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399
Energy & Fuels 1991,5, 399-410
Reviews
Developments in Direct Thermochemical Liquefaction of
Biomass: 1983-1990
D. C. Elliott*
Battelle, Pacific Northwest Laboratories, Box 999, Richland, Washington 99352
D. Beckman
Zeton Inc., Burlington, Ontario, Canada
A. V. Bridgwater
Aston University, Birmingham, United Kingdom
J. P. Diebold
Solar Energy Research Institute, Golden, Colorado
S . B. Gevert
Chalmers University of Technology, Goteborg, Sweden
Y. Solantausta
Technical Research Centre of Finland, Espoo, Finland
Received October 11, 1990. Revised Manuscript Received January 17, 1991
This review catalogs the process research in direct thermochemical conversion of biomass to liquid
hydrocarbon fuels. Subject areas include pyrolysis, high-pressure liquefaction, upgrading of both
pyrolysates and high-pressure oils, supporting analytical and basic research, and technoeconomic
assessments. Much progress is presented for the time period from 1983 to 1990. The pyrolytic
processes with lower investment costs and higher yields of more oxygenated oils are moving more
quickly forward in development. Further development is still required for the upgrading processes
for the production of hydrocarbons from the primary oils. Based on these developments, potential
exists for economical production of substitute liquid hydrocarbon fuels and chemicals from biomass.
Introduction
This paper summarizes the developmenta in the state
of the art of direct liquefaction of biomass from 1983 to
1990. This review is the joint effort from the Working
Group of the International Energy Agency (IEA), Bioenergy activity on direct liquefaction of biomass. The
members of the working group are a team of researchers
representing Canada, the European Community, Finland,
Italy, Sweden, the United Kingdom, and the United Statea.
The information presented in this paper is primarily derived from the research programs which were or are now
under way in the participating countries.
The IEA activity on direct liquefaction of biomass has
evolved in several stages. The objectives of the activity
include
1. identifying potential improvementa to developing
process concepts;
2. evaluating technically and economically the developing processes in direct thermal liquefaction; and
3. promoting information exchange among the participating countries.
0887-0624/91/2505-0399$02.50/0
The initial work of the IEA Working Group, which was

completed in 1984 under the title of Biomass Liquefaction
Test Facility (BLTF), included in its final report a volume
describing the state of the art at that time.' The second
stage of the activity, operating from 1986 to 1988 under
the name Direct Biomass Liquefaction (DBL), continued
the information exchange among the participants begun
in BLTF, but an updated state of the art was not published
as part of the final report? Now, in the third stage of the
activity, Assessment of Liquefaction and Pyrolysis Systems
(ALPS),the expanded group of members has updated the
earlier state-of-the-are review based on the significant
progress made worldwide in this field in the 1980s.
(1) Beckman, D.; Bergh, A.; Elliott, D. C.; Kannel, A. IEA Co-Operatiue Project D l , Biomass Liquefaction Test Facility Project, Volume 2:
State-of-the-Art Reuiew. National Technical Information Service:
Springfield, VA, 1988, DOE NBM-1062 Vol. 2.
(2) Beckman,D.; Elliott,
C.; Gevert, B.;Hbmell, C.; KjebWm, B.;
batman,A,; Solantauta, Y.;"'Ulenheimo, v . Techno-EconomicA8Se88ment of Selected Biomass Liquefaction Processee. Final Report of IEA
Cooperatiue Project Direct Biomass Liquefaction; Technical h e a r c h
Centre of Finland: Espoo, Finland, ISSO, Report 697.
k.
0 1991 American Chemical Society
Reviews
400 Energy & Fuels, Vol. 5, No. 3, 1991
This review is limited to thermal processes that maximize liquid products. By this definition we specifically
omit fermentation fuels, char slurries, or indirect liquefaction products, such as methanol from synthesis gas or
Fisher-Tropsch liquids. The research efforts are categorized according to the two main types of direct liquefaction, pyrolysis and high-pressure liquefaction; biomass
liquids upgrading; other biomass liquefaction research; and
technoeconomic assessments.
Pyrolysis
Pyrolysis processes intended to maximize liquid yields
are presented here. Much of this work is ongoing, and
earlier developments from many of the research groups
were described in the original state-of-the-art review.'
Entrained-Flow Pyrolysis: Georgia Tech Research
Institute, Atlanta, GA. In this system, powdered wood
(0.30-0.42mm) was entrained in a straight tube by a flow
of stoichiometrically combusted flue gases. The heat for
pyrolysis was supplied by these carrier gases. If the carrier
gases were too hot, significant losses from the first-formed
vapors took place to result in higher overall gas yields.
Consequently, fairly large amounts of tempered carrier
gases at 745 "C were used at a carrier-gas-to-biomass
weight ratio of about 8 to supply the heat of pyrolysis to
maximize the yield of oil.
The diameter of the entrained-flow reactor was 15 cm
and the length was 4.4 m, which resulted in a residence
time of 1-2 s. This residence time was a compromise
between the length of time needed to pyrolyze the size of
particles fed on a once-through basis and the need to
minimize the time that the pyrolysis vapors spent in the
reactor. Feeding rates were typically about 15 kg/h and
resulted in yields of 58% organic condensates (moisturefree basis) and 12% char (maf feed) with a total mass
closure of 101% (including the large amount of carrier
gases). The pyrolysate was recovered along with the water
formed in the combustion used to directly heat the carrier
gases, as well as any water formed during pyrolysis, or
which was present as moisture in the feed, resulting in
condensates containing about half water.a4
Vacuum Pyrolysis: Universit6 Laval, Sainte-Foy,
Quebec, Canada. Biomass was pyrolyzed under vacuum
in a staged multiple hearth furnace at typical temperatures
of 350-450 "C. Liquid product fractions were collected
from each stage of the furnace. Feeds studied included
wood chips, bark, agricultural residues, peat, and municipal
solid wastes. Investigationsof energy products, liquid fuels
and charcoal, and chemical products were undertaken.
These studies were conducted in a 20-35 kg/h process
development unit." Work was also undertaken on the
characterization of vaccum pyrolysis products and on the
separation of fine chemicals from the liquid product
fractions using column chromatography.g11
(3) Kovac, R. J.; Gorton, C. W.; ONeil, D. J. Thermochemical Conversion Program Annual Meeting; Solar Energy Research Institute:
Golden, CO, 1988, SERI/CP-231-3356; pp 5-20.
(4) Kovac, R. J.; Gorton, C. W.; ONeil, D. J.; Newman, C. J. Proceedings of the 1987 Biomass Thermochemical Conversion Contractors'
Review Meeting; National Technical Information Service: Springfield,
VA, 1987; CONF-8705212; pp 23-40.
(5) Roy, C.; de C a y i a , B.; Yang, J.; Plfurta, P. In Proceeding8 of the
Seventh Canadran Bioenergy R&D Seminar, Hogan, E., Ed.; Energy,
Mines, and Resources Ministry: Ottawa, Canada, 1989; pp 675-680.
(6) Roy, C.; w a u m i a ! B.; Pakdel, H. In Research in Thermochemical
Biomass Conversion; Bridgwater, A. V., Kueeter, J. L., Eds.; Elsevier
Applied Science: New York, 1988, pp 585-596.
(7) Roy, C.; Lemieux, R.; M a u m i a , B.; Blanchetta, D. In Pyrolysis
Oib from Biomaur: Producing, Analyzing, and Upgrading; Soltea, E. J.,
Milne, T. A,, Eds.; ACS Symposium Seriee No. 378; American Chemical
Society: Washington, DC, 1988; pp 16-30.
Fast Pyrolysis: University of Waterloo, Waterloo,

