Biogas Reforming MSU Biogas to Liquid Fuel System Reaction Conditions: T = 200-350°C, Gas flow rate = 50~300 mL/min, P= 500~1000 psi, Catalyst: 3 grams Oil Phase Water Phase Liquid Sample Reactor System Syngas containing 50 % H 2 , 42 % CO, 2% CH 4 , 1 % CO 2 , and 5% N 2 . Calculation of Conversion / Selectivity N 2 in the syngas was chosen as internal standard for CO conversion calculation The CO conversion and hydrocarbon selectivity were calculated according to Eqs. (1) and (2), respectively, where F 0 and F are the flow rates of the syngas and effluent gas after the reaction, respectively, C i 0 and C i are the concentrations of component i in the syngas and effluent gas, and n is the carbon number in a product i molecular. Agilent 6890 GC-MS On-line Agilent 6890 gas chromatograph system Sample Analysis Perkin Elmer Clarus 680 GC Acknowledgement Funding for this work was provided by the U.S. Department of Energy under Grant DOE-DE-FG36-06GO86025 and DE-FC2608NT01923. The assistance of Ms. Amanda Lawrence of the Electron Microscope Center at Mississippi State University is gratefully acknowledged. A continuous process includes reforming, syngas cleaning, and Fischer–Tropsch (FT) synthesis was developed and evaluated to demonstrate biogas-to-liquid (BTL) hydrocarbon fuel technology. Biogas was first dry reformed to syngas over a home-built reformer. A purification reaction system was designed to remove the impurities in the syngas, i.e., moisture, sulfur, and ammonia etc. A multi-functional cobalt-based catalyst was developed and tested for catalytic converting syngas to liquid fuels. The Fischer-Tropsch diesel fuel was found with the distillate boils in a wider range of 125 to 365 C, 83.4% (mass) of the liquid fuel is C11-C19 products. Summary GC-MS of oil phase from wood chips derived syngas. Gas phase: On-line Agilent 6890 GC with TCD/TCD/FID. Liquid samples: A Perkin Elmer Clarus 680 GC with a FID using ASTM D 5134-92 method. Limited to compounds with carbon numbers less than 14. Another Agilent 6890 GC–MS is also used for liquid sample analysis (qualitative). Distillation of the syncrude was performed following ASTM-D86; flash point was tested according to ASTM-D93. Catalytic Conversion Syngas to Liquid Fuels INTEGRATED REFORMING, SYNGAS CONDITIONING AND CATALYTIC CONVERSION PROCESS FOR BIOGAS TO WIDE-CUT DIESEL PRODUCTION Qiangu Yan, Jason Street, Eugene Columbus, and Fei Yu * Catalyst Gasoline (C4-C10) (%) Wide cut diesel (C11- C19) (%) Waxes (C 20 + ) (%) 10%Co/Al 2 O 3 5.3 82.1 12.6 10%Co- 5%Mo/Al 2 O 3 10.9 81.8 7.3 2%Pd-10%Co- 5%Mo/Al 2 O 3 6.1 83.4 10.5 Liquid hydrocarbon product (C 5 + ) distribution for Co/Al 2 O 3 , Co-Mo/Al 2 O 3 , and Pd-Co-Mo/ Al 2 O 3 catalysts. * Catalyst tests performed at 270 C, 1000 psig, 2000 h -1 , and wood syngas, 48 h on stream. Catalyst Co-Mo Pd-Co- Mo Co Specific gravity at 15 C (Kg/m 3 ) 825 832 840 Flash point ( C) 59 83 95 Average Molecular Weight 145.5 170.6 183.6 Total Oxygen Content (mass %) 0.343 0.044 0.015 Total aromatics 21 18 12 Distillation ASTM D 86, ° C IBP 86 125 138 5 116 156 172 10 128 166 183 15 139 177 195 20 149 189 208 30 170 210 229 40 190 232 250 50 208 251 270 60 224 267 288 70 241 285 303 80 258 300 319 85 268 