Beruflich Dokumente
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Catalytic hydrothermal
gasification of biomass
Douglas C. Elliott, Pacific Northwest National Laboratory, Richland, WA, USA
Received February 8, 2008; revised version received March 5, 2008; accepted March 7, 2008
Published online April 14, 2008 in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.74;
Biofuels, Bioprod. Bioref. 2:254265 (2008)
Abstract: A recent development in biomass gasification is the use of a pressurized water-processing environment
to avoid drying of the biomass. This paper reviews the research undertaken developing this new option for biomass
gasification. This review does not cover wet oxidation or near-atmospheric-pressure steam-gasification of biomass.
Laboratory research on hydrothermal gasification of biomass focusing on the use of catalysts is reviewed here, and
a companion review focuses on non-catalytic processing. Research includes liquid-phase, subcritical processing
as well as supercritical water processing. The use of heterogeneous catalysts in such a system allows effective
operation at lower temperatures, and the issues around the use of catalysts are presented. This review attempts to
show the potential of this new processing concept by comparing the various options under development and the
results of the research. 2008 Society of Chemical Industry and John Wiley & Sons, Ltd
Keywords: hydrothermal gasification; biomass; biomass gasification
Introduction
asification of biomass by thermal methods involving
pyrolysis and/or partial oxidation is well-known as
a method to produce a fuel gas or a synthesis gas,
composed of carbon oxides and hydrogen. Typical methods
use a dry biomass feedstock with typically <10 wt% moisture.
Much of the biomass resource is composed of material
with higher levels of moisture, more typically 50 wt% and
some even consists of wet biomass or biomass in water
slurries at 85 wt% moisture or higher. To efficiently process
such a resource a different technology is required and gasification in a pressurized water environment (hydrothermal
gasification) is a concept under development around the
world.
Correspondence to: Douglas C. Elliott, Chemical and Biological Processes Development, Pacific Northwest National Laboratory,
PO Box 999, Richland, WA 99352, USA. E-mail: dougc.elliott@pnl.gov
254
2008 Society of Chemical Industry and John Wiley & Sons, Ltd
DC Elliott
Chemical
Wet
Biomass
Catalytic
Reactor,
350C
200 atm
Heat
Recovery
Gas
Product
Process
Heat
Electricity
Gas/Liquid
Separation
ht
Pressure
Letdown
Electricity
Clean Water
Pressure Time
Liquid
Gas
H2
29.8
CH4
CO2
CO
C2+
Glucose
None
200
13.6
2h
69.1
Glucose
Ni
200
13.6
2h
61.6
ND
ND
Not analyzed
Glucose
Ni
250
40
2h
74.2
0.2
ND
Not analyzed
Glucose
None
300
83
2h
33.9
0.3
39.0
Not analyzed
Glucose
Ni
300
83
2h
47.3
0.3
28.3
Not analyzed
Glucose
Ni
350
165
1h
ND
ND
11.0
Not analyzed
Glucose
None
374
218
1h
77.8
8.2
25.8
1.3
34.4
38.5
Glucose
Ni
374
218
1h
86.8
10.0
30
1.5
42
27
Glucose
Mixed
374
218
0.5h
65.0
20.2
45.1
3.2
38.5
12.5
0.7
Glucose
Mixed
374
218
0.5h
70.8
23.2
43.1
2.9
40.6
12.6
0.8
Mixed
374
218
0.5h
77.47
18.31
14.5
1.5
19.7
64.2
0.1
Cellulose
0.03
Solid
Not analyzed
After Modell .
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
255
DC Elliott
H2
CH4
CO2
CO
C2+
42
39
12
49
1h
38
15
46
1h
34
16
49
35
24
41
Feedstock
Catalyst
Time
Gas, % of C fed
Wood flour
None
350
1h
15
Wood flour
Ni/Na
350
1h
Wood flour
Ni/Na
370
Wood flour
Ni/Na
380
Wood flour
None
400
1h
19
Wood flour
Ni/Na
400
1h
67
256
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
DC Elliott
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
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258
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
DC Elliott
Gasification of biomass has been demonstrated in a hydrothermal environment with active catalysts over a range of
temperatures, both above and below the critical point of
water. Actual biomass feedstocks have been processed as
water slurries over a heterogeneous catalyst in both batch
and continuous-flow rector systems. Early results in a
batch reactor showed that a wide variety of high-moisture
(~10 wt% dry solids) biomass feedstocks could be converted
to a gas product containing a high level of methane.4 The
data in Table 3 show high conversion at 15 m at 400 C and
the important yield of methane in the presence of a nickel
metal catalyst. But these results, using an alumino-silicasupported nickel catalyst, demonstrate only short-term catalyst activity. A special note is that the addition of alkali to
the processing system (in conjunction with less nickel catalyst) resulted in a reduced methane product and increased
hydrogen product.
