Ind. Eng. Chem. Process Des. Dev.

1984, 23, 725-728 725

Oxygen/Steam Gasification of Wood in a Fixed-Bed Gasifier

Ed G. Baker,* Lyle K. Mudge, and Don H. Mitchell

Battelle Pacific Northwest Laboratories, Richland, Washington 99352

Yield and operational data were obtained for the production of methanol synthesis gas by fixed-bed gasification
of wood with oxygen/steam blasts. Three different species of wood and a densified wood waste product were
gasified in an updraft gasifier with a nominal capacity of about 1 ton of dry wood per day. Gas and liquid product
yield, gas composition, oxygen requirement, and ash quality were determined as a function of wood species, wood
moisture content, and steam content of the blast. Material and energy balance data are presented for 10 runs.

Introduction Table I. Analysis of Wood Used for Gasification Tests

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In the past few years there has been an increasing in- pressed
terest in the production of synthesis gas for methanol and planar
other chemicals from wood. Methanol and ammonia have form eucalpytus wattle pine shavings
Downloaded via UNIV DE LORRAINE on July 11, 2022 at 07:50:14 (UTC).

been made from synthesis gas obtained from wood in the form chips chips chips
0.19 0.26 0.21 0.56
past (Delauney, 1946; Rutherford, 1949), but the tech- density, Mg/m3
31 27 44 5
average moisture,
niques were inefficient and costly. Recent studies have wt %
referred to the use of oxygen gasification of Wood in a heating value, 19.4 19.1 20.1 20.6
fixed-bed, updraft gasifier for the production of synthesis MJ/dry kg
gas (Rooker, 1980; Filho and Zagatto, 1980; Hokanson and ultimate analysis,
Katzen, 1978), but the data available in the open literature wt % (dry basis)
are limited. C 49 49 51 50
The objective of these studies was to obtain yield and H 6 6 6 6
O 44 44 42 44
operational data for the fixed-bed gasification of wood with ash 1 1 1 1
oxygen/steam blasts. We did not operate with pure oxygen
as is done in the PUROX Process (Moses, 1978) since our 0.028 m3 is added each time, which corresponds to a bed
system is not a slagging one. Three different species of height fluctuation of about 0.3 m in the shaft of the ga-
wood and a densified wood waste product were gasified sifier. The distributor/compactor in the gasifier is used
in a fixed-bed gasifier with a nominal capacity of about during the test for determination of the solids level only.
1 ton of dry wood per day.
It is not used to distribute or compact the bed of solids.
The product gases are scrubbed for removal of con-
Description of Experimental Equipment densables in an 2.4 high, 0.2 m diameter column packed
m
A flow diagram of the equipment used in this study is to a 1.2 m height with 25-mm stainless steel rings. Water
shown in Figure 1. Figure 2 shows a schematic of the containing the scrubbed condensables is recirculated
gasifier. The fixed-bed gasifier, which has previously been through the scrubber from a 0.39-m3 tank at the base of
used for air gasification of wood, municipal solid waste, the column. A 210-m3 overflow tank is provided to collect
grass straw, and shredded tires (Mudge and Rohrmann, the liquids scrubbed from the product gas. The tars are
1978), consists of a 2.1-m section of 0.5-m (20-in.). separated from the scrub liquor and both fractions are
Schedule 40 carbon steel pipe. The gasifier has a 0.25-m weighed and analyzed for carbon.
opening for addition of feed and a 76-mm opening for the The product gases are sampled and analyzed with in-line
off-gas line. The gasifier is lined with 25 mm thick KA- gas chromatographs for H2, N2, 02, CO, C02, CH4, C2H4,
OWOOL insulation plus a 76-mm layer of KAOTAB CS C2H4, C2Hg, C3H8, H2S, and COS. After sampling and flow
castable refractory (trademarks of Babcock and Wilcox). measurement, the gases are flared and vented.
The refractory is 95% alumina, rated for service at 1800 Analytical equipment used includes a Carle AGC-S
°C. The effective inside diameter of the gasifier is about analytical gas chromatograph for gas analysis, a Perkin-
0.28 m. The operating height extends 1.5 m above the Elmer 240 elemental analyzer for wood and tar analysis,
rotary grate for ash discharge. The gasification reactants and a Dohrmann DC80 carbon analyzer for scrub liquor
enter below the grate through traced carbon steel lines. analysis. Wood samples were dried at 104-110 °C for 24
Thermocouples are provided to record the temperature h to determine the moisture content. The dried samples
in the ash zone below the grate, in the product gas line into were used for elemental analysis. The heating value of the
and out of the scrubber, and at 0.2-m height intervals wood and tar were determined with a Parr oxygen bomb
above the grate along one wall of the gasifier. All tem- calorimeter.
peratures are recorded every 15 min during the test on a
datalogger. Feed Materials
Wood is added to the feed hopper, which has a capacity Analyses of the different feedstocks that have been
of 0.028 m3. The hopper is closed and purged with an inert tested in the gasifier are shown in Table I. Most of the
gas. A 0.25-m knife gate valve isolates the bin from the runs were made with wood chips containing 27-48 wt %
gasifier. The gate valve is opened to drop the solids into moisture. The chips were irregular in shape but generally
a 0.23 m diameter auger with a 0.23 m pitch that conveys about 25 mm square and 6 mm thick. One densified feed
the solids into the top of the gasifier. A volume of about material was used: planar shavings pressed into 25 mm