311 330 90 280 324 340 95 297 345 390 FBP 320 365 410 Department of Agricultural and Biological Engineering, Mississippi State University, Mississippi State, MS, USA Corresponding Author. Tel: +1 662-325-0206; Fax: +1 662-325-3853; E-mail: [email protected]. Characterization of liquid fuels from syngas Temp (ºC) CO Conversi on (mol%) CO 2 selectivit y (mol%) Hydrocarbon selectivity (mol%) C 1 C 2 C 3 C 4 C 5 + 230 42.3 8.0 4.7 1.3 0.8 1.9 83.3 250 49.8 8.4 5.0 1.5 1.3 2.1 81.7 270 54.9 9.2 5.2 2.0 1.5 2.3 79.8 290 57.4 9.5 5.1 2.1 2.5 2.8 78.0 310 65.6 9.9 5.5 3.0 2.8 3.2 75.6 330 67.2 10.3 5.7 2.9 3.1 3.5 75.2 Tem p (ºC) CO Conver sion (mol%) CO 2 selecti vity (mol%) Hydrocarbon selectivity (mol%) C 1 C 2 C 3 C 4 C 5 + 230 45.5 8.3 4.2 1.5 0.5 1.3 84.2 250 53.3 8.6 4.5 1.6 0.8 1.9 82.6 270 59.5 9.7 4.9 1.9 1.1 2.7 79.7 290 64.8 10.2 5.3 2.3 1.5 2.9 77.8 310 71.2 10.5 5.6 2.5 2.0 3.6 75.8 330 73.3 11.7 6.5 2.6 2.1 3.8 73.3 Temp (ºC) CO Convers ion (mol%) CO 2 selectivi ty (mol%) Hydrocarbon selectivity (mol%) C 1 C 2 C 3 C 4 C 5 + 230 55.1 7.1 3.9 0.8 0.5 1.4 86.3 250 60.5 7.5 4.1 1.1 0.8 2.3 84.2 270 69.4 7.8 4.5 1.3 0.9 2.6 82.9 290 72.8 8.3 5.2 1.9 1.3 2.9 80.4 310 77.3 8.5 5.3 2.3 1.8 3.5 78.6 330 80.2 8.7 5.5 2.8 2.1 3.9 77.0 Syngas Cleaning Lab scale Pilot scale Syngas cleaning for removing ammonia, and sulfur etc. Components NH 3 H 2 S + COS Before Cleaning 200-1000 200-400 ppm After Cleaning <1ppm <10ppb Impurities identified from bio-syngas before and after cleaning. CO conversion, CO 2 and hydrocarbon selectivity over the 10% Co/Al 2 O 3 for the FTS process * •Catalyst tests performed at 6.7MPa, 2000 h -1 , and woody syngas, 48 h on stream.. CO conversion, CO2 and hydrocarbon selectivity over the Co-Mo/Al 2 O 3 for the FTS process * CO conversion, CO2 and hydrocarbon selectivity over the Pd-Co-Mo/Al 2 O 3 for the FTS process * •Catalyst tests performed at 6.7MPa, 2000 h -1 , and woody syngas, 48 h on stream.. •Catalyst tests performed at 6.7MPa, 2000 h -1 , and wood syngas, 48 h on stream.. FT Catalytic Performance Time of stream of CO conversion, light hydrocarbon and liquid product selectivity on the catalyst at 310 o C and 1000 psi over the Pd-Co-Mo/Al 2 O 3 . Typical properties of synthetic fuels from syngas. Temperature( C) H 2 (%) CO (%) N 2 (%) CH 4 (%) CO 2 (%) H 2 /CO 750 48.96 40.82 6.33 1.75 2.01 1.2 775 49.45 41.22 6.27 1.3 1.74 1.2 800 50.06 42.2 6.05 0.96 1.12 1.19 825 50.57 42.7 6.03 0.57 0.78 1.18 850 50.75 43.11 5.93 0.4 0.25 1.18 Product gas composition for simultaneous dry and partial oxidation of biogas (Biogas feedstock: 60% CH 4 , 40% CO 2 ; reforming reaction over a Ni/ -Al 2 O 3 catalyst at 8000 h -1 GHSV and O 2 /CH 4 ratio of 1/6 under atmospheric pressure.) Effect of O 2 /CH 4 ratio on the catalyst performance (Biogas feedstock: 60% CH 4 , 40% CO 2 ; reforming reaction over a Ni/ - Al 2 O 3 catalyst at 8000 h -1 GHSV under atmospheric pressure). SEM images of a Ni-based catalyst samples Fresh Used H 2 -TPR results of the Ni-based catalyst samples. Temperature-programmed methane dry reforming over Ni-based catalysts: catalyst #1 (left) and Catalyst #2 (right). SYNGAS PRODUCTION HYDROCRACKING FISCHER-TROPSCH SYNTHESIS Gasoline, Diesel Natural Gas/Biogas