Ontario, Canada. Researchers developed the Waterloo
Fast Pyrolysis Process, which involved rapid pyrolysis of
biomass in a fluidized sand bed reactor at atmospheric
pressure and temperatures typically from 450 to 500 "C.
Extensive study of the process has been undertaken in two
reactors, a 15-100 g/h bench-scale unit and a 2-3 kg/h
pilot-scale unit. Feedstocks included wood, peat, and
agricultural residues.12-14
Recent research included the following related areas:
1. Pretreatment of wood followed by pyrolysis for the
production of sugars from the cellulose fraction.16J6
2. Recovery of chemicals from the primary liquid
products. 17-19
3. Effect of the use of catalysts in the pyrolysis reaction
which promoted gas production.m
From this research and Ensyn work described below, an
important paper describing the role of temperature in fast
pyrolysis was published.21 It proposed that if the biomass
particle heat-up time to 500 "C, for any reactor, is significantly less than particle residence time, then the temperature of the reactor will be the only variable determining the yields of char, oil, and gases for a given feed
and given gas residence time.
Rapid Thermal Pyrolysis: Ensyn Engineering Associates, Gloucester, Ontario, Canada. The Ensyn
process, referred to as Rapid Thermal Processing, used a
heat-carrying solid particulate to contact the biomass,
giving high heating rates exceeding 10000 "C/s in a specially designed thermal mixer. The feed and solid heat
carrier then passed through a tubular transport reactor in
which the pyrolysis reactions experienced a controlled
residence time at temperature. Pyrolysis temperatures
ranged from 400 to lo00 "C. Feeds studied include various
types of biomass and biomass fractions such as l i i n and
cellulose. Recent research was carried out in a 100 kg/h
pilot
(8)Roy, C.; Pakdel, H. In Proceedings of the Seventh Canadian
Bioenergy R&D Seminar; Hogan, E., Ed.; Energy, Minea, and Reaourcea
Ministry: Ottawa, Canada, 1989; pp 681-686.
(9) Pakdel, H.; Roy, C.; Zeidean, K. In Research in Thermochemical
Biomass Conversion; Bridgwater, A. V., Kueeter, J. L.,Ede.; Elsevier
Applied Science: New York, 1988; pp 572-584.
(10) Pakdel, H.; Roy, C. Biomass 1987,13, 155-171.
(11)Pakdel, H.; Roy, C. In Pyrolysis Oils from Biomass: Producing,
Analyzing, and Upgrading; Soltee, E. J., Milne, T. A., Ede.; ACS Sympoeium Series No. 376; American Chemical Society: Washington, DC,
1988; pp 203-219.
(12) Scott, D. S.; Piskorz, J.; Radlein, D.; Majereki, P.; Czemik, S. In
Proceedings of the Seventh Canadian Bioenergy R&D Seminar, Hogan,
E., Ed.; Energy, Minea, and Resources Ministry: Ottawa, Canada, 1989;
DD 699-704.
- ~ (13) Scott, D. S.; Piskorz, J.; Radlein, D. Ind. Eng. Chem., Process Des.
Dev. 1986,24,581-88.
(14) Piskon, J.; Majereki, P.; Scott, D. S. Can. J. Chem. EM. 1990,
68, 465-472.
(15) Scott, D. S.;Piskorz, J.; Radlein, D.; Czernik, S. In Proceedings
of the Seuenth Canadian Bioenergy R&D Seminar; Hogan,E., Ed.;
Energy, Mines, and Resources Ministry: Ottawa, Canada, 1989; pp
713-720.
(16) Piekorz, J.; Radlein, D.; Scott, D. S.; Czemik, S. In Reseorch in
Thermochemical Biomass Conversion; Bridgwater, A. V., Kueatar, J. L.,
Eds.; Elsevier Applied Science: New York, 1988; pp 557-571.
(17) Radlein, D.; Grinshpun, A.; Piskon, J.; Scott, D. S.J. AM^. Appl.
Pyrolysis 1987, 12, 39-49.
(18) W e i n , D.; Piskorz, J.; Scott, D. S.J.Anal. Appl. &rolysis 1987,
12, 51-59.
(19) Piskorz, J.; Scott, D. S.; Radlein, D. In Pyrolysis Oib from
Biomass: Producing, Analyzing, and Upgrading; Soltea, E. J., M h e , T.
A., Eds.; ACS Symposium Series No.376; American Chemical Society:
Washington, DC, 1988, pp 167-178.
(20) Garg, M.; Scott, D. S.; Piakon, J.; Radlein, D. In Sixth Canadian
Bioenergy R&D Seminar; Granger, C., Ed.; BC Research: Richmond,
B.C., Canada, 1988, pp 476-480.
(21) Scott, D. S.; Plekon, J.; Bergougnou, M. A.; Graham,R.; Overend,
R. P. Ind. Eng. Chem. Res. 1988,27,8-15.
..
Reviews
Vortex Ablative Pyrolysis: Solar Energy Research

Instituta (SERI),Golden, CO. SERI developed the
vortex reactor specifically for the fast pyrolysis of biomass.
The feed particles were forced to slide on the hot cylindrical wall in a helical path through the reactor. The
sliding contact of the particles on the wall resulted in very
high heat transfer to the particle so that ablative pyrolysis
was thought to take place. Partially pyrolyzed particles
exited the reactor tangentially, mixed with fresh feed, and
were recycled back to the carrier gas ejector. The recycle
loop decoupled the residence times of the solids and the
vapors, which allowed the vortex reactor to be insensitive
to the particle size of the feed. The small amount of char
that formed was recycled until it was attrited to a fine
powder (-50 rm).% The typical 2-mm-thick feed particle
made about 30 passes during a total residence time of 1-2
s through the reactor before it was completely pyrolyzed.
Operation was typically at 13-20 kg/h of dry sawdust (-3
mm) with a carrier-gas-to-biomass weight ratio of 1-1.5.
Yields on a dry feed basis have been 67% condensates
(55% moisture-free organic liquids), 13% char, 14% net
pyrolysis gases, and 12% water of pyrolysis for a mass
closure of 94% of the feed (a 98% mass closure, if the
nitrogen carrier gas is included in the calculation^).^^
Interchem has announced the completion of construction
of a vortex reactor for a designed throughput of 1350 kg/h
of dry wood.26
Ongoing studies indicate that a phenolic-rich extract can
easily be prepared from the pyrolysis condensates made
from sawdust, which can be used to replace at least 50%
of the phenol in a phenol-formaldehyde resin at economically attractive costs.% An industrial consortium has been
formed to commercialize this technology.
In related work, the reactor was modified to allow it to
pyrolyze refuse-derived fuel (RDF), which contains tramp
metals and other inert solids. Preliminary operation with
RDF indicated that the plastic-derived condensates interacted with the lignocellulosic-derived condensates to
form an asphalt-appearing material.27i28
Pyrolysis Mill: Colorado School of Mines (CSM),
Golden, CO. The CSM reactor used two specially grooved
disks,6.4cm diameter, made of copper, which were stacked
one on top of the other. The biomass or RDF was centrally
fed between the heated disks. As the bottom disk was
rotated at 4-80 rpm, the feed particles made their way to
the circumference of the disks in a spiral path and were
allowed to fall to a cooler zone. The vapors and gases also
exited a t the circumference of the disks. Maximum reported liquid yields from sawdust were 54% (including
moisture) at disk temperatures of 600 OC, a flow of nitrogen
(22) Graham, R.; Freel, B. A,; Overend, R. P. In Proceedings of the
Seventh Canadian Bioenergy R&D Seminor; Hogan, E., Ed.; Energy,
Minee, and Resources Ministry: Ottawa, Canada, 1989; pp 669-674.
(23) Graham, R. G.; Freel, B. A.; Bergougnou, M. A. In Research in
Thermochemical Biomass Conversion; Bridgwater, A. V., Kueeter, J. L.,
Eds.;Elsevier Applied Science: New York, 1988; pp 629-641.
(24) Diebold, J. P.; Scahill, J. W. In Pyrolysis Oils from Biomass:
Producing, Analyzing, and Upgrading; Soltes, E. J., Milne, T. A., Eds.;
ACS Symposium Series No. 376; American Chemical Society: Waahington, DC, 1988; pp 31-40.
(25) Diebold, J. P.; Power, A. J. In Research in Thermochemical
Biomass Conversion; Bridgwater, A. V., Kuester, J. L., Eds.; Elsevier
Applied Science: New York, pp 609-628.
(26) Johnson, D. In Roceedrngs of the R&D Contractors Meeting on
Biomuss Liquefaction; Hogan, E., Ed.;Energy,
-. Mines, and Resources
Ministry: Ottawa, Canada, in press.
(27) Scahill, J. W.; Diebold, J. P. Thermochemical Conversion Program Annual Meeting; Solar Energy Research Institute: Golden, CO,
1988; SERIfCP-231-3355;pp 237-2146.
(28) piebold, J. P.; Evam, R. J.; ScahiU, J. W. In Energy from Biomass
and Solrd Wastes XIXk Klaes, D. L., Ed.;Institute of Gaa Technolow:
-Chicago, 1990; pp 851-878.
Energy & Fuels, Vol. 5, No. 3, 1991 401
purge gas of 0.5 g of N2per gram of sawdust, and a feeding