0196-4305/84/1123-0725801.50/0 © 1984 American Chemical Society

726 Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984

Table II. Summary of Results with Wood Chips

feedstock eucalyptus wattIe Pine

wt % moisture- 31 51 46 27 27 48 40
(wet basis)
feed rates
kg/h (wet) 23 25 24 29 25 26 23
kg/h (dry) 16 12 13 21 18 14 14
kg/m2 (dry) 270 205 215 362 308 230 230
kg/h 02 4.1 4.2 4.6 4.1 4.1 4.1 4.6
kg/h H20 4.1 4.3 2.6 4.2 2.4 4.3 2.2
product gas flow, nm3/kg dry wood 1.1 1.2 1.1 0.9 1.1 1.1 1.1
carbon recovery
gas products 83 93 83 72 82 84 82
liquid products 23 14 18 24 18 18 18
total 106 107 101 96 100 102 100
gas composition, vol %
h2 27.1 23.7 23.0 27.5 24.6 25.0 21.9
C„Hm 0.6 0.9 0.8 0.4 0.7 0.9 0.9
Ar, N2, 02 1.1 1.2 2.7 1.1 0.9 0.9 1.3
co2 22.6 29.3 29.7 15.1 17.5 25.2 25.3
ch4 4.8 5.2 5.1 4.4 5.2 5.2 5.2
CO 43.7 39.8 38.9 51.6 51.1 42.8 45.3
energy recovery, %°
gas products 59 61 54 62 63 59 57
tar products 7 3 2 5 3 4 6
heating value, MJ /nm3 11.4 10.6 10.2 12.0 12.2 11.4 11.2

“Normalized to 100% carbon recovery.

MECHANICAL DISTRIBUTOR

JL

PACKED SCRUBBER COLUMN STREAM DESCRIPTION

® FEED GAS (AIR. 02. STEAM)

GASIFIER —o. TEMPERATURE MEASUREMENT ® GASIFIER PRODUCT GAS

—o GAS SAMPLE @ GASIFIER PR00UCT GAS IUSED ONLY WHEN

TAKING PARTICULATE SAMPLE)
-—4 FLOW MEASUREMENT
© SCRUBBER WATER
— LIQUID SAMPLE

PARTICULATE SAMPLE
® SCRUBBER WATER

© WATER OVERFLOW

® PRESSURE EQUALIZATION

® ClEANEO PRODUCT GAS (TO SECONDARY BURNER)

© WATER TO WASTE DISPOSAL

Figure 1. Fixed-bed process flow schematic.

diameter pellets about 38 mm long. Variations in ultimate
analysis and heating value of the various materials are
small.

