit consists of the liquid effluent column, distillation column, refining column and end stripper. A heavy incinerator column is designed in order to absorb the heavy by products from the bottom of the refining column. Part of the acetic acid produced is sold to the market and part is sent for production of methyl acetate. Acetic anhydride is produced by the carbonylation reaction of methyl acetate. Feed of methyl acetate enters at 35.3 mol/s, which when throttled in a flash tank from a high pressure of 75 psig to 20 psig results in the vaporisation of methyl acetate at 16.4 mol/s. Methyl acetate and CO are then passed into packed bed reactor, experiencing a pressure drop of 82 kPa. In the packed bed reactor, CO reacts with Ru catalyst to form a coordinated complex which then reacts with methyl acetate to produce acetic anhydride. A stream containing 86.1% acetic anhydride, methyl acetate and CO is then passed through a distillation column where acetic anhydride is obtained as bottom product in liquid form with 99% purity.

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Table of Contents
Executive Summary Project Team List of Tables List of Figures Nomenclature Introduction Relevance of the Project Chapter 1A: Coal Gasification Plant
Coal Feed Preparation and Pulverisation operations Jaw crusher Double roller crusher Coarse Coal Washing Heavy Media vessel Media Recovery Screen Fine Coal Washing - Heavy Media Cyclone Dryer Air Separation: Ion Transport Membrane Silo Coal Gasification Design of reactor Techniques for coal gasification Modelling and Simulation of Fluidised Bed Reactor using Aspen Plus Constraints and Variables involved in optimising reactor performance Assumptions for simulation Sensitivity Analysis- Variation of reactor and temperature Design options adopted Gasifier assembly Coal Feed MULTICORE S160 Steam Feed Water pre-heater (Heat Exchanger) Boiler Calculation and specification of burner Steam and Oxygen Inlet Minimum Fluidization Velocity Residence Time Assumptions Reaction Time for a particle Mean residence Time Reactor Wall Output of Gases Output of Settled Ash From The Bottom Of The Reactor i v vi viii x 1 1 2

Chapter 1B: Syn-gas Purification Plant

Introduction Solid Particle and Fine Particle Removal Cyclone Separator Electrostatic Precipitator Ash handling Heavy Metal Removal: Mercury and Trace Elements Activated carbon bed Activated Carbon Bed Design Principles Economic Life of the Activated Carbon Bed Acid Gas Removal Choice of Chemical Solvent: Activated MDEA CO2 Removal

26

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Strength of Amine (MDEA) solution Design of Tray tower Calculation of number of trays required Treatment of H2S gas: The Claus Treatment plant Claus Process

Chapter 2: Methanol Production Plant

Removal of Methane from Syn Gas Process Flow Diagram Mass balances Preparation of Feed & Catalyst Reactor Design Choice of Reactor Sparger Design Hydrodynamic Considerations Determination of Rate Law and Mass Transfer Coefficient Product Purification/ Reactant Removal Distillation Column Hydrocyclone Ancillary Units Heat Exchanger Pumps & Compressors

49

Chapter 3: Methyl Acetate Production Plant

Introduction ASPEN simulation Mass balance Feed Preparation Storage Pump Design Heat Exchanger Tower Design Reboiler and Condensor Design

81

Chapter 4: Acetic Acid Production Plant

Mass balances Process Flow Diagram Carbonylation Unit Feed Preparation Pumps Compressors Reactor Design Gas Absorber Product Purification Crude Fractionating Column Refining Column Storage Effluent Column Ancillary Units Heat Exchanger End Stripping Column

107

Chapter 5: Acetic Anhydride Production Plant

Process Flow Diagram Design of Flashing Tank Kinetics of Process Design for Packed Bed Reactor Pressure Drop Costing of catalyst Design of Distillation Column

143

Conclusions

156

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Project Team
Team Leader: Rishabh Arora

Subgroup 1: Coal Gasification and Purification of Syn-Gas Members: Sahil Aggarwal (leader), Mradul Raj Jain, Mohd Wasil, Harshit Sinha, Tarun Singh, Suresh Sharma, Kritesh Patel, Mohit Meena

Subgroup 2: Methanol Production Members: Sarthak Nigam (leader), Aryanshi Kumar, Priya Meena, Mayuri Chowdhary, Palash Agarwal, Seema Chouhan, Vipin Yadav, Rishabh Arora

Subgroup 3: Methyl Acetate Production Members: Akash Sood (leader), Tapan Jain, Nishant Kumar, Raman Kumar*, Priya Ranjan*, Nitesh Vijay, Vipul Garg

Subgroup 4: Acetic Acid Production Members: Swarnim Raj (leader), Anshul Bang, Ravindra Verma*, Manish, Satyadeep Roat, Sateesh Meena, Deepak Bonal, Jayesh Meena, Awadhesh Ranjan

Subgroup X: Acetic Anhydride Production Members: Raman Kumar, Priya Ranjan, Ravindra Verma

*These members later shifted to a new subgroup, subgroup X, formed after the second progress report

List of Tables
Table 1: Specifications For Feeder and Crushers Table 2: Coal Output from various units Table 3: Feed to Heavy Media Vessel Table 4: Washing in Heavy Media Vessel Table 5: Feed to Heavy Media Cyclone Table 6: Cyclone Dimensions Table 7: Washed Coal in Heavy Media Cyclone Table 8: Belt Specifications Table 9: Constraints to be followed while simulating RGibbs block in Aspen Plus Table 10: Composition of synthesis gas exiting from the top of the FBR Table 11: Composition of coal after washing % weight Table 12: Specifications of Multi core M-S160 based of operating conditions Table 13: Parameter initial and required Table 14: Assumptions and parameters values Table 15: Calculations for dimensions of FBR Table 16: Power cost of various units Table 17: Ratio analysis for the design of cyclone separator Table 18: Dimensions for the design of cyclone separator Table 19: Design of the Electrostatic Precipitator Table 20: Specifications of activated carbon bed loaded with sulphur. Table 21: Values to solve Ergun equation to calculate minimum fluidization velocity Table 22: Final design of the activated bed and economic runtime Table 23: Table of values used to design tray tower Table 24: Results and dimension specifications for the design of actual tray tower. Table 25: Experimental data for desorption of solution CO2 from activated MDEA Table 26: Operating Line mass balance Table 27: Composition of synthesis gas exiting from the top of the tray tower Table 28: Specifications of design of pump Table 29: Aspen plus results of RGibbs reactor Table 30: Mass balance results on streams Table 31: Apparent maximum poison concentrations for methanol synthesis catalyst Table 32: Parameter values for calculation of breakthrough time Table 33: Breakthrough time through various adsorbent layers Table 34: Comparison of type of reactors for Methanol Synthesis Table 35: Design details of the sparger Table 36: Stream Table Table 37: Tray Sizing results Table 38: Composition of specific heat capacities of inlet streams Table 39: Composition of specific heat capacities of outlet streams Table 40: Design Parameters Table 41: Composition of Inlet Stream Table 42: Composition of Outlet Stream Table 43: Flow Rates Table 44: Pipe Diameter Table 45 Table 46 3 3 4 4 5 5 6 10 11 11 12 15 17 19 20 23 27 28 29 36 36 36 40 40 41 42 43 44 45 51 53 54 54 55 57 69 70 75 76 82 84 84 85 86 86 86 vi

Table 47: NPSHa Table 48: Fluid Temperatures Table 49: Overall heat transfer coefficient Table 50: Feed composition Table 51: Specific volume components Table 52: Wilson Parameters Table 53 Table 54: Activity Coefficients Table 55: KATAPAK catalyst packing Table 56: Saturation Pressure Table 57: General Conditions and dimensions for tray towers Table 58: General conditions and dimensions of sieve tray towers Table 59: Pump Design Table 60: Advantages and disadvantages of reciprocating compressors Table 61: Specifications of reactor Table 62: bubble specification for the reactor Table 63: Temperature and pressure condition for gas absorber Table 64: Composition of Gases entering the absorber Table 65: Dimension of Packed Tower Table 66: Composition for Crude Fractionating column Table 67: Composition for Refining Column Table 68: Dimension for column material of Refining column Table 69: Different Area of Tray Table 70: Dry Pressure drop and different factors Table 71: Hydraulic Head and its factors Table 72: After reactor it is entering into effluent column Table 73: Temperature pressure condition for effluent column Table 74: Storage Data Table 75: Storage of Methanol Table 76: Composition in heat exchanger Table 77: Column Diameter for Stripping Column Table 78: Packing Properties Table 79: Summary of data Table 80: Reactor operating conditions Table 81: Catalyst particle properties and other physical parameters Table 82: Cost estimation Table 83: Feed parameters in distillation column Table 84: Distillate data Table 85: Bottom product Table 86: Calculation of k values and relative volatilities for top product

87 89 91 94 94 94 95 95 96 97 99 100 108 110 115 116 117 117 119 121 124 125 126 127 127 129 129 130 132 133 136 137 145 146 148 148 149 150 150 151

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List of Figures
Figure 1: Process flow diagram of coal gasification unit Figure 2: Heavy media vessel capacity Figure 3: Cyclone Dimensions Figure 4: Lifting Flights Figure 5: BCFZ Fib Figure 6: Design of Silo and belt width Figure 7: Values of cross section angle for trough and surchange angle at diff belt width Figure 8: Variation of syngas composition Figure 9: Diagrammatic view of the exchanger Figure 10: Burner for the boiler Figure 11: Distributor Figure 12: Conical plate in annulus section Figure 13: Ash exit mechanism and hopper configuration Figure 14: Basic model of the reacor Figure 15: Ratio analysis of dimensions for cyclone separator Figure 16: Layout for handling fly ash Figure 17: Treaa distribution for wind barrier Figure 18: COS removal with CO2 removal with new aMDEA formulation Figure 19: Effect of Piperazine concentration in MDEA on CO2 Level in Treated Syngas Figure 20: Effect of Total Amine Strength on CO2 Level in Treated Syngas Figure 21: Counter current multistage cascade, solute transfer from phase R to phase E Figure 22: flow of liquid solvent (MDEA solution) and syngas (vapour phase) in tray tower Figure 23: Manual construction to calculate number of stages in tray tower Figure 24: Pump arangement and layout Figure 25: Clause thermal reactor desing Figure 26: Pore types in nanoporous graphine Figure 27: Enersy barrier for pore A Figure 28: Energy barrier for pore B Figure 29: Process Flow Diagram Figure 30: Homogeneous and churn-turbulent regimes in a column Figure 31: Different models predicting rate law for Liquid Phase Methanol Synthesis Figure 32: Different resistances involved in three phase reactor Figure 33: Variation of concentration of Hydrogen with residence time Figure 34: Variation of H2 concentration in liquid phase with reactor height Figure 35: Plot of concentration of H2 with reactor volume Figure 36: A typical Stairmand cyclone Figure 37: Conventional processing schemes for esterification reaction Figure 38: The Eastman reactive distillation process for methyl acetate manufacture Figure 39: Process Flow Diagram Figure 40: Composition at different trays Figure 41: Temperature Profile Figure 42: Vapor and Liquid flow rates at different trays Figure 43: Methanol storage tanks Figure 44: Relation between Total head and capacity Figure 45: LMTD correction factor Figure 46: Tube side heat transfer factor Figure 47: Shell side heat transfer factor Figure 48: KATAPAK S250 Y catalyst Figure 49: Thermosyphon Reboiler 2 4 5 6 7 9 9 13 16 18 19 19 22 22 27 30 35 38 39 39 41 42 43 44 46 49 49 50 50 58 61 62 64 65 65 68 81 81 82 83 83 83 85 87 92 92 93 96 101 viii

Figure 50: Process flow sheet for acetic acid production plant with help of aspen Plus Figure 51: Schematic of SBCR auxiliarily setup Figure 52: Reciprocating compressor interior view. Figure 53: Working of Reciprocating compressor Figure 54: Stages required for compressor at each stage Figure 55: Slurry bubble column reactor Figure 56: Mass balance on slurry bubble column reactor Figure 57: Material Balance For counter current flow absorber Figure 58: Generalised flooding and pressure drop correlation Figure 59: Crude Fractionating Column Figure 60: McCabe method for stage calculation Figure 61: Storage tank interior design Figure 62: storage tank Figure 63: Examples of Random Packings Figure 64: Material Balance done in Aspen One using CHAO-SEA property Figure 65: Generalised Pressure Drop Correlation Figure 66: A gas injection type packing support Figure 67: A Pan type liquid distributor with bottom holes Figure 68: Process flow diagram for acetic anhydride production Figure 69: Flash tank design Figure 70: Longitudnal catalytic Packed bed reactor Figure 71: Distillation column flow diagram

107 108 110 111 112 113 115 116 118 120 128 130 132 136 137 139 140 141 143 144 145 149

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Nomenclature
T- temperature t- time C- specific heat capacity G- mass flow rate U- average heat transfer coefficient FT- correction factor for LMTD Re- reynolds number di - inner diameter do- outer diameter - viscosity - density e- wall roughness - reaction time Dgl - diffusivity v- velocity V- volume X - weight fraction vapourized HuL - Upstream liquid enthalpy HdV -Flashed vapor enthalpy HdL - residual liquid enthalpy cp - liquid specific heat Tu - upstream liquid temperature, C Td - liquid saturation temperature, C Hv - liquid heat of vaporization DP - pressure drop G - mass velocity of the gas Us- superficial velocity of gas in reactor - porosity in packed bed L - length of reactor D - diameter of reactor Dp- diameter of catalyst particle dt- diameter of tube of the packed bed F - feed to distillation column Xf - mole fraction in feed W- Total moles in bottom product Xb - mole fraction in bottom product D -Total moles in top product Xd - mole fraction in top product Ki - distribution coefficient for i component i- relative volatilities of i component N min - minimum no of plate NR - number of plates of rectifying section Ns - number of plates of stripping section RD min - minimum reflux ratio RD actual -actual reflux ratio Dc - diameter of column H - height of column - Fraction of gas, gas hold up - Interfacial surface tension, N/m - Activity coefficient of species i - Bubble diameter - Orifice diameter, m - Volumetric gas flow rate through each orifice, m3/s - Rate of consumption of Hydrogen - Overall gas-liquid mass transfer coefficient - Gas-liquid interfacial area - Liquid-particle mass transfer coefficient - External surface area of the catalyst pellets / particles per unit volume of reactor - Effectiveness factor based on pore diffusional limitation - Intrinsic reaction rate constant per unit mass of catalyst per sec - Catalyst mass per unit volume of reactor - Saturation concentration of Hydrogen (interfacial gas phase concentration) - Equilibrium concentration of Hydrogen C - Discharge coefficient f - friction factor - Superficial gas velocity HL - height of liquid in the column - Liquid volume - Tank diameter dp - diameter of the sparger pipe - Bubble rise velocity No - number of holes in the sparger Np - number of arms in the sparger Larm - length of each arm of the sparger - Free volume of molecules per mole - Time to initial breakthrough -Time to midpoint of breakthrough -Bulk denstiy of adsorbent (lbs/ft3) - Henrys Law constant (lb moles/lb) L - length of reaction zone X - A factor accounting for initial and final impurity concentration d0 = pitch of the sparger

Introduction
The semester long project taken up by our group aims at developing a commercially and technologically viable process for production of industrially useful and high market value chemicals from Indian coal. The aim of the project is to develop a process plant which converts goal to synthesis gas while handling large amount of ash content and subsequently producing methanol, methyl acetate, acetic acid and acetic anhydride. This involves first the conversion of syn-gas to methanol via the Liquid Phase Methanol (LPMeOH) process. Next it involves the production of methyl acetate from chemical grade methanol using a reactive distillation process and finally to acetic acid and anhydride by the Acetica and Codec processes respectively.

Relevance of the Project

India has abundant geological reserves of coal, having the fifth largest coal reserves in the world. The total estimated reserves by the Geological Survey of India as on April 1, 2011 are 285.86 billion tonnes, of which 114 billion tonnes are proven. The production of coal during the period April, 2010 - March, 2011 as reported was 424.50 million tonnes. Going by the current usage, the current proven reserves would last another 268 years. Apart from that, currently over 70% coal is used in thermal power plants (TPPs) to produce electricity. However, the coal available in India (mostly D, E and F grades) consists of a large amount of undesirable materials like ash (38%), Sulphur (0.41%) and heavy metals like Hg, As, etc. As other more renewable energy sources like wind, hydroelectricity, solar are being developed to meet ever growing energy requirements, it is very unlikely that we will use the large reserves of coal that India has for energy generation. Moreover, methanol, acetic acid and acetic anhydride, each chemical has a number of uses. Methanol is one of the most versatile compounds developed and is the basis for hundreds of chemicals and is second in the world in amount shipped and transported around the globe every year. Acetic acid is an excellent polar protic solvent. It is frequently used as a solvent for recrystallization to purify organic compounds. Acetic acid is used as a solvent in the production of terephthalic acid (TPA), the raw material for the polymer PET. Acetic anhydride finds its greatest application in the production of cellulose acetate from cellulose, which is a component of photographic films. Also, it is used for the synthesis of heroin from the diacetylation of morphine as well as aspirin and paracetamol, making it a globally desired chemical.

Chapter 1A: Coal Gasification Plant

Coal Feed Preparation and Pulverisation operations
Overall Process flow diagram for coal gasification and purification:

Fig1: Process flow diagram of coal gasification unit

The various unit operations and processes involved along the spectrum has been described below. 1. Coal feed preparation and pulverisation operations: Crushing and washing operations 2. Storage of coal in silo: Buffer stock for gasifier/design of silo. 3. Coal gasification: Prediction of syngas composition using Aspen Plus and optimizing performance 4. Design of Fluidised Bed Reactor using CAD tools: Gasifier Assembly. 5. Removal of Solid impurities coarse/fine: cyclone separator 6. Syngas cooling: Preheating water for steam generation 7. Steam generator 8. Air separation unit: Ion exchange membrane 9. Syngas purification: Heavy metal removal in activated carbon bed 10. Syngas purification: Acid gas removal/Choice of solvent/Design of tray tower 11. Number of stages in a tray tower: Operating line and equilibrium curve 12. H2S treatment: Claus Treatment Reactors 2

CRUSHERS : (Contributed by: Mohd Wasil)

Jaw Crusher : Primary Size reduction of Coal from 50cm to 30-50mm Design Parameters [1]:
Crusher Capacity(Q) = 150nbsd n- rpm of drive shaft, b- width of swing Jaw, s- amplitude of swing jaw, d- mean size of crushed coal, D- mean size of crusher feed, -loading factor of crushed coal, -Specific Gravity of Crushed Feed where s is way length of swing jaw(jaw crusher angle = 200) Drive Power of Jaw Crusher = nb( )/0.34

Double Roller Crusher : Size Reduction from 30-50mm to 5-10mm

Design Parameters [1]: Roller Capacity (Q) = 50LDnd L-length of rolls, D- Diameter of rolls, n- speed of rotation of rolls, d- width of slots between rolls, - bulk density of crushed material

Vibrating Feeder [2] Model Max feed size Capacity Spindle Speed Dimensions Motor Power ZSW-200 600mm -----------------

Jaw Crusher [3] PE750*1060 630mm 50-180ton/hr 250rpm

Double Roller Crusher [4] 2PG1008 30mm 40-120ton/hr 70-100rpm 1000*800mm (roll diameter) 90KW

4953*2200*2331mm 2660*2430*2800 mm 15KW 110KW

Table 1: Specifications for Feeder and Crushers

Jaw Crusher Heavy Media vessel Roller Crusher Heavy Media Cyclone Dryer

Output rate (ton/hr)

147 ton/hr

102.9

92.5

74

69

Table 2: Coal Output from various units Coarse Coal Washing: Heavy Media vessel (Contributed by: Mohd Wasil)
3

Coal Washing is done by density based separation of impurities, ash by Heavy Media Vessel. Pure Coal having density less than heavy-media floats and impurities having density greater than the medium sinks. Magnetite (95%-50 micron) is used as media because of its stability and recoverability. Vessels are sized on the tonnage capacity capable of discharging over the float weir.

Size Feed rate(C) Heavy-Media rate(M) %Ash Content

30-50mm 147ton/hr 441ton/hr (M:C=3:1) 38%

Table 3: Feed to Heavy media vessel From Figure 1: For Average Grain Size 40mm, Vessel Capacity is 40 ton/hr ft weir width = 70% 102.9 ton/hr is the amount in float Weir Width = 102.9/40 = 2.57ft = 0.78m Assuming a retention time of 40 min and L/D = 3 [6] Volume of Vessel = 249.08 m3 L = 13.96m , D = 4.65 m

Figure 2: Heavy media vessel capacity [5]

Media Recovery Screen [7]: (Contributed by: Mohd Wasil)

Coal Recovered Media Recovered = = 5.68ton/hr Media recovered D- Average Grain Size = 40mm, SG- Specific Gravity of refuse = 2.2 Specifications [8]: Model-2YK1235, Slope Screen-150, Screen Area-4.2m2, Handling Capacity-20-150m3/hr, Power-7.5kW, Dimension-3705*2393*2339mm %Yield % Ash in Washed Coal 5.68ton/hr 70% 30% 102.9ton/hr

Table 4: Washing in Heavy Media Vessel

Fine Coal Washing - Heavy Media Cyclone (Contributed by: Mohd Wasil)
Table 5: Feed to Heavy Media Cyclone Size Range Feed Rate of Coal(C) Heavy-Media rate(M) Total Feed rate %Ash Content 5-10mm 92.5 ton/hr 277.5 ton/hr (M:C= 3:1) 370ton/hr 30% Figure 3: Cyclone dimensions Input to SDM Cyclone Sizing Software :Density,Feed Rate,Feed Pressure = 100kPa,Cyclone Capacity = 235m3/hr,No. of Cyclones= 1, Cone Angle = 200 Table 6: Cyclone Dimensions Dimensions(mm) [9] Cyclone Diameter Feed Inlet Diameter Inlet height Inlet Width Vortex Diameter Cylinder height Cone height Spigot Diameter Pressure drop(kPa) High Efficiency 666.93 149.39 162.15 108.1 149.39 367.54 778.77 100.04 350.98 High Capacity 403.63 139.91 214.76 71.59 159.52 350.77 415.86 100.91 356.05

Table 7: Washed Coal in Heavy Media Cyclone Coal Recovered %Yield % Ash in Washed Coal 74ton/hr 80% 25%

Dryer: (Contributed by: Mohd Wasil)

Counter-Current Rotary Dryer is used to dry coal. The drying medium (air, flue gases, steam) flows counter-current to moist coal to minimize the chances of ignition of coal. Lifters and Flights are inserted in the shell to increase residence time of coal particles and hence ensuring high heat transfer. Thermal Efficiency of Dryer varies from 30-60%. [10]

Design: 1. Calculation of Length and Diameter

Volume occupied by coal = 0.15*Volume of Dryer [11] Feed rate of coal to dryer = 74ton/hr, Density of coal = 1500kg/m3 Volumetric Feed rate of Coal = 49.33 m /hr Figure 4: Lifting Flights Volume of Coal fed = 49.33 m /3 = 16.44m (Assuming Residence time of 20 min) Volume of Dryer = 109.6 m3 *D2*L = 109.6 D2*L = 139.62 m3 (i)
3 3 3

t=

[12]

t-residence time(min), L-length(m), D-Diameter(m),p-slope of dryer, degrees n-revolution per minute F-Constriction Factor in Dryer due to lifters and flights - angle of repose of coal

t =20min, p =30, n = 3rpm, = 360, F=2 Solving L/D from eq. (i), we get L/D = 8.47..(ii) Solving (i) and (ii), L = 21.35m D= 2.52m 2. Calculation of Heat-Duty of Rotary Dryer:
Heat Duty of Dryer = Heat for evaporation of moisture + Other Losses 6

Generally only 50% of heat supplied is converted to useful work ( = 50%). [12] Hence, heat duty of dryer = 2mS (XA-XB) mS mass flow rate of coal, XA and XB are initial and final mass of liquid per unit mass of coal, latent heat of vaporization mS = 20.55kg/s = 19.33 Kg/s , XA = 0.077 , XB =0.0116, = 2260KJ/Kg Calculating, Heat Duty =6075kW

Air Separation (Contributed by: Mohd Wasil)

Ion Transport Membrane (ITM) is used to obtain pure oxygen. The process is economic, produces pure oxygen contrary to Cryogenic Distillation which is very expensive. The basic principle is that the membrane selectively allows only Oxygen permeate through it, driving force being partial pressure of oxygen across the membrane.

Membrane:
Perovskite Hollow Fibre membranes of the chemical composition BaZrxCoyFezO3 (BCFZ) is selected because of its high Oxygen Permeation Flux and Mechanical Stability Specification: Temperature - 9000C, Outer Diameter = 0.88mm, Wall thickness = 0.175mm,Inner Diameter = 0.705,Length = 33cm [46]

Calculation for Membrane Area :

O2 permeation flux = 7.6 mLmin cm
1 2

[46]

Density of O2 = 1.43g/L,Molecular Weight = 32 O2 permeation flux = 5.66*10-6 mol cm2s-1 Feed rate of O2 = 0.781lbmol/hr = 0.098mol/s Hence Area of membrane = 0.098/5.66*10-6 = 1.73 m2 Cost of Pervoskite membrane = 1000 /m2 = 71330 Rs/m2 Figure 5: BFCZ fibre

Total membrane Cost = Rs 1,23,400

Silo: (Contributed by: Mradul Raj Jain)

For the preparation of required syngas, a constant supply of 69 tph coal feed is required. This constant supply is ensured by silo which also serves the purpose of protecting coal from environmental conditions and ensuring uniform mixing and normalising any variation in composition of coal. Spare silos are required in case of non-functioning of any of the working silos. Coal bulk density, b = 1550 kg/cum [12] Internal friction angle = 30 [13] Friction coefficient, = tan 30 = 0.58 [14] Discharge rate = 69 tonnes/hr Silo should contain sufficient amount of coal so as to sustain production even in case of non-supply of raw coal from mines or any disturbance in any unit operation before it or during their regular maintenance. Assuming a max storage capacity for 2 weeks, total capacity for silo = 69 X 24 X 14 = 23184 tonnes 24000 tonnes / week Silos have a widely varying capacity. Silos of capacity upto 5000 tonnes are easily constructed and do not require special support. Choosing the capacity of silo as 4000 tonnes, 6 silos will be required. Taking L/D=3 [15] Volume of silo = (4000 X 1000)/1550 = r2L = 3D3/4 D = 10.3 m L = 3D = 30.9 m Coal particle size range = 5mm-10mm Outlet diameter (B)= 10 X (max particle size) [16] = 10 X 10 mm = 100 mm = 0.1 m Silos can suffer from various problems like arching, flushing, rat-holing, insufficient flow, inadequate emptying etc. In such cases silos are repaired and become non-functional. In such case, to avoid any effect on the feed rate of coal, spare silos can be utilised. Using 4 silos at a time and keeping other 2 silos spare. Assuming mass flow, and using Johanson Equation, W = b X /4 X B2 X ( g.B/4.tanc)0.5 [16] Where, W = discharge rate in kg/s -c = angle of hopper from vertical 69 X 1000/ (4 X 3600) = 1550 X /4 X (9.8/4.tanc)0.5 X 0.12.5 c = 32.33 For height of hopper, H, Tan c = [10.3/2 - 0.1/2]/H H=8m A rotary valve will be used for discharging coal from hopper. [16] 8

Concrete for Silo

Assuming a thickness of wall = 10 inch = 0.254 m [17] Inner diameter, D1 = 10.3 m Outer diameter, D2 = 10.3 + 0.254 = 10.554 m Total volume of concrete required = volume of silo wall + volume of hopper wall = (r12 r22)L + 1/3.(r12 r22)H = /4 X 30.9 X (10.5542 10.32) + 1/3 X /4 X 8 X (10.5542 10.32) 140 m3 Density of concrete = 2400 kg/m3 [18] Mass of concrete = 2400 X 140 X 6 = 2016 tonnes.

Figure 6 : Design of Silo & belt width

Belt Conveying
Belt conveyors transport coal from one unit operation to other. As coal moves from one unit operation to other, its quantity decreases owing to the feed preparation processes done on it. Thus the capacity and type of belt also varies from one location to other.

Fig.7: Values of cross section angle for trough and surchange angle at different belt width. [47] Surcharge angle for coal = 25 [47] Assuming troughing angle = 20

[47] 9

Where, CSA = cross section area in m2 Table 8: Belt specifications Belt Capacity (Coal) Tonnes per hour Crusher to heavy media separator Heavy media separator to roller press Roller press to cyclone Cyclone to dryer Dryer to silo 146.83 600 0.031 85 Assumed belt width, mm Cross section area (CSA), m2 Velocity, cm/s

102.77

500

0.020

92

92.5 74 69

500 450 450

0.020 0.016 0.016

83 83 77

Coal Gasification Design of reactor: (Contributed by: Sub-Group Contribution)

After feed preparation and pulverisation of coal to appropriate size, we move to next operation in production line i.e. coal gasification. The target is to produce about 500 meteric tonnes per day (MTPD) of hydrogen (H2) and carbon monoxide (CO), the main ingredients of syngas, in molar ration 3:1.

Techniques for coal gasification:

Extensive literature survey lead to the conclusion that there are largely three conventional techniques used for coal gasification today [22]. They are: 1) Moving bed reactor 2) Entrained flow reactor 3) Fluidised bed reactor. Out of the three reactors used in conventional coal gasification above, we chose FBR (Fluidised Bed Reactor) as most of the literature pointed out that it was the type of reactor to be used for ash content coals. Entrained flow reactors posed a problem of slagging due to high operating temperatures [19]. Moving bed gasifiers have non uniform temperature profiles (along radial direction) hence results in high temperatures zones with slagging [19]. Under the light of concerns highlighted previously, FBR offers lucrative solutions to most of the problems. It is important to note that the temperatures within the bed are less than the initial ash fusion temperature of the coal to avoid particle agglomeration [20]. It has operating temperatures in the range (900-1100oC) hence no slagging [19], residence times of the order of minutes (0.5-3 mins) [19], carbon conversion of about 97% [19]. 10

Modelling and Simulation of Fluidised Bed Reactor using Aspen Plus: (Contributed by: Sahil Aggarwal)
Coal from after pulverisation is fed to FBR using centrifugal system (MulticoreS160) made by Schenck Process. Steam from steam generator and pure O2 is obtained from ASU (air separation unit). The composition of synthesis gas and implementation of mass balance on the FBR has been done with the help of Aspen Plus. Over the years the experiments conducted on the analysis of the exit streams from coal gasification units have revealed that the gas composition can be well predicted by minimisation of Gibbs free energy of the product stream while maintaining the phase equilibrium. The block RGibbs in Aspen Plus provides exactly the type of reactor we can be used to simulate the process as it satisfies all the above conditions [21].

