Hazard Waste Engr
Hazard Waste Engr CHE 650
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This 37 page Class Notes was uploaded by Durward Wiegand on Monday September 28, 2015. The Class Notes belongs to CHE 650 at Kansas State University taught by Staff in Fall. Since its upload, it has received 10 views. For similar materials see /class/214962/che-650-kansas-state-university in Chemical Engineering at Kansas State University.
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Date Created: 09/28/15
Carbon Dioxide Generation and Capture Jennifer L Anthony Department of Chemical Engineering Kansas State University Carbon Dioxide Emissions 2001 In Million Metric Tons of Carbon Equivalent World 6582 MMT USA 1579 MMT USA ReSIdoentIal 24 61 ReSId Elec Transport 14 32 Commercial 4 Rest Commo Elec 76 Ind Elec I d t I 14 n us rIa Industrial NonElectricity NonSteam 11 19 Cement Production 114 Ammonia Synthesis 110 N 56 Lime Production amp Use C02 from natural Gas 50 Hydrogen Production 30 Aluminum Production 10 Soda Ash Production amp Use 06 Ethylene Oxide 02 Other Chemical Processes lt10 TOTAL 38 MMT from S Barnlckl Eastman Carbon Dioxide Emissions 2001 In Million Metric Tons of Carbon Equivalent USA 1579 MMT Residential 6 Resid Elec Transport 14 32 Commercial 4 Comm Elec Ind Elec 14 Petroleum 11 Industrial 4 4 Na Gas 19 13 Electricity 612 MMT coai 83 from S Barnicki Eastman Representative 002 Emission Sources Source US Mole Typical Typical Capture Type Emissions CC 2 in Pres ure Methods Source PSIQ AutoDiesel Diffuse 33 13 0 NONE Pulverized Coal Point 32 15 0 NONE Chem Abs Power Nat l Gas Power Point 5 8 0 NONE Integ Gas Point Small 1565 8001000 Phys Abs Chem Abs Combined Cycle IGCC Cement Manufacture Point 07 915 0 NONE Ammonia Synthesis Point 07 1720 400550 Phys Abs Chem Abs Nat l Gas Point 03 05 3001200 Phys Abs Chem Abs Sweetening 10 Membrane lt 5 MSFD H2 Synthesis Point 02 1720 400550 Phys Abs Chem Abs PSwing Ads Ethylene Oxide Point 0015 1015 200250 Chem Abs from S Barnicki Eastman Conventional Fossil Fuel Steam Power Cycle Fuel Rankine cyCIG 25 Pulv Coal Na Gas Combustor I 30 ef crency 1o20 Petroleum steam Drum Excess v HP steam HP Turbine Energy in very LP Aquot steam is lost Blower Jlril condensed wo energy 1 recovery quotquot9quot LP Turbine changer quot J 77 leflCUIt to control Condensate pollution 1 Very LP Steam Po s t 0 quotdense39 Flue gas at low Treatment gt Flue Gas pressure 1 atm 63 tl Me QQKAIL 1I5 5 76 4t NAT IL GAS 8 t6 73 3 from S Barnicki Eastman 002 Capture From Conventional Power Plant Recovery from low pressure 1 atm flue gas Low 002 partial pressure 115 psia Oxygencontaining gas 2 5 Hot flue gas 400800 C May contain NOX Hg 802 H28 other sulfur species amp particulates from S Barnicki Eastman Conventional Methods for CO Capture Method Principle of Separating Separation Agent Physical Absorption Preferential Solubility Liquid Chemical Absorption Preferential Reactivity Reacting liquid Adsorption Difference in affinity for solid Solid adsorbent Gas Permeation Diffusion through membrane pressure gradient membrane from S Barnicki Eastman Typical CO2 Capture Process 002 Off Gas Condenser Lean Gas Separator Drum Lean Solvent Absorber W 335 Cooler lt Condensate COZRich Feed Gas 839 Rich Solution Interchanger Reboiler oMany variations possible Physical absorbent may not require extensive heat input for regeneration COZ offgas