Related batch test results also showed the production of
methane as a secondary gas product over the time at
temperature at the expense of hydrogen and carbon dioxide.
From these results was concluded that the biomass
composition, particularly the non-carbohydrate portion,
played an important role in the level of gasification achieved.
CH4 scf/lb
H2
CH4
CO2
CO
C2+
Cellulose*
97.6
5.5
3.9
43.2
47.8
3.7
Sorghum
94.6
5.5
9.5
38.4
50.5
1.6
Sunflower
87.8
5.1
5.0
45.7
45.5
2.4
Napier grass
100.8
5.2
6.9
40.6
51.1
1.4
Corn stover
72.9
1.5
20.1
16.3
62.0
1.3
Water hyacinth
73.1
4.0
11.3
35.9
49.6
0.8
0.9
Kelp
78.8
2.9
7.1
41.9
48.4
1.5
Douglas fir
49.8
2.6
21.6
29.0
47.6
1.8
Grape pomace
44.5
3.1
9.6
40.2
47.7
1.0
Spent grain
55.7
3.9
9.6
43.1
44.2
1.4
Potato waste
46.4
2.0
27.6
20.4
50.2
1.8
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
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DC Elliott
% of COD conversion
H2
CH4
CO2
CO
Corn DAF
84.6
18 750
11.0
35.7
50.4
2.4
Apple pomace
97.1
5 800
6.4
40.3
51.4
1.8
98.4
4 100
5.4
35.9
57.0
1.7
Potato crumbs
99.8
290
6.2
54.2
38.7
0.8
Potato flesh
99.7
475
7.0
45.9
45.4
1.4
Potato peels
99.2
680
10.0
43.1
45.1
1.8
Yellow onion
99.7
650
15.0
34.2
48.9
1.8
35
260
C2+
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
DC Elliott
100
90
80
Feedstocks Key
70
WSU manure #2
deStarched Corn Fiber
deStarched Millfeed
DDG, MGP
NREL SSF resid
washed TVA resid
BCI wood resid
60
50
40
30
20
10
0
No Cat Ru/TiO2 Ru/Ni
Cu/Ni
Ru/C
RuTiO2 Ru/Ni
Ru/Ni
370
400
350
Metal wt%
2
Amount of catalyst, g
0.375
Yield, %C as gas
39.0
TON*
108
Ru/Al2O3
0.150
43.4
89
Ru/C
0.150
46.9
69
Rh/C
0.161
31.4
45
Pt/C
0.288
29.1
68
Pt/ Al2O3
0.720
20.6
47
Pd/C
0.158
13.9
33
Pd/ Al2O3
0.158
6.0
21
Ni/ Al2O3
17
0.300
4.8
*TON = (mol of product gas carbon)/(mol of surface metal atoms, based on CO adsorption).
After Osada et al.39
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
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DC Elliott
262
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
DC Elliott
Process economics
Vogel and Waldner have generated some process economic
estimates for a supercritical application of the technology.49
They conclude that using a wood feedstock $67/tonne would
yield a gas product valued at $10.3/GJ ($9.8/million Btu). The
182 wet tonne/day plant (39 467 l/h), operating at 420 C and
30 MPA, would have an installed capital cost of $5.9 million.
Ro et al. completed a system analysis for use of subcritical
gasification with hog manure feedstock.50 The analysis
suggests that catalytic hydrothermal gasification of flushed
swine manure feedstocks with solids concentration greater
than 0.8 wt% can be a net energy producer. The installed
capital cost for the 1580 l/h unit (serving 4400 head swine
feeder-to-finishing farm), operating at 350 C and 22 MPa,
would be $0.99 million. The net product gas would have
a value of $47 006 per year at $8/million Btu. The authors
conclude that the costs are higher than a conventional
anaerobic digestion lagoon system; however, the high rate
of conversion of the organic matter into gas drastically
decreases the land requirement for manure application and
resulting costs in transportation and tipping fees. In addition,
the catalytic gasification process would destroy pathogens
and bioactive organic compounds, it would produce relatively clean water for reuse, and the ammonia and phosphate
byproducts have potential value in the fertilizer market.
Summary
Catalytic hydrothermal gasification of biomass has been under
development for over 25 years. Recognition of this processing
concept and extension of its development outside the USA
has only occurred in the last 12 years. The development has
included recognition of the shortcomings of conventional
catalyst formulations and advances in new catalyst formulations, including both supports and metals for use in hot water
environments. Although the continuous-flow processing of
biomass slurries with these catalyst systems has now been
demonstrated with high conversion to gas and important
yields of methane, commercialization still remains in the
2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:254265 (2008); DOI: 10.1002/bbb
263
DC Elliott
Acknowledgement
Pacific Northwest National Laboratory is operated for the
US Department of Energy by Battelle under Contract DEAC06-76RLO 1830.
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