Run Procedure
A layer of ceramic balls was placed on the grate and
startup was initiated by addition of lit charcoal to the
gasifier. Wood addition began immediately thereafter and
an air blast was used. After a 2-4 h heatup period the air
blast was replaced by an oxygen/steam blast. The oxygen
and steam flows were maintained at a predetermined rate
and the bed depth in the gasifier was maintained between
1.2 and 1.5 m above the grate by batch addition of wood
every 15-20 min.
The product gas was analyzed approximately every half
hour with the in-line gas chromatograph. Consistent gas
Figure 2. Schematic of gasifier. quality and flow rate indicated steady-state operation. At
 Ind. Eng. Chem. Process Des. Dev., Vol. 23, No. 4, 1984 727

Table III. Typical Gasifier Thermal Efficiency with Green Table IV. Effect of H20/02 Ratio on Gasification of
Wood Chips Pressed Planar Shavings
% of pressed
wood planar
energy feedstock shavings
cold clean gas 60 kg H20/kg 02 in blast 0.5 1.0 2.0
tar 5 feed rate
water-soluble organics (pyroligneous acids) 15 kg/h (wet) 36 29 17
sensible heat (including evaporation of wood 11 kg/h (dry) 35 27 16
moisture) kg/(m2 h) (dry) 587 460 269
kg/h 02 9.1 6.8 4.6
kg/h H20 4.6 6.8 9.1
the end of each run, ash was removed by rotating the grate
product gas flow, nm3/kg dry wood 0.99 1.2 1.1
and dropping the ash and ceramic balls out the bottom of carbon recovery
the gasifier. gas products 72 78 73
liquid products 20 23 24
Results and Discussion total 92 101 97
gas composition, vol %
Table II summarizes the results obtained with wood 25.9 30.6 37.2
h2
chips as the feed material. All tests were made at at- CnHm 0.3 0.3 0.2
mospheric pressure. Measured temperatures in the gasifier Ar, N2, 02 0.5 1.0 1.6
ranged from 100-150 °C for the product gas leaving the co2 19.1 26.2 33.6
reactor to 500-1200 °C 0.4 m above the grate. The tem- ch4 5.1 4.9 4.5
CO 49.1 37.0 22.9
perature may be considerably higher in the combustion
energy recovery %“
zone right above the grate, but no thermocouple was lo-
gas products 59 61 52
cated in this zone. tar products 4 7 7
The wood feed rate used in the tests, 23-29 kg/h, cor- heating value, MJ/nm3 11.8 10.8 9.6
responds to about a 1-h solids residence time in the gasifier. “Normalized to 100% carbon recovery.
The feed rate was limited by our ability to get wood into
the gasifier. During a brief accelerated run a rate of 68 value of the tars ranged from 23.3 to 27.9 MJ/kg for the
kg/h of wet wood chips was achieved with no apparent same reason. A sample of tar from one series of runs had
processing problems or reduction in gas quality. a viscosity of 3500 cP at 50 °C.
Oxygen consumption ranged from 0.20 to 0.36 kg/kg of In almost all cases the ash removed from the gasifier was
dry wood with the wetter feedstocks requiring more oxy- heavily fused. Only at a high steam-to-oxygen ratio (2:1)
gen. Two different steam rates were used, 1.0 and 0.5 was a light, fluffy ash found. Even in this case some
kg/kg of 02. The steam rate primarily affects the gas slagged pieces were found. The major constituents of the
composition and the quality of the ash. These points will ash in order were Ca, Fe, Si, Mg, and Al.
be discussed later.
The material and energy balances were quite similar for Operation Problems
the seven runs listed in Table II. About 80% of the carbon The primary operational problem encountered during
in the wood was converted to gas products and about 20% these tests was “bridging”. Bridging occurred only with
to liquid products (tar and pyroligneous acid). Table III wet woods (>45 wt % moisture) and was more common
shows the thermal efficiency of the gasifier for a typical at low throughputs. Bridging was indicated by a sharp
run. The energy content of the cold clean gas is about 60% increase in the C02 content in the gas and a drop-off in
of the original wood energy. For the drier feeds (27-31 wt the product gas flow rate. In the case of extreme bridging
% moisture) it averaged 61%, and for the wetter feeds oxygen breakthrough occurred and was detected in the
(+40 wt % moisture) it was about 58%. Another 5% of product gas. Bridging problems would probably be less
the original wood energy is recoverable as tar. The energy severe in a larger diameter gasifier.
content of the pyroligneous acids (methanol, acetic acid,
acetone, aldehydes, ketones, etc.) and the sensible heat of Conclusions
the product gas are lost when the gas is scrubbed. Heat As a result of these studies the following conclusions
either lost from the system or unaccounted for averaged regarding oxygen/steam gasification of biomass are offered.
about 10% of the original wood energy. Wood chips with up to 50 wt % moisture content can
The gas composition is similar for all the feedstocks. be successfully gasified with only a small loss thermal
The gas composition is determined primarily by the steam efficiency (compared to dry wood). A rate of 640 kg/m2
content of the blast. This can be seen most clearly in Table h based on dry wood is attainable.
IV, which shows the effect of steam on the gasification of An oxygen rate of 0.20-0.36 kg/kg of dry wood is re-
pressed planar shavings. Increasing the steam rate in- quired for gasification. Woods with higher moisture con-
creases the production of H2 and C02 at the expense of tents require more oxygen.
CO via the water gas shift reaction. Moisture content of Gas composition is determined primarily by the steam
the feed has only a small effect on the dry gas composition content of the blast. The moisture content of the feed
as the moisture is evaporated primarily at low tempera- material has only a small effect on gas quality.
tures in the top of the gasifier and does not affect reactions The fraction of wood carbon that is converted to liquid
in the gasifier. Some increase in C02 content in the gas products is about 20%. The wood species, wood moisture
with increased moisture in the wood can be seen in Table content, and steam content of the blast have little effect
II. on this yield.
Composition of the tars ranged from 50-70 wt % C, The ash removed from the gasifier was heavily fused
7.5-9.5 wt % H, and 21-41 wt % O. Separation of the tars except when a high steam-to-oxygen ratio (2:1) was used
was messy and difficult and there was almost always some in the blast.
water associated with the tar. This undoubtedly accounts Bridging can be a problem with wet wood and low
for the wide variation in the composition. The heating throughputs in a small diameter gasifier.
728 Ind. Eng. Chem. Process Des. Dev. 1984, 23, 728-732