rate of 13 n/h.29J"
Fluid-Bid Pyrolysis: Technical Research Centre
of Finland (VTT),Espoo, Finland. Flash pyrolysis of
wood, bark, and peat was studied in a small continuous
(100g/h) fluid bed unit during 1986 and 1987.s11s2This
work was a collaboration between the University of
Waterloo and VTT.
Material balances for the unit were produced, and
products were characterized.% The organic liquid products were separated and identified by gas chromatography-mass spectrometry and characterized by infrared
spectrophotometry and gel permeation chromatography.
The maximum yield of organic liquid products obtained
from pine bark was about 50 wt % and that obtained from
peat was about 40 wt % . The liquid products contained,
at low temperatures below 600 "C, significant amounts of
high-molecular-weightsubstances.
Pyrolysis for Liquids with Partial Combustion:
Alten-Alternative Energy Technologies (a Consortium of KTI and Italenergie), Raiano, Italy. The pyrolysis plant, developed by Alten, has been in operation
from 1985,and was the largest biomass pyrolysis unit (500
kg/h) dedicated to liquid fuel production in Europe. Feed
was screened, rechipped, and dried in a rotary drier before
entering the reactor. Feedstocks tested included wood
chips, olive husks, straw, and vine trimmings. Air was
added to the reactor to give a partial combustion reaction
to provide reaction heat. The reactor operated at about
500 "C and 1 atm. Char byproduct was recovered in a hot
gas cyclone; vapor and gas streams passed through a
quench vessel where they were cooled and condensed by
direct contact with recycle product water. The mixture
of oil and water was separated in a gravity separator.
Excess water was removed from the recycle stream with
a chemical oxygen demand of 150000 ppm.
The yield of raw oil was 20-25 wt % with a similar yield
of charcoal. The raw oil was black and fairly viscous (55
CPat 70 OC). It contained around 31 wt % oxygen, 15 wt
% water, and 10 wt % char in suspension. The density
of the raw oil was 1.195 g/mL.M-37
Low-Temperature Pyrolysis for Liquids and
Charcoal: Tubingen University, Tubingen, West
Germany. The operating principle was to use low temperature (1350"C) and long reaction times (160min) to
give low oxygen content oils.Mi38 The principle was li(29) Reed, T. B. Thermochemical Conversion Program Annual
Meeting; Solar Energy Research Institute: Golden, CO, 1988, SERI/
CP-231-3355;pp 247-258.
(30) Reed, T. B. In Research in Thermochemical Biomass Conversion;
Bridgwater, A. V., Kuester, J. L., Eds.; Elsevier Applied Science: New
York, 1988; pp 192-202.
(31) Scott, D. S.;Piskorz, J.; Westerberg, I.; McKeough, P. Fuel Process. Technol. 1988,18, 81-95.
(32) Arpiainen, V.; Lappi, M.; Nissilii, M. Flash-Pyrolysis of Peat,
Wood, Bark and Lignin. Part 3. Tests with Peat and Pine Bark;
Technical Research Centre: Espoo, Finland, 1989.
(33) Arpiainen, V.; Lappi, M. J. Anal. Appl. Pyrolysis 1989, 16,
355-376.
(34) Bridgwater, A. V.; Graasi, G. Biomass Pyrolysis Liquids Upgrading and Utilisation; Elsevier Applied Science: London, in press.
(35) Antonelli, L. In Energy from Biomuss 4, Proceedings of the !Third
Contractors' Meeting; Graeai, G., Pirrwitz, D., Zibetti, H., Eds.; Elsevier
Applied Science: London, 1989; p 485.
(36) Antonelli, L. Energy from Biomass 4 , Proceedings of the Third
Contractors' Meeting; Graeai, G., Pirrwitz, D., Zibetti, H., Eds.; Elsevier
Applied Science: London, 1989; p 531.
(37) Antonelli, L. Improvement of Pyrolysis Conversion Technology
Utilising Agricultural and Forestry Wastes; EEC Contract No. EN3B0121-1, interim and final reports; European Economic Community:
Brussels, 1988, 1989.
(38) Bayer, E.; Kutubuddin, M. In Research in Thermochemical
Biomass Conuersion; Bridgwater, A. V., Kuester, J. L., Me.; Elsevier
censed to several organizations in Europe, North America,

and Australia, and several plants of up to 2 tons/h were
operating or were under construction based on sewage
sludge or municipal solid w a ~ t e . ~ ~ ~ ~
At a laboratory scale, both batch and continuous screw
reactors were used with sewage sludge, MSW, wood, and
agricultural waste. In the batch tests, dewatered sludge
or other biomass was heated slowly to 300-350 "C in an
oxygen-free environment for about 20 min, and the liquid
product collected in an ice-cooled bath. The continuous
unit was based on an indirectly heated auger kiln. No
additives were needed as the silica, silicates, and heavy
metals present in the sludge were claimed to act as catalysts. The vapor was condensed and collected. Oil yields
ranging from 18 to 27 wt % and char yields from 50 to 60
wt % were achieved. The H:C atomic ratio was around
1.7 and the oxygen content about 15 wt 90from biomass
and below 5 wt % from sewage s l ~ d g e . ~ ~ * ~ l
Updraft Fixed-Bed Pyrolysis for Charcoal and
Bio-Oil: BioAlternative S.A., Switzerland,Spain, and
Italy. Feedstocks tested included wood, MSW, bark,
sawdust, grape wastes, olive oil wastes, and coconut shells.
The feed, in particle sizes ranging from 5 to 500 mm, was
first crushed and dried (optimal moisture content 10% to
15%) before being transported to the top of the reactor
from the feed hopper. A unit 3 m high and 1 m in diameter
had a capacity of about 50 kg/h. It was fitted with an
interlocked twin feed hopper fed by a screw feeder. A
horizontal stirrer and a vibrator were used to prevent
bridging of the feed in the reactor. The heat necessary for
the reaction was obtained through internal combustion,
regulated by a system of air injection tuyeres. The system
was operated at slightly below atmospheric p r e s s ~ r e . ~ * ' S ~
Product vapor left the top of the reactor at 120 "C and
was contacted with hot pyrolysis oil to condense a single-phase product oil while keeping most of the water in
the gas phase. The gas with about 10-20% water was
blown to a boiler for cofiring with fuel oil, thereby incinerating the wastewater.A3The oil yield was 6 1 3 % and the
char yield was 28-32%. The H:C atomic ratio of the oil
was 1.46; the oxygen content was about 35 wt %; the
viscosity varied from 250 CPa t 60 "C to 10 CPat 70 "C;
and the density was 1.21 g/mL. The liquid product was
successfully used as a boiler fuel.
High-pressure Liquefaction
The focus of biomass liquefaction has shifted away from
high-pressure processes in the past 5 years. Research has
shown that the fast pyrolysis oils, although of higher oxygen content, are less viscous and can be produced in
greater yields at less cost. Since the high-pressure oil
appears to no longer hold any significant advantage in the
upgrading arena, the production cost of the primary oil
appears to be decisive. Most of the research efforts described in this section are continuations of work cited in
the earlier review.' Many of the original programs described in the earlier review are no longer active, and only
a few new studies have begun.
(39) Bridle, T. R.; Campbell, H. W.; Sachdev, A.; Marvan, 1. Thermal
Convemion of Sewage Sludge to Liquid and Solid Fuels. Can.Soc. Chem.
Eng. Conf., Toronto, Oct 1983 1983.
(40) Bridle, T. R. Enuiron. Technol. Lett. 1982, 3, 161.
(41) Bayer, E. Proceedings of the Conference Verfahrenstechnik der
Klarschlammoerwertung; VDI: Baden-Baden, 1984; pp 141-156.
(42) BioAltemative. In Proceedings of a Worhhop held in L'Aquila,
Italy; EUR 11382 EN; Mattucci, E., Graesi, G.,Palz, W., Eds.; Commission of the European Communities: Brussels, 1989; p 206.
(43) Manufacturer's information: BioAlternative, S.A., Engollen,
Neuchatel, Switzerland.
Reviews
One attempt has been made at a unified treatment of

