Compact Heat Exchange Reactor (CHER) for Synthesis of Liquid Fuels

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1 2014 Clean Coal Technology Fund Research Symposium Compact Heat Exchange Reactor (CHER) for Synthesis of Liquid Fuels Yulong Zhang, Vijay Sethi Beau Braunberger, Sameep Deshpande Western Research Institute Laramie, WY August 20, Clean Coal Technology Fund Research Symposium 1

2 Energy conversions in WRI CO2 captured in the process CO+H2 Feed Syngas Generation Conversion Products 2

3 Reaction Heat of Syngas Conversions Synthesis of methanol 250C 2H 2 + CO = CH 3OH H = 23.6kcal Synthesis of DME 2H + CO = 1/ 2C Synthesis of ethanol H 250C 2H 2 + CO = 1/ 2C2H OH + H O H = 36.1kcal Fischer-Tropsch 5 O + H O 2 H 250C = 30.1kcal 1 lb Reaction heat 2nH 250C + nco = CnH 2n + nh 2O H = 46. 9kcal 2 Narrow temperature variation range required Boil 42 lb H2O Reaction heat management is critical!!! 3

4 Traditional Synthesis Gas Conversion Reactors Those reactors are not suitable for small scale. 4

5 Compact Heat Exchange Reactor FinTec Channels are formed from folded, corrugated fins which are brazed into the reactor structures. Materials: aluminum, stainless steel and nickel alloys. CompRex, LLC offers commercial scale CHER. 5

6 Compact Heat Exchange Reactor Features of CHER Excellent heat transfer Enhanced mass transfer Modular, easy to scale up and down Easy catalyst loading/unloading than microchannel reactor Process intensification due to improved heat and mass transfer Temperature profiles FIXED BED REACTOR Temp Temp Axial Flow > Axial Flow > COMPACT REACTOR ` Radial 6

7 WRI Prototype CHER Features FinTec construction Max temperature 700 F Max pressure 1750 psi Channel 10x3, length 12 Volume 66 ml Temperature measurement 3 outside, 1 inside Heat transfer oil heat/cooling 7

8 Reactions on bench scale CHER Synthesis of methanol Synthesis of DME ( one step) Fischer-Tropsch synthesis Synthesis of mixed alcohols 8

9 2H + CO = CH 3OH Catalyst: Mega Max 800 Reactor: CHER Catalyst loading: 20g H 250C 2 = Synthesis of Methanol 23.6kcal T (F) P (psi) SV (1/h) H2/CO CHER FixedBed Yield (g/g/h) times of process intensification was shown. 9

10 DME synthesis DME synthesis 2H + CO = 1/ 2C H O + H CO+ 2H 2 O = CH 3 OH (methanol synthesis) O 2CH 3 OH = CH 3 OCH 3 + H2O (methanol dehydration) H 2 O + CO = CO 2 + H 2 (WGS) Reactor: CHER Catalyst: in house, loading 63g H 250C = 30.1kcal CO Conversion % CO Conversion 10 CO Conversion STY of DME Temperature F H2/CO ratios STY of DME g/g/h CO conversion (%) Space Velocity: /h, Pressure: 800 psi STY of DME g/g/h 10

11 Fischer-Tropsch Synthesis 2nH 250C + nco = CnH 2n + nh 2O H = 46. 9kcal 2 Catalyst: cobalt Reactor: CHER Catalyst loading: 50 g Reaction conditions: T= C P=300 psi SV= /h Running for 1 month Fischer Tropsch Synthesis 11

12 Temperature distribution of CHER Temperature difference between center to outside channel, caused by heat loss of the outside channel 12

13 Table 1. Octane number of some alcohols Mixed alcohol synthesis Mixed alcohols are C1-C5 alcohols for gasoline blending (higher octane number, energy density) WRI developed a proprietary NiMo carbide based catalyst for mixed alcohols synthesis hour run was performed and catalyst is stable. Alcohols Octane Octane Energy Oxygen Number (RON) Number (AKI) Density (MJ/L) Content (wt%) Gasoline Methanol Ethanol Propanol Butanol Pentanol

