integrated reforming, syngas conditioning and …
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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 % H2, 42 % CO, 2% CH4, 1 % CO2, and 5% N2.
Calculation of Conversion / Selectivity
N2 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 F0 and F are the flow rates of the syngas and effluent gas after the reaction,
respectively, Ci0and Ci 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 (C20+)
(%)
10%Co/Al2O3 5.3 82.1 12.6
10%Co-
5%Mo/Al2O3
10.9 81.8 7.3
2%Pd-10%Co-
5%Mo/Al2O3
6.1 83.4 10.5
Liquid hydrocarbon product (C5+) distribution for
Co/Al2O3 , Co-Mo/Al2O3 , and Pd-Co-Mo/ Al2O3
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/m3)
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%)
CO2
selectivit
y
(mol%)
Hydrocarbon selectivity
(mol%)
C1 C2 C3 C4 C5+
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%)
CO2
selecti
vity
(mol%)
Hydrocarbon selectivity
(mol%)
C1 C2 C3 C4 C5+
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%)
CO2
selectivi
ty
(mol%)
Hydrocarbon
selectivity
(mol%)
C1 C2 C3 C4 C5+
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 NH3 H2S + COS
Before Cleaning 200-1000 200-400 ppm
After Cleaning <1ppm <10ppb
Impurities identified from bio-syngas before and
after cleaning.
CO conversion, CO2 and hydrocarbon selectivity
over the 10% Co/Al2O3 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/Al2O3 for the FTS process*
CO conversion, CO2 and hydrocarbon selectivity
over the Pd-Co-Mo/Al2O3 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 310oC and 1000 psi
over the Pd-Co-Mo/Al2O3 .
Typical properties of synthetic fuels from syngas.
Temperature( C) H2 (%) CO (%) N2 (%) CH4 (%) CO2 (%) H2/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% CH4, 40% CO2; reforming reaction over a Ni/ -Al2O3 catalyst at
8000 h-1GHSV and O2/CH4 ratio of 1/6 under atmospheric pressure.)
Effect of O2/CH4 ratio on the catalyst performance (Biogas
feedstock: 60% CH4, 40% CO2; reforming reaction over a Ni/ -
Al2O3 catalyst at 8000 h-1GHSV under atmospheric pressure).
SEM images of a Ni-based catalyst samples
Fresh Used
H2-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