the biomass liquefaction experimental data in the literaturea4 That study concluded that the rate-determining
step was dissolution of the solid substrate. Further, the
processes could be readily separated into those based on
hydrolytic cleavage in aqueous media followed by formation of oil product and those that primarily use pyrolysis
to simultaneouslysolubilize and produce oil in nonaqueous
media.
Extrusion-Fed Reactor System: University of Arizona, Tucson, AZ. The liquefaction of biomass in
pressurized solvents was demonstrated at The U.S. Department of Energy's (DOE) Biomass Liquefaction Experimental Facility, formerly at Albany, OR, in the late
1970s and early 1980s.' This process was operated at 21
MPa pressure, 20 min residence time, with a sodium
carbonate catalyst at a throughput of 18 kg of wood/h.
Research in this area was shifted to the University of
Arizona in the early 1980s and has focused on improving
the solids content of the slurry of biomass solids fed into
the high-pressure reactor. Higher contents of biomass in
the feed allow a smaller, more economical reactor vessel
to be used for a given throughput.
Mixtures containing as much as 60% wood flour in
product oil have been pumped into pressurized containers,
using a modified extruder originally designed to extrude
plastics. With this technique, early liquefaction experiments at the University of Arizona were conducted at
375-400 OC, 5.5-21 MPa pressure, on 40% wood flour in
Albany oil with a residence time of between 1 and 4 h, and
both with and without carbon monoxide and sodium
carbonate catalyst. Recent exprimentation was directed
toward the recycling of the product oil containing approximately 40% fresh wood flour, along with water and
carbon monoxide to result in a carrier oil composed primarily of material made at the University of Arizona. The
fluid product distilled from the carrier oil had a heating
value of 37 MJ/kg and a residual oxygen content of
7-10%
Rough calculations of the oil yield showed that
it was 80% to close to 100% of that theoreticallyattainable
(48% to 58%, depending on assumptions)."
The
throughput of dry wood was 5-14 kg/h.
Peat Liquefaction: Royal Institute of Technology
(KTH), Stockholm, Sweden. Liquefaction of peat at
KTH was accomplished by two different methods. In the
wet concept, the peat was not dried before liquefaction and
the water could be decanted off after liquefaction. In the
other method, the peat was dried and liquefied in a hydrogen donor solvent.
The wet process research especially addressed the effect
of selection of raw materials. The calorific value and the
oxygen content were better bases of selection of peat for
liquefaction than the degree of humification. The conclusions concerning the peat raw material were general and
could probably be used in systems other than liquefaction
of wet peat.4g62
(44) Overend, R. P.; Chomet, E. In Research in Thermochemical
Biomass Conuersion; Bridgwater, A. V., Kuester, J. L., Eds.; Elsevier
(46) White, D. H.; Wolf, D.; Zhao, Y. Prepr. Pap.-Am. Chem. SOC.,
Diu. Fuel Chem. 1987,32(2), 106-116.
(46)White, D. H.; Wolf, D. Thermochemical Conuersion Program
Annual Meeting; Solar Energy Research Institute Golden, CO, 1988,
SERI/CP-231-3355, pp 67-66.
(47) White, D. H.; Wolf, D. In Research in Thermochemical Biomass
Conuersion; Bridgwater, A. V., Kuester, J. L., Ede.; Elsevier Applied
Science: New York, 1988; pp 827-842.
(48) BjBmbom, E.; Oleson, B.; Karleson, 0.Fuel 1986,65,1061-1066.
(49) BjBrnbom, P.; Karleson, 0.;
H6mell, C.; BjBmbom, E.; Pyamali,
M. Int. Peat J. 1987,2, 137-162.
Energy & Fuekr, Vol. 5, No.3, 1991 403
Reviews
Liquefaction of dry peat has been carried out in a synachieved in less than 1min. The physical processes which
thetic solvent containing tetralin, naphthalene, and poccurred at the macro scale were evaluated in particular
cresol to evaluate the type of properties needed for a reby using a scanning electron microscope.m@ The photographs obtained clearly showed the softening and flowing
cycle solvent.63 As has been generally found, the hydrogen-donating properties of the solvent are more effective
of the matrix at temperatures of 280 OC. Other activities
included steam/water pyrolysis of cellulose and analysis
if the solvent contained hydroaromatic functionality. The
dissolution of the peat was increased with the hydrogenof products for valuable chemical^.^^
donating capacity of the solvent. The molecular distriHigh-PressureLiquefaction: V",
Espoo,Finland.
bution was increased with increased dissolution.
High-pressure liquefaction of peat was studied experiA method for analyzing the content of different funcmentally from 1982 to 1986.88 Although the studied
tional groups has been developed based on infrared
concept was assessed feasible, interest toward synfuel respectra, as were calibration curves on a large number of
search in Finland was diminishing. The emphasis was
compounds with different functional groups." Related
shifted to conversion of black liquor, since the process
work dealt with analysis by gel permeation chromatograconcept studied offered considerable p ~ t e n t i a l . ~ ~
p h ~ . ~ ~
The peat liquefaction research that began at V" in the
Liquefaction via Solvolysis: University of Sherbeginning of the decade was concluded with an experibrooke, Sherbrooke, Quebec, Canada. Investigations
mental study of the hydroprocessing of peat tar in
of processes for the fractionation and liquefaction of
1988-1989 together with the University of Toronto.70
biomass were undertaken. The importance of solvent type
High yields of liquid hydrocarbons were produced. The
on these processes was identified.Mi57 Poplar or aspen
study confirmed one of the results of the DBL project,
wood and cellulose were treated in aqueous media at
which concluded peat was the most economic feedstock
temperatures from 150 to 270 "C, using passage through
alternative for biomass-based transportation fuel proa homogenizing valve to solubilize the c ~ m p o n e n t a . ~ ~ duction.
~~
Peat has chemical properties that make it suitable
Further studies were reported with the woods in nonafor conversion to liquid products.
queous media, creosote, and ethylene glycol.soS1 With the
Presently the emphasis on direct liquefaction at VTT
homogenizing valve as a pretreatment means for prepais focused on the conversion of black liq~or.7~" The yield
ration of the feed slurry, oil yields of 4040% were obof organic phase is around 40 wt % of black liquor organics.
tained at 340 "C in 4-6 min at a feed rate of 4 kg/h (of
Production of fuel oil substitute at a pulp mill offers
dry wood) in a tubular reactor system.
considerable promise in some cases. The primary liquid
More recent processes studied were (1)thermomechanproduct has been successfully hydrotreated in batch teats.75
ical vapor-cracking, (2) continuous steam/aqueous fracThe aim of upgrading is to improve the quality of liquid
tionation, and (3) thermochemical solvolytic process.
product for a gas turbine fuel.
These studies were aimed at determining and optimizing
A major part of the black liquor research has been the
the recoveries of the various biomass fractions. The
analytical effort.7B*T7
Among others, methods to determine
feedstock tested was poplar wood (Populus deltoides)F2
the degradation products of holocelluloses have been deSteam/Water Liquefaction: University of Toronto,
veloped.
Toronto, Ontario, Canada. Recent research at the
Cooperation on upgrading of black liquor and degraded
University of Toronto involved the rapid steam/water
lignin within the European Community JOULE program
pyrolysis of wood at sizes significantly larger than typical
is planned.
powdered feeds. In laboratory studies, poplar or willow
Some research work on peat hydrotreatment was also
wood, in the form of chips, sticks, and dowels up to 3 cm
conducted earlier at the University of Oulu, Finland.78
diameter, was pyrolyzed by steam injection at temperatures from 330 to 350 "C, in a 600-mL cylindrical batch
r e a c t ~ r . ~Acetone-soluble
~,~
oil yields of 40-50% were
(64)Boocock, D. G. B.; Chowdhury, A.; Koeiak, L.; Fruchtl, R. A. In
(50) Bjambom, P.; Bjambom, E. Fuel 1987,66,779-784.
(51) Bjbmbom, P.; Bjbmbom, E:Fuel 1988,67, 1589-1592.
(52) BjBmbom, E.; BjBmbom, P.; K a r h n , 0.Fuel Process. Techno[.
1988,17, 263-276.
(53) HBmell, C.; Bjambom, P. Fuel 1989,68,491-497.
(54) Karlsson, 0. Fuel 1990,69,613-616.
(56) Karlsson, 0. Fuel 1990,69,608-612.
(56) Vanaeee, C.; Chornet, E.; Lemonnier, J. P.; Heitz, M.; Overend,
R. P. In Sixth Canadian Bioenergy R&D Seminar; Granger, C., Ed.; BC
Research: Richmond, B.C., Canada, 1988; pp 457-462.
(57) Heitz, M.; Vincent, D.; Chomet, E.; Overend, R. P.; Sastre, H. In
Research in Thermochemical Biomass Conversion; Bridgwater, A. V.,
Kuester, J. L., Eds.; Elsevier Applied Science: New York, 1988, pp
429-438.
(58) Heitz, M.; Carrasco, F.; Rubio, M.; Chauvette, G.; Chornet, E.;
Jaulin, L.; Overend, R. P. Can. J. Chem. Eng. 1986,64,647-650.
(69) Abatzoglou, N.; Bouchard, J.; Chornet, E.; Overend, R. P. Can.
J. Chem. Eng. 1986,64,781-786.
(60)Vaneme, C.; Lemonnier, J. P.; Eugane, D.; Chomet, E.; Overend,