Acknowledgment
We wish to thank Ralph Fredrickson and Ray Katzen
of Raphael Katzen Associates and Gary Schiefelbein of the
Biomass Program Office at PNL for their support. We also
wish to acknowledge technicians Gary Roberts, Wayne
Wilcox, Bill Riemath, Ed Leonard, and Rob Cuello, who
contributed greatly to the success of these studies.
Registry No. 02, 7782-44-7; methanol, 67-56-1.
Literature Cited
Delauney, R. "Le Methanol De Synthese A Partlr Du Bols’’; Centre de Perfec-
tionnement Technique, Paris, 1946.
Filho, V. B.; Zagatto, A. J. A. “Abstracts of Papers”, 179th National Meeting
of the American Chemical Society, Houston, TX, March 1980; American
Chemical Society, Washington, DC, 1980.
Hokanson, A. B.; Katzen, R. Chem. Eng. Prog. 1978, 79(11), 67.
Moses, C. T.; Young, K. W.; Stern, G.; Ferrel ACS Symp. Ser. 1978, 76, 63.
Mudge, L. K.; Rohrmann, C. A. ACS Symp. Ser. 1978, 76, 126.
Rooker, J. H. “Proceedings, Fourth Symposium of Energy from Biomass and
Wastes"; Institute of Gas Technology, Chicago, IL, 1980.
Rutherford, R. W. Meeting of the Institution of Chemical Engineers, London,
Oct 1949. Institution of Chemical Engineers, London.
Received for review March 14, 1983
Accepted December 16, 1983
The results included here were obtained in two separate studies.
One was funded by the South African Forestry Council through
Raphael Katzen Associates, Cincinnati, OH, and the other by the
Biomass Energy Systems Division of the U.S. Department of
Energy.