often at low pressure oMay require pre compression depending on feed gas pressure from S Barnicki Eastman Physical Absorption Solubility of 002 in solvent NO reaction Typical absorbents Methanol Nmethyl2pyrrolidone methyl glymes of EG oligomers trinbutyl phosphate propylene carbonate water not very good Regeneration often can be accomplished with A P limited or no AT Under optimal conditions generally much less energy usage than chemical absorption from S Barnicki Eastman Chemical Absorption Chemical reaction of absorbed 002 with solvent Typical absorbents Primary secondary tertiary hindered amines MEA DEA MDEA TEA 2 AMP Alkali metal hydroxides or carbonates NaOH K2003 Na2CO3 1st 2nd amines limited 05 mol COZImol Amine Tert amp hindered can reach 10 molmol Regeneration by AT amp often A P Solution concentration limited by solubility corrosion andor reactivity with 02 contaminants from S Barnicki Eastman Chemical vs Physical Equilibrium PC02 above Liquid atm Chemical solvent Good at low inlet PCO Can reach very low outlet P002 ie lt 10 ppm possible Sharp rise in outlet PCO when loading reaches rxn stoichiometry MeOH 0 C 20wt DEA 50 C MOO50105 Physical solvent Better at high inlet P002 Loading proportional to P002 0 Cannot reach very lowoutlet 0 10 20 30 40 50 60 70 PCO ie usually 012 but 002 volvol absorbent some can reach ppm levels from S Barnicki Eastman Range of Applicability For H28 amp 002 Removal Within optimized region 1000 costs about equivalent between methods 100 iiiiwtiitmmmummm ifquot Syn Gases Low P Combustion Sources AutoDiesel Nat l Gas Power Plant Pulverized Coal Power Plant Cement Kilns Acid Gas Partial Pressure in Feed psia Szn Gases Ammonia H2 01 001 01 1 10 Acid Gas Partial Pressure in Product psia from S Barnicki Eastman Amine Processes Reacts with 002 to form carbamate complex Many commercially available processes Choice dictated by removal requirements stability to stream components Generally can be selective between for H28 002 Good for PCOZ 01 psi or higher Susceptible to O2 degradation other contaminants can be controlled Good stage efficiencies from S Barnicki Eastman Carbonate Processes Basic idea similar for many akali amp alkali earth hydroxides amp carbonates Choice dictated by cost amp solubility in water Nonselective between H28 CO2 Very best for PCOZ above 10 psi but can work at lower PCOZ Vacuum stripping for CO2 removal to less than 1000 ppm Poor stage efficiencies tall absorption towers Improved with amine as catalyst from S Barnicki Eastman Components of Energy Balance in Absorptive Capture Absorber Remove heat of absorption amp reaction Cool lean recycle solvent sensible heat Stripper Heat rich solvent to boiling point Supply heat of desorption amp reaction Generate strippingreflux vapors Possible Power Plant Capture Addons Cool flue gas to absorber conditions Compress feed gas to overcome pressure drop in Absorber Post compression of CO2 to desired product pressure from S Barnicki Eastman Heat of Reaction Representative Absorbents 1m 55 Wm w 5 18A 156 L2 E from S Barnicki Eastman Potential Absorbents For Flue Primary Amines Secondary Amines Tertiary Amines Hindered Amines Mixed Amines Hot Potassium Carbonate Ionic Liquids Gases MEA 25 wt DEA 35 wt DIPA 40 wt DGA 40 wt TEA 40 wt MDEA 40 wt 2 AMP 40 wt 2 iPrAMP 40 wt 30 wt 2 BAE 3 wt 2 MP 24 wt MDEA6 wt MEA 30 wt Unactiv or activ w DEA AMP from S Barnicki