R. P. Can. J. Chem. Eng. 1988,66, 107-111.
(61) Vaname, C.; Chomet, E.; Overend, R. P. Can. J. Chem. Eng. 1988,
66,112-120.
(62) Bouchard, J.; Nguyen, T. S.;Chomet, E.; Overend, R. P. In Proceedings of the Seuenth Canadian Bioenergy R&LISeminar; Hogan, E.,
Ed.; Energy, Mines, and Resources Ministry: Ottawa, Canada, 1989; pp
42-29.
(63) Boocock, D. G. B.; Chowdhury, A.; Koaiak, L. In Research in
Thermochemical Biomcure Conversion;Bridgwater, A. V., Kueeter, J. L.,
Ede.; Elsevier Applied Science: New York, 1988; pp 843-853.
Proceedings of the Beuenth Canadian Bioenergy R&D Seminar; Hogan,

E., Ed.; Energy, Mines, and Resources Ministry: Ottawa, Canada, 1989;
pp 693-698.
(65) Boocock, D. G. B.; Porretta, F. J. Wood Chem. Technol. 1986,6,
127-144.
(66) Boocock, D. G. B.; Kosiak, L. Can. J. Chem. Eng. 1988, 66,

121-126.
(67) Boocock, D. G. B.; Allen, S. G.; Chowdhury, A.; Fruchtl, R. In

Pyrolysis Oils from Biomass: Producing, Analyzing, and Upgrading;
Soltes, E. J., Milne, T. A., Eds.; ACS Symposium Series No. 376; American Chemical Society: Washington, DC, 1988; pp 92-103.
(68) McKeough, P.; Tulenheimo, V. Techno-EconomicAssessment of
High-Pressure Peat Liquefaction; Technical Research Centre: Eepoo,
Finland, 1987; Research Report No. 492.
(69) Technical and Economic Prospects for a Black Liquor Conuersion Process; Study for V l T by Jaakko P6yry Ltd.,Helsinki, 1987.
(70) Oasmaa, A. "Upgrading of Peat Pyrolysis Oil". Internal report,
Technical Research Centre: Espoo, Finland, 1989.
(71) Johaneson, A. Biomass 1984,4, 155-160.
(72) McKeough, P.; Johanason, A. Pyrolysis Oils from Biomass:
Producing, Analyzing, and Upgrading; Soltes, E. J., Milne, T. A,, E&.;
ACS Symposium Series No. 376; American Chemical Society: Washington, DC, 1988; pp 104-112.
(73) McKeough, P.; A h , R.; Oasmaa,A,; Johaneeon, A. Roc. 4th Ew.
Conf. Biomass, Orleans, Fr. May 11-15,1987 1987.
(74) A h , R.; McKeough, P.; Oasmaa, A.; Johansson, A. J. Wood
Chem. Technol. 1989,9, 265-276.
(75) Elliott, D. C.; Oasmaa, A. Energy Fuels 1991,5, 102.
(76) A h , R.; Oasmaa, A. Acta Chem. Scand. B 1988, 42, 563-666.
(77) AlBn, R.; Oasmaa, A. Holzforschung 1988,43, 166-158.
(78) Ala-aho, P. Turueteollisuw 1984,5, 62-67 (in Finnish).
Reviews
High-pressure Liquefaction: Manoil/University of