Constraints and Variables involved in optimising reactor performance:

We have imposed several constraints on RGibss reactor while calculating the final gas composition of synthesis gas. These have been tabulated below. H2/CO mole ratio (H2 + CO) mass ( tonnes/day) 3 500 tpd ~ 500,000 kg/day Tolerance = 0.1 Tolerance = 100 lb/day ~ 45 kg/day

Table 9: Constraints to be followed while simulating RGibbs block in Aspen Plus. Note: These constraints have been dictated by the optimised conditions required for methanol production unit. Another limit to which we have to adhere is CO2/(CO+CO2) (mole ratio) = 0.3 which we have dealt with later by absorbing excess CO2 produced in MDEA solvent in gas purification operation. While imposing the above constraints on the RGibbs block we have minimised the consumption of input resources which can also be quantified in terms of sum of mass input of steam, coal and oxygen by using optimisation function in Model Analysis Tools in Aspen Plus. The variables involved in the simulation process is mass flow rates of steam, coal & oxygen; temperature of the FBR. With the above constraints and optimisation variables, the material and energy balance for the fluidised bed reactor as predicted by Aspen Plus (RGibbs block) is as follows: 500 TPD H2 and CO Mole Flow kmol/s C O2 CO CO2 H2 76.7 *10-2 26.2*10-3 0 0 14.2*10-2 0 9.84*10-5 0 0 0 0 2.17*10-23 16.99*10-2 36.17*10-2 50.97*10-2 0 0 0 0 0 COAL OXYGEN PRODUCT STEAM

11

H2O C2H4 C2H6 C3H8 C3H6 H2S COS CH4 S Total Flow kmol/s Total Flow kg/s Total Flow m3/s Temperature K Pressure bar Density kg/m3 Average MW gm/mole

70.9*10-3 0 0 0 0 0 0 0 2.2*10-3 1.01 11.69 4.16 300 8.1 1550 NA

0 0 0 0 0 0 0 0 0 9.84*10-5 3.1*10-3 2.4*10-3 300 8.1 1.3 32

54.66*10-2 4.5*10-7 1*10-5 1.9*10-9 7.310-10 2.2*10-3 3.7*10-5 23.55*10-2 2.97*10-15 1.83 35.41 17.41 930 8.1 2.03 19.39

1.32 0 0 0 0 0 0 0 0 1.32 23.72 51.11 445 8.1 4.21 18.02

Table 10: Composition of synthesis gas exiting from the top of the FBR. Note: Column COAL essentially refers to quantities of elements present in Indian coal (composition has been tabulated below). These elements amount to 68.4% by weight of coal. Hence the actual coal requirement i.e. including ash and inerts is obtained by dividing the total flow (kg/sec) in Column COAL by a factor of 0.684 and again by 0.9 to account for residence time calculations and carbon conversion (explained in assumptions below). A superficial analysis of the product synthesis gas shows that the concentration of H2S comes out to be around 1215 ppmv. The main ingredients of the syngas obtained are 19.8% by vol. of CO2, 9.3% CO, 27.9% H2, 29.9% H2O and finally 12.9% methane. We have used the following composition of coal after feed preparation and washing & drying operations [23]: Ash Moisture carbon H 30% 6.82% 49.18 3.06 Table 11: Composition of coal after washing %wt 12 Oxygen N2 Sulphur 8.94 1.62 0.38

Assumptions for simulation:

There are three main underlying assumptions that we have made while simulating the reactor environment which are as follows: 1. Process occurs at steady state and isothermal; 2. The ash recycled out of the system can contain unreacted carbon and inerts (which otherwise would not react with either steam or O2 under any condition); 3. We have also assumed 90% conversion of carbon present in coal as opposed to 97% [19] cited in literature to accommodate for errors in residence time experienced by individual particles of coal on a probability basis. This works out to 1010 tpd (tonnes per day) of coal; 2050 tpd of steam and about 268 kilograms per day of pure oxygen which is a pretty decent value.

Sensitivity Analysis- Variation of reactor and temperature: (Contributed by: Sahil Aggarwal)
We also studied the sensitivity analysis, again using the Model Analysis Tools in Aspen Plus. This feature allows to study the composition of syngas with respect to changing variable of choice. Hence it can exploited to study the effect of temperature and pressure on fluidised bed reactor modelled by RGibbs block. The results of varying temperature and pressure on the composition of syngas while keeping other variables constant have been plotted below:

Figure 8(a): Variation of syngas composition with temperature (at 1 atm).

13

Figure 8 (b): Variation of syngas composition with pressure (at 943K). Using the conditions imposed on the FBR the optimum temperature is 930 K. We have chosen the reactor pressure to be at 8 atm keeping in view the volumetric flow of product gas.

Design methods adopted:

Some of the key innovations which we learnt while doing literature survey and implemented in our setup are as follows: 1) Instead of feeding in more conventional slurry form directly after washing operations (i.e. without drying water) we have dried it before conveying it to the FBR. This decision intuitively comes from cost estimation. Since water in coal will have to be evaporated so that coal can reach reactor conditions, this would mean that well have to burn some of the syngas to provide for sensible and latent heat of water. This would mean that product synthesis gas would have had more CO2, hence higher separation costs in downstream gas purification operations since we do not intend to produce CO2 as our prime product. Though this would have been the case for IGCC applications where we syngas is used to produce mechanical energy in turbines, hence more volume is required. 2) On similar arguments of economics, we have decided to use pure O2 rather than ambient air as a source of oxidiser. Because the nitrogen in air must be heated to the gasifier exit temperature by burning some of the syngas. Also because of the dilution effect of the nitrogen, the partial pressure of CO2 in air-blown gasifier syngas will be one-third of that from an oxygen-blown gasifier. This increases the cost and decreases the effectiveness of the CO2 removal equipment downstream [20].

14

Reactor (Gasifier) assembly:

The main assembly of Gasifier has been discussed step by step from feed to product. Design specification of each subunit is presented.

Coal Feed: (Contributed by: Tarun Singh)

After the feed gets piled up in the silos it is fed to the main gasifier for conversion from coal to syngas. For feeding the coal feed to the reactor MULTICORE S160 would be used which is a centrifugal system for pressure feed. MULTICORE S160: (Contributed by: Tarun Singh) Property Flow Rate Pressure Manufactured by Schenck Process [36]. 2 such units used (in case one malfunctions, itll keep the process continuous). Accuracy upto +- .5% of flow rate. Make use of centrifugal force to pressurize and pump the coal feed, provided with a prefeeder to take the feed from silo before pressurizing it. Automated control system for pressure and flow rate. Multi Core Specs 60 - 120 t/hr Our Requirement 64 t/hr

Withstand and generate up to 30 bar feed We would use 2 such units at 8 bar each. pressure. Max 10% allowed. Assuming feed to be moisture free. Pulverized to 5 mm.

Moisture

Flow Properties Needed

Free flow to slightly sluggish, pulverized to granular (8mm).

Table 12: Specifications of Multi core M-S160 based of operating conditions.

Steam Feed: (Contributed by: Tarun SIngh)

Steam to the gasifier is generated in 2 units:1 2 Water Preheater - Would use the heat in syngas to preheat water at room temperature to a steam plus water mixture at 100 degrees celsius. Boiler - Would take the steam plus water mixture from preheater to final conditions required in the gasifier.

15

Water preheater(Heat Exchanger): (Contributed by: Tarun Singh)

A typical shell and tube heat exchanger. Inlet Conditions Water at 27 degrees Kelvin and 1 bar pressure. Syngas at 700 degrees Celsius and 8 bar pressure (density = 2.232kg/m3 and specific heat = 1.02 KJ/Kg*K). Total Heat available = G*C*(T) = 22748.04 KJ/sec.

Outlet Conditions Water + Steam at 100 degrees 1 bar pressure. Syngas at 70 degrees and some bar.

After balancing the configuration (mostly data for pipes and coefficients from [5]) Heat transfer needed 22748.04 KJ/sec. U = 150 W/m2K, Tavg=211.289, FT = 1 [7]. Area for this heat transfer came out to be 71.88 m2. OD 1.9 schedule 80 tubes in a 39 inch shell(160 schedule being on the safer side as pressure drop is quite high), 17/8 inch square pitch [7] were opted for the exchanger(after doing iterations on the tube count and dia. of both shell and tube sides). Tube count is 252. Length of tubes = 5.2m. Water inside the tube and syngas on the shell side (for pressure drop reasons as pressure drop on the shell side would be higher and we need pressure drop on shell side). 2.6m baffle spacing (large space for lesser pressure drop we dont need too much of it).

Figure 9: Diagrammatic view of the exchanger

16

Pressure drop in our configuration Hydraulic diameter for the tubes i.e. water side Dhydraulic is Di and syn side is Do-Di. Rewater = *v*di/ = 13.5*105. Resyn = 13.5*105. Relative roughness of wrought iron pipes = 45*10-6 / .202(e [5]) = .000223. From Moodys Charts friction coefficient came out .018 for tube and .015 for shell. Now P in the entire pipe and shell calculated using The Darcy-Weisbach equation (though this has a fault that syngas is compressible in our case) which assumes fully developed, steady and incompressible flow (may be violated). P came out to be 232.27 Pa for steam. So suitable for our case since we need less pressure pressure drop. P came out to be 6.9 bar for syngas (due to the high flow rate in small dia).

Boiler: (Contributed by: Mohit Meena)

Table 13: Parameter initial and required Parameter Mass flow rate of water Mass flow rate of steam Pressure Temperature Inlet condition 6.82kg/s 16.876kg/s 1 bar 373k Outlet condition 25kg/s 8 bar 973k

Capacity of boiler Q/t=1*(2-1)+2*(4-3) 65486 kJ/s we have to convert preheated water to steam. Inlet have both steam and water So we are using burner for generating steam.

17

Burner for boiler :-

Figure 10: Burner for the boiler Calculation and specification of burner Heat releases up to 13000 kJ/s. High turndown capabilities. 10:1 on 2 oil. 15:1 on natural gas Nine different styles and three different sizes Heating surface area using( Q/t=(k*A*T)/x )1.23 m2 Dimension of heating chamber (1.11x1.11x1.11)

We have to install five burner. Each one has capacity of 13000 KJ/S (MEGAFIRE Burner). Total required power is 65486 kWatt. Container is made up of stainless steel.

Steam And Oxygen Inlet: (Contributed by: Suresh Sharma) Steam generated from steam generator is inserted into gasifier from bottom. The bottom plenum is divided into two parts to supply O2 into the draught section and steam into the annulus sections separately [29]. O2 is supplied through distributor of holes sizes 2-4 mm. A typical distributor plate is shown in Fig. 1

[30].
Steam is supplied through conical plate into annulus section as shown in Fig. 2.

18

Figure 11: Distributor

Figure 12: Conical plate in annulus section

Minimum Fluidization Velocity: The Ergun equation, the well-established relation for the pressure drop over packed beds of spherical particles, can be used to describe the behaviour of a fluidized bed at the minimum fluidization velocity correctly. At minimum fluidization condition u becomes umin [25].

The mixture gas viscosity can be calculated from this correlation [26].

Table 14: Assumptions and parameters values Inlet pressure Temperature Assuming spherical particles, so sphericity Assuming bed void fraction at umin is Average particle diameter(dp) Bed density( gravity(g) ) 8 atm 700 C 1 0.5 [27] 0.0075 m 800 kg/m 9.8 m/s2 19
3

Table 15: Calculations for dimensions of FBR Mixture viscosity( ) From steam table specific volume of steam at inlet condition Steam+Oxygen Density( ) umin uin = 2umin Volume flow rate of steam+O2 Reactor area(A) = (volume flow rate)/uin Reactor diameter(D) Delta P per unit length taking =0.8 at uin ( ) 3.5714x10 Pas 0.55 m3/kg [28] 1.78 kg/m3 2.79 m/s 5.58 m/s [27] 51.11 m3/s 9.14 m2 3.41 m 1.03*10 Pa/m
4 -5

Residence Time: (Contributed by: Tarun Singh)

For design of the actual bed mean residence time of a particle in the bed is needed. For average residence time Shrinking Core Model was used assuming the diffusion to be the controlling step for the reaction [31] . Assumptions Diffusion through the ash layer is the slowest step. SCM is chosen for residence time [31]. Feed gas composition taken same throughout the bed [31]. Mixed flow assumed [31] Effect of pressure on diffusivity is neglected [32]. Reaction Time for a particle Diffusivity of steam for complete diffusion inside a particle (micro as well as macro pores) is Dsteam 5.2x10-8 m2/sec (700oC) [33]. Max average diffusivity when diffusion only through macropores 10-6 m2/sec [32]. Now, = (bulk*R2)/(6*b*Dsteam*Cbulk) for reaction time range (2 diffusivities) [31]. b=1, bulk = 1550 kg/m3, R = 5mm, Cbulk from aspen results. On calculating 607 min > > 34.60 mins. We choose to continue with lower limit i.e. 34.60 mins as complete conversion is not practical plus would ask for an infinite bed.

20

Mean residence TimeSince the residence time for each coal particle would be different so residence time cannot be taken equal to the reaction time. An average mean residence time is needed which can be used for further design. For this, RTD technique for a mixed flow with diffusion controlled SCM model is used [31]. For a mixed flow following DSCM, (1-X) = 1/5(t*) 19/420(t*)2 where t* = (/tavg) and tavg is the required mean residence time. Assuming 95% conversion. t* came out to be .26. So the MRT is 133 mins.

Reactor Height: (Contributed by: Tarun Singh)

From the obtained fluid velocity, Area and MRT values reactor height is estimated. The results are v=2*vmf (Previous knowledge of fluidization). Area of Reactor G(vol. flow rate)/V = 9 m2. Bed Volume = MRT*G = 98 m3. Bed Height 11m.

Reactor Wall: (Contributed by: Tarun Singh)

After the estimation of height the issue in hand is what should be the material used to design such a structure. Used here is typical layout with three layers [41-43]:1 The inner hot face layer(100mm) is a high-quality brick (87% chromium oxide, marketed as Zirchrom900, patented by saint gobain) suitable for temperatures up to about 1600C. 2 3 The intermediate layer(20mm) is castable bubble alumina(Alumina-chrome Chromcor 12). The outer cold face(40mm) is a silica firebrick lining (Bubble alumina RI34 or Alundum AN599) with good thermal insulation properties. This three-layer design combines the properties of high temperature-resistance and good insulation. At the same time, it hinders the propagation of cracks that may arise in the hot face through to the vessel shell. Output Of Gases: (Contributed by: Harshit Sinha) The gases escape from the gasifier at 62,673.32 m3/hr, which is equal to 17.4 m3/s. Since the area of the reactor is roughly 9 m2, and our gas flow rate nearly 18 m3/s, we have a 2m/s exit velocity from the gasifier, which is a reasonable value. From here, the gases are sent to a heat exchanger, before going to the cyclone separator unit.

21

Figure 13: Ash exit mechanism and hopper configuration Output Of Settled Ash From The Bottom Of The Reactor: Ash settles both at the bottom of the reactor and goes out as fly-ash. At the bottom, we have a fine grate, on which a lot of the ash settles. There is a hopper on this grate, and using a scraper (manual or automated) we can make the ash fall into the hopper, from where it goes into the pipe and then the ash treatment unit. The density of settled ash is around 0.65 gm/cc[8]. 20,510.3 kg/hr (or 5.7 kg/s of ash in total) is exiting as both fly and settled ash. Weve designed the bottom pipes and hopper for the total ash, so as to be on the safe-side. There are no potential harms on the overdesign of pipes when it comes to ash-exit at the bottom. This means we need the pipe to handle ~8769 cc/s, which can be done using an 8 inch Schedule 40 pipe quite well. Basic Google Sketup Model: (Contributed by: Harshit Sinha and Tarun Singh)

Figure 14: Basic Model of the reactor (done in google sketchup) 22

Raw material and resource requirement of the units till this point: (Contributed by: Harshit Sinha and Tarun Singh)
Following are estimates of the raw materials needed for the plant operation upto this point. 1

Coal feed
We are using 3528 tonnes of grade E (3400-4200 GCV) coal per day for gasification. The prices of Coal as per Coal India notification (1/1/2012)[48] are:

GCV 4000-4300 3700-4000 3400-3700

Price per tonne (INR) 640 600 550 Table 16a: Cost of different grades of carbon used. We take an average of these (assuming an equal mix) , i.e. INR 21,05,040 per day.

Daily Water Costs

Shadow price is the maximum price that a firm is willing to pay for an extra unit of water. For the Chemicals Industry this is equal to Rs. 3.164 for 1000 litres[49]. We need 4.4*10^9 litres per day. The cost of water comes out to be an astonishing 1,39,72,000 INR.

Power Requirement
The cost of Industrial power is 3.3 INR per unit of electricity [50]. 1 unit is 0.01 kW Utility Air Separation Unit Feeder and Crusher Multicor S160 Total Requirement (kWh) 38609 756000 72000 866609 Table16b : Power(Electricity) cost of various units. Price(INR) 127412 2494800 237600 2859812

23

References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. Coarse Size Reduction of Raw materials, Heidelberg Cement India Limited DSMAC ZSW Series Vibrating Feeder Specifications http://www.dcrusher.com/v3/products/feederscreen/zsw-vibrating-feeder.html DSMAC PE Series Jaw Crusher http://www.dscrusher.com/v3/products/crushing-equipments/jawcrusher.html 2PG Series Double Roller Crusher http://www.dscrusher.com/v3/products/crushing-equipments/2pgroller-crusher.html Smart Dog Mining,An Introduction to Dense Media Vessels http://www.smartdogmining.com/tools/Notebook/Process/MineralProcess.html Separator Vessel Selection and Sizing, http://www.klmtechgroup.com/Engineering%20Design%20Guildelines.htm Smart Dog Mining,Vibrating Screens, http://www.smartdogmining.com/tools/Notebook/Process/MineralProcess.htm DSMAC YK Series Vibrating Screen http://www.dscrusher.com/v3/products/feeder-screen/yk-circularvibrating-screen.html Smart Dog Mining,SDM Cyclone Sizing http://www.smartdogmining.com/tools/Software.html rd Handbook of Industrial Drying by Jerzy Pikon and Arun S. Mujumdar,3 edition Albrights Chemical Engineering Handbook Drying of Raw Materials,Heidelberg Cement India Limited Anudhyan Mishra (10505028), Assembly of coal quality of some Indian coals, National Institute of Technology, 2009 Dr. J. Y. Ooi, Arching propensity in coal bunkers with non-symmetrical geometries, School of Civil and Environmental Engineering, University of Edinburgh, September 2005 Physical properties of agricultural materials and food products, friction of solids and flow of granular solids, page 246 http://bioen.okstate.edu/home/jcarol/Class_Notes/BAE2023_Spring2011/FrictionNotes.pdf Ralph Foiles, Dust explosion venting of silos http://www.processprotection.net/pdf/1.pdf Karl Jacob, Bin and Hopper Design, The Dow Chemical Company, Solid Processing Lab, March 2000. Mostafa H. Mohmaud, Standard Practice for Design and Construction of Concrete Silos and Stacking Tubes for Storing Granular Materials (ACI 313-97), ACI Committee 313, January 1997 Density of concrete, The Physics Factbook, Glenn Elert (McGraw-Hill Encyclopedia of Science and Technology) http://hypertextbook.com/facts/1999/KatrinaJones.shtml Lori Allison Simpson, Massachusetts Institute of Technology, The suitability of coal gasification in Indias energy sector, September 2006: http://dspace.mit.edu/bitstream/handle/1721.1/38569/154723366.pdf?sequence=1 Jeffery Phillips, Different Types of Gasifiers And Their Integration With Gas Turbines: http://www.netl.doe.gov/technologies/coalpower/turbines/refshelf/handbook/1.2.1.pdf Sheida Saeidi, Josh McElfresh and Joyce Stillman, Final Design for Coal-to-Methanol Process, University of California, La Jolla, California 92037, USA Department of Mechanical Engineering, Chemical Engineering: http://www.academia.edu/333252/Final_Design_for_Coal-toMethanol_Process National Energy Technology Laboratory (NETL), U.S. Department of Energy (DOE), Gasifipedia: http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/4-gasifiers/4-1_types.html Properties of Coal, Coal gasification: http://www.productivity.in/knowledgebase/Energy%20Management/c.%20Thermal%20Energy%20sy stems/4.1%20Fuels%20and%20Combustion/4.1.3%20Properties%20of%20Coals.pdf A.K. Singh, B.N. Prasad and A.V. Sahay, Potential for underground coal gasification in India, Central Mine Planning and Design Institute, India. www.cmpdi.co.in/docfiles/coal_gasification.pdf Powder Technology, 75 (1993) 67-78. Calculation of the viscosity of the gas mixtures by F. J. Krieger RM-649 13 July 1951. Energy Vol. 23, No. 6, pp. 475488, 1998. Kerns handbook. Y.J. Kim et al. / Fuel 79 (2000) 6977.

16. 17. 18. 19. 20.

21. 22.

23. 24.

25. 26. 27. 28. 29. 30.

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31. 32. 33. 34.

35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.

American Journal of Engineering and Applied Sciences, 2012, 5 (2), 170-183. Levenspiel Handbook. Perrys Handbook. Effective diffusivity of moisture in low rank coal during superheated steam drying at atmospheric pressure by Zdzisaw Pakowski*, Robert Adamski, Sawomir Kwapisz, Chemical and Process Engineering 2011, 33 (1), 43-51. Wasteless combined aggregate-coal-fired steam generator/melting converter by L.S.Pioro, Volume 23, Issue 4, 2003, Pages 333337, Waste management, Sciencedirect. Binders, R.C. (1973), Fluid Mechanics, Prentice Hall, Inc. (Engle Wood Cliffs, NJ). Schenck Process and Manjunatha Varambally. Binders, R.C. (1973), Fluid Mechanics, Prentice Hall, Inc. (Engle Wood Cliffs, NJ). Kerns handbook. Various sources. For example: http://www.aqua-calc.com/page/density-table/substance/cinderscoma-and-blank-coal-blank-ash. Refractory wall structure and damper device. US patent no. US 20040094078 A1. Gasification by Christopher Higgins and Martin Van Der Burdt. http://www.refractories.saint-gobain.com/Gasification.aspx website for the Saint gobain gasification refractories information and their uses. Introduction to Transport Phenomena book appendix www.maxoncorp.com/Files/pdf/B-lt-megafire.pdf T.Schiestel,M.Kilgus,S.Peter,K.J.Caspary,H.Wang,J.Caro.Hollow Fibre Perovskite Membranes for Oxygen Separation,Journal of Membrane Science,Volume 258 Masons Engineers(NZ) Ltd. http://www.masons.co.nz/quick-reference-charts#fourth New Pricing of non-coking coal based on GCV with effect from (1/1/2012): http://www.coalindia.in/Documents/Revised_2nd_Ver_Coal_Price_for_uploading_310112.pdf

49. Suresh Chand Agarwal and Surender Kumar, Industrial Water Demand in India, Challenges and Implications for water pricing. Available on : http://www.idfc.com/pdf/report/2011/Chp-18Industrial-Water-Demand-in-India-Challenges.pdf 50. Industrial Power Tarrifs: www.indiastat.com/power/26/powertariff

25

Chapter 1B: Syn-gas Purification Plant

Treatment and Conditioning of syngas - Purification of syngas
Introduction: (Contributed by: Sahil Aggarwal)
The syngas produced in the fluidised bed reactor contains a lot of impurities in the form of fly ash which gets entrained out of the reactor owing to high gas velocities; gases like H2S, COS which are acidic in nature; heavy metals like Hg, etc. which are toxic in nature and lastly by products like heavy hydrocarbons, excess CO2, steam etc. In the context of Indian coal, syngas purification has more value attached to it because of the use low grade coal having high sulphur and heavy metal impurities. This leads to huge expenses which have to be incurred in the form of infrastructure required to remove impurities, hence the cost at which a desired (set by emission laws) degree of purification is obtained becomes important. In the era of environmental crisis, where a significant amount of air pollution worldwide is caused by chemical industries, laws have become more stringent regarding the emission levels of hazardous substances, in particular acid and greenhouse gases. However, while it is easier for developed countries to follow these set limits at the expense of lower profits, it is not the case with developing countries like India where the industries are still struggling to meet costs of production and generate whatever meagre profits they manage to by competing with giant chemical manufacturers who are virtually monopoly holders of the entire chemical market. Keeping this imbalance in mind, the emission regulations vary from country to country, but a more critical review of the environmental report and rising political tension points out to the possibility that one day these emission standards will be made uniform for all. So, Indian industries need to come up with more innovative techniques for purification that are cheaper and more cost effective for syngas purification. We have tried to use the best and the latest techniques available in literature to model the purification setup. The arrangement includes cyclone separator to remove solid impurities, electrostatic precipitation to remove finer solid impurities, heat exchanger to tap heat energy of hot syngas to preheat water to generate steam to be later fed to FBR, activated carbon bed to get rid of heavy metal impurities, tray tower to remove H2S, COS, CO2 and other trace heavy hydrocarbons, regeneration of loaded solvent, treating flue gas from regenerator column to remove CO2 and get H2S rich gas which goes for processing to Claus Reactors.

Cyclone Separator: (Contributed by: Kritesh Patel)

The flue gas coming from the gasifier contains ash along with it. To separate the dust from the gas we are using cyclone separator. The gas enters the cyclone and is guided around a central pipe. The heavy dust particles are not able to follow the air path around the pipe due to higher inertia. The dust particles impacts the cyclone wall and drop at the bottom of the cyclone. As the cyclone 26

becomes narrow at the bottom, as a result of this the smaller dust particles not able to follow the air path (which spirals around in smaller diameter now) become separated and also fall at the bottom of the cyclone. The base of the cyclone is submerged in water to form water seal which prevents gas from escaping. There are different models correlating the cyclone diameter to the other parameters of the cyclone. My calculation is based on the new design which is obtained by optimization of Muschelknautz method [1].

Figure 15: Ratio analysis of dimensions for cyclone separator a/D b/D /D H/D h/D S/D B/D 0.618 0.236 0.622 4.236 1.618 0.620 0.382 Table 17: Ratio analysis for the design of cyclone separator 27

Feed:
Flow rate, G = 281019.39 lb/hr = 35.41 kg/sec = 0.127 lb/ = 650 kg/ = 3.5 * Pa s we can calculate the cyclone diameter by equating the terminal = 2.035 kg/

A cut point diameter (d) of 10

velocity attained by the particle by Stokes law and by the cyclone design [2]. By cyclone Terminal velocity, By Stokes Law Terminal velocity, = g is gravity =

Equating both the equation we get the following dimension

Dimension Diameter Inlet height Inlet width Overall height Cylinder height Outlet diameter Dust outlet diameter Outlet length

Symbol D A B H H

Value 2.08 1.28 0.49 8.81 3.36 1.29

Unit M M M M M M M M

B S

0.79 1.29

Table 18: Dimensions for the design of cyclone separator 28

Now the entering velocity of the gas, Now calculating the pressure drop across the cyclone based on the equations [3]

where

q= +

By putting all values and G=0.005 (Wall friction factor) we get

Now the syngas which still has some ash particles is sent to the heat exchanger and then to ESP for the removal of remaining ash particles

Electrostatic Precipitator (contributed by: Kritesh Patel):

The gas after cooling is sent to electrostatic precipitator which consists of series of vertically negatively charged wires running through positively charged pipes. The electric field within these pipes ionizes the tar particles which are negatively charged and are attracted to inner surface of pipe where they condense and fall in drops to the slanted base. The gas from here is further sent to the other units (e.g. to remove further impurities in the solid free syngas). It is known that Electrostatic precipitators can achieve over 99% cleaning efficiency (White 1963). Now the syngas is at a lower temperature which will increase the efficiency of the electrostatic precipitator. The design of electrostatic precipitator is taken same as used for Hequ Power Plant [4] which is used for ash of same composition as of Indian coal. Some of the specifications are No. of chambers No. of fields Channel per chamber Height of plate Length of plate Spacing Gas pressure drop Efficiency 2 5 38 15.24 m 19.725 m 400 mm 200 Pa 99.85 % Table 19: Design of the Electrostatic Precipitator 29

The ash particles are collected from the bottom and the solid free syngas is sent to further purification.

Ash handling: (Contributed by: Mohit Meena)

Total ash 42500 lb/h Bottom ash 8460 lb/h Fly ash 33960 lb/h

Fly ash:
Particle of fly much finer and the particles of ash are carried away with the flue gases and get collected at various locations along the flue gas by Esp. Particle of fly ash is very small so it can come with flow

Bottom Ash:
When a sufficient amount of bottom ash drops into the hopper, it is removed by means of highpressure water jets and conveyed by sluiceways either to a disposal pond or to a decant basin for dewatering, crushing, and stockpiling for disposal or use. In this system, the ash slag discharged from the furnace is collected in water impounded scraper installed below bottom ash hopper. The ash collected is transported to clinkers by chain conveyors.

Pneumatic conveying of fly ash:

Assumption and calculation Conveying distance 150 m Minimum conveying velocity of Ash 400 fpm (from source) Conveying velocity 480 fpm System capacity Material flow rate 236 tph Mass flow rate of air 18.3 lb/min Bulk density of fly ash 30lb/cub. ft Solid loading ratio 428 Pipe line is cross section area .545 ft Pressure across 150 meter pipe 186.11 psig

Figure 16: Layout for handling fly ash

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Pressure Pneumatic Conveying System operates on batch/continuous operating concept and can also convey the much coarser particles of bottom ash Pipelines: - fly ash conveyed through a normal mild steel pipeline would probably wear a hole through a 90bend within one day of operation. Thick walled spun alloy cast iron is a normal specification for pipeline. In extreme cases is may be necessary to line the pipeline with basalt.