Vapor Adsorption of n-Hexane and n-Heptane on Retorted Oil

Shales

Enayat O. Pedram and Anthony L. Hines*

Department of Chemical Engineering, University of Wyoming, Laramie, Wyoming 82071

Adsorption isotherms of n-hexane and n-heptane on two different retorted oil shales were determined gravimetrically
at 284.3, 293.7, and 303.2 K up to their saturation pressures. The analyses of the experimental data were carried
out by using Poianyi's potential theory and the theory of pore filling proposed by Dubinin and co-workers. A single
generalized characteristic curve which correlates the equilibrium adsorption for different hydrocarbons was obtained
by using the ratio of characteristic free energies. Using die equilibrium data and surface area which was obtained
by standard nitrogen adsorption, the area occupied by these hydrocarbon molecules on each shale was determined
and has been compared with the literature values. The surface areas for retorted Colorado and Utah shales are
2.1 X 103 m2/kg and 3.4 X 103 m2/kg, respectively. This Indicates that there is very little internal surface area.

Introduction Experimental Section

The two trillion barrels of oil contained in the Green
River oil shale formation of Colorado, Utah, and Wyoming
exceed the total combined reserves of oil and natural gas
from other sources (Nowacki, 1981). Recovery of shale oil
is usually achieved by either one or a combination of two
major processes. In one of these processes, the shale is
mined and the oil is recovered in an above-ground retorting
facility. In the other major process, oil is recovered from
the underground shale formation in an in site process. At
the retorting temperatures and in the presence of water,
the carbon that remains in the shale should be activated
to some extent and should provide an effective adsorbent
for hydrocarbon and combustion gases. Thus, the huge
volume of spent shale represents a potential adsorbent for
controlling off-gases.
In recent studies (Pedram, 1978; Hasanain, 1980), the
adsorption of S02 and HjS on spent shale was investigated
by using a fixed-bed adsorption system. They indicated
that a nonlinear equilibrium relationship existed between
the adsorbate and the spent shale. In this study the ad-
sorption of n-hexane and n-heptane vapor on two different
types of spent shales was investigated. The equilibrium
adsorption data were correlated by the BET model (Bru-
nauer et al., 1938; Brunauer, 1945), the adsorption po-
tential theory (Polanyi, 1914,1916,1920), and the theory
of pore filling proposed by Dubinin and co-workers (Du-
binin, 1960, 1967; Bering et al., 1966, 1972).
Materials. Two types of retorted oil shale were used
in this work. One was obtained from Anvil Points, CO,
and contained 1.24 X 10“4 m3 of oil/kg of shale (29.6
gal/ton of shale). It was retorted in the 150 ton simulated
in situ oil shale retort located at the Laramie Energy
Technology Center in Laramie, WY. The second type of
spent shale was obtained from Hell’s Hole Canyon, UT.
It contained 1.28 X 10~4 m3 of oil/kg of shale (30.6 gal of
oil/ton of shale) and was retorted in an adiabatic batch
retort that was designed to simulate the above ground
Superior Oil direct heated retort.
Each shale sample was prepared by crushing it to a fine
consistency and sieving it to the desired size. The shale
was then thoroughly mixed to yield a homogenous sample
so that variations in the properties of the shale would not
mask the effects of retorting conditions. The samples
selected in this experimental work ranged in size from 20
to 40 U.S. mesh. The n-hexane and n-heptane adsorbates
used in this study had purities of 96.9% and 99.9%, re-
spectively.
Apparatus. The experimental adsorption studies were
carried out gravimetrically using a Cahn R-100 electro-
balance which has a sensitivity of 0.5 pg. The sample
weight was monitored with a strip chart recorder that was
connected to the electrobalance control unit. A refriger-
ated-heated constant temperature bath and a copper
circulation coil wrapped around the sample hangdown tube

0196-4305/84/1123-0728$01.50/0 © 1984 American Chemical Society