Manchester Institute of Science and Technology,
Manchester, United Kingdom. Some early work was
carried out with a ruthenium catalyst supported on alumina silicate in an aqueous medium, but recent work was
carried out in tetralin or recycle oil with a nickel catalyst.7w1 Liquefaction of cellulose and organic constituents
of dry municipal refuse, dried sewage, and straw was
studied in the temperature range of 250-400 "C at about
10 MPa pressure and without additions of reducing gas.
Oil yields were about 35 wt %.
Catalytic Hydroliquefaction: Institute of Wood
Chemistry, Hamburg, Germany. A single-step process
was investigated at the Federal Research Centre for Forestry and Forest Products in Hamburg. Catalytic hydroliquefaction in the liquid phase was conducted using a
three 1-Lcapacity autoclave system, consisting of a reactor,
hot separator, and cooler for simulation of a continuous
process. Small biomass particles were mixed with recycle
oil (starting oil was a mixture of pyrolysis oil with pitch
tar from tall oil distillation) with catalysts.82-86
The most favorable results were obtained with palladium
on active charcoal or iron catalysts.sB The conversion
reaction was carried out at about 20 MPa of hydrogen at
380 "C for 15 min. Liquid products in the gas phase were
flash-distilled in the hot separator. The bottom residue
was used as carrier oil, and the remaining products were
cooled down to room temperature to yield a light and
middle distillate net product with a boiling range between
80 and 360 "C. The oil was 99% miscible with n-hexane
and had an oxygen content of about 12%. With respect
to the energy balance, 59% of the input energy (biomass
and hydrogen) was contained in the net product
High-pressure Liquefaction and Hydrotreating:
Technical University of Berlin, Berlin, Germany, At
the Technical University of Berlin the conversion of
biomass was studied in a two-step process. In the first
stage, the biomass was extracted with tetralin at 300-400
"C at about 4 MPa pressure. The extract, which yielded
about 55%, was mixed again with tetralin and catalytically
hydrotreated with sulfided NiMo catalyst at 35 MPa, at
temperatures between 300 and 450 "C, and a carrier oil
to biomass derived oil ratio of 2. The oil from biomass had
an oxygen content below 1%.88
Iron-Catalyzed Pressurized Aqueous Pyrolysis:
Ecole Nationale Superieure de Chimie, Rennes,
France. Laboratory-scale batch autoclaves were used to
study liquefaction of poplar in water slurries at 340 "C.
Iron seemed to be an effective additive but was oxidized
in the process to Fe304. The addition of other iron additives such as oxalate and hydroxide gave nearly as good
(79) Bean, F. R.; McAuliffe, C. A. 'Conversion of Municipal Waste to
Fuel"; Canadian patent No. 1,164,378, issued March 27, 1984.
(80) Benn, F. R.; McAuliffe, C. A. 'Conversion of Municipal Refuse
to Fuel"; UK patent application No. 2,166,1546, filed Sept. 15, 1984.
(81) Bult, J. M. E. "The MANOIL Project", presented at the 89th
AMual Conference of the Institute of Wastes Management, Torbay, UK,
June 16-19, 1987.
(82) Meier, D.; Larimer, D. R.; Faix, 0. Fuel 1986,65, 910-915.
(83) Meier, D.; Larimer, D. R.; Faix, 0. Fuel 1986,66, 916-921.
(84) Meier, D.; Fuchs, K.; Faix, 0. In Energy from Biomass and
Wastes X Klaee, D. L., Ed.;Institute of Gas Technology: Chicago, 1987;
pp 785-800.
(85) Meier, D.; Faix, 0. In Research in Thermochemical Biomass
Conuersion; Bridgwater, A. V. Kuester, J. L., Eds.; Elsevier Applied
Science: New York, pp 804-815.
(86)Meier, D.; Faix, 0. R o c . 4th Int. Symp. Wood Pulping Chem.,
Paris 1987; 2, 407-410.
(87) Meier, D.; Faix, 0. Euroforum New Energies, R o c . Int. Congr.,
Saarbrucken, FRC, Oct.24-28 1988,670-672.
(88)Nelte, A.; Meier Zu Kokcker, H. Euroforum New Energies, Proc.
Int. Congr., Saarbrucken, FRG, Oct. 24-28 1988,673-675.
results while the addition of oxides or sulfate was ineffective. The addition of chloride had a profound negative
effect on the liquid product yields. The iron effect was
most useful in slow heatup types of experiments. Fast
heatup experiments were found to be more useful for
higher yields of oil production (>40% CH2Cll soluble).
The use of reducing gas appeared to have little effect on
the liquefaction compared to the use of inert gas only at
4-6 MPa initial pressure.miw
Combined Solvolysis and Upgrading: University
of Technology, Compiegne, France. An acid-catalyzed
phenolic depolymerization of wood was used to liquefy oak
in water in 260 O C (30min at temperature). A secondary
hydrotreatment at 330 "C, 30 min, CoMo catalyst, and 2
MPa of hydrogen initial pressure followed to produce an
oil product and regenerate the phenol. The process was
studied batchwise with batchwise recycle of the upgraded
product for up to seven cycles. Water yield was high, 30%
on dry wood basis. Gas production and product oil viscosity increased throughout the tests. Phenol consumption
continued through the first five cycles and then ceased.
Hydrogen consumption was small, <1.5% on dry wood
basis. Light product fraction yield was presented as 25%
and heavy fraction at 30%. Coke yield was 5% and gas
yield was 10%.g1*g2
Alkali-Catalyzed Liquefaction: National Research
Institute for Pollution a n d Resources, Tsukuba,
Ibaraki, Japan. Extensive testing in batch reactors was
performed to evaluate the liquefaction of biomass in water
slurries in a pressurized system at 250-400 "C. Many types
of wood and several fermentation stillages were tested as
feedstock. A heavy oil product which spontaneously separated from the water phase upon cooling was produced
in all cases when an alkali-metal carbonate catalyst was
added to the system. The typical yield from the stillages
at 300 "C was around 50% of an oil containing up to 6%
nitrogen with about 35 MJ/kg. The energy content and
the mass yield of heavy oil were inversely related; and
lower yields of higher energy products were produced at
higher temperature or longer residence
Upgrading of Biomass Liquefaction Products
Research efforts continue to develop methods of upgrading both pyrolysis oils and high-pressure liquefaction
oils. These efforts include pyrolysate upgrading by catalytic hydroprocessing and by zeolitic catalytic cracking.
High-pressure oil upgrading by catalytic hydroprocessing
is also being tested. A limited review of this work has
already been p u b l i ~ h e d . ~ ~
(89) Soyer, N.; Hyvrard, F.; Bruneau, C.; Brault, A. In Pyrolysis Oils
from Biomass: Producing, Analyzing, and Upgrading; Soltes, E. J.,
Milne, T. A., Us.; ACS Symposium Series No. 376; American Chemical
Societv: Washineton. DC. 1988: DD 220-227.
(9OjBestue-Ltibazuy, C.; Soye;,-N.; Bruneau, C.; Brault, A. Can. J.
Chem. Eng. 1985,63, 634-638.
(91) Bouvier, J. M.; Gelus, M.; Maugendre, S. In Pyrolysis Oils from
Biomass: Producing, Analyzing, and Upgrading; Soltee, E. J., Milne, T.
A,, Eds.; ACS Symposium Series No. 376; American Chemical Society:
Washington, DC, 1988; pp 129-138.
(92) Bouvier, J. M.; Gelus, M.; Maugendre, S. Appl. Energy 1988,30,
--
A F A--.
R.
(93) Yokoyama, S.-Y.; Ogi, T.; Koguchi, K.; Nakamura, E. Liq. Fuels
Technol. 1984,2(2), 155-163.
(94) Ogi, T.; Yokoyama, S.-Y.; Koguchi, K. J . Jpn. Pet. Inst. 1985,
28(3), 239-245.
(95) Yokoyama, S.-Y.;Ogi, T.; Koguchi, K.; Murakami, M.; Suzuki, A.
J . Jpn. Pet. Inst. 1986,29(3), 262-266.
(96)Yokoyama, S.-Y.: Suzuki, A,: Murakami, M. Chem. Lett., Chem.
SOC.Jpn. 1966,649452.
(97) Yokoyama, S.-Y.; Ogi, T.; Koguchi, K.; Minowa, T.; Murakami,
M.; Suzuki, A. In Research in Thermochemical Biomass Conversion;
Bridgwater, A. V., Kueeter, J. L., Eds.; Elsevier Applied Science: New
York, 1988; pp 792-803.
Reviews
Energy & Fuels, Vol. 5,No.3, 1991 405
Two-step Catalytic Hydrotreating of Pyrolysis
Oils: Pacific Northwest Laboratory (PNL),Richland,
WA. A two-step hydrotreating process was developed for