Ash silo: (Contributed by: Kritesh Patel)

The ash from the ESP is sent to the silo using pneumatic system to store ash and for further use. The silo is usually design with the storage capacity of 3 days. [32] The design of the silo is discussed below Calculation

For bottom ash [6]

Mass flow rate of ash= 4.1 tonnes/ hour (assuming 20% bottom ash) Density of bottom ash = 650 kg/ Angle of repose of ash = Friction coefficient, Storage capacity for 3 days storage = 4.1 *24*3 = 295.2 tonnes For silo taking the L/D ratio to be 3 [33] Equating the dimension of the silo based on the volume LD2 / 4 = 295.2 X 1000/650 D = 5.78 m L = 17.34 m Now the size of coal is ranging from few micro meter to 10 mm Outlet diameter (B) > 6 X (max particle size) > 6 X 10 mm (no arching condition) So, taking hopper outlet diameter to be 70 mm

Assuming mass flow, and using Johanson Equation, W = b X /4 X B2 X ( gXB/4Xtan c)0.5

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W = discharge rate in kg/s, c = angle of hopper from vertical 4.1*1000/3600=650* *

c = 40.3o
Now calculating the height of the hopper tan H = 3.4 m

For fly ash

To design fly ash silo we have to look into the flow patterns that the fly ash shows and the stresses that will be acting. Now we will design fly ash silo of diameter 5 m as flow characteristics for that is available [34] Density of fly ash, flyash = 1141 kg/m3 [34] D = 5m L = 15m Volume that will be stored in on silo = 294.4 m3 Mass of ash that will be stored = 1141 X 294.4 = 335.9 tonnes Mass flow rate of ash= 16.4 tonnes/ hour (assuming 80% fly ash) Storage capacity for 3 days storage = 16.4 *24*3 = 1180.8 tonnes Number of silos required = 1180.8/335.9 = 4 Using Jenikes equation, [34] Dmin = (fc,crit X H()) / ( X g) fc,crit = critical yield stress in N/m2 , Dmin = minimum hopper diameter to prevent arching Now H () = 2.2 for conical hoppers fc,crit = 1152 N/m2 [31] Dmin = 22.7 cm c = 20o Now calculating the height of the hopper

32

tan H = 6.9 m Concrete that will be needed to build silo= Assuming a thickness of 10 inch Inner diameter = 5 m (fly ash silo) Outer diameter 5.25 m (fly ash silo)

Volume of concrete for silo = X [ X 17.4 X ((6)2 - (5.78)2) + /3 X 3.4 X ((6)2 - (5.78)2] + X [4 X X 15 X ((5.25)2 - (5)2) + 4 X /3 X 6.9 X ((5.25)2 - (5)2)] = 179.05 Mass of concrete needed= 2400 X 179.05 429.7 tons

Ash Disposal: (Contributed by: Kritesh Patel)

Now, once the ash is stored in the silo we have to dispose it properly. It will be transported to the land filling site, cement industry and at other places with the help of trucks of around 1000 ( 28 ) capacity. The truck is a pneumatic truck having one or more compartments, with each compartment having a hatch on the top and an air circulating device, such as an air pad, an air stone, or a cyclone at the bottom of each compartment, together with a compartment exit pipe. As is well known in the art, the trucks are constructed so that with all hatches and appurtenances closed, the truck is air tight avoiding ash particle to be disposed to environment [7] .A 4 inch diameter pipe ASTM 40 steel pipe air discharge hose from trailer outlet was connected to a pipe which terminates at dry ash storage. Ash will be removed from the silo on a daily basis. Ash generated in one day= 756.9 No. of trucks required per day = 756.9/28 27 trucks Now assuming the process of ash removal to be continuous. Max time required to load a truck = (24*60)/27 min = 53.33 We have to load a truck in approximately half an hour as some time will be needed to attach the pipe to the truck and other activities. So the flow rate of ash needed to fill the truck in minimum 0.5 hour = 28/0.5 = 36.4 tonnes/hour Since we are using a pipe of 4 inch diameter pipe 33 = 56

Thus, the velocity at which the ash should flow > 56 / (3.14*10.16*10.16*

) > 1.91 m/s

The trucks will be sent to the sites for ash disposal. The landfilling operation involve a lot of problems like ash disposal to environment, ground water contamination due to leaching, destruction of local vegetation. To check these landfilling should be done as discussed in next part.

Landfill design [8] (Contributed by: Kritesh Patel)

The design of the landfill is required in order to minimize need for further maintenance, prevent the post-closure escape/release of solid waste constituents, leachate, and landfill gases to the surface water, groundwater, or atmosphere, prevent direct contact with ash materials, minimize infiltration to groundwater, mitigate soil erosion and runoff, promote establishment of vegetative cover. Firstly the ash will be mixed with bauxite which reduces the pH value and the toxicity and also reduce effectively both the arsenic and boron content. [9] After that ash will be disposed to the land and for dust control during disposition, a water truck will be used, at the discretion of the field oversight personnel, to apply a fine mist of water over the placed ash to control airborne emissions. A 40-mil linear low density polyethylene (LLDPE) geo membrane will be placed over the entire landfill site as the barrier layer component of the Coal Ash Landfill cover system. A 12-inch layer of sand will be placed over the 40-mil LLDPE geo membrane. The sand layer provides physical protection for the geo membrane, but more importantly allows subsurface drainage of accumulated water over the geo membrane.

A 6-inch layer of general fill will be placed over the subsurface sand drainage layer such that there is a total of 18 inches of barrier protection soil cover over the geo membrane. A 6-inch layer of topsoil will be placed over the general fill layer to support a vegetative growth over the entire landfill cover system.

Wind barrier design [9] (Contributed by: Kritesh Patel)

Wind barriers are an effective method to prevent the dispersion of dust from the disposal sites. Poplar trees will be planted in four rows. The rows should be perpendicular to the dominant wind direction. The distance between each row and between trees should be six metres. Every second line will be shifted three metres, so that the trees stand in triangles, providing a better coverage. Hazel will be planted on the wind coming side, in two rows, also shifted and separated by 6 metres.

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Fig 17 Tree distribution for wind barrier

Heavy Metal Removal: Mercury and Trace Elements (Contributed by: Sahil Aggarwal) Activated carbon bed:
Mercurys presence in air and water has increased dramatically in the past century owing to emission from thermal power plants. The total mercury pollution potential from coal in India is estimated to be 77.91 tonnes per annum [11]. The mercury emission study carried out by NTPC in some thermal power plants indicate that the mean values of mercury concentration in coals of Indian origin are close to average concentration of 0.272 ppm [10], major portion of mercury gets emitted through stack and also remains associated with fly ash whereas, only a small portion is found to retain with the bottom ash. Hence it is conservative to assume that all the mercury partitions into the gas phase. It is convenient to remove mercury with carbon activated beds as most of the literature survey pointed out and the experience at coal gasification units worldwide reinforce this theory. The Calgon Type-HGR carbon has been used for low-pressure drop adsorption of mercury from natural gas since the early 1970s [10]. Calgon Carbon HGR granular activated carbon is sulphur impregnated carbon. The mercury reacts with sulfur as the gas goes through the sulfur bed to form HgS. After the sulphur on the carbon is exhausted, the spent adsorbent is shipped to a hazardous chemicals disposal site. HgS is a very stable compound and its long-term storage presents no problems. The spent carbon can also be incinerated and the mercury recovered from the incinerator gas via cooling and condensation [12]. 35

Specifications of HGR type bed [13]:

Apparent density Sulphur content by weight Screen size by weight , U.S. Sieve series Table 20: Specifications of activated carbon bed loaded with sulphur. 593 kg/m3 (approx.) 10% min On 4 mesh Through 10 mesh 5.0% max. 5.0% max.

Activated Carbon Bed Design Principles:

Using Ergun equation, we calculated minimum fluidisation velocity. This is the maximum allowable velocity above which the bed would lift upwards and potentially crush & cause attrition of the particles. The values used for while calculating dimensions of the bed have been tabulated: Bulk density of bed Viscosity of syngas (assumed) Sphercity of granular particles Porosity of bed U.S. Sieve series No. 4 [12] 593 kg/m3 5*10-5 kg/m.s 1 0.4 4.76mm U.S. Sieve series No. 10 [12] Size of particles assumed Density of syngas Residence time (calculated) [10] 2mm 4mm 2 kg/m3 15 secs

Table 21: Values to solve Ergun equation to calculate minimum fluidisation velocity. The minimum velocity comes out to be about 0.8 m/s. The residence time for Pittsburgh type HGR bed is about 30 seconds. But since the mercury content in terms of concentration in Indian coal is almost double compared to US coal, the residence time required will be half since the driving force of adsorption process will be doubled. Assuming that only 5% of the sulphur will actively pick, the carbon bed will load up 5.66 tonnes of mercury by the end of its life [12]. Mercury content in Indian coal is 0.272 ppm. The dimensions of bed obtained are as follows: Minimum fluidisation velocity Diameter of bed Length of bed Amount of carbon granules reqd. 0.8 m/s 5.18 m 11.8 m 147.5 tonnes Hg removal rate Hg adsorbed on bed Saturation time Pressure drop 9.54*10-6 kg/s 5.66 tonnes 18.8 years 0.675 atm

Table 22: Final design of the activated bed and economic runtime

The gas will exit at temperature of 343K.

36

Economic Life of the Activated Carbon Bed:

Hence the economic life of bed will last about 18.8 years.

Acid gas removal: (Contributed by: Sahil Aggarwal)

Literature Survey: Methods available
Raw synthesis gas (syngas) produced from coal gasification needs to be cleaned of sulfur-bearing acid gases (primarily hydrogen sulfide (H2S) and carbonyl sulfide (COS) to meet either environmental emissions regulations and to protect downstream catalysts for chemical processing applications. A number of methods are available for acid gas removal from synthesis gas produced coal fired plants. Some of the more commonly used methods are chemical solvents, physical solvents, membranes, and cryogenic fractionation.

Comparison between physical and chemical solvents:

Ethanolamines (MEA, DEA, MDEA, DGA, etc.) and hot potassium carbonate are chemical solvent processes which rely on chemical reactions to remove acid gas constituents from sour gas streams. The regeneration of chemical solvents is achieved by the application of heat whereas physical solvents can often be stripped of impurities by reducing the pressure without the application of heat. Physical solvents tend to be favoured over chemical solvents when the concentration of acid gases or other impurities is very high [15]. Since the solubility of acid gases in physical solvents is based on Henrys Law the solubility of a compound is directly proportional to its partial pressure in the gas phase, it is conservative to assume that absorption usually takes place at very high pressure. Chemical solvents are more effective for low acid gas partial pressure applications than physical solvents [16].

Choice of Chemical Solvent: Activated MDEA

MDEA has become popular with the natural gas industry because it has a high H2S/CO2 selectivity, is very stable against degradation and is the least corrosive of the amines. Overall, there are hundreds of MDEA units worldwide in various applications. It is being used for synthesis gas treating in IGCCs at several commercial and demonstration sites. The overall advantages claimed for the formulated selective MDEA solvents are that the solvent circulation is reduced significantly and that smaller trays can be used in the absorption tower. The MDEA solvent content can be higher than that of other amines because it is less corrosive, reducing the circulation rates further [12]. This leads to a much smaller and a less expensive plant. MDEA has been able to achieve 4ppmv of H2S in outlet feed when the input is 0.6 mole% H2S, upto 20% of COS input of 30ppmv while offering CO2 slip (needed for downstream, operations). Hence, we have decided to use MDEA for AGR.

H2S removal: MDEA became popular with the natural gas industry because of its high selectivity for
H2S over CO2. MDEAs reaction with H2S is almost instantaneous. 37

COS removal: MDEA does not combine with COS chemically. Only limited physical COS absorption
takes place with MDEA. COS can be physically removed by MDEA only with very high solvent circulation rates, at which point the CO2 is also removed quantitatively. Since well using 98% wt MDEA and COS inlet is only 20ppmv, we are pretty confident that major amount of COS will be removed while absorbing 80% of the inlet CO2. The graph below explains the same:

Figure 18: COS removal with CO2 removal with new aMDEA formulation [10].

CO2 Removal:
The downstream production operations to produce methanol require CO2/(CO+CO2) mole ratio to be about 0.3 which would mean that well have to get rid of 80% of the inlet CO 2 from syngas i.e. we can only allow a CO2 slip of about 20%. MDEA can also be formulated for high levels of CO2 removal. For this task, various additives (activators) are used. The kinetics of the CO2 reaction with MDEA is highly improved with such additives allowing for reasonable absorber sizes and solvent circulation rates [12]. Although methyldiethanolamine, MDEA, can be activated by a number of amines, piperazine is the most commonly used promoter in applications involving CO2 removal from syngas [16]. BASF has used piperazine in its activated MDEA formulations. Piperazine, even at low levels (about 5%) enhances the rate of CO2 absorption an order of magnitude over non-activated MDEA [12].

MDEA Piperazine composition:

Figure below shows how the relative concentrations of piperazine and MDEA in a 50 wt% totalamine blend affect the CO2 left in the treated gas. It is apparent from the figure that about 4 wt% piperazine is needed to achieve < 1000 ppmv CO2 and that 5 or 6 wt% piperazine allows one to achieve in the vicinity of 100 ppmv CO2 [17].

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Figure 19: Effect of Piperazine concentration in MDEA (Total 50 wt% amine) on CO2 Level in Treated Syngas [17]. Since we need 20% of inlet CO2 in outlet, this would mean that we need about 200,000 ppmv of CO2 which implies that we need to use very little amount of piperazine since it is very sensitive to CO2 absorption.

Strength of Amine (MDEA) solution:

Figure below explains the effect of MDEA concentration (in wt%) on the CO2 concentration (in ppmv) in the treated syngas.

Figure 20: Effect of Total Amine Strength on CO2 Level in Treated Syngas [17]. 39

It is surprising to find that higher the amine strength worse the treating. Since we need about 200000 ppmv of CO2 in the treated syngas, this would mean that well have to use almost pure MDEA solvent and hence the decision.

Design of Tray tower: (Contributed by: Sahil Aggarwal)

We have designed a tray tower for absorption of CO2, H2S and COS absorption using MDEA solvent activated with piperazine: We have followed the procedure given in Robert E. Treybal, Mass Transfer Operations to design tray tower (page 158-176). A tray tower looks like the one in the following figure: The following table gives values of different components used in the design of the tray tower: Density of MDEA solvent Density of syngas (1atm, 373K) Vapour flow rate Q (vapour rate) (1atm, 373K) q(liquid rate) 1000kg/m3 0.652 kg/m3 1.28 kmol/s 39.2 m3/s 0.168 m3/s Table 23: Table of values used to design tray tower The following results were obtained for the design of tray tower. W/T Steel Plate thickness Tray spacing (t) VF (flooding velocity) V (Velocity of liquid) (0.8VF) Vow (weeping velocity) Vo (velocity of vapour) 0.7 1.935 mm 1m 5.05 m/s 4.04 m/s 7.49 m/s 44.82 m/s hw (height of weir) h1 (height of liquid over weir) h3 (downcomer backup) Check on flooding condition T (tower diameter) Distance of weir from centre Pressure drop for gas per tray 190 mm 105.6 mm 122.3 mm 417.3 < 500 1.385m 1.3126 m 1200 Pa do (hole diameter) Pitch (p) Surface tension of liquid f friction factor [17] 4.5mm 12mm 0.04 N/m 0.0045

Table 24: Results and dimension specifications for the design of actual tray tower.

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Calculation of number of trays required:

The process we have used is steady state counter-current process. The procedure for obtaining number for stages from equilibrium (thermodynamic conditions) and operating line (mass balance on the tray tower) has been describes in the following figure:

Figure 21: Counter current multistage cascade, solute transfer from phase R to phase E. However we faced a lot of difficulties in getting the exact number of stages for a variety of reasons. Firstly, the operating line is exactly not a straight line due to changing flow rates of gas and liquid in tray tower especially when significant amount of gas is dissolved. Secondly, although the analysis is not strictly valid for multicomponent mass transfer which is actually the case, we have made a convenient assumption that since CO2 is the major commodity, we will construct a tray tower based on absorption of CO2 into activated MDEA. This is a very valid assumption keeping in mind that the moles transferred for H2S, COS and other heavier hydrocarbons on timely basis is negligible compared to that rate of absorption of CO2 in the solvent. For H2S it is 0.8% of CO2 absorption, for COS it almost 0, hence the assumption is well justified. Thirdly, the equilibrium data for solubility of CO2 in activated MDEA solution for the composition and conditions we have used is not conveniently available. However we were successful in getting the data for desorption of CO2 from activated MDEA solution, which almost serves the purpose and also gets rid of the issue of stage efficiencies since the equilibrium curve obtained by plotting it would not be a theoretical one but an experimental one. The data has been tabulated below [20]:

Temperature, K 343

xout Extrapolated

X 4.06

yout Extrapolated

Y 0.395 41

Where,

343 0.755 3.08 0.252 0.34 343 0.647 1.83 0.208 0.26 343 0.571 1.33 0.166 0.2 343 0.365 0.57 0.086 0.09 343 0.301 0.43 0.058 0.06 343 0 0 0 0 Table 25: Experimental data for desorption of solution CO2 from activated MDEA. X = concentration of CO2 in liquid phase (MDEA solvent), mole CO2/ non-mole CO2; Y = concentration of CO2 in gas phase (syngas), mole CO2/ non-mole CO2;

Hence assuming X and Y for this experiment are in equilibrium, we can get the experimental equilibrium curve. The operating line can be plotted by getting value of X and Y at top and bottom of tray tower and connecting by the assumed straight line. The counter current flow scheme has been depicted below:

Figure 22: flow of liquid solvent (MDEA solution) and syngas (vapour phase) in tray tower.

Operating line (Mass balance on the tray tower):

Top Bottom X = 0.2 X = 2.5 Y = 0.0785 Y = 0.395

Table 26: Operating Line mass balances

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The construction to calculate number of stages/trays required to achieve required degree of separation for given mass flow rates of activated MDEA and syngas is as follows:

Figure 23: Manual construction to calculate number of stages in tray tower. Hence the number of stages comes out to be 8. With a tray spacing of 1 metre, the height of the tower comes out to be 8 metres. The expected pressure drop is 9600 Pa ~ 9.5% of initial total gas pressure.

Composition of the syngas after Acid gas removal:

500 TPD H2 and CO Mole Flow kmol/s CO CO2 H2 CH4 Total Flow kmol/s 16.99*10-2 7.27*10-2 50.97*10-2 23.55*10-2 98*10-2 Total Flow kg/s Total Flow m3/s Temperature K Pressure atm Density kg/m3 Average MW gm/mole 12.74 17.41 373 0.92 0.53 13 PRODUCT

Table 27: Composition of synthesis gas exiting from the top of the tray tower

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Design of Buffer Tank for MDEA solution and pump: (Contributed by: Suresh Sharma)

Figure 24: Pump arrangement and layout Density of fluid Volume flow rate Volume of tank (assuming 2 hours buffer) Diameter of tank (assumed) Length of tank (SI units) Head generated 1000 kg/m3 0.168 m3/s 1210 m3 15 m 6.9 m 168 kg/sec 6.94 m Vopt = 12 0.1/0.36 (fps units) Diameter of pipe Reynolds number f friction factor Hf head due to friction Length of pipe (assume) Power required (assumed efficiency of 0.65) rpm of impeller 1.5 m/s 0.38 m 5644 0.036 0.11 m 10 m 77.5 hp

Diameter of impeller

4.125 inch

700 rpm

Table 28: specifications for design of pump

Treatment of H2S gas: The Claus Treatment plant: (Contributed by: Harshit Sinha and Suresh Sharma)
CLAUS PROCESS
The Air (Prevention and Control of Pollution) Act [24], 1981 was passed to regulate all kinds of emissions (Including Air Pollution) by Industrial Plants. Also, the National Ambient Air Quality 44

Standard, Central Pollution Control Board, Government of India notification [25] (18/11/2009) sets the standards for SO2 emissions at: SO2: 50 80 /m3 (Per annum) /m3 (24 hours) Table 29: Aspen Plus results for RGibbs Thermal Claus reactor (Reaction -1) Input Output

H2S

17.57 Kmol/hr

H2S

12.23 Kmol/hr

O2

8 Kmol/hr

SO2

5.33 Kmol/hr

H2O

5.33 Kmol/hr

We have used a 2/3-step Claus process, simulating the first thermal reactor by RGIBBS reactors in Aspen. The Claus process consists of a thermal step, which happens at around 1000 degrees celcius and 1.5 bar gauge pressure. The main reaction, which happens here, is: 2H2S +3O2->2SO2+2H2O (Reaction -1 ) By rule of thumb we introduce nearly 30 % by weight (of total) of O2 into the thermal reactor. We give the requisite residence time, in order to allow full stoichiometric conversion. We design the reactor as a two-chamber system, with one chamber being where reaction takes place, and the other leading to the exit-pipe being barricaded by closeable slits. The reaction pipe spacing allows circulatory meeting of the two inlet gases and adequate region and time for reaction.

45

Figure 25: Claus Thermal Reactor Design The second reactor is a catalytic reactor, and the reaction here is: 2H2S + SO2 -> 3S + 2H2O Hr = -108 kJ moL-1 Temperatures (about 470-620 K) over an alumina- or titanium dioxide-based catalyst. The Claus process is equilibrium-limited, adequate residence time has to be provided in order to allow this reaction. It is expected that in this reactor, the remainder of the Hydrogen Sulphide gets transformed into yellow sulphur. The second reactor (or multiple reactors) can be modelled by using SULSIM package, the availability of which is a problem. Models in Aspen HYSIS or PROMAX work by assuming simple thermodynamic equilibrium, whereas more complex models are needed for the second stage(s). We have thus tried to review data from various sources [3][4][5] to find out whether we will be a successful in converting our gases in sulphur. It is our expectation that we will be able to recover a high amount of sulphur during this catalytic process. This is followed by separation, where we will be condensing the sulphur obtained, and the remainder gases will be passed on to another incinerator, where we will be completely burning off the remainder non-SO2 compounds into SO2. A commercial claus reactor is however quite complex whose modelling requires significant professional insight, well beyond the scope of this project. Hence our modelling of the reactor is limited.

46

References: 1. Analysis and Optimization of Cyclone Separators Geometry Using RANS and LES Methodologies by Khairy Elsayed Submitted to the Department of Mechanical Engineering, in partial fulfillment of the requirements for the degree of Doctor in Engineering Vrije Universiteit Brussel October 2011 Advisor: Prof. Dr. Ir. Chris Lacor 2. Coulson and Richardsons CHEMICAL ENGINEERING VOLUME 2 FIFTH EDITION Particle Technology and Separation Processes. 3. Alex C. Hoffmann and Louis E.. Steins Gas Cyclones and Swirl Tubes: Principles, Design and Operation 4. GUO LING, WANG LIQIAN, DING JINWU AND MICHAEL ZHU, SIZING AND DESIGN EXPERIENCES OF THE ELECTROSTATIC PRECIPITATORS FOR TWO 600 MW POWER GENERATING UNITS 5. Bernard H. Schonbach,Director of engineering Allen-Sherman_Hoff company, Operation and Maintenance Guidelines for Silo Unloading Equipment 6. Karl Jacob, The Dow Chemical Company, Solid Processing lab, Bin and hopper Design 7. Pound; Joseph H. (Mount Prospect, IL), American Fly Ash Company (Des Plaines, IL), U.S. Patent Documents, patent no. 4313762 Slurry system for wasting fly ash having nonleachable, self-sustaining end product 8. Conestoga-Rovers & Associates 651 Colby Drive Waterloo, Ontario Canada N2V 1C2 Final Closure And Post Closure Plan Coal Ash Landfill Cover System Ash Landfill Permit Sw-09/01 Invista Site Seaford, Delaware 9. Reintegration of coal ash disposal sites and mitigation of pollution in the West Balkan Area Handbook on treatment of coal ash disposal sites FR, BOKU, BTUC 10. United Nations Environment Programme, A report on hazardous substances and coal combustion in India: http://www.unep.org/hazardoussubstances/Portals/9/Mercury/Documents/para29submissi ons/India-Response%20to%20questionnaire-COAL.pdf 11. Prashant Agrawal, Anugya Mittal, Manoj Kumar, S K Tripathi, Mercury Exposure in Indian Environment due to Coal Fired Thermal Power Plants and Existing Legislations, Department of Forensic Medicine, Institute of Medical Sciences Banaras Hindu University, Varanasi, U.P. 12. Nick Korens, Dale R. Simbeck, Donald J. Wilhelm, SFA Pacific, Inc., Engineering and Economic consultants, PROCESS SCREENING ANALYSIS OF ALTERNATIVE GAS TREATING AND SULFUR REMOVAL FOR GASIFICATION, prepared for US Dept. of Energy. 13. Product Bulletin, HGR for mercury removal, Granular Activated Carbon, http://www.calgoncarbon.com/media/images/site_library/84_HGR_MercuryRemoval_0108 R.pdf 14. Sigma Aldrich conversion tables, particle size conversion: http://www.sigmaaldrich.com/chemistry/stockroom-reagents/learning-center/technicallibrary/particle-size-conversion.html 15. Barry Burr and Lili Lyddon, A COMPARISON OF PHYSICAL SOLVENTS FOR ACID GAS REMOVAL, Bryan Research & Engineering, Inc., Bryan, Texas, U.S.A. 16. U.S. Department of Energy, Gasifipedia, Acid Gas removal. 17. R. Scott Alvis, Nathan A. Hatcher & Ralph H. Weiland. CO2 Removal from Syngas Using PiperazineActivated MDEA and Potassium Dimethyl Glycinate, Optimized Gas Treating, Inc. rd 18. Robert E. Treybal, Mass Transfer Operations, 3 Edition, Chapter 6: Equipment for Gas-liquid Operations, Tray towers (page 158-176). th 19. The Chemical Engineers Handbook, 5 Edition, fig 5.26. 20. Guo-Wen Xu, Cheng-Fang Zhang, Shu-Jun &in, and Bin-Chen Zhu, Desorption of COz from MDEA and Activated MDEA Solutions, Research Institute of Inorganic Chemical Technology, East China University of Science and Technology, Ind. Eng. Chem. Res. 1995,34, 874-880. 47

21. http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/5-support/522. 23. 24. 25. 26. 27.

28.

29. 30. 31. 32. 33. 34.

9_water-gas-shift.html. Coal Gasification and Its Applications By David A. Bell, Brian F. Towler, Maohong Fan I. Fiedorrow, R., 1984; Hung, H., 2006. Act, 1981: http://www.moef.nic.in/legis/air/air1.html Notification for Standards of emissions: http://envfor.nic.in/downloads/rules-andregulations/Latest_48_FINAL_AIR_STANDARD.pdf (2010) Abedini et al. Modeling and Simulation of Condensed Sulphur in catalytic beds of Claus Process: Rapid Estimation, Chemical Engineering Research Bulletin 14 (2010) 100-114 (2008) Sassi and Gupta, Sulfur Recovery from Acid Gas Removal using the claus process and high temperature air combustion (HiTAC) Technology, American Journal of Environmental Sciences 4(5): 502-511, 2008 (1993) Monnery et al. Modelling the modified claus process reaction furnace and the implications on plant design and recovery, Canadian Journal of Chemical Engineering, Volume 71, Issue 5, 711-724. http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/5-support/59_water-gas-shift.html. Coal Gasification and Its Applications By David A. Bell, Brian F. Towler, Maohong Fan I. Fiedorrow, R., 1984; Hung, H., 2006. Bernard H. Schonbach, Director of engineering Allen-Sherman Hoff company, Operation and Maintenance Guidelines for Silo Unloading Equipment Marietta silos, http://www.mariettasilos.com/59 S. Behera and S. Das, Characterisation of Bulk Materials Flowability for Design of Hopper using Jenike Shear Cell, Regional Research Laboratory, Bhubaneswar - 751013

48

Chapter 2: Methanol Production Plant

Removal Of Methane From Syngas
Methane is particularly difficult to remove from syngas due to similarity of its properties with carbon dioxide and carbon mono oxide. The processes generally used to separate methane from gases that is scrubbing etc. will also absorb a significant amount of CO and CO 2. The most efficient way of removing methane without significantly affecting CO and CO 2 is by using a membrane separator. There are several different types of membrane separators available in the market most of which work on the principle of separating the species on the basis of molecular size. Nanoporous grapheme, which selectively filters out methane, was chosen as the membrane material for our membrane separator. This membrane has two types of pores called pore A and pore B. These pores differ only in the fact that pore B has hydrogen in the pore region while pore A does not.

Figure 26: Pore types in nanoporous Graphene The energy for passing of molecules through these pores has been studied by Andreas W. Hauser and Peter Schwerdtfeger in their paper Methane-selective nanoporous graphene membranes for gas purification. The relative energy barrier for passing of CO2, CO, N2 and H2 were found by them to be as follows

Figure 27: Energy barrier for pore A

49

Figure 28: Energy Barrier for pore B Syngas coming into the separator has only CO, CO2, H2 and CH4. For designing our membrane reactor, we have used the energy barrier for CO to be the same as N2, this assumption is valid because the structure of N2 is very similar to that of CO, they are also identical in terms of electronic structure. The probability of transmission of an atom from one side of the membrane to the other was found to be

We are concerned only with the relative probabilities of transmission of CH4 and other components, so we take ratio of these probabilities, which would give us the mole fractions of gases on the other side. This ratio comes out to be a ratio of two complementary error functions, which when simplified in the limiting case comes out to be Ratio = exp ((E1-E2)/KbT) Calculating for the relative transmission of CH4 and CO which have the closest energy barriers, we get a ratio of 1689595, which is a very large value, so we can assume that methane is almost removed from the mixture after just one membrane separation.