Eastman Conventional Power Plant Capture Solvent Loading Relative Equilibrium Capacity for C02 Pot Carb AMP activ PrimaryAmInes Pot Carb DEA activ 2nd Amines Pot Carb no activ Tert Amines 6 MEA24 MDEA 3 2 MPz30 2 BAE MiXEdAmines MDEA PotCarbonate TEA DIPAsulfolane 2 iPrAMP DGA DEA 2 AMP MEA 00 05 10 15 20 Relative Capacity Depends on reaction equilibrium Secondary effect of solution concentration Large effect on energy usage and equipment size from S Barnicki Eastman Energy Usage Analysis 15 002 in flue gas at 1 atm absolute pressure 90 recovery of 002 in flue gas Precompression of flue gas to overcome pressure drop in absorber 147 psia to 18 psia Postcompression of recovered 002 to 10 and 100 atm in two stages w interstage cooling from S Barnicki Eastman Energy Usage CO2 Capture Compression MEA 34 M BTU Ton CO2 Total Energy Usage for Recoveryamp Compression MEASystem 34 million BTUton C02 Energy Usage for 002 Absorption from Low 52 Pressure Flue Gas 52 I Absorption Pot Carb AMP activ Pot Carb DEA activ Pot Carb no activ 2ndAmines 6 MEA24 MDEA TertAmines 3 2 MPz30 2 BAE Mixed Amines MDEA TEA DIPAsulfolane 2 iPrAMP DGA DEA 2 AMP 23 MEA 29 l 2nd stage 10 100 am 851 PotCarbonate 2AMP 28 M BTU Ton CO2 Total Energy Usage for Recovery amp Compression 2AMP System 28 million BTUton coz I Absorp ion I Feed Compr I 15 stage 1 10 am 00 10 20 30 40 50 60 70 80 million BTUton coz I 2nd stage 10 100 am from S Barnicki Eastman Alternative solvents Ionic Liquids R o x NI x 13 x x We RR 4R2 N R v R1 3 N BF4 R1 R2 CF3SOZ2N 39m39daz lum tetra alkylammonium pyrrolidinium CI N03 G x T1 CH3002 N P X F R Fl R3 CF3803 1 pyridinium tetra alkylphosphonium Example 1nbuty3methyimidazolium hexafluoro hos hate Organic salts bmim39 PF39i 6 Liquid at ambient conditions Negligible vapor pressure Water stable lLs Wilkes and Zaworotko 1992 Solvent for a variety of industrial reactions Using bmimPF6 to Separate Gas Mixtures Conventional Absorber To GC 8 Feed Gas 3 bmimPF coated on o o glass6beads 0 C02 In N2 8 Column Diameter 1 in 8N Column Height 3 in 8 Mass bmimPF6 12 g Feed Gas Feed Gas 10 co2 in CH4 8N Proofofconcept experiments show lLs have potential as a g gas separation media ON 0 O Should not contaminate gas phase nonvolatile Also worked in supportedliquid membrane configuration Breakthrough Curves 12 9000 NAmOOO 0 o 12 10 O 00 9000 ONAO 150 200 Time min Comparison of MEA and bmimPF6 Monoethanolamine High absorbing capacity Low hydrocarbon solubility High volatility Limited temperatures High Ahrxn with 002 Low viscosity bmim PF6 Lower absorbing capacity Low hydrocarbon solubility No volatility Stable at high temperatures Lower Ahabs with 002 Relatively high viscosity Energy using MEA to Capture 002 Total energy 34 million BTUton CO2 Slightly compress the feed gas to 12 bar 015 million BTUton CO2 Desorb the 002 in the stripper 29 million BTUton CO2 Compress the 002 offgas to 100 bar 2 stages at 018 million BTUton CO2 each from S Barnicki Eastman Simplified TemperatureSwing Process Solvent Lean Gas C02 Off Gas gt gt 01 bar v 100 oo2 vacuum Absorber Stripper 25 C 100 C 1 bar At 10 002 01 bar 002 Feed Gas COZrich Solvent Solvent Energy Balance Qz AhabsmCpAT Q energy needed for desorption Ahabs enthalpy of absorption for bmimPF6 or the enthalpy of reaction for MEA m mass of solvent to absorb 1 kg 002 Cp heat capacity of the solvent AT temperature difference between the absorption