production of hydrocarbon fuels from biomass pyrolysis
oils. All studies were performed in a continuously fed 1-L
fixed catalytic bed. In the first step, a low-temperature
(no"C, 13.8 MPa) catalytic (sulfidedcobalt-molybdenum
on alumina) treatment was used to process the thermally
unstable pyrolysate into a tar similar to the high-pressure
liquefaction product. This tar was then hydrodeoxygenated and hydrocracked by conventional hydrotreating techniques (400 "C, 13.8MPa) to produce gasoline.
The use of the sulftded cobalt-molybdenum catalyst at 350
"C and 13.8 MPa in a single-step process with the pyrolysate produced only limited quantities of hydrocarbon
product before the catalytic bed plugged with cokelike
material.
The low-temperature stabilization of pyrolysis oil was
determined to be a catalytic hydrotreating process. Although hydrogen consumption was low (30 L/L of oil),
operation in the absence of hydrogen eventually led to high
levels of coke formation on the catalyst. In the absence
of the catalytic metals, the bed plugged almost immediately.WJw
The two-step process was also performed in a single
reactor vessel by means of a nonisothermal catalyst bed.
In that case the pyrolysate was fed with hydrogen to the
bottom of the upflow reactor, which was maintained at low
temperature (<300 "C). The feed flowed (0.1 L of oil/L
of catalyst/h LHSV)upward into the higher temperature
(400 "C) portions of the catalyst bed and exited the top
as a mixture of water vapor, hydrocarbons, and carbon
oxide gases. Yields of 0.4 L/L of oil of a hydrocarbon
liquid (<1% oxygen) were achieved.lol A similar successful test was performed with a peat-derived pyrolysate,
and gasoline-range hydrocarbons were produced.lo2
Catalytic Hydroprocessing of Updraft Gasifier
Oils: Texas A&M University, College Station, TX.
Experimentation involved both batch reactor studies and
trickle-bed tests. Twenty different catalysts were tested
in the batch reactor with either a decalin or methylcyclohexane solvent system for pine pyrolysate. Nobel metal
catalysts (5% Pt or Pd on support) generally gave superior
results in hydrocarbon conversion and water yield compared with more conventional hydrotreating catalysts.
Trickle-bed experiments were used to study the effects of
reaction temperature, pressure, and space velocity on oxygen removal from pine pyrolysate in decalin solvent. The
Pt/A1,03 catalyst exhibited the best activity for oxygen
removal, while the Ni-W catalyst was dropped from further study because of its inactivity. The results were
modeled, and a clear trend of the effect of pressure and
temperature on oxygen removal was noted; however, space
velocity had no clear effect.
The trickle-bed reactor consisted of an 81.3-cm-long 316
SS tube. The bottom 30.5 cm contained an inert support
with the top 50.8 cm packed with catalyst. The bottom
~~
(9s) Elliott, D. C. In Research in Thermochemical Biomass Conuer-
eion; Bridgewater, A. V., Kuester, J. L., Eds.; Elsevier Applied Science:

New York, 1988, pp 1170-1176.
(99) Elliott, D. C.; Baker, E. G. In Energy from Biomass and Waste
X , Klaes, D. L. Ed.; Institute of Gae Technology: Chicago, 1987; pp
765-784.
(100) Elliott, D. C.; Baker, E. G. 'Process For Upgrading Biomass
Pyrolyzates"; U.S. patent No. 4,795,841, issued January 3, 1989.
(101) Baker, E. G.; Elliott, D. C. In Research in Thermochemical

(102) Elliott, D. C.; Baker, E. G.; Piskon, J.; Scott, D. S.; Solantaueta,
Y. Energy Fuels 1988,2, 234-235.
55.9 cm of the reactor was immersed in a salt bath so that

the bottom half of the catalyst bed was a t uniform temperature. A t the same time the temperature of the nonimmersed top half decreased linearly from near the reaction temperature at the top of the salt bath to 190 O C at
the top of the reactor. Typical operating conditions were
hydrogen feed of 100 mL/min per gram of pyrolysate oil
at 5.2-10.4 MPa; liquid feed diluted at 2 g of decalin per
gram of pyrolysate oil; weight hourly space velocities of
0.5-3.0 g oil/(g of catalyst h); and temperature of 400 "C
with a catalyst load of 60 g.lo3JM
Catalytic Hydrotreating: Universit6 Catholique de
Louvain, Louvain, Belgium. Two different pyrolysis oils
produced at the pyrolysis unit in Raiano, Italy, and operated by Alten Consortium were hydrotreated in a batch
reactor. The catalysts tested at typical hydrotreating
conditions were CoMo, NiMo, and NiMo on a phosphorus-treated alumina support. One of the oils was produced
from wood and contained 30% oxygen; the other was
produced from olive husks, a lignin-rich material, and
contained 15% oxygen and 3% nitrogen.
The hydrotreatment was effected in two stages (at 250
and 380 "C), but the wood-derived oil showed only a very
limited upgrading because the batch reactor did not allow
optimal contact time. Under the same conditions the
olive-husk-derived oil showed 70% hydrodeoxygenation
but only 58% hydrodenitrogenation. With this oil the
hydrogen consumption rate was very high above 230 "C.
Wood-derived oil showed good conversion only in the
presence of a hydrogen donor solvent (tetralin). The
difference in the reactivity of the oils may be due to the
oxygen content and the nature of the oxygenated functional groups; in fact, the olive-husk-derived oil consisted
mostly of phenolic hydroxyl with a very low acid content.
This study reemphasized that the nature of the oils to be
treated is very important and suggested that bio-oils derived from lignin constitute the best feed for hydrotreatment.106J0e
Catalytic Hydrotreatment of Fast Pyrolysis Lignins: University of Waterloo, Waterloo, Ontario,
Canada. Catalytic hydrotreatment has been undertaken
in a continous-flow reactor with the lignin-derived pyrolysis
fraction from the Waterloo Fast Pyrolysis Process. A
nonisothermal catalyst bed was used containing sulfided
CoMo catalyst. Reported yields were 6144% of light
organic liquids (0.5% oxygen, by difference) from the
pyrolytic lignin; pyrolytic lignin was 21.2% of the original
hog fuel feed. A substantial aromatic content (38% aromatic carbon by 13C NMR) remained in the upgraded
product with naphthenes and hydroaromatics also prominent.lo7
Low-Pressure Zeolitic Upgrading: SERI,Golden,
CO. An altrenative to the high-pressure upgrading of the
pyrolysis oil is to use zeolite catalysts at atmospheric
pressures without added hydrogen. Although the molecular weight of the condensed pyrolysis oils has been found
typically to be between 500 and 2000, researchers at SERI
determined that the pyrolysis vapors generally had much
lower molecular weights, less than 200. The molecular size
(103) Soltes, E. J.; Lin, S-C. K. Progress in Biomass Conversion; Academic Press: New York, 1984; Vol. V, pp 1-68.
(104) Soltes, E. J.; Lin, 5-C. K.; Sheu, Y-H. E. Prepr. Pap.-Chem.
1987, 32(2), 229-239.
(105) Churin, E.; Grange, P.; D+non, B. EEC Contract EN3B-0097-B,
Final Report; European Economic Community: Brussels, 1990.
(106) Chur!n, E.;Maggi, R.; Grange, P.; Delmon, B. In Research in
Thermochemrcal Bcomass Conversion; Bridgwater, A. V., Kueeter, J. L.,

(107) Piskon, J., Majereki, P., Radlein, D., Scott, D. S. Energy Fuels
1989,3,723-726.
Reviews
and shape of most of the identified compounds were small