Process Flow Diagram

Figure 29: Process Flow Diagram 50

The following Process Flow Diagram was chosen considering the various processes already prevalent in the chemical industry. The feed is first passed through a guard bed to remove poisons, then it is mixed with recycle stream and compressed and sent to the reactor. The reactor also has a stream of fresh catalyst and oil. The output from this reactor is passed through a hydrocyclone, part of whose downflow is recycled and part is purged. The upflow consists of methanol and water, which are sent to a distillation column to produce market grade Methanol.

Mass Balance
The plant design was based on a total input rate of 500 MTPD of impure syngas entering the plant. Methanol needed by plants downstream was 71.78 MTPD for Acetic Acid plant and 45.315 MTPD for Methyl Acetate plant. The production of methanol was to be higher than these requirements. Mass Balance on the reactor system was done using ASPENTM HYSYS software. For mass balance the incoming streams were taken to be of the composition obtained after purification [as obtained from subgroup-1]. The stream was passed through a guard bed for removing any catalyst poisons and reducing their concentration to the order of some ppb. The composition of stream was assumed unaffected by the change small change in concentration of catalyst poisons from the guard bed. The stream after passing through the economizer (heat exchanger) and compressor was assumed to be at 70 bar pressure and 250 degrees Celsius (reactor conditions). The conversions of individual reactions were assumed from literature and the final conversion was found from ASPEN software. The final methanol output after refining mass balance twice comes out to be 453 MTPD.
Stream Molar flow rate (kgmol/hr) CO Input Recycle Mixed Stream (Reactor Input) Reactor output Hydrocyclone Purge Output stream 2600 1002 3858 0.193 0.080 0.151 CO2 0.101 0.182 0.115 Composition (mol. fractions) H2 0.705 0.7375 0.664 H2 O 0 0 0.066 CH3OH 0 0 0

2951

0.059

0.135

0.548

0.102

0.153

2196 1186 755.2

0.070 0.079 0

0.182 0.182 0

0.737 0.737 0

0 0 0.399

0 0 0.600

Table 30: Mass Balance Results 51

Catalyst (contributed by Palash Agarwal)

Modern methanol production has been made more efficient through use of catalysts capable of operating at lower pressures and temperatures as compared to catalysts used in 1920s that required extremely vigorous conditions of pressures ranging from 30-100 MPa, and temperature of about 400C. The catalyst to be used in our reactor is a mixture of copper, zinc oxide, and alumina oxide. At pressures of 5-10 MPa and temperatures of 220-275C, it can catalyse the production of methanol from carbon monoxide and hydrogen with high selectivity [23].

Role Of ZnO
The ZnO in the catalyst formulation creates a high Cu metal surface area, hinders the agglomeration of Cu particles and interacts with Al2O3 to form a spinel that provides a robust catalyst support and inhibits dimethyl ether formation. It also limits sulphur poisoning by diverting sulphur away from Cu sites. Catalyst Properties The formulation will have about 50-60 wt% CuO, about 20% ZnO and rest Al2O3. Presence of CO2 has a positive effect on the methanol formation of the copper/zinc oxide catalyzed reactions. It conditions and prevents damage to the catalyst. Generally, 6 vol % CO2 is added to the syngas feed. Bulk density of catalyst- 1200 kg/m3 Porosity Of catalyst - 0.27 Other Catalyst Formulations Additional catalyst formulations have been proposed with the intent of increasing methanol yields. The addition of heavier alkali metals (such as cesium, Cs) to Cu/ZnO mixtures improves methanol yields but lighter alkali metals (such as potassium, K) tend to increase production of higher alcohols. Copper-thorium oxide (Cu/ThO2) intermetallic catalysts have demonstrated high methanol formation from CO2-free syngas, but deactivate rapidly in the presence of CO2 [28]. Supported palladium (Pd) catalysts have also demonstrated methanol synthesis activity in CO2-free syngas at 0.5-11 MPa between 260-350C.[29] Since, our syngas contains CO2 , hence they cant be used in our case.

Catalyst Activation
We use the in situ activation procedure for catalyst activation where reduction of the entire charge of the fresh catalyst takes place within the reactor at one go. Mineral oil is mixed with fresh catalyst slurry using an agitator in reduction vessel and fed to reactor. A stream of CO2 diluted with N2 is injected from bottom of vessel and a heating/cooling jacket helps in heat removal. The catalyst slurry is then activated using a series of temperature program steps. In situ activation works on concept of temperature programming the reactor and maximizing the on stream time of the catalyst. Temperature programming involves starting at the lowest temperature at which desired conversion is achieved and gradually increasing temperature as the catalyst ages to maintain a constant activity.

52

Poison Removal System

Synthesis gas produced from coal gasification contains a number of impurities which can deactivate the methanol catalyst.
Poison Sulphur as H2S Metal Carbonyls Fe(CO)5 ;Ni(CO)4 Chlorine as HCl Phosphorous as PH3 Apparent Maximum Allowable Concentration 0.1 ppm < 1 ppm 1 ppb < 2ppm

Table 31: Apparent maximum poison concentrations for methanol synthesis catalyst In the standard fixed bed reactor, which was, used traditionally, the front end of the catalyst bed acted as a poison removal system. On the other hand, in a slurry reactor, which we are using, the catalyst poisons are spread throughout the system. Hence, efficient catalyst poison removal is an essential aspect of the liquid phase methanol process. The main methanol catalyst poisons are Fe(CO)4, Ni(CO)4, COS, H2S, and HCl that result in site blocking or sintering, which yields decreased activity or change in selectivity. Catalyst guard beds need to be installed for removal of these compounds. A number of commercially available adsorbents were screened for their ability to remove the poisons. Adsorption isotherms were measured at various carrier gas pressures and two temperatures on several adsorbents, including active carbons, zeolites, alumina, silica gel, metal oxide impregnated active carbons, metal oxide promoted zinc oxide, metal oxide promoted alumina, and spent methanol catalyst. By monitoring the approach to equilibrium as a function of time, mass transfer coefficients for the adsorption of these trace impurities were also determined. From this adsorbent screening, the preferred adsorbent for removal of each catalyst poison was identified. The equilibrium and kinetic adsorptive properties for each poison/adsorbent system were used to design a poison removal scheme. Estimation of Mass transfer Zone Lengths To design the adsorption system, mass transfer zone lengths are to be estimated using a technique developed by Rosen[30]

MTZ=2(1-ti/tm)L
Guard Bed Layer 1 Adsorbent Poison

tm=L KH /G
Kh (lbmole /lb) 400 K(hr-1) Density (lbs/ft^3) 1.1 80

ti=tm-2*X(tm/K)0.5
X Inlet Conc (ppm) 5 Outlet Conc (ppm) 0.01

Methanol Spent Catalyst Methanol Spent

H2S

HCl

1000

2.3

80

2.5

20

1ppb

53

Catalyst 2 3 4 HY Zeolite Fe(CO) 5 30 24 3.8 463.2 56.1 28.2 40 30 30 2 1.7 2.1 5 1 10 0.01 0.01 0.01

Activated Ni(CO)4 carbon (BPL) Impregnated Carbon (FCA) COS

Table 32: Parameter values for calculating breakthrough time

Poison H2S HCl Fe(CO)5 Ni(CO)4

L (ft) 3 3 3 3

tm (hr) 328.8 822.19 12.33 7.39

ti(hr) 259.64 727.6 11.67 6.15

MTZ length (ft) 1.26 .69 0.32 1.01

Table 33: Breakthrough time for through various adsorbent layers So we that a 3ft bed of spent methanol catalyst would last roughly 13 days for H2S with inlet of 5 ppm and outlet .01 ppm. Similarly a 3 ft bed of activated carbon would last for roughly 12 hours.

Reactor Design (contributed by: Aryanshi Kumar, Rishabh Arora, Priya Meena, Palash Agarwal)
Methanol production involves highly exothermic reactions. The production of methanol from synthesis gas involves three simultaneous reactions CO + 2H2 --> CH3OH (1) CO + H2O --> CO2 + H2 (2) CO2 + 3H2 --> CH3OH + H2O (3) All three reactions are highly exothermic having heat of reactions around 21.7, 9.8, and 12.8 kcal/gmol respectively, at the reactor operating conditions [1]. In order to carry out the production of methanol safely and efficiently, a reactor having a good temperature control is needed.

Choice of Reactor (contributed by Aryanshi Kumar)

Methanol synthesis is done by the catalytic conversion of hydrogen and carbon monoxide from coal-derived syngas by either conventional gas phase processes using fixed bed reactors, or with a liquid phase methanol process (LPMeOH) using a slurry reactor [2].

54

Fixed Bed Reactor Reaction conditions Pressure = 4.1-11.7 MPa Temperature = 200-315C Poor temperature control Requires high H2/CO ratio in order to achieve temperature control; CO concentration at the reactor inlet is normally limited to about 10-to15%, after dilution with recycled H2. For stoichiometric adjustments, water-gas shift reaction and CO2 removal are carried out. Catalyst deactivation and replacement COS poisoning and deactivation due to water, of catalyst, are negligible in fixed bed, but can be problematic in liquid phase reactors [3]. Introduction of fresh catalyst requires process shutdown, i.e. uninterrupted operation is not possible. Catalyst Particle Size Generally above 1 mm in diameter.

Slurry Reactor Reaction conditions Pressure = 7 MPa Temperature = 220-270C Better temperature control Presence of mineral oil - mineral oil acts as a heat sink and provides better temperature control and uniform heat distribution. However, this mineral oil used needs to be separated downstream. Thus, a higher per pass conversion of feed is achieved. Catalyst deactivation and replacement At high CO2/CO ratios, production of H2O hinders catalytic activity by sticking to the catalyst and restricting availability of catalyst surface. However, spent catalyst can be removed and fresh catalyst can be removed on stream, without interrupting operation. Catalyst Particle Size Powder form, i.e. ~ 25-50

Per-pass conversion Provides much lower per pass conversions Sparger considerations than slurry reactors (FBR conversions are Sparger design is crucial in slurry bubble limited to about 25% due to feed [3]) column reactors to avoid channeling. Table 34: Comparison of type of reactors for Methanol Synthesis After analyzing the pros and cons of each, we decided to go with the slurry reactor. The thought process behind this decision was as follows Temperature control is a major advantage of using a slurry reactor [1]. The methanol synthesis reaction is highly exothermic, and while reaction kinetics are too slow at very low temperatures, continuous high temperature application reduces catalyst activity and also lowers the per pass conversion. In fixed bed reactors, H2 is recycled to control the reaction and thereby the extent of heat liberated. Generally distillation costs are much lower than compression costs [3]; fixed bed reactors have higher compression costs, due to higher operating pressures and higher recycling of unreacted gas feed. Therefore, the slurry should compensate for the increased distillation requirements by lowering compression requirements. Assuming S removal in the purification stage is efficient, COS poisoning concerns should be very less highly efficient techniques for the same have been developed. Due to the ease of on-stream catalyst removal, the issue of catalyst deactivation due to formation of water can be easily handled by optimizing rate of catalyst removal and introduction of fresh catalyst

55

Sparger Design (contributed by Priya Meena)

The various spargers commercially available can be broadly classified into two categories: plate and pipe type spargers. Plate type spargers are used for small diameter columns and pipe type spargers are used for large diameter columns. Out of the various spargers commercially available, spider sparger was used. When the superficial gas velocity is very high, this sparger becomes the preferred choice, since large amount of length can be accommodated. The orifices are oriented downwards and on the each side of the arm. There are no orifices oriented on the top of the arms so that solid particles cannot block the orifices and the gas should be able to lift any solid particles which might settle at the bottom flange. There are 80 holes on each side and bottom of the arm and a total of 240 on each arm of the sparger [26]. A gas distributor for a slurry bubble column should satisfy the following conditions [24]: The gas should be rapidly mixed in the slurry The catalyst should be well dispersed over a wide range of flow to the reactor Stagnant zones, especially, at the bottom of the reactor, must be avoided Penetration of catalyst particles into the gas distributor must be minimized The distributor should not induce unacceptable attrition of the catalyst Non-uniformity in sparging (product distribution) results in weeping. Weeping in pipe type spargers primarily occurs when kinetic energy of gas through the holes is insufficient to support the liquid head above the sparger holes, which can happen because of nonuniformity of sparging. Non-uniformity in sparging through pipe type spargers results due to the following reasons: 1 The friction of the fluid against the internal surface of the pipe makes the pressure fall in the direction of flow 2 The momentum of gas decreases due to deceleration of the fluid, as the fluid escapes out of the holes. [27] The gas sparger is designed such that the reactor can operate in the fully developed hydrodynamic regime. This condition is attained if Weber number is maintained at a value 2 within the range of sparger geometry in combinations with the operating conditions [37]. We = x ug2x dT4/ N2o x do3x When the holes faces downward, bubbles detach from the aeration holes in the opposite direction as that of the liquid flow. To detach from the aeration holes, the bubbles must overcome the resistance to the liquid flow. This influences the bubble behavior in two ways. First, the bubbles suffer a higher pressure from the aeration holes to overcome the liquid flow. This increases the bubble size. Furthermore, once the bubbles detach from the aeration holes, the pressure difference between the inside and outside of the bubble reduces significantly because the liquid and bubbles now flow in the same direction, resulting in further bubble expansion. The increased bubble size also enhances bubble rise velocity. Second, when bubbles detach from the aeration holes, they must detour around the sparger arms and rise through the space between adjacent sparger arms. This space is narrow and must be shared by bubbles detaching from aeration holes on neighboring arms. Consequently, bubble coalescence is greatly enhanced [38]. 56

Vo,crit = 1.25 * ( ((

G)

x g x do)/

G)

x 0.44 x (L/do)-0.12x (

/ do)-0.145 x (HL/do)0.67)0.5

do2 x No = DT2 x ug/ Vo,crit Ltot = ( / do) x do x No

Ltot = Np x Larm f = 0.0476 x Re0.52 x Eu-0.37 x ( C = 0.112 x Re0.064 x Eu-0.26 x ( / Larm)0.81 x ( / Larm)0.39 x ( / do)-1.49 x ( do/dp)-1.06 / do)-0.79

Hole Diameter Diameter of sparger pipe Pitch Length of the arm Number of Sparger Pipe Total Number of Holes Critical Weeping Velocity Discharge Coefficient Friction Factor

0.005m 0.08m 4 1.8m 12 2860 9.89 m/sec 0.00759 0.00443 Table 35: Design details of the sparger

Hydrodynamic Considerations (contributed by Aryanshi Kumar, Priya Meena, Palash Agarwal, Rishabh Arora)
Flow Regime - The preferred flow regime to operate a commercial slurry bubble column reactor for FT synthesis is the churn-turbulent regime, because of the necessity to deal with very large syngas inputs and to improve heat transfer to cooling surfaces. Increasing the superficial gas velocity above a certain point (>0.05-0.1 m/s) increases the interactions among the gas bubbles, and enhances the coalescence and breakup of these bubbles creating a wider bubbles size distribution. Large and fast-rising gas bubbles induce strong circulations and create back-mixing or re-circulation zones wherein the small gas bubbles are entrained. This regime is therefore characterized by strong gas-liquid mixing and optimal mass/heat transfer [17].

57

Figure 30: Homogeneous and churn-turbulent regimes in a column [43] The churn turbulent regime is characterized by a wide distribution of bubble sizes. In order to simulate the hydrodynamics of the slurry bubble column operating in this regime, we adopted a generalized two-phase model [4]. This approach has a dilute phase and a dense phase. The dilute phase comprises of the fraction of gas which flows through the reactor as large bubbles (greater than 20 mm in size) and the dense phase comprises of the rest of the fraction of gas entrained in liquid as small bubbles. Gas holdup - The total gas hold up, , which is an important hydrodynamic parameter

affecting reactor performances, is the sum of both the contribution of the dilute as well as the dense phase and is influenced by system properties, pressure, solids concentration and column size [32]. The gas holdup is a function of gas superficial velocity, temperature, liquid viscosity, concentration of solids and nature of gas and it increases with increasing gas velocity and operating pressure; whereas it decreases with increasing liquid viscosity and solid concentration. It is calculated as follows [22] Here, = 0.035 N/m kg/m3 In our case, = 0.00071 Pa.s g = 21 kg/m3 =1.5 * 10-5

= 0.205

Bubble Size -The average bubble size in a bubble column has been found to be affected by gas velocity, liquid properties, gas distribution, operating pressure and column diameter. The bubble size increases with increasing superficial gas velocity, solid concentration (up to a certain value), liquid viscosity and surface tension. Bubble size at sparger orifice is given by the following correlation by Bhavaraju et. al 58

[18] Q (flow through each orifice) = 0.64/2860 m3/s, where no. of orifices = 2860 => Q = 2.24 x 10-4 m3/s bubble size at orifice, db = 0.006 m Bubble rise velocity - The bubble rise velocity is given by[25] Putting the values, db= 6 mm and using other values as above, = 0.217 m/s Due to high rising velocity of large bubbles, we can assume plug flow for the dilute phase. The motion of the large bubbles churns up the dense phase causing backmixing of slurry, which guarantees good catalyst dispersion. The extent of backmixing depends on many factors, such as aspect ratio, internal configuration, and superficial gas velocity. In largescale reactors equipped with longitudinal cooling tubes, as is the case with us, the dense phase is fairly well mixed [6]. However, in order to have greater reactor productivity and greater conversion per volume of reactor, we know that plug flow is desired. For concentrated slurries, having fraction of solid catalyst concentration, , the gas entrapped in the dense phase as small bubbles can be neglected [7]. Thus all the gas can be thought to pass through the reactor as bubbles of diameter > 20 mm. Superficial gas velocity and reactor diameter estimate- For churn turbulent regime, the superficial gas velocity, , is estimated to be in the range 0.05-0.1 m/s [9]. Assuming that = 0.1 m/s at the reactor conditions (7 MPa, 250oC), we can estimate the reactor diameter using the volumetric flow rate as follows Molar flow rate of feed gas = 3800 kmol/hr = 1.03 kmol/s Assuming ideal gas, at reactor conditions Volumetric flow rate, Q = 0.64 m3/s => Diameter of reactor, = 2.85 m => Height of reactor, h = 28.5 m (taking L/D= 10 [26]) Verification of well dispersed catalyst slurry and optimized catalyst particle size In order to ensure that the catalyst particles are well-dispersed in the liquid phase purely due to gas-agitation, we use a modified version of the Ergun equation (assuming a conservative 40% voidage for spherical catalyst particles)

(p l)(1-)g = 150g(1-)2umf / 3dp2 + 1.75(1-)(p l)umf2 / 3dp

Modification - p in the Ergun equation is replaced by (p l) to account for the buoyant force due to the mineral oil. 59

This simplifies to 4.27 x 106 umf + 5.06 x 106 umf - 3.25 x 103 = 0
2

umf = 6.42 x 10-4 m/s

Since, this is well below the assumed superficial gas velocity (0.01 m/s), therefore, our assumption of a well dispersed catalyst slurry in the churn turbulent regime holds. In addition, Espinoza et al. [51] showed that catalyst particle sizes should be such that their Archimedes No. lies between 0.02 and 250 in order to have an optimum particle size for slurry bubble column reactors. In our case, Ar = gdP3L(PL)/L2 = 0.87 which lies within the optimum range. Hence our choice of dp = 50 microns lies in this range. Pressure Drop across the reactor - The pressure drop across the reactor is sum of hydrostatic pressure drop and pressure drop due to frictional forces.To estimate it, we made use of Lockhart-Martinelli model.

Here, = Total pressure drop =Hydrostatic pressure drop =Three phase frictional pressure drop calculated using LockhartMartinelli model. = Frictional pressure drop in gas phase C= 10 for churn turbulent regime. - height of mixing of 3 phases = 18m - Reactor diameter = 2.85m -Gas Holdup =.207 =Viscosity of gas phase =1.5*10^-5 =Superficial gas velocity =0.1 m/s -Slurry density = 690.03 kg/m3 = LockhartMartinelli parameter X= LockhartMartinelli parameter= 50 = Reynolds number of gas = friction factor On putting the values in the above relations, We get =96.548KPa

60

Determination of Rate Law and Mass Transfer Coefficient (contributed by Aryanshi Kumar, Rishabh Arora)
A comparative study by Setinc and Levec [19] showed the variation of the different models established in order to predict the rate of methanol synthesis and compared them to small scale experimental values observed. The models by Bussche and Froment [20] and Lee et al.[21] (which is based on a mass transfer coefficient type correlation) predicted the rate fairly accurately. The correlation developed by Lee et al. was selected for its ability to predict the rate of reaction at CO2/(CO+CO2) ratios greater than 0.3 fairly accurately despite its relative simplicityRH2=Kla (cH2ig-cH2,eq)

Figure 31: Different models predicting rate law for Liquid Phase Methanol Synthesis In a three-phase reactor, a number of steps have to be completed before the reactant can be converted into product on the active sites of the catalyst. For the equation under consideration, i.e. that derived by Lee et. al., only reactions (2) and (3) were considered, since research has shown that the rate of methanol production is proportional to the concentration of CO2 in the feed stream[19], implying that reactions (2) and (3) play a dominant role in the liquid phase methanol synthesis process, especially at higher feed concentrations of CO2. Under this assumption, the following steps have to be completed before the reactant can be converted into the product on the active sites of the catalyst. These have been shown in the figure below Transport of reactant species from the bulk gas phase to the gas-liquid interface Transport of species from the gas-liquid interface to the bulk liquid phase Transport of species from the bulk liquid to the catalyst surface Intraparticle diffusion of reactants 61

Adsorption of reactants on the active sites of the catalyst Reaction on the sites to yield products Desorption of the products from the sites Intraparticle diffusion of products Transport of products from the catalyst surface to the bulk liquid Transport of products from the bulk liquid to the gas-liquid interface Transport of products from the gas-liquid interface to the bulk gas phase

Figure 32: Different resistances involved in three phase reactor [8] The expression for rate law considering these steps is as follows -

It has been shown that for high catalyst loading (high values of w), and small catalyst pellet sizes (<50 microns) [31], the overall rate is gas-liquid mass transfer controlled. Thus, we can neglect the contribution of the other two terms. Furthermore, it has also been shown that it is safe to assume the overall gas-liquid mass transfer coefficient which is composed of both gas film mass transfer coefficient as well as liquid film mass transfer coefficient, can be assumed to have negligible contribution of the gas side resistance [32]. For Witco-40 oil [33] = 1.0376 7.465*10-4 T where, T is in Kelvin and is in g/cm3 is in g/cm.s

= 0.01 exp(1.839 4.166*10-3 T) where, T is in Kelvin and At 250 oC kg/m3 mPa.s

For the feed gas, average molecular weight ~ 13 g/mol (taking into account the composition) 62

=> density of gas phase (assuming ideal gas equation) Diffusivity of Hydrogen in Witco-40 mineral oil is given by -

21 kg/m3

[33] In our case, = 2 x 10-5 cm2/s = 2 x 10-9 m2/s The liquid film mass transfer coefficient would depend on many operating variables and the properties of the fluid flows -

There are several models that estimate the dependence of this term [10-16]. Out of these, Akita and Yoshidas model has been shown to be fairly accurate [11] which gives the relation-

=>

s-1

For the purpose of calculating the CH2 value, i.e. saturation concentration of hydrogen in the liquid phase, the given gas-phase mole fractions had to first be converted to the corresponding liquid phase mole fractions. This was calculated using Henrys Law, giving the relationH * xH2,eq* = PT*yH2,eq where and A = -11.1158, B = 1438.0219, C = 1.9043 for H2 in Witco-40 oil A = 88.926, B = 6417.1251, C = -11.6130 for CO in Witco-40 oil A = 4.2363, B = -629.7551, C = 0.0 for CO2 in Witco-40 oil ln((H, bar)/10)= A + B/T + C lnT

Calculating for P = 70 bar, T = 523 K, we get HH2 = 350 bar HCO = 500 bar HCO2 = 205 bar The feed saturation mole fraction of H2 in the liquid-phase, xH2,o= 0.133 Overall saturation mole fraction of the syngas feed in the liquid phase, xg,o 0.25

So far, we have considered that two routes of methanol formation occur. These are1 Direct conversion of CO2 to CH3OH 2 Conversion of CO to CO2, followed by conversion of CO2 to CH3OH

63

The second reaction includes the following two stepsCO + H2O --> CO2 + H2 CO2 + 3H2 --> CH3OH + H2O The overall mole balance of these two reactions gives us the original reaction (1)CO + 2H2 --> CH3OH As a result, for the purpose of chemical equilibrium calculations, we have considered only reactions (1) and (3). Literature survey gave values of overall conversion of CO 70% & that of CO2 10% at equilibrium. => yH2,eq = 0.419 => xH2,eq = 0.0838 (Using Henrys law) The gas and liquid phase densities, average molecular weights and saturation mole fractions were used to determine the concentration of H2 in the liquid phase, givingCH2,o = 0.39 mol/L CH2,eq = 0.1336 mol/L

Figure 33: Variation of concentration of Hydrogen with residence time Gas-phase mass balances were performed using-

Where Cg,H2 = CL,H2 x mH2, and mH2 is the solubility of H2 ( 2.96 at 250 oC)

64

Figure 34: Variation of H2 concentration in liquid phase with reactor height Assuming plug flow model of gas phase,

Figure 35: Plot of H2 concentration as a function of volume of mineral oil

65

Results (contributed by Aryanshi Kumar)

Initial estimates/assumptions Orifice diameter, do = 5 mm Viscosity of liquid (Witco-40 mineral oil) at 70 bar, 523 K Viscosity of gas at 70 bar, 523 K, Density of liquid at 70 bar, 523 K = 0.000015 = 647 kg/m3;

= 0.00071

Reactor Diameter, DT = 2.85 m Reactor height, L = 28.5 m Catalyst loading, = 0.35 (epsilon s)

First estimate made using ug = 0.1 m/s (for churn-turbulent regime) and feed molar flow rate 3800 kmol/hr => Reactor Volume = = 181.72 m3

Final values In keeping with the graphs obtained Length of the reaction zone in reactor = 18 m Volume of mineral oil (liquid phase) in the active region = 50 x 103 L = 50 m3 => DT = 2.8, and L = 23 m (L =18 m) => L/DT = 8.21 (which complies with the general recommendation of L/D>6) = 0.32 Ug = 0.1 m/s Vb = 0.207 m/s => residence time, = L/Vb = 86.9 s (matches with graphical results) W = 40,000 kg Amount of methanol produced = 450 kmol/hr = 125.4 mol/s

Hydrocyclone (contributed by Sarthak Nigam)

Hydrocyclones are used to separate out the solid catalyst particles from the slurry/ gaseous mixture obtained from the reactor. A problem that arises here is the quantification of gases, oil and catalyst rising from the reactor. The modeling of this hydrocyclone was therefore done under certain assumptions of modeling. The reactor has been designed in keeping with the disengagement of oil in mind. The reactor has a diameter of 2.8 meters and a liquid height of 18 meters, along with a disengagement zone of 4m above the liquid and 1 meter below the liquid (sparger/gas distribution zone). The cyclone can therefore be assumed to be operating at no oil input and hence is an air cyclone. Similarly, the reactor was assumed to be well mixed so that the ratio of catalyst to gas coming out of the reactor and in the reactor are the same, hence the catalyst coming out of the reactor can be quantified. Rector volume = (/4)*(2.8)2*(18) = 110.835 kg/m3 Catalyst inside reactor = 40,000 kg 66

Mass of catalysts per unit volume of reactor = 40,000/110.835 = 360.896 kg/m3 Outgoing vapor moles = 2951 kgmol/hr [from aspen simulation and mass balance] Volume of vapor (calculated using ideal gas law) = 0.509 m3/sec Mass of catalyst leaving with vapor = 360.896*0.509 = 183.696 kg/sec There are many types of cyclones that have been designed for high efficiency, high throughput or for general purpose. For the separation of catalyst particles (sized between 25-50 micrometers), a high efficiency Stairmand cyclone was chosen as the design standard, which would be used for sizing. The various standard ratio of dimensions for a Stairmand were obtained from literature[34]. For finding out the diameter of the cyclone, the ratios were used to obtain all the dimensions of the cyclone in terms of the diameter of the cyclone. These dimensions were then used to find out the particle terminal velocity of the last particle that would be retained according to the equation as follows

The value of U0 was found in terms of D (diameter of cyclone) and equated to the terminal velocity of a particle falling in a solution

here, velocity is an unknown and is calculated by taking the mass weighted average of the various components and then adjusting for the solid amount (using Einsteins equation). The viscosities of various components are calculated using Sutherlands formula[40]. = o*(a/b)*(T/To)3/2 [Sutherlands formula]

Here, T0 is a reference temperature (experimentally determined) a and b depend on temperature as follows a = 0.555To + C b = 0.555T + C for methanol at 250 Celsius = 0.0227 cp for steam at 250 Celsius = 0.0229 cp for hydrogen at 250 Celsius = 0.01279 cp for CO at 250 Celsius = 0.02665 cp for CO2 at 250 Celsius = 0.02505 cp Average viscosity = 0.02334 cp Also, Volume of catalyst = mass of catalyst/density of catalyst = (183.696)/1200 67 [from literature] [from literature] [from sutherlands formula] [from sutherlands formula] [from sutherlands formula]

= 0.153 m3/sec Volume fraction of solids = 0.153/(0.153+0.509) = 0.23 Viscosity adjusting for solids = viscosity without solids * (1+2.5*solid fraction) = 0.0367 cp From the equality of U0 the particle cut diameter is obtained in terms of the diameter of cyclone. The particle cut diameter was chosen to be 25 micrometers because we are using catalyst particles in the range of 25-50 micrometers. The obtained cyclone diameter comes out to be

Figure 36: A typical Stairmand cyclone D = 1.1089 meters b = 0.22178 meters De = S = 0.55445 meters H = 4.435 meters h = 1.66335 meters a = 0.55445 meters B = 0.4158 meters

The pressure drop in a cyclone is quantified as follows [41]

[K: Proportionality factor] => Pressure drop = 0.3422 bar [42]] [assuming K = 10-4 for a typical cyclone of this size

68

Distillation Column (contributed by Seema Chouhan)

Designing of the distillation column was done using Aspen Plus Software. Feed Stream, top product stream and bottom product stream labeled respectively as Distill and Bottoms were added to the column. NRTL base method was used for calculations that Aspen Plus will perform. First step involves getting a rough estimate for required number of stages .As the column is not operating at 100% efficiency optimization of total number of stages will take place ahead. Also, a TXY plot is generated and is used to do McCabe-Thiele diagram. The diagram generated will provide an estimate of equilibrium stages using McCabe-Thiele diagram. To achieve 99% purity (Grade AA methanol) further optimizations will be done by changing number of stages in column and by changing location of feed plate. Procedure will be continued until desired purity is achieved. Sieve Plates are preferred Pressure drop is low as compared to bubble cap trays Their fundamentals are well established, entailing low risk. The trays are low in cost relative to many other types of trays. They can easily handle wide variations in flow rates. They are lighter in weight. It is easier and cheaper to install. Maintenance cost is reduced due to the ease of cleaning. As maintenance, fouling tendency and effects of corrosion are least in sieve trays Sieve Trays are at an advantage when the service is fouling or corrosive or when turndown is unimportant. Location of Feed Plate The Kirk bride method is used to determine the ratio of trays above and below the feed point. log (ND / NB) = 0.206 log [ (B/D) (xHK / xLK ) ( ( xLK)B / (xHK) D)2 ] Where ND, Number of plates above feed = 20 NB, Number of plates below feed = 20 Assumed Tray Spacing: 24 inches

Bottoms Temp F Pressure psi Vapor Frac Mole Flow lbmol/hr Mass Flow lb/hr Volume Flow cuft/hr 319.2 110.86 0.00 664.307 12379.169 239.308

Distill 149.0 14.7 0.00 1000.624 31650.656 679.851

Feed 77.0 1015.26 0.00 1664.931 44029.825 846.497

69

Enthalpy MMBtu/hr Mole Flow lbmol/hr METHANOL WATER Mole Frac METHANOL WATER

-77.869

-101.401

-184.652

29.335 634.972

971.228 29.335

1000.624 664.307

0.044 0.956

0.971 0.029
Table 36: Stream Table

0.601 0.399

Section starting stage Section ending stage Stage with maximum diameter Column Diameter Downcomer area / Column Area Side downcomer velocity Side weir length

2 39 2 6.212 ft 0.1000014 0.054 ft/sec 4.514 ft Table 37: Tray Sizing Results

Murphree plate efficiency defined in terms of the vapor Compositions by: Emv = (yn - yn-1) / (ye - yn-1) = 0.7 Where, ye is the composition of the vapor that would be in equilibrium with the liquid leaving the plate. The overall column efficiency and the Murphree plate efficiency are related by an equation derived by Lewis (1936): EO = log [1+Emv (mV/L-1)] / log (mV/L) Where, m is slope of equilibrium line Nact, actual stages = Number of ideal stages / EO = 57 stages Height of column Hc= (Nact-1) Hs+ H+ plates thickness Tray Spacing, HS = 0.6m H =0.5m each for liquid holdup and vapor disengagement =1m 70

Total thickness of trays = 0.005* 57 = 0.285m Height of column = 34.885 m Ac = An + Ad Where, downcomer area (Ad) = 0.2804 m2, net area (An) = 2.5236 m2 cross sectional Area of column (Ac)= 2.804 m2 Active Area(Aa) = Ac - 2 Ad = 2.2432 m2 Hole Area (Ah) take 10% of Aa = 0.224 m2 Weir Height: 40 to 50 mm is recommended for columns operating above atmospheric pressure Weir liquid Crest, how = 750 [ LW / ] 2/3 = 28.7 mm where, = weir length,m LW = liquid flow rate, kg/s Weep Point : The minimum design vapour velocity through the holes is given by: Uh = [K2 - 0.90(2.54 - dh ) ] / ( ) 1/2 = 17.86 m/s dh = hole diameter ,mm K2 = a constant, dependent on the depth of clear liquid on the plate, obtained by Weep-point correlation (Eduljee, 1959) Dry Plate drop: The pressure drop through the dry plate can be estimated using expressions derived for flow through orifices hd = 51 [uh / Co] 2 / = 80 mm liquid where the orifice coefficient C0 is a function of the plate thickness, hole diameter, and the hole to perforated area ratio. C0 can be obtained from Discharge coefficient, sieve plates (Liebson et al., 1957). uh is the velocity through the holes, m/s. Residual Head : The simple equation proposed by Hunt et al. (1955) can be used: hr = (12.5 X 103 ) / =15.08 mm liquid Total Pressure Drop : ht = hd + ( hw+how ) + hr = 173.78 mm liquid Plate Pressure Drop : Pt = 9.81 x 10 -3 ht

=1.412 KPa

where Pt = total plate pressure drop, Pa(N/m2), ht = total plate pressure drop, mm liquid.