and desorption step Parameters Ahm 30 wt MEA in H20 Ahabs bmimHP F61 m30 wt MEA in H20 m bmimPF6 Op 30 wt MEA in H20 CP bmim PFsl 854 kJ mol 002 161 kJ mol 002 17kgkgCO2 5914 kg kg 002 418kJkg K 10 kJ kg Kow 25 kJ kg K high Actual Cp for bmimPF6 At 25 00 140 kJkgK At 100 00 148 kJkgK Energy for CO2 Absorption and Recovery Temperatureswing 25 C to 100 C 002 partial pressure 01 bar bmimPF6 MEA 30 wt low Cp I high Cp mass solventkg 002 5914 17 Cp kJkg K 10 25 418 Ahabs or 11th lekg C02 37102 19103 mCpAT lekg C02 44105 11106 52103 Q lekg C02 44105 11106 71103 Q million BTUton C02 382 954 61 w 29 millionBTU lonCO2 Q Ahabs mCpAT Energy for CO2 Absorption and Recovery Temperatureswing 25 C to 100 C 002 partial pressure 01 bar bmimPF6 MEA 30 wt low Cp I high Cp mass solventkg 002 5914 17 Cp kJkg K 10 25 418 Ahab or Ah kJkg C02 37102 19103 M lt CpAT lekg C02 44105 111Lgt 52103 Q lekg C02 44105 11106 71103 Q million BTUton C02 382 954 61 N 3 4 millionBT U N I lonCO2 Q Ahabs mCpAT Energy for CO2 Absorption and Recovery Temperatureswing 25 0C to 100 oC CO2 partial pressure 01 bar A bmimPF6 EA 30 wt low Cp high Cp mass solventkg C02 5914 17 Cp kJkg K 10 25 418 Ahabs or Ahxn lekg C02 37102 19103 mCpAT lekg C02 44105 11106 52103 Q lekg C02 44105 11106 71103 Q million BTUton C02 382 954 Chemical Absorbent Determined by Stoichiometry 05 mol C02mol MEA Energy for CO2 Absorption and Recovery Temperatureswing 25 C to 100 C 002 partial pressure 01 bar A bmimPF6 EA 30 wt AW Cp high Cp mass solventkg 002 I 5914 17 Cp kJkg K 10 25 i 418 Ahabs or Ahrxn kJkg C02 37102 19103 mCpAT kJkg C02 44105 11106 52103 QkJkg C02 44105 11106 71103 Q million BTUton C02 582 954 physical Absorbent Chemical Absorbent p002 dependent Limited by Stoichiometry 05 mol COZImol MEA Feed Pressure Effects Temperatureswing calculations but with varying 002 partial pressures 1000 b 39 PF I c quotR mm O o 800 f 6 Wp O bmlmPF6 high Cp E 600 MEA 400 D I l m 90 c 0 g 60 E V 30 O O 01 1 2 Partial Pressure of 002 bar Pressure Swing Absorber Lean Ionic Liquid Lean Gas Absorber COZRich Feed Gas I P 1 atm CO2 Saturated Ionic Liquid CO2 Off Gas P 1 atm Compressor Compressor Using MEA to Capture 002 Total energy 34 million BTUton CO2 Slightly compress the feed gas to 12 bar 015 million BTUton CO2 Desorb the 002 in the stripper 29 million BTUton CO2 Compress the 002 offgas to 100 bar 2 stages at 018 million BTUton CO2 each from S Barnicki Eastman Ideal L Henry s Constant to Compete with MEA bmimPF6 25 cc Temperatureswing 25 C to 100 0C H 53 bar PC02 01 bar PC02 1 bar PC02 2 bar low Cp high Cp low Cp high Cp low Cp high Cp mass solvent kg CO2 90 36 90 36 90 36 Cp kJkg K 10 25 10 25 10 25 H bar at 25 C 11 05 11 52 23 11 H bar at 100 C 42 20 42 19 84 39 Ideal L Henry s Constant to Compete with MEA bmimPF6 25 cc Temperatureswing 25 C to 100 0C H 53 bar PC02 01 bar PC02 1 bar PC02 2 bar low Cp high Cp low Cp high Cp low Cp high Cp mass solvent kg CO2 90 36 90 36 90 36 Cp kJkg K 10 25 10 25 10 25 H bar at 25 C 11 05 11 52 23 11 H bar at 100 0C 42 20 42 19 84 39 bmimTf2N 25 0C H 30 bar Jim Davis TSIL with amine on cation H 3 bar Conclusions bmimPF6 not capable of replacing MEA Need higher 002 carrying capacity Combination temperatureswing and pressure swing for 002 capture and solvent regeneration could decrease energy usage Necessary improvement seems within reason
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