14 250C 2H 2 + CO = 1/ 2C2H 5OH + H 2O H = 36.1kcal Catalyst: NiMo2C Particle size mesh Catalyst loading: 91g Reaction Temperature F Pressure: psi H 2 /CO: 1-2 Synthesis of mixed higher alcohols with CHER Mixed Alcohol Synthesis T (F) P (psi) SV H2/CO Convrsions (%) Alcohols Distribution (wt%) STY g/gcat/h Xco XH2 MEOH ETOH C2+OH Conventional fixed bed 0.2 g/gcat/h 3-4 times process intensification 14

15 Description of Pilot Scale CHER Two CHERs with 2L catalyst loading capacity (1750 psi, 750F) Heat transfer oil heating system 7 x 35 channels, 2 feet length Syngas supply: 1000 psi (1500psi), 150 SLPM Syngas recycle: yes Online gas analysis: feed and offgas Computer Controlled operation with minimum supervising, interlocked safety feature 15

16 Process Diagram of the Pilot CHER 16

17 Overview of the Pilot CHER System CHER Heater 17

18 Computer control system 18

19 Table 11 Summary of samples at various Time-on-Stream Operations of the pilot CHER Methanol Synthesis Reaction Catalyst: MK-121 (Topsoe) Catalyst loading: kg Pressure: 1000 psi Temperature: 582F Three Runs performed: 24h, 120h, and 115h Run#1 Run#2 Run#3 testing of the operability of the pilot CHER Seven stages varied by N2 dilution and recycle Nine stages, simulating digester gas (CO2 added) 19

20 Stable operation shown by stable temperature Temp 1: top Temp2: middle, edge Temp3: middle center Temp4: middle, edge Temp5: bottom 20

21 Run #1, Yield of Methanol with TOS Yield of methanol (%) Time on Stream (min) Product is 98+% methanol; the rest is water and higher alcohols 21

22 Test Summary Table: Test #2, Summary of the Test (120 hours) Test period Flow Rate, SLPM H2 CO N2 Recycle Ratio Space Conv to Velocity, std Methanol% ltr/hr-kg DP Psi T F P psi Recycle increases yield dramatically; pressure drops are low. 22

23 Test Period Flow rates, SLPM H2 CO CO2 Recycle Ratio Test #3, Summary of Results (115 hours) Test Summary Table: SV std ltr/hr-kg X % to MeOH Yield, bpd DP Psi T, F P psig Yield, bpd Comm Test Periods Process intensification 23

24 Applications of CHER Wyoming stranded natural gas Bio-digester gas Rocky mountain beetle killed trees Agriculture wastes Municipal solid wastes carbonaceous feed either in remote location or limited supply Distributed, portable synthesis gas conversion plants 24

25 Summary Clean transportation fuels could be made from coal, natural gas and/or biomass through new conversion technology Compact heat exchange reactor has excellent performance for highly exothermic synthesis gas conversion reactions Pilot CHER was installed and tested with 3 runs operating smoothly with precise and uniform temperature control Process intensification is shown with CHERs CHER is an optimum choice for monetize Wyoming stranded natural gas 25

26 Acknowledgement Team Thomas Barton Jerrod Isaak Chart Energy and Fuels Stacy Ellis (CompRex, LLC) Joshua Meranda Bob Tweed Nico Wibisono Roger Shoefelt Financial support Wyoming Coal Conversion Task Force DOE Cooperative Agreement DE-FC26-98FT40323 Chart Energy & Chemicals Questions and Comments? 26

Morris Argyle Assistant Professor Department of Chemical and Petroleum Engineering. School of Energy Resources Symposium Casper, WY February 28, 2007

Coal Gasification: What Does It Mean for Wyoming? Research and Development Initiatives of the University of Wyoming Morris Argyle Assistant Professor Department of Chemical and Petroleum Engineering School