Downcomer design [back-up]:

Head loss in the downcomer can be estimated using the equation given by Cicalese et al. (1947) hdc = 166 [ Lwd / Aap] 2 =2.47 mm 71

where Lwd = liquid flow rate in downcomer, kg/s, Am = either the downcomer area Ad or the clearance area under the downcomer Aap; whichever is the smaller, m2. The clearance area under the downcomer is given by: Aap = hap lw = 0.0548 m2 Where hap is height of the bottom edge of the apron above the plate. This height is normally set at 5 to 10 mm below the outlet weir height: hap = hw - (5 to 10 mm) = 40 mm In terms of clear liquid the downcomer back up is given by: hb = (hw + how) + ht + hdc = 0.254 m hb < 1/2 (Tray Spacing + weir height) 0.254 <0.329 So, tray spacing is acceptable.

Ancillary Units
Compressor Design: (contributed by Mayuri Chowdhary and Vipin Yadav)
The compressor is positioned in the beginning to pressurize inlet stream from 1 atm to 69.08 atm, to be fed later to reactor. TYPE - Adiabatic Reciprocating Multistage compressor Reason: Reciprocating compressors are typically used where high compression ratios (ratio of discharge to suction pressures) are required per stage without high flow rates, and the process fluid is relatively dry. Both of these conditions hold true for our stream. These types of compressors are usually motor-driven and are nearly always double acting. It is adiabatic because the unit is not cooled by an external heat exchanger, so the fluid follows an isentropic path. Since the compression ratio is quite high, multistage compressor would be preferred so as to reduce the power required by the compressor unit. Assumptions: 1) Mechanical efficiency of compressor = 80% 2) Site elevation = 0 ie. local barometric pressure is ignored Calculations: For number of stages : R = Pb/Pa = 69.08/1 =69.08 Since this value is greater than 15, number of stages = 3 [45] Pressure drop at the end of each stage : Pb/Pa = (69.08)1/3 = 4.1 72

= Cp/Cv = 1.323

Power required by each stage:

where, Pb = power, kW q0 = volume of gas compressed, std m3/sec, evaluated at 0oC and 760 mm Hg =0.023 m3/sec Ta = inlet temperature = 373 K Pb/Pa = compression ratio Hence, power consumed by each unit using the above equation= 29.53 kW Therefore overall power consumption= 3X 29.53 = 88.59 kW Since the process is adiabatic, the following relation can be used to calculate the exit stream temperature: P1-T= constant Using this relation, exit temperature: Tb= 580 K Hence, the temperature at the end of compressor unit is 580 K, which is further added to the recycle stream through economizer and then sent to the reactor.

Pump Design (contributed by Mayuri Chowdhary and Vipin Yadav)

The reactor output stream consisting product methanol also carries along with it catalyst particles as well as mineral oil. Cyclone separator and mineral oil remove majority of catalyst particles and the remaining catalyst particles are further separated from methanol from the oil separator unit. This separated mineral oil and catalyst mixture is sent back to the reactor through pump. Since the mixture to be pumped is a mixture of oil and solid particles, the selection of pump is also important. Pump Selection: Pneumatically powered diaphragm pump is used for this purpose, since they Have good suction lift characteristics. Can handle sludges and slurries with a relatively high amount of grit and solid content. Have good self-priming capabilities. Can handle highly viscous liquids. There are two diaphragm chambers and two flexible diaphragms. Clamped in sandwich fashion at their outer edges, the shaft-connected diaphragms move simultaneously in a parallel path. Due to this, it is ideally suited for pumping solids in suspension which may tend to settle out, particularly when the pumping rate is reduced or when the pump is shutdown.

73

Diaphragm Selection: Buna-N is used as membrane, since it is suitable for handling oil based fluids and used mainly in case of petroleum/mineral oils, turpentine, kerosene and motor oils. [46] Design Specifications: Input feed rate to the pump= 23.71 m3/h For this flow rate, the pump dimensions required are: Length (l)= 278 mm Width (w) = 270 mm Height (h) = 450mm Port size= R 2 (hence pipe length= 0.762 m) [47] Using these specifications, the calculations can be further made as follows: 1. Volume of chamber (V): V= [(l2/8)+(h2/6)] Hence, volume= 1.36 X 10-4 m3 2. Discharge (Q): Q= V*(n/60)*(1/1000) Where n= rpm of motor -7 3 Hence, Q= 32.3 X 10 m /s 3. Power of motor: P= QH/1000 Where Q=Discharge of the pump H=head in m Y= Density of oil =Efficiency of the pump Hence, power= 2.09 W 4. Frictional loss: Where f= frictional head loss l= pipe length (m) d= diameter of pipe= 15 mm v= velocity of fluid in pipe (m/s) = Q/(/4)d2 -9 Hence, hf= 2.88 X 10 m

74

Heat Exchanger Design (contributed by Vipin Yadav and Mayuri Chowdhary)

F =4.115 x 10^4 Kg/s (Same for both inlet ie. after mixing and outlet stream) Heat exchanger is required to heat the inlet stream (after mixing) to reactor temperature ie. 250C and cool down the outlet stream from 250C to 115C. So, the first step is selection of heat exchanger requires heat calculations at both stages. Inlet Stream (after mixing with Recycle):

Tin = 217 C F = (1.177 + 2.938) x 10^4 Kg/hr = 4.115 x 10^4 Kg/hr Feed Mole fraction Cp at 217C (KJ/K) Cp at 250C (KJ/K)

H2 CO CO2

0.714 0.162 0.123

14.51 1.062 1.010

14.52 1.07 1.035

Table 38: Composition of Specific Heat capacities of inlet streams [48]

75

Cp (avg) = 10.661 KJ/Kg Q = m*Cp*T = > Q = (4.115 x 10^4)/3600 x 10.661 x (250 - 217) = 4020.745 KJ/s

Outlet stream: Possibility of methanol condensation in temperature range 250C- 115C was checked using Boiling point calculations for methanol by Antoine calculations . Boiling Point came out to be 248C which is quite close to 250C. So, Phase change in outlet stream is ignored. Tout = 250C F = 4.115 x 10^4 Kg/hr

Feed

Mole fraction

Cp at 250C (KJ/K) 14.52 1.07 1.035 3.9

Cp at 115C (KJ/K)

H2 CO CO2 CH3OH

0.548 0.059 0.135 0.153

14.47 1.047 0.93 1.92

Table 39: Composition of Specific Heat capacities of inlet streams [48] Cp (avg) = 9.59 KJ/Kg K Q = m*Cp* T => Q = (4.115 x 10^4)/3600 x 9.59 x (115-250) = 14798.57 KJ/s As we can see the heat which needs to be removed from outlet stream is much higher as compared to the heat which needs to be given to inlet stream. Now we have 2 options : Option 1: Either to use an economizer which will carry out exchange between feed and product streams but problem with that is relatively small heat required for inlet stream. Even after economizer, another heat exchanger (with water as coolant ) would be required to cool down the remaining heat from outlet stream. 76

Option 2 (Adopted in design): Since, heat difference between inlet and outlet streams is quite high, we can proceed with separate heat exchangers for inlet and outlet streams with water as cooling fluid in one exchanger and steam in another one . Furthermore, a storage tank can be installed which will store the outlet streams in between and we can subsequently heat water and use it for various other operations in plant according to our own convenience. Shell and Tube Heat Exchanger for Outlet Stream (Single Pass) [49] : Heat to be removed ie. Q(outlet stream) = 14798.57 KJ/s Shell size 21 inch ID; 158 Tubes 1.25 in. OD 13 BWG, 160 length Baffle spacing = 6 inch apart ; No. of baffles=1 Q = 50492844 BTU/hr Feed rate of water (coolant) = 47.84 Kg/s LMTD = 213.94F R = 1.824; S = 0.416 Tc = 336.2 F; tc = 130.28 F External Surface area/ft= 0.3271 ft2/ft Area = 158* 0.3271 *160 = 826.96 ft2 Ud (Design overall Coefficient) = 257.92 Btu/ (hr). (ft2). (oF) Dirt Factor Rd= 0.0018(hr). (ft2). (oF)/ Btu Uc (Clean Heat Transfer Coefficient) = 481.46 Btu/ (hr). (ft2). (oF)

Shell and Tube Heat Exchanger for Inlet Stream (Single Pass)[49]: Steam is used to heat up inlet stream Heat to be removed ie. Q(inlet stream) = 4020.745 KJ/s Shell size 15.25 inch ; 160 Tubes 0.75 in. OD 18 BWG, 16 0 length Baffle Spacing = 12 inch apart ; No. of baffles = 1 Q = 15271873.81 BTU/hr Feed rate of steam = 71.94 Kg/s LMTD = 211.43 F R = 0.848 ; S= 0.379 Tc= 235.76 F ; tc= 446.36 F External Surface Area/ft = 0.1963 ft2/ft Area = 160 * 0.1963 * 160 = 502.53 ft2 Ud (Design overall Coefficient) = 511.6 Btu/ (hr). (ft2). (oF) Dirt Factor Rd= 0.0013(hr). (ft2). (oF)/ Btu Uc (Clean Heat Transfer Coefficient) = 1527.62 Btu/ (hr). (ft2). (oF)

77

Costing for Heat Exchanger : Material of Construction would be Stainless Steel 316 grade Cost for HE = Fd * Fm * Fp * Cb *50 (in Rs.) [50] Where, Cb = exp[8.821 0.30863(lnA) + 0.0681(lnA)^2] Fd = exp[-0.9816 + 0.0830(lnA)] Fp = 1.1400 + 0.12088(lnA) Fm ( depends on material chosen ie for grade 316 SS) = 0.8603 + 0.23296(lnA) A = Area of Heat Exchanger For Heat Exchanger on Inlet Stream Area (A)= 502.53 ft2 Cb = 13849.44 Fd = 0.628 Fp = 1.892 Fm = 2.309 => Cost = Rs. 18,99, 795 For Heat Exchanger on Outlet Stream Area = 826.96 ft2 Cb = 18434.88 Fd = 0.654 Fp = 1.952 Fm = 2.425 => Cost = Rs. 28,53,510 Total cost for heat exchangers = Rs. 47,53,300

78

References 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Commercial Scale Demonstration of the LPMeOH Process, E.C. Heydorn, B.W. Diamond, Air Products and Chemicals, R.D. Lilly, Eastman Chemical Company, June 2003 Gasifipedia, Supporting Technologies, National Energy Technology Laboratories, US DoE www.netl.doe.gov Products from SynGas-Methanol (Catalyst), SunGrant BioWeb bioweb.sungrant.org R. Krishna, J. Ellenberger, S.T. Sie, Chem. Eng. Sci. 51 (1996) 2041. Palashs 21 page paper R.L. Espinoza, A.P. Steynberg, B. Jager, A.C. Vosloo, Appl. Catal. A 186 (1999) 13. R. Krishna, J.W.A. de Swart, J. Ellenberger, G.B. Martina, C. Maretto, AIChE J. 43 (1997) 311 Fogler Nader Ali Adel; Simulation of Gas-to-Liquid (GTL) Process in Slurry Bubble Column Reactor (2008) Ozturk SS, Schumpe A, Deckwer WD. Organic liquids in a bubble column: holdups and mass trsansfer coefficients. AIChE J 1987;33:147380. Akita K, Yoshida F. Gas hold-up and volumetric mass transfer coefficients in bubble columns. Ind Eng Chem Process Des Dev 1973;12:7680 Hikita H, Asal S, Kikukawa H, Zalke T, Ohue M. Heat transfer coefficient in bubble column. Ind Eng Chem Process Des Dev 1981;20:5405 Kang Y, Cho YJ, Woo KJ, Kim SD. Diagnosis of bubble distribution and mass transfer in pressurized bubble columns with viscous liquid medium. Chem Eng Sci 1999; 54:4887 Kawase Y, Moo-Young M. Heat transfer in bubble column reactors with Newtonian and nonNewtonian fluids. Chem Eng Res Des 1987;65:1216 Schumpe A, Grund G. The gas disengagement technique for studying gas holdup structure in bubble columns. Can J Chem Eng 1986;64:8916 Shah YT, Godbole SP, Deckwer WD. Design parameters estimations for bubble column reactors. AIChE J 1982;28:35379 de Swart, J.W.A., et al., Size, Structure and Dynamics of "Large" Bubbles in a TwoDimensional Slurry Bubble Column. Chem Eng Sci 1996 Bahavaraju SM, Mashelkar RA, Blanch HW. Bubble motion and mass transfer in nonNewtonian fluids. AIChE J 1978;24:106376 Marko Setinc, Janez Levec, On the Kinetics of Liquid-Phase Methanol Synthesis over over commercial Cu/ZnO/Al2O3 catalyst. Chem Eng Sci 1999;54:3577-3586 K.M. Vanden Bussche, G.F. Froment, A steady state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al2O3 catalyst. J Catalyst 1996;161:1-10 http://www.google.com/patents/EP1203759B1?cl=en Hikita, Asai,S.,Tanigawa, Segawa,Kitao: Gas Hold-Up in Bubble Columns Chem. Eng. J., 20 (1980) 59-67. Methanol Catalyst Poisons: A Literature Study ,Cornelissen, S. Clevers, Deventer, 2007 Thomas Gutermuth, Manfred Ruppel, Dag Schanke, Pal Soraker; Slurry bubble column reactor; EP 2367616 A1 Mendelson, H.D. (1967) The Prediction of Bubble Terminal Velocities from Wave Theory. AIChE J., 13, 250-253. Laurent Sehabiague ; Modeling, Scale-up and Optimization of Slurry Bubble Column Reactors for Fischer-Tropsch Synthesis. Ph.D. Dissertation, Swanson School of Engineering, University of Pittsburgh, Pittsburgh, USA, 2012. Anand V. Kulkarni, Shrikant V. Badgandi, Jyeshtharaj B. Joshi; Design of ring and spider type spargers for reactor: Experimental measurements and CFD simulation of flow and weeping; Chemical Engineering Research and Design 87 (2009): 1612 1630 Klier, K. (1982). "Methanol Synthesis." Advances in Catalysis, 31, 243-313

21 22 23 24 25 26

27

28

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29 Herman, R. G. (1991).New Trends in CO Activation, L. Guczi, ed., Elsevier, Amsterdam,281285 30 Adsorbent Evaluation for Removal of Catalyst Poisons From Synthesis Gas,Air Products and Chemicals,Sept 1990. 31 C. Maretto, R. Krishna; Design and optimisation of multi-stage bubble column slurry reactor for Fischer Tropsch synthesis; Catalysis Today 66 (2001): 241-248 32 Bubble column reactors, Nigar Kantarcia, Fahir Borakb, Kutlu O. Ulgen, Oct, 2004. 33 Vetkav R. Parameswaran, Makarand R. Gogate, Byung Gwon Lee & Sunggyu Lee, Mass Transfer in Liquid Phase Methanol Synthesis Process, Fuel Science and Technology International (2007) 34 Coulson and Richardson particle technology and separation processes 35 Hydrodynamic simulation of cyclone separators by Utikar, R., Darmawan, N., Tade, M., Li, Q, Evans, G.,Glenny, M. and Pareek, V. 36 The sizing and selection of hydrocyclones by Richard A.Arteburn 37 Behkish, A., Hydrodynamic and Mass Transfer Parameters in Large-Scale Slurry Bubble Column Reactors. Ph.D. Dissertation, University of Pittsburgh, Pittsburgh, USA, 2004 38 Chengzhi Tang, Theodore J. Heindel; Time-dependent gas holdup variation in an airwater bubble column. Chemical Engineering Science 59 (2004) 623 632 39 Chemical Engineering Design Volume 6 by RK Sinnott 40 Viscosity calculater http://www.kayelaby.npl.co.uk/general_physics/2_2/2_2_3.html 41 Cyclone design equations and formulae http://www.ajdesigner.com/phpcyclone/cyclone_equation_pressure_drop.php 42 Environmental Engineering by Ruth F. Weiner http://books.google.co.in/books?id=xZjkd3W0iSMC&pg=PA392&lpg=PA392&dq=typical+valu es+of+proportionality+factor+for+cyclones&source=bl&ots=_xgrzELqWb&sig=6lnDXu7hCxG90AqyOdaTRXBPSI&hl=en&sa=X&ei=fBRtUcPOGsjOrQfaroGADw&ved=0CDAQ6A EwAA#v=onepage&q=typical%20values%20of%20proportionality%20factor%20for%20cyclon es&f=false 43 R. Krishna, A Scale-up Strategy for a Commercial Scale Bubble Column Slurry Reactor for Fischer-Tropsch Synthesis. Oil & Gas Science and Technology Rev. IFP, Vol. 55 (2000), No. 4, pp. 359-393 44 Scaleup of Slurry Bubble Column Reactor for fischer troph,Laurent Sehabiague,2003. 45 Compressor sizing http://trukare.com/document_library/Blackmer/Compressors/CompSelectionandSizing.pdf 46 http://www.psgdover.com/en/wilden/tech-info/diaphgrams/selecting-a-diaphragm 47 http://panmeridiantubular.com/pipeglossary.html 48 Specific heat capacity data: http://www.engineeringtoolbox.com/ 49 Shell and tube exchanger design: http://www.engr.iupui.edu/me/courses/shellandtube 50 L.B. Evans, A. Mulet, A.B. Corripio, and K.S. Chretien, Costs of pressure vessels, storage tanks, centrifugal pumps, motors, distillation and absorption towers, in Ref. 2, pp. 140-146, 177-183. 51 Optimized particle distribution for slurry bubble column reactors, Patent No - US 7183327 B2

80

Chapter 3: Methyl Acetate Production

High-purity methyl acetate is used in large amounts as an intermediate in the manufacture of a variety of polyesters such as photographic film base and cellulose acetate. A major use of methyl acetate is as a volatile low toxicity solvent in glues, paints, and nail polish removers. Acetic anhydride is also used in the production of acetic anhydride through carbonylation. The two most common methods for chemically manufacturing methyl acetate are Carbonylation of methanol Esterification reaction between methanol and acetic acid to produce methyl acetate and water. We chose the esterification process mainly because it can be implemented through a reactive distillation scheme which offers several advantages over the conventional processes for the carbonylation of methanol or conventional esterification. Conventional processes use one or more liquid-phase reactors with large excess of one reactant in order to achieve high conversions of the other. A typical flowsheet of a conventional process is shown where the reaction section is followed by eight distillation columns, one liquidliquid extractor and a decanter. This process requires a large capital investment, high energy costs and a large inventory of solvents.

F Figure 37: Conventional processing schemes

for methyl acetate manufacture

Figure 38: The Eastman reactive distillation process

for carrying out the esterification reaction, consisting of one reactor followed by nine distillation columns.

In the RD process for methyl acetate, invented by Eastman Chemical Company (Agreda, Partin, & Heise, 1990; Siirola, 1996), the entire process is carried out in a single column as shown in Fig. 4. In this single column high-purity methyl acetate is made with no additional purification steps and with no unconverted reactant streams to be recovered. By flashing off the methyl acetate from the reaction mixture, conversion is increased without using excess of one of the reactants.

81

The reactive column has stoichiometrically balanced feeds and is designed so that the lighter reactant MeOH is fed at the bottom section and the heavier acetic acid is fed at the top. The column consists of three sections. The reaction takes place predominantly in the middle section, shaded grey below the point of sulphuric acid injection. The bottom section, serves to strip off the MeOH from water and return it to the reaction zone. The vapours leaving the reactive section consists of the MeOAcMeOH azeotrope which is broken in the rectifying section by addition of AcOH which acts as entrainer. The RD column represents an entire chemical plant and costs one-fifth of the capital investment of the conventional process and consumes only one-fifth of the energy.

Simulation on Aspen Hysys

Simulation of Reactive Distillation column was performed assuming chemical and phase equilibrium in reactive trays and for the rest of the non-reactive trays phase equilibrium was assumed. We changed the number of reactive trays, stripping trays and rectifying trays to get maximum possible conversion and high conc. of methyl acetate. Most of them time the simulation did not converge. The result shown below is after many iterations and the maximum conversion we got. We also changed the distillate rate to get high conc. of methyl acetate.

Figure 39 Process Flow Diagram Table 40 Design Parameters: No. Of Trays in Stripping Section No. Of Trays in Reactive Section No. Of Trays in Rectifying section Distillate rate Reflux Ratio 13

18

59.0287 kgmol/hr 1.699 82

Pressure at Condenser Pressure at re- Boiler Feed tray for Methanol Feed tray for acetic acid Total No. of Trays

90kPa

97kPa 13th from Bottom

31st from bottom

35

Results Obtained:

Figure 40 Composition at different trays

Figure 41 Temperature Profile

Figure 42 Vapor and Liquid flow rate at different Trays

Production of Methyl Acetate: Input:

Acetic Acid: 145.51 MTPD Methanol: 45.32 MTPD Output: Methyl Acetate: 173.50 MTPD

83

Material Balance: Table 41: Composition of Inlet stream Stream Methanol Acetic Acid 0.99 0.95 Concentration Flow Rate(kgmol/hr) 58.75 61.22

Table 42: Composition of Outlet Stream Stream Conc. Flow Rate (kgmol/hr) Acetic Acid 0.0001 0.0172 Methyl Acetate 0.9524 0.0145 Water

Methanol

Distillate Bottoms

0.0001 0.0173

0.0475 0.9509

59.0287 60.9413

Conversion= Moles of limiting reactant reacted/ Moles of limiting reactant In our case, Equi-molar feed is given to reactor and there is only one reaction that is taking place. So, % Conversion = Moles of Methyl Acetate produced/Moles of Methanol * 100 = (59.0287*.9524 + 60.9413*0.0145)/ (58.75*.99) * 100 = (56.2172 + 0.8862)/58.16 * 100 = 98.18 % Mole balance of methanol: Methanol Inflow = methanol reacted + Methanol Unreacted 58.16 = 57.1034 + 59.0287*0.0001 + 60.9413*0.0173 58.16=58.16

Feed Preparation and Storage

Storage
Guidelines for designing, fabricating, constructing, repairing, and safeguarding above-ground methanol storage tanks is essentially the same as that for liquid transportation fuels such as ethanol and gasoline, and flammable liquid feed stocks such as benzene, acetone, and toluene. One important consideration is flammability range. Because the upper flammability limit of methanol is 36 percent by volume (vol%) compared to that of gasoline which is 6-7 vol%, methanol vapor can ignite and burn inside tank vapor space. Methanol tanks can be constructed of either carbon steel or 300 series austenitic stainless steel [7]

84

Fig. 43 Methanol storage tank Acetic acid is a corrosive and flammable and thus certain precautions are necessary if it is to be stored and handled safely. Tanks constructed from the following materials are suitable for storing acetic acid. PVC or polypropylene ball valves can be used for acetic acid.

Pump Design
We have been given the flow rates of methanol and acetic acid by SG2 and SG3. The height to which the feed needs to be pumped was determined by the location of feed tray in the reactive distillation column. It was found to be the 13th and the 31st tray for methanol and acetic acid respectively. The length of the piping system for both methanol and acetic acid was assumed to be 200 ft which included provision for pipe length from storage to pump, pump to heat exchanger and then to the column. Leeway was given for elbows, joints and other points where pipe was unnecessarily lengthened.

Table 43: Flow Rates

Flow rate (kmol/hr) Temperature (oC) Density (kg/m3) [1] 770.12 Vapor Pressure (kPa) [1] 56.2 Height (ft)

Methanol (99%) Acetic Acid (95%)

58.75

54

40

61.22

86.67

989.36

34.6

76

Pipe Selection
The material used for the pipes was steel due to its availability and strength. Commercial stainless steel was used for both methanol and acetic acid because they can attack and corrode [2] carbon steel. Stainless steel has higher capital cost than carbon steel, but offers the advantage of lower life cycle maintenance cost. The pipe diameters [3] were chosen so as to obtain reasonable flow velocities to reduce pumping power required. 85

Table 44: Pipe Diameter Pipe Outer Diameter (inches) 2.5 3 Schedule No. 80 80 Velocity (ft/s) .81 .79

Calculation of Total Dynamic Head

Here z2 was neglected as pump was assumed to be on the ground level. v22was neglected because the feed was coming from a storage tank.P1andP2 were the same, i.e., atmospheric pressure. The Darcy-Weisbach Equation was used to calculate head loss .

Here the was determined from the Colebrook Equation

The absolute roughness for both the pipes was found to be 0.00015. [4]

Table 45
z (ft) Methanol Acetic Acid 40 76 v (ft/s) 0.81 0.79 hf (in) 3.82 1.85 h (ft) 40.42 76.16 hH20(ft) 31.13 75.34 P (psi) 147.48 357.00

Determination of Pump Characteristics

The pump characteristics were determined from a characteristic curve, usually supplied by the manufacturer Table 46
Flowrate (m /s) .0073 .0113
3

hH20(m) 9.4 22.6

86

Fig. 44: relation between total head and capacity

Calculation of NPSH

Table 47 NPSHa Impeller Dia. (mm) Methanol Acetic Acid 90 120 Power Supplied (kW) 0.8 3 Efficiency (%) NPSHa(in)

50 68

40.56 87.05

Thus, we have obtained all important parameters that define a pump. Also, we need to check whether the value of NPSHa obtained is greater than the NPSHr supplied by the manufacturer of the pump to ensure stable operation without cavitation.

Costing
A preliminary analysis of commercially available pumps [6] gives a rough cost of $ 20-100 per set for bulk orders of over 500. This is a stainless steel, single stage, self priming pump.

Design of a Shell and Tube Heat Exchanger

Shell and tube heat exchanger consists of a shell with a bundle of tubes inside it. One fluid runs through the tubes, and another fluid flows over the tubes (through the shell) to transfer heat between the two fluids. The principal components of an STHE are: shell, shell cover, 87

tubes, channel, channel cover, tube sheet, baffles, and nozzles. The Standards of the Tubular Exchanger Manufacturers Association (TEMA) describe these various components in detail. Classification based on construction: Fixed tube sheet: - A fixed-tube sheet heat exchanger has straight tubes that are secured at both ends to tube sheets welded to the shell. The principal advantage of the fixed tube sheet construction is its low cost because of its simple construction. In the event of a large differential temperature between the tubes and the shell, the tube sheets will be unable to absorb the differential stress, thereby making it necessary to incorporate an expansion joint. This takes away the advantage of low cost to a significant extent. U-tube: - As the name implies, the tubes of a U-tube heat exchanger (Figure 3) are bent in the shape of a U. There is only one tube sheet in a U Tube heat exchanger. However, the lower cost for the single tube sheet is offset by the additional costs incurred for the bending of the tubes and the somewhat larger shell diameter (due to the minimum Ubend radius), making the cost of a U-tube heat exchanger comparable to that of a fixed tube sheet exchanger. Floating head: - The floating-head heat exchanger is the most versatile type of STHE, and also the costliest. In this design, one tube sheet is fixed relative to the shell, and the other is free to float within the shell. This permits free expansion of the tube bundle, as well as cleaning of both the insides and outsides of the tubes. Thus, floating-head STHEs can be used for services where both the shell side and the tube side fluids are dirty making this the standard in petroleum industry. Classification based on service Basically, a service may be single phase (such as the cooling or heating of a liquid or gas) or two-phase (such as condensing or vaporizing). Since there are two sides to an STHE, this can lead to several combinations of services. Broadly, services can be classified as follows: single-phase (both shell side and tube side); condensing (one side condensing and the other single-phase); vaporizing (one side vaporizing and the other side single-phase); and Condensing/vaporizing (one side condensing and the other side vaporizing). Design Data The data that must be furnished before design can begin: 1. Flow rates of both streams. 2. Inlet and outlet temperatures of both streams. 3. Operating pressure of both streams. This is required for gases, especially if the gas density is not furnished; it is not really necessary for liquids, as their properties do not vary with pressure. 4. Allowable pressure drop for both streams. This is a very important parameter for heat exchanger design. Generally, for liquids, a value of 0.50.7 kg/cm2 is permitted per shell. A higher pressure drop is usually warranted for viscous liquids, especially in the tube side. For gases, the allowed value is generally 0.050.2 kg/cm2, with 0.1 kg/cm2 being typical. 5. Fouling resistance for both streams. If this is not furnished, the designer should adopt values specified in the TEMA standards or based on past experience. 6. Physical properties of both streams. These include viscosity, thermal conductivity, density, and specific heat, preferably at both inlet and outlet temperatures. Viscosity data 88

must be supplied at inlet and outlet temperatures, especially for liquids, since the variation with temperature may be considerable and is irregular (neither linear nor log-log). 7. Heat duty. The duty specified should be consistent for both the shell side and the tube side. 8. Type of heat exchanger. If not furnished, the designer can choose this based upon the characteristics of the various types of construction described earlier. In fact, the designer is normally in a better position than the process engineer to do this. DESIGN FLOW RATES:- Methanol- 4100 lb/hr, Acetic Acid- 7700 lb/hr INLET and OUTLET Temperatures:- Methanol- Ti- 129.2 F, To- 167 F Tavg= 148.1 F Acetic Acid- ti- 188 F, to- 167 F tavg= 177.5 F 2 0 FOULING FACTOR:- 0.002 (hr)(ft )( F)/Btu combined for both streams (Taken from TEMA standards) VISCOSITY:- Methanol- 0.34 cp and Acetic Acid- 0.55 cp at average temperatures of flow streams. SPECIFIC HEAT CAPACITY:- Methanol- 0.68 Btu/(lb)(F), Acetic Acid- 0.65 Btu/(lb)(F) Heat Duty:Q= Wcp(m)T(m)= 4100*0.68*(167-129.2)= 1,05,105 Btu/hr Mean Temperature Difference Calculation:Table 48: Fluid Temperatures Hot Fluid 188 167 21 High Temperature Low Temperature Difference

Cold Fluid 167 129.2 37.8

Difference 21 37.8 16.8

LMTD= (t2-t1)/ln(t2/t1) = (37.8-21)/ln(37.8/21)= 28.58 F R= 21/37.8= 0.55 S= 37.8/58.8= 0.64 This gives the correction factor, FT= 0.9 Therefore, t= 25.72 F Exchanger:Shell side Tube side [10] ID(Di)= 23.25 in Length of tubes(L)= 16 ft Baffle space(B) = 0.4(Di) = 9.3 in OD, BWG, Pitch(PT)= 1in, 14 BWG, 1.25 in Passes= 1 Passes= 4, Flow area per tube(at)= 0.546 in2 Assumption:-Now, for organic compounds like methanol and acetic acid the overall heat transfer coefficient fall in the range 20-50 Btu/(hr)(ft2)(F). So assuming a value of UD= 35 Btu/(hr)(ft2)(F). [9]

89

Now, Q= UAt A= Q/(Ut) A= 116 ft2 Number of Tubes, NT= A/(doL)= 116*12/(3.14*1*16)= 28 tubes Acetic acid is flown in tube side as it is more corrosive and methanol is flown in the shell side. Tube Side Calculation:Cross Flow area, at= NT*at/(144*no.of passes)= 28*0.456/(144*4)= 0.026 ft2 Mass velocity(Gt)= W a/at= 7700/0.26= 296153.84 lb/(hr)(ft2) = 1.33 lb/(ft)(hr), D= 0.07 ft Re= DGt/= 15587.04 & L/D= 228.57 Using the above data, jH= 45 [11] At tavg = 177.5 F, CP= 0.65 Btu/(lb)(F) and k= 0.106 Btu/(hr)(ft2)(F)/(ft) Therefore, (cP/k)1/3= 2.01 hi= jH(k/D)(cP/k)1/3 hi= 45*(0.106/0.07)(2.01) hi/= 137 hio/= hi/*(ID/OD)= 137*(0.834/1)= 114.25 hio/= 114.25 Shell Side Calculation:Flow area, as= Di*CB/144PT aS= 0.30 ft2 Mass velocity, GS= Wm/aS= 4100/0.3= 13666.67 lb/hr(ft2) De= 0.0825 ft m= 0.82 lb/(ft)(hr) Re= GSDe/m= 2375 JH= 24 [11] At T = 148.1 F, cP= 0.68 Btu/(lb)(F), k= 0.099 Btu/(hr)(ft2)(F)/(ft) (cPm/k)1/3= 1.78 ho/= jH(k/De)(cPm/k)1/3 ho/= 51.26 Tube wall Temperature:Tw= Tavg+ (ho/)/( hi/+ ho/)(tavg-Tavg) Tw= 157.5 F For shell side, At Tw= 157.5 F, w= 0.75 lb/(ft)(hr) [8] = (/w)0.14= 1.01 ho= 51.77 Btu/(hr)(ft2)(F) For tube side, w= 1.57 lb/(ft)(hr) = (/w)0.14= 0.97 hio= 114.25*0.97= 110.82 Btu/(hr)(ft2)(F) Clean Overall Coefficient:Uc= (110.82*51.77)/(110.82+51.77) 90

[8]

Uc = 35.29 Btu/(hr)(ft2)(F) Given Rd= 0.002 (hr)(ft2)(0F)/Btu Rd= (Uc-Ud)/(Uc*Ud) Therefore, Overall Heat Transfer Coefficient Ud= 32.96 Btu/(hr)(ft2)(F) It can be clearly seen that assumed values and calculated value of Ud are very close, hence our assumption was correct. Pressure Drop:Shell side, Re= GSDe/m= 2375 f= 0.0025ft2/in2 s= 0.79 D= 23.25/12= 1.94 ft No. of crosses, N+1= 12L/B= 21 P= fGs2D(N+1)/(5.22*1010*Des ) P= 5.5 x 10-3 psi Tube side, Re= 15587.04 f= 0.00025 ft2/in2 s= 1.05 P= fGt2Ln/(5.22*1010*D*s*) Pt= 0.37 psi One velocity head= 0.005 Pr= (4n/s)(V2/2g)= 0.076 psi PT= Pt+Pr = 0.37+ 0.076 PT= 0.446 psi Allowable pressure drop= 1 psi.

[11]

[11]

[8]

Table 49. Overall Heat Transfer Coefficient 91

Fig 45. LMTD Correction Factor

Fig 46. Tube side Heat Transfer factor 92

Fig 47. Shell Side Heat Transfer Factor

Tower Design
Calculation for reactive part of distillation column
Kinetics of Reaction
Methyl acetate (MeOAc) is made by the liquid-phase reaction of acetic acid (AcOH) and methanol (MeOH) catalyzed by an acid ion-exchange resin in the temperature range of 313325 K and at a pressure of 1 atm.The reaction is: MeOH + AcOH <=> MeOAc + H2O A new activity-based model that utilized the Langmuir-Hinshelwood Hougen-Watson (LHHW) isotherm was developed recently [1]. The new reaction rate was able to predict the experimental data very well.The reaction rate expression and constants are:

rMeOAc = {k1(HOAcMeOH - MeOAcH2O/keq)}/{(1+KHOAcHOAc + KMeOHMeOH + KMeOAcMeOAc +KH2OH2O)}

Mcat K1 = mass of catalyst = activity coeff = 6.942 X 10-9 exp (-6287.7/T) = 64.56Kmole/Kgcathr at T = 340k 93

Keq = 2.32exp(782.98/T) = 23.2 at T = 340 k KAcOH = 3.18 KMeOH = 4.95 KMeOAc = 0.82 KH2O = 10.5 Table 50 Feed Composition Flow rate (Kmol/ hr) Conc (mol fraction ) Volum e flowrat e (m3/hr) 2.34 Density (Kg/m3 )

Methan 58.75 ol Acetic Acid Total 61.25

0.99

800

0.95

3.38

1050

120

5.72

CALCULATION OF ACTIVITY COEFFICIENT[13]:

Acetic Acid-component 1 Methanol- component 2 Methyl Acetate-component 3 Water- component 4 Table 51:Specific volume of Components Specific volume in cm3/mole Acetic Acid Methanol Methyl Acetate Water 57.54 44.44 79.84 18.07

Table 52 :WILSON PARAMETERS: a11=0 a21= 547.32 48 a22=0 a31= 696.50 31 a32= 31.193 a41= 658.02 66 a42=46 9.5509 94

a12=25 35.201

9 a13=11 23.144 4 a14=23 7.5248 a23=81 3.1843

2 a33=0 a43=19 18.232

a24=10 7.3832

a34=64 5.7225

a44=0

where aij is interaction energy in Cal/mol ij- = Vj/Viexp(-Aij/RT) 12 = (V1/V2) exp (-a12/RT) =(57.54/44.44) exp (-2535.2019/(0.08206*329.15)) =2.2319*10-41 Table 53 11=1 12=2.2* 10^-41 22=1 13=6.3* 10^-19 23=4.6* 10^-14 33=1 14=4.8* 10^-4 24=4.6* 10^-2 34=1.1* 10^-10 44=1

21=5.0* 10^8

31=2.01 32=5.7 5*10^11 41=8.2* 10^-12 42=1.1* 10^-8

43= 3* 10^-27

lni = 1 ln { ( mj=1 ijxj) - mj=1(jixj/mk=1(kixk)} ln a1 = 1- ln(0.43*1 + 0.02*2.2* 10^-41+ 0.5 * 6.3 * 10^-19+ 0.05 *4.8* 10^-4) Table 54 Activity coefficients 1= 1.7 2 = 1.5 3 = 1.8 4 = 1.2

Calculating column diameter

The diameter of the colm can then be calculated from Wankat eouation: D(m) = 6.26 x 10-3[Vmax(moles/hour)]0.5 [T(k)Mw/P(Pa)]0.25 where Vmax = 2 Vfeed = 2*(58.75 + 61.2) = 240 Kmol/Hour T = 340 k Mw = (60+32+74+18)/4 = 46 P = 1atm = 101325 Pa
[12]

D =2.0m
95

Calculating Catalyst load[14]

Using packed bed equation catalyst load is calculated for 99% conversion. W =Fin (dx/-rMeOAc) Fin = 58.1 Kmol/hr By substituting r from eq (1) W obtained is W = 3600 Kg

Catalyst Packing Used[15]

In this case Suzler KATAPAK-S 250 Y packing is used. Katapak-S is a structured packing in which catalyst granules are embedded. In Katapak-S (S stands for Sandwich), the catalyst granules are layered between two corrugated sheets of metal wire gauze forming a sandwich structure. Individual sandwiches are assembled together to create open cross-flow channels. This structure combines the characteristic of a catalyst support with the wellknown advantages of an outstanding mass transfer device. The catalyst is embedded in the Katapak-S structure; therefore, it is not entrained with the products. Thus, catalyst loss is minimized and an expensive filter stage is not needed.

Fig. 48 KATAPAK S 250 Y catalyst Table 55 : KATAPAK-S Catalyst Height Diameter Wet catalyst content Catalyst(vol fraction) 0.21 m 0.162 m 3.2 Kg/m 0.25

Therefore Density of catalyst = 740 Kg/m3 Total volume of tray spacing required(Vo) = 3600/740 = 4.86 m3

96

Determination of number of Equilibrium stages by FenskeUnderwood-Gilliland method[17]

Nmin = ln [(xLK/xHK) D (xHK/ xLK) B] / ln (LK/HK) avg Where, xLK = Mole fraction of the light key xHK = Mole fraction of the heavy key Nmin = Minimum number of stages (LK/HK) avg = Average geometric relative volatility of the Light key to the Heavy key. (LK/HK) avg = [(LK/HK)D (LK/HK)B ](1/2)

Determination of average geometric relative volatility

Table 56 : saturation pressure Compo nent Psat(Pa ) MeOH AcOH MeOAc H2O

[18]

71206

10035

97551

16401

LK/HK = PLKS /PHKS In Distillate and Bottom product : LK/HK = PsatCH3COOCH3 / PsatH2O = 5.9 (LK/HK)avg =[( LK/HK)D(LK/HK) B]^(0.5) = (5.9*5.9)^0.5 = 5.9 In Feed stream : LK/HK = PsatCH3OH / PsatCH3COOH = 7.1 Number of Equilibrium stages Nmin = ln [ (LK/HK)D (LK/HK)B ] / ln (LK/HK)avg

(xLK)D = (xCH3COOCH3)D = 0.98 (xHK)D = (xH2O)D = 6.6*10^-3 (xLK)B = (xCH3COOCH3)B = 1.2*10^-5 (xHK)B = (xH2O)B = 0.98 (LK/HK)avg =5.9 Nmin = ln [ (0.985055) / (0.006690)D * (0.989881) / (0.000012)B ] / ln (5.9478) = 17.1 No. of Equilibrium stages = 18

97

Calculating Weir Height

Effective area (Aeff) for catalyst load on a sieve tray is 85% of total area. Therefore tray height is Aeff = *4/4*.85 =2.67 m2 V0 = Aeff*ht*(no. of trays) ht = 0.11 m

Tray Design of Stripping Section(Sieve trays)[19]

Liquid Flow Rate for this Section Ls = 95.8 kgmol/hr Liquid Flow Rate for this Section Gs = 34.8 kgmol/hr Avg. Molecular weight Liquid = .68*18 + .32*74 = 35.92 kg/kmol Avg. Molecular weight Vapor= 0.82*74+.18*18 = 63.92 kg/kmol Density of liquid l = 978.24 kg/m3 Density of Vapor G = 2.05 kg/m3

Vapor Rate, Q = 34.8*63.92/2.05 m3/hr = 1085/3600 m3/s = .30 m3/s Liquid Rate, q = 95.7*35.92/978.24 m3/hr = 3.514/3600 m3/s = 0.976 * 10-3 m3/s We assume Hole Diameter to be 4.5 mm. So, Plate thickness = 2 mm Therefore, Hole Area / Active Area = 0.907*(.0045)2/ (0.012)2 = 0.1275 Let tray spacing, 6 =0 .6 m (q/Q)(L /G )0.5 = (0.976 * 10-3 /0.3)( 978.24 / 2.05)0.5 = 0.071 = .0744*t + 0.01173 = 0.045 = 0.0304*t + 0.015 = 0.033 (, are calculated using table 6.2 in Mass transfer operation by Robert E. Treybal) Surface Tension, = 0.053 N/m CF = [* log(1/((q/Q)(L /G )0.5)) + ](/0.020)0.2 = 0.094

Superficial Velocity of Gas, VF = CF((L-G)/G)0.5 = 2.05 m/s at flooding V = 80% VF = .8 * 2.05 = 1.64 m/s An = Q/V = 0.30/1.64 = 0.18 m2 Weir Length, W=0.7*T So, Tray area used by downspout is 8.8% At = 0.18/(1-0.088) = 0.197 m2 Tower Diameter, T = (4(1.97)/)0.5 = 0.5 m 98

W = 0.7 * T = 0.35 m Ad = 0.088*0.197 = 0.01736 m2 q/W = 2.7*10-3 m3/(m*s)

Table 57[19]: General Conditions and dimensions for tray towers

99

Table 58: Sieve tray

REBOILERS AND CONDENSER REBOILER :

Reboilers are used with distillation columns to vaporise a fraction of the bottom product. Three principal types of reboiler are used: 1) Forced circulation, 2) Thermosyphon 3) Kettle type We use thermosyphon reboiler because it is most economical for most application.

100

Fig. 49 Thermosyphon Reboiler

The circulation rate, heat-transfer rate and pressure drop are all interrelated, and iterative design procedures must be used. The fluid will circulate at a rate at which the pressure losses in the system are just balanced by the available hydrostatic head.
A typical design procedure will include the following steps:

1. Calculate the vaporisation rate required. 2. Estimate the exchanger area; from an assumed value for the overall heattransfer coefficient. Decide the exchanger layout and piping dimensions. 3. Assume a value for the circulation rate through the exchanger. 4. Calculate the pressure drop in the inlet piping (single phase). 6. Divide the exchanger tube into sections and calculate the pressure drop section by section up the tube 7. Calculate the pressure drop in the outlet piping Compare the calculated pressure drop with the available differential head; which will depend on the vapour voidage, and hence the assumed circulation rate. If a satisfactory balance has been achieved, proceed6. not, return to step 3 and repeat the calculations with a new assumed circulation rate. 7. Calculate the heat-transfer coefficient and heat-transfer rate section-bysection up the tubes. . 8. Calculate the rate of vaporisation from the total heat-transfer rate, and compare with the value assumed in step 1. If the values are sufficiently close, proceed. If not, return to step 2 and repeat the calculations for a new design. 9. Check that the critical heat flux is not exceeded at any point up the tubes. 10. Repeat the complete procedure as necessary to optimise the design. Approximate methods can be used for preliminary designs. Fair gives a method in which the heat transfer and pressure drop in the tubes are based on the average of the inlet and outlet conditions.

101

The basis and limitations of the correlation are :[20] 1. Conventional designs: tube lengths 2.5 to 3.7 m (standard length 2.44 m), preferred diameter 25 mm (1 in.). 2. Liquid in the sump level with the top tube sheet. 3. Process side fouling coefficient 6000 W/m2

4. Heating medium steam, coefficient including fouling, 6000 W/m2 C. 5. Simple inlet and outlet piping. 6. For reduced temperatures greater than 0.8, use the limiting curve (that for aqueous solutions). 7. Minimum operating pressure 0.3 bar. 8. Inlet fluid should not be appreciably sub-cooled. Approximate design method for mixtures :[21] For mixtures, the simplified analysis used by Kern can be used to obtain an approximate estimate of the number of tubes required. The calculation procedure is Procedure 1. Determine the heat duty. 2. Estimate the heat transfer area, using the maximum allowable heat flux. Take as 39,700 W/m2 for vertical reboilers. 3. Choose the tube diameters and length. Calculate the number of tubes required. 4. Estimate the recirculation ratio, not less than 3. 5. Calculated the vapor flow rate leaving the reboiler for the duty and liquid heat of vaporisation. 6. Calculate the liquid flow rate leaving the reboiler for the vapor rate and recirculation ratio. 7. Estimate the two-phase pressure drop through the tubes, due to friction. 8. Estimate the static head in the tubes and the available head. 9. Compare the total estimated pressure drop and the available head. If the available head is greater by a sufficient amount to allow for the pressure drop through the inlet and outlet piping, proceed. If the available head is not sufficient, return to step 2, and increase the number of tubes. 10. Calculate the convective heat transfer coefficient using simple methods. Hermosyphon design correlation[22] Concentration of water and methanol are = 0.98 & 0.02 here concentration of methanol in the bottom is negligible compare to water so we neglect the methanol during our calculation. We have rate of vaporization = 30.56 kg mol/h The collom bottom pressure = 97 KPas and Temp = 80 C
102

Boiling point of water at 97KPas = 99 C Critical temperature of water = 374 C Latent heat = 2660 KJ/Kg specific heat = 4.2 KJ/Kg We assume that the steam is coming in the reboiler to evaporate bottom product at 100 C and 10 atm Pressure. Heat loss by steam = Heat gain by water which is at 80 C = 18*30.56(2260000+20*4200) = mass of (steam) * 2260000 Mass of water (staem) = 754 Kg/h Volume of the water used to generate steam = nRT/P (gas law) Volume = 128 Lt/h = 36 Lt/sec Steam saturation Temp = 179 C Mean overall T = (179-99) = 80 C Reduced Temp Tr = (99+273)/(374+273) = 0.6 From above figure design heat flux is approximately = 68000 W/m2 Heat load = 30.56*18*2260/3600 = 345 kW Area required = 345*1000/68000 = 5 m2 For general design consideration we use 2.44 m long tube with internal dia 25 mm and outer dia 30 mm. Area of one tube = 25* 10-3*2.44 = 0.192 m2 Number of tubes = 5/0.192 = 27 Bundle diameter Db = do(Nt/K1)1/n1 (empirical relation) Here we are using square pinch, so for 1.25 square pinch Db = 30(27/0.215)1/2.207 = 268 mm A fixed tube sheet will be used for a thermosyphon reboiler. shell diametrical clearance =11 mm Shell inside Dia = 268+11 = 279 mm Outlet pipe diameter, take area as equal to total tube cross-sectional area = 27*(25*10-3)2 /4 = 0.013 m2 Pipe Diameter = (0.013*4/)1/2 = 0.13 m =130 mm

CONDENSER
Four condenser configurations are possible: 1.Horizontal, with condensation in the shell, and the cooling medium in the tubes 2.Horizontal, with condensation in the tubes. 3.Vertical, with condensation in the shell. 4.Vertical, with condensation in the tubes. Horizontal shell side is the most commonly used types of condenser. The normal mechanism for heat transfer in commercial condensers is filmwise condensation. Dropwise condensation will give higher heat-transfer coefficients, but is unpredictable.In model of condensation laminar flow is assumed in the film, and heat transfer is assumed to take place entirely by conduction through the film. Condensation outside horizontal tubes :
103

Using Kerns method, the mean coefficient for a tube bundle is given by

where kL = condensate thermal conductivity, W/mC L = condensate density, kg/m3 v = vapour density, kg/m3 L = condensate viscosity, Ns/m2 g = gravitational acceleration, 9.81 m/s2 h = W c/LNt L = tube length Wc = total condensate flow Nt = total number of tubes in the bundle Nr = average number of tubes in a vertical tube row Calculation For Condensor: Reflux ratio = 1.699 = reflux/distillate Distillate = 59.028 Kg mol/h Total feel =(1+1.699) *distillate = 2.699*59.028 = 159.31 Kg mol/h Condenser operates at 90 KPas. The vapour will enter the condenser saturated at 53C and the condensation will be complete at 52.8C. Composition in vap = 0.952 methyl acetate, .0475 water, methanol and acetic acid are negligible. Avg mol wt. = 74*0.95+18*0.05 = 71g For further calculation we assume that there is only methyl acetate in vapor. Latent heat of methyl acetate = 410 KJ/Kg We again assume that Cooling water is available at 30C and the maximum temperature rise is10C.Plant standards require tubes of 20 mm o.d. 16.8 mm i.d.4.88 m long, of admiralty brass. The vapors are to be totally condensed and no subcooling is required. Heat transferred from vapor = 159.31*71*410/3600 = 1288.2 kW Flow rate of cooling water = 1288.2/10*4.2 = 30.67 Kg/sec Assume overall coefficient = 800 W/m2C Mean temperature difference: the condensation range is small and the change in saturation temperature will be linear, so the corrected logarithmic mean temperature difference can be used. R= 53-52.85/40-30 = 0.015 S= 40-30/53-10 = 0.23 For a horizontal exchanger, condensation in the shell, four tube passes. For one shell pass, four tube passes, Ft= 0.9 Log mean temp Tlm = (53-40)-(52.85-30)/ln(53-40/52.85-30) = 17.4 C Tm = Ft*Tlm = 0.9*17.4= 15.7C
104

Trail Area = 1288200/600*15.7 = 137 m2 Surface area of one tube = 20* 10 *4.88* = 0.305 m2 Number of tubes = 137/0.305 = 449 Use square pitch, Pt =1.25*20 mm = 25 mm Tube bundle diameter Db = 20(449/0.158)1/2.263 = 672 mm Number of tubes in centre row Nr = Db/Pt =672/25 = 27 Shell-side coefficient : Assume condensing coefficient of 1500 W/m2 C Mean Temp shell side = 53+52.85/2 = 52.92 Tube side = 30+40/2 = 35 let wall temp = T (52.92-T)*1500 = (52.92-35)*800 T= 44 C Mean temperature condensate = 44+52.92/2 = 48.5 C At 48.5 C L = 0.33 mPs/m2 L = 932 Kg/m3 kL = 0.10 W/m C vapour density at mean vapour temperature v = 90000*71/8.314*1000*(52.92+273) = 2.36 Kg/m3 h = W c/LNt = 11311/3600*4.88*449 = 1.43*10-3 Kg/s m Nr = 2*27/3 = 18 From above equation hc = 0.95*0.10(932(932-2.36)*9.81/0.33*10-3*1.43*10-3)1/3 18-1/6 = 1540 W/m2 C Close enough to assumed value of 1500 W/m2 C, so no correction to T needed. Tube-side coefficient : Tube cross-sectional area = /4(16.8*10-3)2 449/4 = 0.025 m2 Density of water at 35C = 993 kg/m3 Tube velocity = 30.67/993*0.025 = 1.23 m/s hi = 4200(1.35+0.02T)ut0.8/di0.2 where, hi = inside coefficient, for water, W/m2C, T = water temperature, C ut = water velocity, m/s, di = tube inside diameter, mm hi = 4200(1.35+0.02*35)*1.230.8/16.80.2 = 5780 W/m2 C Fouling factors -as neither fluid is heavily fouling, use 6000 W/m2 C for each side. kw =50 W/m C Overall coefficient : 1/U = 1/ho +1/hod + do ln(do/di)/2* kw + do/di * 1/hid + do/di * 1/hi where U = the overall coefficient based on the outside area of the tube, W/m2C, ho = outside fluid film coefficient, W/m2C, hi = inside fluid film coefficient, W/m2C,
105

-3

hod = outside dirt coefficient (fouling factor), W/m2C, hid = inside dirt coefficient, W/m2C kw = thermal conductivity of the tube wall material, W/m C, di = tube inside diameter, m do = tube outside diameter, m. 1/U = 1/1540+ 1/6000+ 20*10-3 ln(20/16.8)/2*50 +20/16.8*1/6000 + 20/16.8* 1/5780 = 1.255*10-3 U= 796 W/m2 C Close enough to estimate firm up design.

References[1] [2] Dortmund Database: http://www.ddbst.com/ Sepuldeva et. al, Repeated use of supported H3PW12O40 catalysts in the liquid phase esterification of acetic acid with butanol, Applied Catalysis A:General, 2005, 18-24 [3] McCabe, Smith, & Harriott, 7th ed., Appendix 3 [4] http://www.efunda.com/formulae/fluids/roughness.cfm [5] Coulson and Richardson, Chemical Engineering, 2nd Edition, 1973. [6] http://www.alibaba.com/products/centrifugal_pump_3kw/--------------119-2224.html [7] http://www.methanol.org/AtmosphericAboveGroundTankStorageMethanol-(1).pdf [8]. Kern, D.Q. , Process Heat Transfer, McGraw-Hill, New York, 1950. [9]. Chemical Engineering Design, Coulson & Richardson, Volume 6, Fourth Edition. [10]. Tubular Exchanger Manufacturers Association, Standards of the Tubular Exchanger Manufacturers Association, 7th ed., TEMA, New York (1988). [11] Perry, R.H., Green, D.W., Eds. Perrys Chemical Engineers Handbook, 7th Edition, McGraw-Hill, New York, 1997. [12]. P. C. Wankat, Equilibrium Staged Separations, PTR Prentice Hall, Englewood Cliffs [13]. Unit Operations in Chemical Engineering- Mccabe and Smith. [14]. Chemical Engineering (Vol. 6)- Coulson and Richardson [15]. Fluid dynamics in reactive distillation packing Katapak-S Chemical Engineering Science Volume 54, Issue 10, May 1999, Pages 13671374 http://www.sciencedirect.com/science/journal/00092509/54/10 [16]. W. Song, G. Venimadhavan, J. M. Manning, M. F. Malone, and M. F. Doherty, [17]. M. Gadalla, M. Jobson Shortcut Models for Retrofit Design of Distillation Columns Chemical Engineering Research and Design Volume 81, Issue 8, September 2003, Pages 971986 http://www.sciencedirect.com/science/journal/02638762 [18]. E.R. Gilliland (1940). Industrial Engineering Chemistry, Vol.32:1220 [19]. Mass Transfer Operations Robert E. Treybal [20]. Chemical Engineering, Volume 1, Sixth edition Fluid Flow, Heat Transfer and Mass Transfer J. M. Coulson and J. F. Richardson with J. R. Backhurst and J. H. Harker [21]. Unit Operations in Chemical Engineering- Mccabe and Smith [22]. BERGMAN, H. L. (1978a) Chem. Eng., NY 85 (June 19th) 99. Fired heaters Finding the basic design for your application

106

Chapter 4: Acetic Acid Production

Mass Balance (contributed by: Swarnim Raj and Anshul Bang) The plant is designed Production of 172 MTPD acetic acid. It requires an input of 103 MTPD of methanol (from subgroup 2) and 73.6 MTPD. Out of we are storing 85 MTPD of acetic acid for selling purposes. And the rest of acetic acid is sent subgroup 3 for production methyl acetate. Mass Balance on the reactor system was done using ASPENplus software. Presently demand of acetic acid is (World): 6.5 million tonnes per year (Mt/a) [1].In India presently there 20 companies producing acetic acid with installed capacity of 150,000 TPA[2]. The above number for production of acetic acid was decided on the basis of demand of acetic acid in India. We will be producing 15 % of total demand of acetic acid. Process Flow Diagram for Acetic Acid Production (contributed by: Swarnim Raj and Satyadeep Roat)

Fig 50. Process flow sheet for acetic acid production plant with help of aspen Plus Firstly Fresh methanol is split and fed to two countercurrent absorbers (B5 and B7). Here Methanol is contacted with the reactor off gas (primarily unconverted CO) in high-pressure absorber B7 and also with light gases generated and released downstream in low-pressure absorber B5. This absorption scheme maximizes the recovery of valuable methyl iodide that would otherwise exit the system with the vent gas, causing unnecessarily high chemical consumption and yield loss. The methanol feed streams (together with the recovered methyl iodide) exiting the absorbers are recombined, heated in B20, and then mixed with the effluent from the recycle surge drum to yield the combined liquid feed stream to carbonylation reactor. 107

Compressed, pure CO is introduced at the bottom of carbonylation reactor. The carbonylation reaction is carried out continuously at about 180C (356F) and 638 psig (42 atm). The heat of reaction is removed by passing the catalyst- liquid mixture through the reactor downcomer to generate low-pressure steam that supplies a significant portion of the plant energy requirements. Most of the unreacted CO and other gaseous by-products are separated from the liquid effluent in B28. The liquid effluent from b28 containing product acetic acid, is introduced to crude fractionating column B30 to recover the net acetic acid product, and to reject dissolved CO and light by-product gases into the combined lowpressure offgas line. The lighter liquids are phase-separated into aqueous and organic fractions in reflux drum , with 99% of the aqueous material (mostly water) returned to the reaction system and all of the organic liquid (mostly methyl iodide promoter and methyl acetate intermediate) recycled to the reactor. The recovered net acetic product is sent to downstream purification. The portion of liquid not vaporized is mixed with other recycle streams, and returned to the reactor for absorption and recovery of the reaction heat. The crude acetic acid is sent to the dehydration column B34 to remove most of the remaining water and residual organic materials. Excess water is purged from the system through column. The dried acetic acid is routed to refining column B35. The product is withdrawn as a side stream and sent to storage. The bottom effluent from column where heavy by-products (primarily propionic acid) are removed in the bottom draw off. Carbonylation Unit Centrifugal pump : (contributed by: Swarnim Raj) Centrifugal pump is used to transport methanol from storage tank to gas absorber

Fig 51: Schematic of SBCR auxiliarily setup Table: 59 Pump Design: Density of methanol Flow rate RPM 791.8 kg m-3 30 gpm , 1.8 kg/ sec 1900 108

Length of pipe Total frictional head loss Diameter of pipe(standard stainless steel) Friction factor Suction head loss Total dynamic head WHP BHP(with efficiency 0.75)

50 m 0.78 m of slurry 1.0 in. 0.0193 0.47 m of methanol 9.83 m = 32.25 feet of methanol 0.6 hp 0.8 hp

Adiabatic Pump: (contributed by: Anshul Bang) Adiabatic pump is used to increase the pressure of methanol coming from gas absorber so that it reaches the required pressure of 42 atm for reactor Data for methanol : Specific volume = 1262 / Thermal Expansion Coefficient( ) = 425 x Specific Heat capacity = 2.74 KJ/kg k Assuming Pump Efficiency = 75 % equations used for pump : = = ----------- (i) ------------ (ii) = ----------- (ii)

Using equation (i) (ii) and (iii) we get = 5.24kJ/kg = 6.98 kJ/kg, and temperature rise to be 2.5 0 c , So final temperature is 57.540 c and pressure is 42 atm out of adiabatic pump of 11 hp

Compressor Design (contributed by: Swarnim Raj) Compressors are intended to compress a substance in a gaseous state. In our process flow sheet we need compressor to compress the Carbon Monoxide coming from subgroup 1 from 1 atm, 1000 c to 42 atm, 1800 c. We are using reciprocating compressor as our flow rate is not too high but pressure requirement is comparable enough.

109

Advantages Simple design, easy to install Lower initial cost Large range of horsepower

Disadvantages Higher maintenance cost Many moving parts Potential for vibration problems

Special machines can reach extremely high pressure

Foundation may be required depending on size

Two stages models offer the highest Efficiency

Many are not designed to run at full Capacity

Table 60 : Advantages and Disadvantages of Reciprocating Compressors [3] Intercoolers are provided between stages on multistage machines. These heat exchangers remove the heat of compression from the gas and reduce its temperature to approximately the temperature existing at the compressor intake. Such cooling reduces the volume of gas going to the high-pressure cylinders, reduces the power required for compression, and keeps the temperature within safe operating limits.

Fig 52: - Reciprocating compressor interior view

110

Fig 53: - Working of Reciprocating compressor

Use of Multi stage compressor: [4] a. To limit the discharge temperature of each stage to acceptable levels from the standpoints of both compressor design restraints and the fouling tendency of the compressed gas. b. To reduce compressor stage" inlet temperatures thereby reducing the amount of work (head) required to achieve a given pressure ratio. c. Provide the condition for include intercooler between stages, that will help reduce horse power require for compression, and keeps the temperature within safe operating limits. Calculations:Using the iso entropic equation of states = CONSTANT Based on this calculating the power required by = = Power, KW q = volume of gas compressed, std m3/s, evaluated at 00 c and 760 mm hg T = inlet temperature using data for CO q = 0.024 m3/sec T= 1000 c Pa (inlet pressure) = 1 atm Pb (outlet pressure) = 42 atm Cp = 1.047 kJ/kg k, Cv = 0.72 kJ/kg k, =1.4541 Power comes out be 165.56 kw = 221 hp Efficiency of compressor = 80 % Stages calculations :[5]

111

Fig 54:- Stages required for compressor at each stage compressor is losing heat with the help cooling water.

Similarly, for temperature at each stage calculation :

Pa,Ta = Inlet Pressure, temperature respectively Pa,Tb = Exit Pressure,temperature respectively So at each stage temperature T1, T2, T3 are Shown in the Fig 1c. and respective temperature due to cooling of water T1*, T2*, T3* Temperature T1*, T2* , T3* are calculated using Iteration so that final temperature must be around 450 k required by reactor Mass flow rate of CO m(dot) = 2984.47 Kg/hr Heat load in each cooler = m*cp*dt = 2984.47* 1.042*[548.8-388.8] = 49,570.834 kJ/hr Total heat load = 3*49,570.834 = 148712.50 KJ/hr Water Requirement for intercoolers :Cp(water) = 4.2 KJ/Kg k Temperature rise in water (T) = 20 SO, m*cp*dt = 148712.50 m=148712.5020*4.2= 1770.38 Kg/hr 3.4 Reactor design (contributed by: Swarnim Raj and Anshul Bang) Slurry bubble column loop reactor: It consists of a gas bubbled through a slurry of organic liquid solvent (inert) carrying suspended catalyst particles of definite morphology (shape and size) in a co-current or counter-current manner leading to transfer of gaseous components from gas phase to bulk liquid phase via contacting interface and further to catalyst surface where it is selectively converted to desired products and re-released into the liquid phase. The unconsumed gas and liquid slurry containing the desired product (and by-products) are separated and collected at the outlet end of the contactor which are further subjected to separation and recycle operations.

112

Fig 55: - Slurry Bubble column Reactor

Description: ACETICA PROCESS adopts a bubble column loop reactor designed for effective usage of resin catalysts. This reactor is composed of a riser unit and a down-comer unit. As the carbon monoxide reactant gas is introduced and dispersed at the bottom of the riser unit, small bubbles are formed. Those bubbles efficiently contact and react with methanol and resin catalysts when they rise in the column. The bubble column loop reactor has the following features: High contact efficiency among the gas-liquid-solid three phases. Because there are no rotating elements, high air-tightness is achieved. Resin erosion can also be reduced. Reaction heat can be easily removed by installing a heat exchanger at the down comer unit, achieving a more precise control of reaction temperature. Reactor specifications: The Acetica process uses a bubble-column reactor (chosen for its excellent three-phase contacting) to minimize catalyst attrition and improve reactor flexibility. Methanol and CO are both introduced at the bottom of the reactor. The compressed CO is fed through a sparger ring to maximize distribution. The two feeds together with the recycle liquid (containing essentially acetic acid, water, methyl iodide, and methyl acetate) and catalyst flow up the reactor, where almost all of the CO is consumed in the carbonylation reaction. A moving impeller is not needed for mixing. The difference in density between the CO-rich riser and CO-depleted downcomer drives the circulation. Unreacted CO and other gaseous byproducts are vented from the top of the reactor. A portion of the reactor liquid effluent containing the acetic acid product is disengaged by gravity from the solids in the recycle slurry and sent to downstream purification. The remaining catalyst-liquid mixture is routed 113

through the reactor downcomer, cooled, and returned to the bottom of the reactor riser to absorb the large heat of reaction and maintain circulation. The downcomer liquid is cooled with boiler feedwater, and the steam obtained by recovery of reaction heat supplies a large portion of the plant energy requirements. Catalyst retention in the reactor is almost 100%. Reaction: CH3OH + CO --> CH3OOH 2CH3OH ----> CH3OCH3 + H2O Role of promoter CH3OH + CH3OOH --> CH3COOCH3 + H2O CH3OH+ HI --> CH3I + H2O Water gas shift reaction CO + H2O ----> CO + H2 CH3OH + H2 -----> CH4 + H2O (1) (2) (3) (4) (5) (6)

Modelling SBCR : The chemical equations presented are based on following mass balances: a) For gas phase (large bubbles) in plug flow (dispersion effects) b) For gas phase (small bubbles in well-mixed flow) in each section (TIS model) c) For slurry phase (liquid + suspended catalyst) in well-mixed flow d) For solid phase (suspended catalyst particles) in well-mixed flow

Design of SBCR: Properties and calculations: Reaction Kinetics: Rate law to be used in the SBCR design: Rate law to be used in the SBCR design:

here k = 158.8 x

exp (-72200 / RT )

/sec-mol

Assuming SBCR to behave as CSTR: Design equation of CSTR: W = FAo X / (-rA )exit

114

Mass Balance for reactor:

Fig 56: - Mass balance on slurry bubble column reactor Table 61: Specifications of reactor: FAo (molar flow rate of methanol) X (conversion of methanol) 132948 mol/hr 0.98

(-rmethanol )exit W (weight of catalyst in reactor) Bulk density of catalyst Volume of catalyst in reactor Volume of slurry in the reactor with s=0.3 Diameter of tank with (L/D=5) Length of tank Volume of tank

30.3 mol/ 1.225 kg 12410 kg /m3 9.87 x 3.29 x 2.57 m 13 m 68

115

Bubble specifications : = = = = 0.71 SF = 1 for (1) (1 + )

(large bubble velocity) (SF) (AF) (general) <0.125 Table 58 : bubble specification Large Bubble diameter 45 mm

(dense phase) (dense phase bubble velocity) (large bubble velocity) SF (scale correction factor ) AF (acceleration factor)

0.06 0.02 m/s 2.01 m/s 1 3 0.27 0.095

Gas Absorber (contributed by: Satyadeep Roat) Main purpose of a gas absorber to absorb methyl Iodide into methanol. This is done to maximize the recovery of methyl iodide that would otherwise exit the system. To achieve this methanol feed is mixed with the gases coming out from carbonylation reactor.

Fig 57: Material Balance For counter current flow absorber X1Lm1 + Y1Gm1 = X2Lm2 + Y2Gm2 116

Table 63 : Temperature and pressure condition Parameter Temperature Pressure Inlet 55oC 1atm Outlet 55 oC 1atm

Table 64: Composition of Gases entering the absorber Gases CO CO2 H2 CH4 HI CH3I Volume (g - mol) 3545 360 0 75 60 10940 fraction 0.153 0.016 0.000 0.003 0.003 0.471 % vol 15.27 1.55 0.00 0.32 0.26 47.12

Assumption made 1. As the gas and liquid streams flow through the absorber, their total mass does not change appreciably (i.e., Gm1 = Gm2 and Lm1 = Lm2)

Mole fraction of CH3I in gas phase

Y1 = 73% CH3I by volume = 0.73 mole fraction of CH3I Y2 = 90% reduction of CH3I from Inlet concentration = 10% of Y1 = 0.073

Mole Fraction of CH3I in the liquid leaving the absorber

X1 = Y1/H = 0.73/5.88 = 0.12

Minimum Liquid to Gas Ratio

Lm/Gm = (0.73 0.073) / (0.12-0) = 5.47 g mol of methanol / g-mol of gases Exhaust gas molar flow rate Gm = QG (1 g mol of air / 0.026 m3) Exhaust stream flow rate QG = 579 m3/sec (Assume) Gm = 62.08 g mol of air/sec (Lm/Gm)min = 5.47 Lm = Gm(5.47) (Gm)min = 24131 Kg/min (Lm)min = 24131 x 5.47 117

=132000 g mol of methanol/min = 132 kg mol of methanol/sec = 4253 kg/sec

Fig 58: Generalised flooding and pressure drop correlation [6] From the Graph = 0.12

G = 40.61 Kg/sec . m2 at flooding f = percent flooding velocity = 75% of flooding G opp = 0.75 G = 30.46 kg/sec .m

118

PACKED TOWER DIAMETER

Area A = G/Gopp = 62.08/30.46 = 2.03 m2 d = (4x2.03/3.14)1/2 d = 1.61 m

PACKED TOWER HEIGHT

Also Z = HTU*NTU Where Z = height of packing HTU = height of Transfer unit NTU = Number of Transfer unit Z =Hog * Nog

NOG = 3.306 HOG = 2.607 Z = NOG * HOG = 8.61 m of Packing height Parameter Tower Diameter Tower Height Value (m) 1.61m 8.61m Table 65: Dimension of Packed Tower

119

Purification Unit Crude Fractionating Column: (contributed by: Manish)

As the name suggests, the crude fractionating column breaks the product into different heavy and light fractions. In the chiyoda technology process it separates the mixture of acetic acid and water from the liquid effluent coming from the effluent column. It contains the net acetic acid, light by product gases and dissolved CO. The Fractionating Column recovers the net acetic acid product and reject dissolved CO and other light by product gases into the combined low pressure off gas line. This separation is achieved through extractive distillation.

Fig 59: Crude Fractionating Column Extractive Distillation: The feed coming from the effluent column contains mainly the heavy key component as acetic acid and the light key component as water. Acetic acid and water does not form an azeotropic mixture further the mixture has a low relative volatility of 1.03 at 118C, hence extractive distillation is used to separate them. In the extractive distillation the separating agents are not vaporized and thus the energy consumption is little. In the extractive distillation, the selection of a suitable solvent is fundamental to ensure an effective and economical design. The separating agent used is sulfolane, because of its high separating tendency as compared to other agents. It is evident that the interaction between acetic acid or water and these separating agents is mainly physical force including the van der Waals bonding and hydrogen bonding. Designing of Crude fractionating Column: The relative volatility of acetic acid and water is 1.03 which is quite low. As my system is non foaming and diameter calculated is larger than 0.67 m so I am going to use Tray column. Also as average temperature calculated for my distillation column is higher that is approximately equal to 98oC. So I prefer Tray column. Sieve trays are preferred in the column because of their low pressure drop, relatively low cost, lighter weight, easier to install. Further they can be operated with varying flow rates and maintenance cost is reduced due to easy cleaning passage. One has to take care of various operations while 120

designing since large flow rate can cause blowing, coning, raining, dumping, weeping and flooding. Component Feed Fraction xf 0.07 0.65 0.22 0.07 Bottom Fraction xb 0 0.99 0 0.01 Top Fraction xd 0.21 0.0005 0.62 0.17

Methyl Iodide Acetic Acid Methyl Acetate Water

Table 66: Composition for Fractionating column Number of Stages: The minimum no. of stages Nmin is obtained from Fenske equation which is, Nmin = LN[(xLK/xHK)D(xHK /xLK)B] LN (LK/HK) Average geometric relative volatility = 1.53 Nmin = 24 Minimum Reflux Ratio Rm: Using Underwood Equation Rm = 4.154 , Actual Reflux Ratio,R = 6.23 Theoretical Number of Plates: Gilliland related the number of equilibrium stages and the minimum reflux ratio and the no. of equilibrium stages with a plot that was transformed by Eduljee into the relation; N- (Nmin \N+1)=0.75[1-(R-Rmin/R+1)0.566] N= 39 Actual number of stages: Overall Tray Efficiency:

Eo = 56.60% No. of actual trays = 39/0.566 = 68 Location of feed Plate: The Kirk bride method is used to determine the ratio of trays above and below the feed point.

Number of Plates above the feed tray = ND = 47 Number of Plates below the feed tray = NB = 21 Determination of the Column Diameter: Flow Parameter: FLV = Liquid Vapor Factor = 0.056, Vnf = 1.67 m/sec Assume 90% of flooding then Vn=0.9Vnf actual vapor velocity, Vn=1.51 m/sec Net column area used in separation is 121

An = mv/Vn mv = 2.1184m3/sec Now, net area An = mv/Vn = 1.41m2 Assume that downcommer occupies 15% of cross sectional Area (Ac) of column Where, Ad = downcommer area thus: Ac = An + Ad Ac = An + 0.15(Ac) Ac=1.65 m2 So Diameter of Column Is Ac =(/4)D2 D = 1.45 meter = 5ft Liquid flow arrangement: Maximum liquid flow rate = 0.005 m3/sec So from Huand and Hodson figure cross flow single pass plate is selected . Plate Design: Column Diameter Dc= 1.45 m Column Cross-sectional Area(Ac)= 1.65 m2 Down comer area Ad = 0.15Ac = 0.25 m2 Net Area (An) = Ac - Ad =1.41 m2 Active area Aa=Ac-2Ad = 1.16 m2 Hole area Ah take 10% Aa = 0.1 1.16 =0.0462 m2 Weir length , Ad / Ac = 0.248 / 1.654 = 0.15 From downcomer area and weir length relation, Lw = 0.733 m Weir length should be 60 to 85% of column diameter which is satisfactory Take weir height, hw= 50 mm Hole diameter, dh= 5 mm Plate thickness = 5 mm Check Weeping:

Umin is the minimum design vapor velocity In order to have K2 value from weep point correlation how=750[(Lm/lw*)2/3] Maximum liquid rate Lm= 4.7 kg/sec Minimum Liquid Rate At 70% turn down ratio = 3.3Kg/sec At Maximum rate ( how)= 20 mm Liquid At Minimum rate (how) = 16 mm Liquid hw + how = 50 + 16 = 66 mm Liquid from weep point correlation K2 = 30.50 So, U (min) = 9 m/sec Now maximum volumetric flow rate (vapors) Base = 2.12 m3/sec, Top = 1.14 m3/sec At 70% turn down ratio Actual minimum vapor velocity =minimum vapor rate / Ah= 12.81 m/sec 122

So minimum vapor rate will be well above the weep point. Plate Pressure Drop: Dry Plate Drop: Max. Vapor velocity through holes (Uh) = Maximum Volumetric Flow Rate / Hole Area = 18.30 m/sec Perforated area Ap (active area) =1.16 m2 Ah/Ap = 0.100 From discharge coefficient, sieve plates. plate thickness/hole diameter = 1.00 We get, Co = 0.84 hd= 48 mm Liquid

Residual Head (hr):hr = (12.5*103 / L)= 13.3 mm Liquid So, Total pressure drop = 131.35 mm liquid Down comer Liquid Backup: Caused by Pressure Drop over the plate and resistance to flow in the downcomer it self. Downcomer back up: hb = (hw+ how) + ht + hdc Aap is the clearance area under the downcomer, m2 Aap =hapLw Where hap the height of bottom edge of apron above the plate. hap = hw (5 to 10 mm) hap = 40 mm so, Area under apron Aap = 0.05 m2 As this is less than area of downcomer Ad so using Aap values in above formula. So, hdc = 1.95 mm As a result, hb = 203.24 mm = 0.203 m hb < (Tray spacing + weir height) 0.20 < 0.25 So tray spacing is acceptable The main resistance to flow in downcomer will be caused by constriction in the downcomer outlet, and head loss in the down comer. Check Residence Time: Sufficient residence time should be allowed in the downcomer for the entrained vapors to disengage from liquid stream to prevent aerated liquid being carried under the downcomer. tr =Ad hbc L/L(max) tr = 10 sec It should be > 3 sec. so, result is satisfactory Check Entrainment: Liquid flow factor FLV = 0.056 (un) actual velocity = (maximum volumetric flow rate at base Vm / net area An) (un) actual velocity = 1.51 m/sec Velocity at flooding condition Uf = 1.67 m/sec So Percent flooding =un/ uf = 0.90 = 90% From entrainment correlation for sieve plates 123

Fractional entrainment () = 0.0750 Well below the upper limit of () which is 0.1 Below this the effect of entrainment on efficiency is small No of Holes: Area of 1 Hole = (/4) Dhole2 = 0.00002 m2 Area of N Holes = 0.1158 m2 So, Number of Holes = 5900 Height of column: Hc= (Nact-1) Hs+ H+ plates thickness No. of plates = 68, Tray spacing Hs = 0.50 m , H=1 m, Hc = 35 meters Design data: No. of tray= 68 Pressure = 101.325 Kpa Height of column = 35 m Diameter of column=1.45m Hole size = 5 mm Pressure drop per tray=1.2 Kpa Tray thickness = 5 mm Active holes = 5900 Weir height = 50 mm Weir length = 1 m Reflux ratio = 6.23 Tray spacing =0.5 m Active area = 1.16 m2 Percent Flooding =90% Entrainment = 0.075

Further Processing: After the product acetic acid is fractionated, it is further sent to refining column for removal of water and final purification of acetic acid.

Refining Column (contributed by: Sateesh Meena)

Mass Balance Total Product Flow Rate = 2Kg/sec Table 67: Composition for Refining Column Component Acetic Acid Propionic Acid Feed Flow Rate 2.29 Kg/sec Acetic Acid Propionic Acid Bottom Side Flow Rate 0.29 kg/sec Acetic Acid Propionic Acid 0.25 0.04 4.5 10-3 4.42 10-4 86.45 13.54 124 2.22 0.07 3.69 10-2 9.49 10-4 97.75 2.25 Mass Flow Rate(Kg/sec) 1.97 0.03 Mole Flow Rate(K mole/sec) 3.28 10-2 4.21 10-4 Mole Friction Percentage 98.73 1.27

XB=0.86 Temperature =400 K

XF=0.98

XD=0.99

pressure=100 Kpa

Average molecular weight of distillate is 60.175 Kg/Kmole & volume of 1 kmol at 400 K & 100 Kpa is come out to be 22.69 m3 so density of vapor is 1.81Kg/m3

=1.01 m3/sec Liquid density=725.175 Kg/m3

=4.21 10-4 m3/sec Column Material :Material of column depend on feed property and temperature of column Stainless steel Table 68: Dimension for column material of Refining column Hole Diameter d0 Plate thickness l (0.65* d0) Pitch P (d0/0.33) Tray spacing 3mm 1.95 mm 9.09mm 0.50 m 98.79 10-3

Tower Design

Critical Temperature:- The temperature at which surface tension of the subsistence is zero. T2 =400K, T1 where surface tension is known, Tc =573 for acetic acid

=2.019 m.sec

=75.42 10-3 125

=16.25 dynes/cm

Value come out be 0.00834 its less than 0.1 so use 0.1 =0.0744 t + 0.01173 & =0.0304 t + 0.015 because Ao/Aa <0.1than both and are multiply by (5 (Ao/Aa) + 0.5) and value come out 48.60 10-3 & 30.01 10-3 respectively. Because acetic acid is a foaming compound taking actual velocity is 73% of flooding velocity. V=1.478 m/s Table 69: Different Area of Tray 0.68 0.711 m2 95.1510-2 m Weir length W =0.55T Downspout area Liquid rate /weir length (q/W) 52.33 10-2 m 2.76 m2 8.04 10-4 m2/m-s 53.59 10-2 m2 for perforated sheet

Tentatively choose a weir length W=0.55 T & downspout is 3.877 % Weir Crest h1 and weir height hw

When taking W= W eff

h1=5.78 10-3 m

Weff = 0.9656 W again

=5.89 10-3 m Repeat with new value of h1 0.012 m

W eff = 0.9649 W so h1=58.94 10-4 m Set weir height hw=

126

Dry Pressure Drop Fanning friction factor f depend on Reynolds number and relative roughness of column Table 70: Dry Pressure drop and different factors 4.62 10-2 m

1.2139 68.32 10-3 m2 Velocity through orifice V0 =Q/A0 14.79 m/sec 191121.35

Viscosity Fanning friction factor Hydraulic Head HL

0.42 cp 0.0262

Table 71: Hydraulic Head and its factors 8.25 10-3 m

73.74 10-3 m

Gas velocity based on active area Va= Q/Aa Residual Pressure Drop

1.8854 m/sec

=8.85 10-4 m Total gas pressure drop = 5.938 10-2 m Tray pressure drop =0.00256 psi or 17.650547 Pa Pressure loss at liquid entrance

=0.56 10-2 m Ada =.31 10-2 m Backup in downspout = 6.4 10-2 m Checking on flooding 127

=81.89 10-2 m Because h1 + hw+ h3 < t/2 so my assuming tray spacing (0.50) its perfectly satisfied Weeping Velocity

Weeping velocity = 0.068 m/sec Weir set = 0.418 T =0.3978 Z=2 Times weir set = 79.56 10-2 m Weeping will not occur till velocity through orifice reduce to weeping velocity Entrainment Actual velocity/flooding velocity =0.73 = 0.73 E=0.0035 from graph (mass transfer operations. R. treybal..fig no. 6.17) Tower Height:Minimum reflux ratio

so we can use 1.2 times actual reflux ratio R=3.6 Ideal Number of stage =4 Actual no of stage taking is 6 Height of column is 3 meter

Fig 60 : McCabe thiele method for stage calculation [7][8]

128

LIQUID EFFLUENT COLUMN (contributed by: Deepak Bonal) basis - 1 hour data taken from the above and calculation in Lb/hr Table 72: After reactor it is entering into effluent column mass flow H2o CH3I CH2o2 CH3OH HI CO2 CH4 7.61 132.64 75.84 15866.740lb/hr 4680.69 126.93 63.46

Table 73: Temperature pressure condition for effluent column Temp( k) Pressure (psi) Vapour fraction 320 638 0.166

we are using absorbent (cao -mgo ) enhanced its absorbing capacity with the help of hydration process. cao-75% mgo -25 % density -3.41g/cm3 mass of absorbent -1.381 kg dia of spherical particle -1um porosity-0.4 volume of absorbent-404.9m3 l/d=1.75 diameter=5.5m height =9.625m total no. of particle =771*10 18 no. of particles in 1 layer=96.35*10 12 height of bed came out =8m Storage of acetic acid(product) L/D=1.5

129

As it is not used on regularly basis it is just for in case we are not able to supply to distributors due to natural calamity or bad weather condition so here we can store our product of a week. Table 74 : Storage Data vol. of acetic acid(m3/day) Diameter height no. of tanks 1642.85 4m 6m 22

Fig 61 : Storage tank interior Design

Temp should be below 30 degree Design and construction of tank [9] it is for 80% acetic acid 1. Stainless steel grade 304 ,316,314 2.High density polyethene 3.propylene and rubber lined carbon steel

130

Level measurement For measuring a level of liquid we use hydrostatic gauge fabricated with stainless steel of suitable grade or gauge glass covered from all sides (especially for 80% acetic acid). Pipework it should be made from the same material from which tank is made. A vapour tight manhole is provided for cleaning and inspection purposes, as it is a polar solvent earthing point should be fitted on the tank and this should be connected to the good earth. I m using pvc or polypropylene ball valves for my pipeworks. For delivery of product to heigher level we are using self- priming centrifugal pumps mechanically sealed with PTFE wedges . If heating is provided, thermostatic temperature control is strongly recommended to ensure that the temperature of the acetic acid does not exceed 30C. At higher temperatures the rate of corrosion of stainless steel by acetic acid increases and flammable mixtures of air and acetic acid are possible. The fitting of low and high temperature alarms are provided in our storage tanks. Heated tanks, pumps and pipelines should be insulated to prevent heat losses and reduce heating costs.ACETIC ACID CORROSIVE TO SKIN is painted on all acetic acid bulk tanks. Emergency instructions, in case of splashing, should be shown at the main places of work. An adequate number of eye baths or wash bottles containing water (for use until a source of running water can be used) should be kept in the working area. Buckets of sodium bicarbonate may also be kept in the working area for skin use only. if we get 99.5% acetic acid and it is desired to supply 80% acetic so we can do it For the dilution of 99.5% by mass acetic acid to 80% by mass: W = 244.1 M W -is the amount of water to be added in litres M- is the amount of 99.5% acid in tonnes. W =( M x (X - 80) x 125.24)/10 X-initial concentration of acetic acid. W-is the amount of water added in litre. M- amount of acid in tonnes. W =( 1 x (99 - 80) x 125.24) /10 litres per tonne = (19 x 125.24)/10 = 238.0 litres per tonne Cost of acetic acid in market =32 Rs/kg [10] cost of product=1207522.32*32=38,640,714.24 Rs Storage of raw material (methanol)

131

Fig 62: Storage tank according to literature L/D ratio =0.5 [11] As tank height increase , plate thickness increases, besides requirements for foundations & earthquake protection get more sophisticated and so do requirements for tanks stiffness, to resist buckling (and bending moments so more expensive . Space is not a constraints here (assumption)[ r12] volume of 1 tank should not be more than 1000m3 (literature) taking 25% extra into consideration while handling methanol for extra storage and spillage consideration volume of methanol(m3) Diameter height No. of tanks 113597.49 13.65m 6.825m 14

Table 75: Storage of Methanol Design and construction of tanks carbon steel with interior surface coated with epoxy resin will serve our purpose in working and economic ways rather than using 300 series austenitic stainless steel which is expensive. it is installed with side ways agitator according to API-650 .We generally avoid top mounted agitator because it is more tedious as the vessel have to bear the load of agitator static as well as dynamic load and thrust on the walls.

Heat Exchanger Design (contributed by: Jayesh Meena)

Process Conditions: methanol Inlet (i) Flow rate = 4254.34 kg/hr (ii) Temperature = 57.546 deg C (iii) Pressure = 42 atm 132

Outlet (i) Flow rate = 4254.34 kg/hr (ii) Temperature = 180 deg C (iii) Pressure = 42 atm Superheated steam is used as a heating medium to heat methanol feed from 57.546 deg C to 180 deg C. We need to have a steam at temperature above the outlet temperature of methanol (180 deg C), so that no temperature cross occurs throughout the exchanger, as cross leads to low LMTD and as a result low heat recovery. Steam is taken at 15 atm pressure, which has a saturation temperature of 198 deg C. Table 76: Composition in heat exchanger Hot fluid(superheated steam) 198 198 0 Higher Temp Lower Temp Difference Cold Fluid (methanol) 57.546 180 122.454 Difference 50.454 72 21.546

All temperatures are in deg C. Selection of Basic Heat Exchanger Type. This choice is based on : (i) Likelyhood of fouling - for methanol, inside fouling factor = 5680 W/m2 deg outside fouling factor = 2840 W/m2 deg fouling need to be considered while calculating Heat transfer coefficient,U (ii) Difficulty of cleaning. (iii) Special materials requirements. Steam as a heating medium introduces difficulties such as : Hot steam condensate is fairly corrosive and care must be exercised to prevent condensate from accumulating within the exchanger where continuous contact with metal will cause damage. It is advantageous in heating to connect the steam to the tubes of the heater rather than on the shell. in this way since the condensate may be corrosive, the action can be confined to the tube side alone, whereas if the steam is introduced in the shell, both may be damaged. When steam flows through the tubes of a 1-2 exchanger, there is no need for more than 2 tube passes. Since steam is an isothermally condensing fluid, the true temperature difference and LMTD are identical. For isothermal fluid(steam), pressure drop in tube = (f*G*L*n)/(5.22*10^10*D*s*) Procedure for estimating area Shell side Q = W*C*dT Q=4254.34*0.64*(180-57) Q=334901644.8 cal = 1402166.206449 KJ = 1.402 * 106 KJ Tube side Q = 0 LMTD = (T1-t2)-(T2-t1)/(ln(T1-t2)/(T2-t1)) =((198-180) (108-57.546))/ln((198-108)/(108-57.546)) =48.88 deg C 133

 Assumed data : Di = 1.049 inches = 0.0874 ft DO = 1.315 inches = 0.1096 ft XW = 0.133 inches = 0.0111 ft Methanol coefficient = 1020 Water = 1700 Inside Fouling Factor = 5680 Outside Fouling Factor = 2840 DL = (DO DI)/(ln(Do/DI)) = (0.1096 0.0874) / (ln(0.1096/0.0874)) = 0.0983 ft Overall coefficient, UO = 459 W/m2 deg C Total outside heat transfer area , Ao = Q/Uo*LMTD = 1402166.20/(459 * 48.88) =62.49 sq m

Applying Constraints Operating Constraints: P(tube) , P(shell) V(tube) , V(shell) Geometrical Constraints: Shell diameter Tube length Ratio of Baffle spacing and shell diameter Area targeting Given A set of p(tube) and p(shell)

Cost Targeting Capital cost of exchanger and pump. Cost of power. Pump efficiency Plant operation(hrs/yr) Annualization factor (/yr)

134

End Stripping Column (contributed by: Awadhesh Ranjan)

1. CHOICE OF PLATE OR PACKED COLUMN : Plate columns can be designed to handle a wider range of liquid and gas flow-rates than packed columns. Packed columns are not suitable for very low liquid rates. The efficiency of a plate can be predicted with more certainty than the equivalent term for packing (HETP or HTU). Plate columns can be designed with more assurance than packed columns. There is always some doubt that good liquid distribution can be maintained throughout a packed column under all operating conditions, particularly in large columns. It is easier to make provision for cooling in a plate column; coils can be installed on the plates. It is easier to make provision for the withdrawal of side-streams from plate columns. If the liquid causes fouling, or contains solids, it is easier to make provision for cleaning in a plate column; manways can be installed on the plates. With small diameter columns it may be cheaper to use packing and replace the packing when it becomes fouled. For corrosive liquids a packed column will usually be cheaper than the equivalent plate column. The liquid hold-up is appreciably lower in a packed column than a plate column. This can be important when the inventory of toxic or flammable liquids needs t be kept as small as possible for safety reasons. Packed columns are more suitable for handling foaming systems. The pressure drop per equilibrium stage (HETP) can be lower for packing than plates; and packing should be considered for vacuum columns. Packing should always be considered for small diameter columns, say less than 0.6 m, where plates would be difficult to install, and expensive. Packed column is selected for our operation.
[18]

2. TYPES OF PACKING:
The main requirements of packing are as follows: It should provide a large surface area: a high interfacial area between the gas and liquid. Should have an open structure: low resistance to gas flow. Should promote uniform liquid distribution on the packing surface. It should promote uniform vapor gas flow across the column cross-section. The two major classifications of packings are: i Packings with a regular geometry: such as stacked rings, grids and proprietary structured packings. 135

ii

Random packings: rings, saddles and proprietary shapes, which are dumped into the column and take up a random arrangement.

Raschig Rings

Pall Rings

Berl Saddles

Intalox Saddles

Super Intalox Saddles Fig 63: Examples of Random Packings

Metal Hypac

3. PACKING SIZE:
The recommended packing size ranges are: Table 77: Column Diameter for Stripping Column Column Diameter <0.3 m 0.3 to 0.9 m >0.9 m Use Packing Size <25 mm 25 to 38 mm 50 to 75 mm

Packing used here is ceramic intalox saddle because: a One of the most efficient packings b Little tendency to nest and block areas of bed c Gives a fairly uniform bed d Higher flooding point e Lower pressure drop

136

Table 78: Packing Properties (Generated using Packed Column Calculator by Katmar Softwares)

4. MATERIAL BALANCE:
Material In = Material Out Stream 1 + Stream 2 = Stream 3 + Stream 4

Fig 64: Material Balance done in Aspen One using CHAO-SEA property

5. DESIGN CALCULATIONS[19][20][21]:
5.1 HEIGHT EQUIVALENT OF THEORETICAL PLATE (HETP) HETP =
-0.19 0.21

137

Where, A= Size of packing = 38mm = Surface tension of liquid = 29 mN/m = Overall viscosity of feed stream = 0.000414 Pa s HETP is calculated as 0.0357m 5.2 NUMBER OF TRANSFER UNITS (NTU) Number of transfer units is calculated as followed. NTotal = Where, =L/HG = 0.0045 L=Molar liquid flow rate = 0.00483 mol/sec G=Molar gas flow rate = 62.08 mol/sec H=Henrys Law Constant = 79.52 Pa/mol fraction x2=Solute contents in liquid inlet stream mol fraction = 0.0083 x1=Solute contents in liquid exit stream mol fraction = 0.00009 y1=Solute contents in gas at bottom mol fraction = Ntotal ~ 5 5.3 HEIGHT OF OVERALL GAS TRANSFER UNIT (HOG) Height of overall gas transfer unit is calculated as follows HOG = HETP X HOG is calculated as around 1.45 m approximately 5.4 COLUMN HEIGHT Packing height is calculated as: HTotal = HOGx NTotal HTotal ~ 7.28m An allowance of 0.5 m can be made for detachment of vapors at top and at bottom for liquid. Hence, HTotal = 7.78 m 5.5 FLOODING VELOCITY Flooding velocity requires the calculation of the superficial velocity that is given as VOG = (G)/(A g) VOG ~ 6m/s As general rule superficial velocity is 40% to 60% of the flooding velocity. Taking superficial velocity as 60% of the flooding velocity, then the flooding velocity is given as VF ~ 9.6 m/s 5.6 PRESSURE DROP AND COLUMN DIAMETER For pressure drop calculation we require flow factor and gas mass velocity. Flow factor X is calculated as: X= X = 0.01 Column diameter, D= 1.128 Where, L = Mass flowrate of liquid 138

G = Mass flowrate of gas D ~ 0.83 m Let, Y = (G2F Y = 0.07 Using Eckert generalised correlation for the pressure drop in packed columns for the coordinates (0.01, 0.07), the pressure drop is found to be approximately 290 Pa/m of packing height.
[22] 0.1

)/ (

( l-

g)

x gc)

Fig 65: Generalised Pressure Drop Correlation (Generated using the software Packed Column Calculator by Katmar Softwares)

MECHANICAL DESIGN[23]:
THICKNESS OF SHELL Material selection: Stainless Steel 304 Shell thickness is calculated as, ts = where, ts=Thickness of shell p=Design pressure = O.P. 1.1 = 24818 kPa = 24.8 N/mm2 D=Inside diameter = 0.8 f=Design stress = 145 N/mm2 J=Joint efficiency = 85% c= Corrosion allowance = 2mm ts = 30.8 mm 139

SHELL WEIGHT Shell weight is calculated as Shell Weight = Volume of shell Density of shell material Shell weight = 12670 kg HEAD SELECTION AND THICKNESS Elliptical head has been selected because it is used for high pressure requirements and its manufacturing is easy as compared to other types. Material of construction is low alloy steel. Thickness of elliptical head is calculated with following formula th = where, th=Thickness of head p=Design pressure = O.P. 1.1 = 24818 kPa = 24.8 N/mm2 Cs=Stress concentration factor = 1.77 Rc=Crown Radius = 0.83m f=Design stress = 240 N/mm2 J=Joint efficiency = 85% c= Corrosion allowance = 2mm th ~ 32 mm HEAD WEIGHT Weight of elliptical head is calculated as, W = W = 58 kg x
m

PACKING SUPPORT:
The best design of packing support is one in which gas inlets are provided above the level where the liquid flows from the bed; such as the gas-injection type. These designs have a low pressure drop and no tendency to flooding

Fig 66: A gas injection type packing support 140

LIQUID DISTRIBUTOR:
The pan-type construction is selected because it provides liquid level balance. Vapor passage is provided by circular gas risers as well as around the periphery of the pan.

Fig 67: A Pan type liquid distributor with bottom holes

References[1] Hosea Cheung, Robin S. Tanke, G. Paul Torrence "Acetic Acid" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. [2] Department of Scientific and Industrial Research, [DSIR]- Executive summary tsr125 [3] Ref. KLM TechnologyGroup Practical Engineering Guidelines for Processing Plant Solutions COMPRESSOR SELECTION AND SIZING Author: Rev 01- A L Ling Rev 02- Viska Mulyandasari [4] Ref. KLM TechnologyGroup Practical Engineering Guidelines for Processing Plant Solutions COMPRESSOR SELECTION AND SIZING Author: Rev 01- A L Ling Rev 02- Viska Mulyandasari [5] ref. :- mccabe smith 7th chapter 8th edition page 221 [6] Source : Calvert et al 1972 [7] Mass Transfer operation By:-Robert E. treybal [8] Fluid Phase Equilibria 54 (1990) Masahiro kato, Hiroshi yoshikawa and Yamaguchi Department of industrial chemistry ,faculty of engineering Nihon University Koriyama Fukushima Japan [9]BP chemicals/BP p.l.c/feb 2002 [10] ref .http://www.indian-chemicals.com/chemiprices.htm [11] ref.che resource /invision/topic/13879 [12] ef.che resources/invision/topic/9034-tanks-ld-ratio [13] Heat Exchanger design targets for minimum area and costs , K Muralikrishna and U.V Shenoy, Department of Chemical Engineering and Computer Aided Design Centre , IIT Bombay [14]Underwood, A. J. V. (1934). The calculation of the mean temperature difference in multipass heat exchangers. Journal of the Institute of Petroleum Technology, 20, 145 158. [15]Process Heat Transfer: Principles, Applications and Rules of Thumb By Thomas Lestina, Robert W. Serth [16]Bowman, R. A., Mueller, A. C., & Nagle, W. M. (1940). Mean temperature difference in design. Transactions of the ASME, 62, 283. [17]Donald Q Kern - Process Heat Transfer [18] Strigle, R.F., Jr. Random Packings and Packed Towers. Houston, TX: Gulf Publishing,1987. [19]. Perry, R.H., and D.W. Green. Perrys Chemical Engineers Handbook, 7th ed. New York: McGraw-Hill, 1997; p. 15-86 [20] Harriott, P. Chemical Reactor Design. New York: Marcel Dekker, 2003; Chapter 8 4a. Carl R. Branan. Rule of Thumbs for Chemical Engineers, 4th ed. Butterworth-Heinemann, 2005; p. 109-113; p.143-152

141

[21] Eckert, J.S. Chem. Eng. Prog. 66(3):39 (1970) [22] Gavin Towler, R.K. Sinnott. Chemical Engineering Design: Principles, Practice and Economics of Plant and Process Design, 2nd ed. Butterworth-Heinemann, 2013; p. 279-302; p. 807-923

142

Chapter 5: Acetic Anhydride Production (by: Raman Kumar, Priya Ranjan, Ravindra Verma)
Process Flow Diagram

Fig 68: process flow diagram for acetic anhydride production

Prod+Rea = Methyl Acetate + CO+ Acetic Anhydride CENPUMP= Blower

Flash tanks
Operation
Flash tanks can be an important part of many fluid systems. sudden evaporation or "flashing" occurs when hot liquid at some higher pressure is suddenly released to a lower pressure. .Heat that causes this flashing is the difference between the enthalpy of the liquid at the higher pressure and the enthalpy of saturated liquid at the lower pressure.The enthalpy of evaporation (the heat required to change the liquid to steam at the lower pressure) determines how much of the liquid can be converted to vapour by the heat available . The flash evaporation of a single-component liquid is an isenthalpic process and is often referred to as an adiabatic flash . The following equation, derived from a simple heat balance around the throttling valve or device, is used to predict how much of a single-component liquid is vaporized.

143

% of flash steam = heat energy available due to change in pressure / energy required for change of phase

If the enthalpy data required for the above equation is unavailable, then the following equation may be used.

Note: words "upstream" and "downstream" refer to before and after the liquid passes through the throttling valve or device.

Designing of flash tank

Fig 69: flash tank

Required rate of methyl acetate required after flashing = 16.4 mol/sec High Pressure Amount of liquid Amount of steam Temperature 1 0 303K Low Pressure 1-x x 353 144

X = 289.8 x 50/ 25800 = 0.5616 X = 56.16 % Table 79: summary of data Required methyl acetate flowrate Input of methyl acetate in flash tank Volume of vapour of methyl acetate Methyl acetate condensate Condensate volume generation rate Total volume requirement 16.4mol/sec 35.3 mol/sec 0.4667m3/sec 18.9 mol/sec 1.409 m3/sec 2m3/sec

Assuming a rectangular flash tank And L/D = 2 Diameter = 1.082 m Length = 2.164m

Packed Bed Reactor :

fig 70: Longitudnal catalytic packed bed reactor *H.Scott Fogler elements of chemical reaction engineering , 3 edition pg21 Kinetics of process :
Reaction conditions for kinetics study :
Pressure 5 MPa and temperature of 343K. Ruthenium based homogeneous catalyst is used ,promoted by alkali metal. Process is assumed to be 1st order irreversible reaction model. 145

The rate equation governing this model is:- [1]

r = -dcA/dt = K cA= 3.0286*103 exp{(- 8.124*104)/RT} cA

Designing equation for packed bed reactor:

Assumption of packed bed reactor:[2]
o The pressure drop is very small (calculated from ergun equation) o There is no decay of catalyst used(ruthenium)i.e . decay constant a =1. o Reactor is assumed to be isothermal packed bed reactor. o Constant temperature is maintained by the help of coolant in the packed bed of the reactor column.

Designing equation for packed bed reactor:

dX/dW = - rA/FA0 W = FA0 where , rA= rA/b [I] [II] [III]

and rA = -dcA/dt = K cA= 3.0286*103 exp{(- 8.124*104)/RT} cA , cA = cA0 (1-X)

from above the equations ,on integrating equation [I] , equation governing the weight of catalyst comes out to be: W = (FA02/v0) b *ln(1/(1-X))*3.0286 *103 * exp{(- 8.124*104)/RT} [IV]

Reaction conditions data : Table 80: Reactor operating conditions

Feed rate of methyl acetate (FAo ) Volumetric flow rate (vo) 16.4 mole/sec 6.96*10-3m3/sec

Conversion of methyl acetate (X) Temperature of reactor(T) Pressure of the reactor (P) Void fraction of packing of catalyst in reactor () Density of catalyst particles (cp) Bulk density (b= cp)= 12.45*103 *0.53 By using above value and equation we get :

92.53 % 343K 5MPa 0.53

12.45*103kg/m3 6.59 *103kg/m3

146

W={(16.42/97.4*10-6)*6.59*103*ln((1)/(1-0.9253))*3.0286*103*exp((-8.124*104)/(8.314*343} Weight of the catalyst in the reactor is, W =60.67kg. Volume of the reactor (V): V = W/ b= 60.67/6.59 =9.2 m3 V=(3.14*D2/4)L [V]

Modelling assumption:
o We dont know either the length(L) and diameter(D )of the reactor ,so we assume L/D =6, as the pressure drop is very small. o L/D ratio is smaller for lower pressure drop across the reactor . V= {(3.14*L3)/(4*36)} =9.2 m3. length(L)=7.5m , from L/D= 6 , Diameter(D)= 1.25m

Residence time calculation (t):

t=V/vo= (9.2/6.96)*103 =22min

Superficial velocity (Us):

A is the area of reactor = {3.14* (1.25)2}/4 =1.226 Us = 6.96*10-3/1.226 =5.67*10-3m/sec. Calculation of number of tubes in the reactor: Here we use tubes of similar dimensions in the reactor for proper distribution of catalyst in the reactor. And number of tubes in the bed of the reactor is calculated with the help of diameter of the bed. We assume each tube with diameter 0.25 m in the bed. No. of tubes = D/ dt =1.25/0.25 = 5 So, 5 tubes will be used in the reactor. Us= vo/A ,

Pressure drop calculation in packed bed

Assumption for pressure drop calculation in packed bed :[3]
The material flow through the reactor as a plug. All of the substrate stream flows at the same velocity, parallel to the reactor. There will be no back or radial mixing in the reactor. All material should have same residence time at any given reactor cross-section area. 147

All production emerging with the same residence time and all substrate molecule having an equal opportunity for reaction.

Ergun equation(for laminar flow): P/L= (G/ gcDp) *(/(1-)3 ){150* m/Dp} Where , DP is pressure drop .

[VI]

G= Us , is the average density of fluid,= (1+2)/2=(992+1082)/2=1007 kg/m3 1 & 2 are density of methyl acetate and acetic anhydride in the reactor. Mass velocity(G)= (1007)* (5.67*10-3)=5.7kg/m2-s Table 81: Properties of catalyst and other physical parameters Mass velocity (G)= Us =(1007)* (5.67*10-3) Porosity( ) Diameter of particle(Dp) Viscosity( .) gc 5.7kg/m2-s 0.47 0.508*10-2m 0.10832Pa-s 1

By using data from table 2 and equation [VI] :

P/L= (5.7*0.532*150*0.01832)/(1007*1*.005082*0.473) =0.082MPa. So, the pressure drop in the reactor = 0.082MPa.

Costing of catalyst
Catalyst used: Catalytic condition:[4] Ruthenium

o the catalyst is added in the form of ruthenium oxide i.e. ruthenium(IV)dioxide,anhydrous ruthenium(IV) dioxide or tertaoxide o Generally during the carbonylation of methyl acetate ruthenium will be in the form of a coordination complex of ruthenium and the phosphonium salt that may or may not contain carbon monoxide ligands.

Cost of the ruthenium catalyst: TABLE 82 : cost estimation

1 troy ounce(31.1gm) in($) 85 [5] 148

Total weight of catalyst(kg) Total cost of catalyst($)

60.67 165818.6

Design of distillation column

Distillation is a process that separates two or more components into an overhead distillate and bottoms. The bottoms product is almost exclusively liquid, while the distillate may be liquid or a vapor or both

Fig 71 : Distillation column flow diagram .

Assumption : [1] composition of component are known . purity of distillate and bottoms are known . The quality of the feed are known. Height-to-diameter ratio should be less than 20 to 30. Column shell should be thicker to withstand pressure of the column. Feed to the distillation column is F = 63.4 kmol/hr , which contains 3 components Table 83 : feed parameters in distillation column Feed in (kmol/h) (nf) Acetic anhydride Methyl acetate Carbon monoxide (CO) 54.6 Mole fraction in feed (xf)

0.861

4.4 4.4

0.0694 0.0694

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Assumption of percentage recoveries (P.R) for top product [2] Table 84 : Distillate data
Percentage recoveries (P.R i) Acetic anhydride Methyl acetate 0.04 Moles (kmol/h) Mole fraction in distillate (xd) 0.208

54.6 x 0.04 = 2.184 4.4 x 0.92 =4.048 4.4 x 0.97 =4.268

0.92

0.385

Carbon monoxide (CO)

0.97

0.406

Total moles in Distillate

D = 2.184 + 4.048 + 4.268 = 10.5kmol/h

Assumption of percentage recoveries (P.R) for bottom product Table 85 : Bottom product
Percentage recoveries (P.R i) Acetic anhydride Methyl acetate Carbon monoxide (CO) 0.94 Moles (kmol/h) Mole fraction in bottom (xb) 0.9906

54.6 x 0.94 = 51.324 4.4 x 0.08 = 0.352 4.4 x 0.03 =0.132

0.08 0.03

0.0067 0.0025

Total moles in bottom W = 51.324 + 0.352 + 0.132 = 51.808 kmol/h

Calculations of K-values and relative volatilities for the feed stream :

Pt = Total pressure ( 760 mmHg ) Ki= distribution coefficient for i component i= relative volatilities , , Psat = saturated vapor pressure Temp = 113.66 *C

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Antoine equation is :

For Acetic anhydride A = 7.12 B = 1427.77 C = 198.05 ( These are antoine constants ) sat log P = 7.12 - 1427.77 / (113.66 + 198.05) so , Psat = 346.73 mmHg For methyl acetate : Psa = 1840.77 mmHg For carbon monoxide : Psat = 781.22 mmHg Ki =Pisat/ Pt For acetic anhydride K1 = 346.73 / 760 = 0.456 For methyl acetate K2 = 1840 .77 / 760 =2.421 For carbon monoxide K3= 781.22 / 760 = 1.02 i= Ki/K, relative volatilities are with respect to acetic anhydride for all components 1 acetic anhydride---acetic anhydride = 0.456 /0.456 = 1 2 methyl acetate---acetic anhydride = 2.421 / 0.456 = 5.30 3 carbon monoxide---acetic anhydride = 1.02/ 0.456 = 2.23 Similarly,

Calculations of K-values and relative volatilities for top product:

Saturated vapor pressure ( Psat) at (95.4 *C) Acetic anhydride Methyl acetate 190.5 Value of Ki relative volatilities w.r.t acetic anhydride ( i) 0.250/0.250 = 1

190.5 / 760 = 0.250 1552.49/760 = 2.042 530.12 / 760 = 0.697

1552.49

2.042/0.250 = 8.168

Carbon monoxide (CO)

530.12

0.697/0.250 = 2.788

Table 86: calculation of k values and relative volatilities for top product

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Calculations of K-values and relative volatilities for bottom product

Saturated vapor pressure ( Value of Ki Psat) at (122.39 *C) Acetic anhydride Methyl acetate 462.38 relative volatilities w.r.t acetic anhydride ( i)

462.38/760 = 0.60 0.60 / 0.60 = 1

2332.66

2332.66/760 = 3.069 949.23/760 = 1.248

3.069/0.60 = 5.115

Carbon monoxide (CO)

949.23

1.248 / 0.60 = 2.08

Table 86 : Calculation of k values and relative volatilities for bottom product

Calculation of average Relative volatilities :

average i = (top i x bottom i x feed i)1/3 acetic anhydride = (1x1x1)1/3 = 1 , methyl acetate= (5.30 x 8.168 x 5.115 )1/3 = 6.04 carbon monoxide = (2.23 x 2.788 x 2.08 )1/3 = 2.34 If relative volatilities of components is less than 1.1 , distillation becomes very expensive and extraction or reactive distillation should be considered.

Calculation of minimum number of plates by using Fenske equation [3]

N min = { log(0.406*0.99)/(0.208*0.0025)}/(log2.34) =7.82 we used saturated vapor for the feed stream , so q=0

Calculation of parameter:

here HK < < LK => 1 < < 2.34 after solving this equation = 2.13 satisfy this 152

Calculation of minimum reflux ratio, RD min by using underwood equation:[4]

minimum reflux ratio RD min comes out , RD min = 3.933 RD actual = 1.5 x RD min =5.899

Calculation of actual plate no by using Gilliand correlation

X = {(R - RDmin) / R+1} = 0.284

=> Y =0.374

=> N = 8.194/ 0.626 = 13 plates

Calculation of NR and Ns for the feed location by using kirk bridge method:-[5]
NR = number of plate of rectifying section Ns = number of plate of stripping section log (NR/NS) = 0.206 log [(W/D)*(XfHk/XfLk)*(XbLk/XdHk)2] from the above mole fraction values NR/ Ns = 1.16

NR = Nactual - Ns , so Ns = Nactual /{ NR/ Ns +1} = 13/ 2.16 = 6 NR = 13 - 6 =7

Calculation of column Diameter and Height [6]

Acetic anhydride ywi

Methyl acetate

Carbon monoxide .0025 x 1.25=.003 kg/kmol

.99 x0.60 = .0067 x 0.594 3.069= .02

( MW of mixing ) =(102 x .594 + 74x.020 + 28 x .003) = 62.155

*w = (62.155 kg/kmol ) x (51.808 kmol/hr) x (1hr / 3600 s) = 0.894 kg/sec

153

Vapor density of mixture-

= 1 x 62.155/ 0.082 x 395.54 =1.916 kg/m3 Liquid density of mixture-

= 1080 kg/m3 x 0.99 + 932 kg/m3 x .0067 + 1.15 kg/m3 x .0025 = 1075.44 kg/m3 Fluid velocity-

assuming that lt = .5 m uv = 0.453x[(1075.44 -1.916) /1.916 ]1/2 = 1.072 m/s Diameter of the columnDc = [28 x W / vap x uv x 22 ]1/2 = [ 28 x 0.894 / 22 x 1.916 x 1.072 ]1/2 = 0.744m Height of the columnH = lt x (N+1) = 0.5 x (13 + 1) =7m Total production of acetic anhydride from the plant = 51.324 kmol/hr which is 98.9 % pure

154

References
Stanley M. Walas (1988). Chemical Process Equipment: Selection and Design. ButterworthHeinemann. ISBN 0-409-90131-8 2. Mcbe Smith, unit operations of chemical engineering 492-493 3. CUI Bo, DONG Li-li; Studies on Kinetics of Carbonylation of Methyl Acetate to Prepare Acetate Anhydride 4. Hil C.G An introduction to chemical engineering kinetics and reactor design , New york: wiley, 1977, chap8 nd 5. Levenspiel, O: chemical reaction engineering . 2 edn , New York : Wiley ,1972, Chap 4and 5 6. Ulrich G.D., A guide to chemical engineering reactor design and kinetics ; 1993 7. Coulson and Richerdson , vol 6 ,chemical engineering design pg 34,105,216,502,485 8. Industrial data from BASF manufacturing company http://apps.catalysts.basf.com/apps/eibprices/mp/ 9. Patents : US 4519956 A 10. Perrys Chemical Engineers Handbook, edited by R. H. Perry and D. W. Green, McGraw-Hill, Inc., New York, NY 11. Mass transfer operations Robert Treybal third edition , Mc Graw Hill , Inc New York .
1.

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Conclusions
The process technologies suggested in our plant for conversion of Indian coal to useful chemicals are among the most efficient techniques. Achieving the gasification of high ash content Indian coal with a good degree of conversion ensures that the abundantly available coal in India can be utilised better. Separation of unwanted gases and solids from the product stream is an important consideration and requires large investments in technologies due to high impurities in India coal. Sulphur removal too, is an important step in order to protect downstream equipment. Liquid phase methanol synthesis as well as production of acetic acid from methyl acetate involves a slurry bubble column reactor which is widely used, but mostly based on simulations and experimentations. However, the design of SBCRs is complicated. Empirical correlations exist, each varying on how each factor affects the design parameter. Hence, considering only those correlations which are applicable and widely accepted is important. Gas-agitated SBCRs inherently have very high heat transfer rates; therefore, reduced reactor cost and the ability to remove and add catalyst online are principal advantages of such reactors in which reactions are exothermic. Reactive distillation is a useful technique for equilibrium limited reactions as in the case of production of methyl acetate by the esterification of methanol. Despite being invented in 1921, this technique is still relatively new with very few commercially operated plant designs incorporating RD columns. Its high complexity involving simulations of non-linear dynamics keeps it still at a design stage. RD offers greater conversions and selectivity due to its design. For equilibrium limited reactions, the continuous removal of product in situ helps the reaction to shift in the forward direction. It looks promising, despite its complexity, as it offers investment as well as operating cost reductions in the form of energy requirements and product to feed ratio. Over the past decade, many companies have res We can improve our plant design by modifying the configuration of plants in such a way that methyl acetate, which is produced using the RD column, is produced as a byproduct in the acetic acid process. This way, the need for high selectivity for the SBCR design of acetic acid, and more importantly, the large investment and operating costs of the methyl acetate plant will be avoided. Thus, the need for sophisticated techniques would be reduced, and much cruder techniques could be used.

156