enough to enter the H-ZSM-5 pore. Preliminary experiments with H-ZSM-5 catalyst confirmed that a small
amount of catalyst was sufficient to change the product
slate from the oxygenated pyrolysis vapors to a highly
aromatic gasoline product. This process has been studied
extensively by using the molecular beam/mass spectrometer (MB/MS), which allowed the product slate to be examined in real time as the catalyst aged in a fixed bed of
10 g of H-ZSM-5 catalyst. A process variable study was
conducted to identify optimal operating conditions, which
were found to be quite different from those used to convert
methanol to gasoline. Empirical equations were fit to the
data to result in parametric contour plots illustrating the
effects of the process variables on the yields. Hydrocarbon
product yields, including olefins, were around 15 wt % of
the dry feed, when steam was used as the carrier gas, at
a weight hourly space velocity of between 1 and 4 g of
wood/(g of catalyst-h) at 525 0C.108-110 Concurrently,
research has been conducted with a larger fEed-bed reactor
having 100 g of catalyst and fed a small slipstream of fresh
pyrolysis vapors directly from the vortex reactor at
SERI.111J12 Hydrocarbon yields, including olefins, from
the slipstream reactor have been 20-25%, including 3 4 %
heavy oils.113 Recent research has been directed toward
recovery of the gaseous olefins as part of the gasoline
product. The gasoline produced consists primarily of alkylated benzenes, e.g., toluene, xylenes, ethylbenzene, and
isopropylbenzene (~umene)."~
Catalytic Processing of Vaccum Pyrolysis Oils:
Laval, Sainte-Foy,Quebec, Canada. Processing similar
to the SERI work was performed at Laval with vacuum
pyrolysis oil fractions. In the Laval setup, the pyrolysis
condensates were preheated in helium and swept into the
bed of 1.0 f 0.2 g of H-ZSM-5. Six pyrolysis fractions were
tested a t temperatures from 350 to 450 "C and LHSV of
0.5-2.5 h-l. Products including gases, coke, C5X10, BTX,
oxygenates, and residuum were collected, quantified, and
analy~ed."~
In a related study, low-temperature catalytic hydrotreatment of the vacuum pyrolysis oil was performed. A
5% Ru on y-alumina catalyst was used at 80-140 "C with
up to 2 h at temperature for an initial hydrogenation/
stabilization step. A subsequent batch step of hydrodeoxygenation at 350 "C was performed with a COO-W03
on y-alumina catalyst to produce an upgraded oil product
(<lo% oxygen content). Other experiments showed that
(108) Evans, R. J.; Milne, T. A. In Pyrolysis Oils from Biomass:
Producing, Analyzing, and Upgrading; Soltes,E. J., Milne, T. A., Eds.,
(109) Evans, R. J.; Filley, J.; Milne, T. A. Thermochemical Conversion
Program Annual Review Meeting; Solar Energy Research Institute:
Golden, CO, 1988; SERI/CP-231-3355; pp 33-43.
(110) Milne, T. A.; Evans, R. J.; Filley, J. In Pyrolysis Oils from
Biomass: Producing, Analyzing, and Upgrading; Soltes, E. J., Milne, T.
A., Eds.; ACS Symposium Series No. 376; American Chemical Society:
Washington, DC, 1988, pp 910-926.
(111) Diebold, J. P.; Scahill, J. W. In Pyrolysis Oils from Biomass:
Producing, Analyzing, and Upgrading; Soltes, E. J., Milne, T. A., Eds.;
(112) Diebold, J. P.; Scahill, J. W. Energy Prog. 1988, 8(1), 54-65.
(113) Scahill, J. W.; Diebold, J. P.; Power, A. J. In Research in
Thermochemical Biomass Conversion;Bridgwater, A. V., Kuester, J. L.,
(114) Diebold, J. P.; Scahill, J. W. Thermochemical Conversion Program Annual Review Meeting; Solar Energy Research Institute: Golden,
CO, SERI/CP-231-3356; 1988, pp 21-32.
(115) Renaud, M.; Grandmaison, J. L.; Roy, C.; Kaliaguine, S. In Pyrolysis Oils from Biomass: M w i n g , Analyzing, and Upgrading;Soltea,
E. J., Milne, T. A., Eds.; ACS Symposium Series No. 376; American
Chemical Society: Washington, DC, 1988, pp 290-310.
copper chromite was an ineffectivehydrogenation catalyst

for the vacuum pyrolysis oils."6
Catalytic Hydrotreatiag/Hydrocracking: PNL,
Richland, WA. Catalytic hydrotreatment of high-pressure liquefaction oils was also studied at PNL using the
continuous-feed, fixed-bed reactor. Commercial hydrotreating catalysts (sulfided CoMo or NiMo on Al,OJ and
conditions (350-400OC and 13.8MPa of H2)were used to
hydrodeoxygenate and hydrocrack the biocrude oils. The
hydrocarbon product, primarily gasoline-range cyclic alkanes and aromatics (75octane [R + M]/2), was produced
in high yields; however, low space velocities were required
(0.1). At high space velocities (OS),a low oxygen, highly
aromatic crude oil was produced. Cracking and hydrogenation of the higher molecular weight components were
concluded to be the rate-limiting steps in the upgrading
process.
Advanced processing configurations were also studied,
including two-stage hydrotreating with hydrocracking of
heavy product and hydrotreating with recycle of heavy
components. Initial tests indicated that both systems
could improve the processing rate and reduce hydrogen
consumption. The combined hydrotreating and hydrocracking systems also had increased yields of gasoline-range
material. Improved catalysts for the hydroprocessing were
identified as a key to process i m p r o ~ e m e n t . ~ ~ ~ - ~ ~ ~
Catalytic Hydrotreating: University of Toronto,
Toronto, Ontario, Canada. Upgrading studies through
catalytic hydrotreatment of model compounds has been
undertaken in a batch reactor system. Early tests were
made with a nonsulfided NiMo on alumina catalyst with
phenol and anisole as the feedstocks." A more in-depth
study of phenolics, including different isomers of dihydroxybenzenes, methoxyphenols, and methylphenols,
was also reported.l2I Since the NiMo catalyst was used
in the oxide form, much higher temperatures were required
in the tests, 350-500 "C, than reported in the bio-oil
treatment work by others.
Zeolitic Processing of Bio-oils: University of Saskatchewan, Saskatoon, Saskatchewan, Canada. Research was undertaken on the upgrading of biomass-derived oils to fuels and chemicals using zeolite (ZSM-5)
catalyst. Wood-derived high- and low-pressure pyrolysis
oils, plant/vegetable oils (flax,sunflower, canola, etc.), and
tall oil (derived from soap skimmings recovered from black
liquor from Kraft pulping operation) were tested. Experiments were conducted in a microreactor operating at
temperatures from 370 to 520 OC and atmospheric pressure.122-124Recent experiments with feeding tetralin with
both high-pressure pyrolysis oils and fast pyrolysis oils
(116) Gagnon, J.; Kaliaguine, S. Ind. Eng. Chem. Res. 1988, 27,
1783-1788.
(117) Elliott, D. C.; Baker, E. G. Proceedings of the 20th IECEC,
Society of Automotive Engineers: Warrenton, PA, 1985; Vol. 1, pp
586-594.
(118) Baker, E. G.;Elliott, D. C. In Pyrolysis Oikr from Biomass:
Producing, Analyzing, and Upgrading;Soltes, E. J., Milne, T. A., Eds.;
(119) Elliott, D. C.; Baker, E. G. Thermochemical Conversion R o g "
Annual Review Meeting; Solar Energy Research Institute Golden, CO,
1988; SERI CP-231-3355; pp 45-56.
(120) K lury, R. K. M. R.; Tidwell, T. T.; Boocock, D. G.B.; Chow,
D. H. L.; Can. J. Chem. 1984,62, 2540-2545.
(121) Kallury, R. K. M. R.; Restivo, W. M.; Tidwell, T. T.; Boocock,
D. G. B.; Crimi, A.; Douglas, J. J. Catal. 1986,96, 535-543.
(122) Prasad, Y. S.; Bakhshi, N. N. Can. J. Chem Eng. 1986, 64,
278-284.
(123) Prasad, Y. S.; Bakhshi, N. N. Can. J. Chem Eng. 1986, 64,
285-292.
(124) Furrer, R. M.; Bakhshi, N. N. In Research in Thermochemical
Reviews
showed some advantages over the ZSM-5catalyst.'%
Extraction and Catalytic Processing: Chalmers
University of Technology, Giiteborg, Sweden. Oil from
high-pressure directly liquefied biomass (PERC TR-12
from the Albany facility) was upgraded to transportation
fuels by various methods. Extraction of the crude TR-12
oil to remove the salts and heavy organics was followed by
hydroprocessing, distillation, and catalytic cracking. The
yields of transportation fuels were low, 35%, because of
the low yield in the initial extraction step. However, it was
clearly shown that transportation fuels could be produced
by this
Extraction was performed with several solvents to produce different fractions of the TR-12 oil. The fractions
were then catalytically treated to determine if the deactivation of the hydroprocessing catalyst varied among the
fractions of the crude oil. However, it was shown that only
desalting was necessary to eliminate the deactivation effect
(the TR-12 oil contains about 1% sodium as salts). In the
first hours in a run,high-surface-areacatalyst designed for
hydrodesulfurization showed higher activity than a catalyst
with large pores produced for hydrodemetallization.
However, deactivation was lower with the large-pore catalyst.134
The reactivity and reaction path for hydrodeoxygenation
of methyl-substituted phenols was studied with sulfided
cobalt-molybdenum on alumina catalyst. The reaction
proceeded through two paths, and two active sites for the
two paths were suggested.'%
Hydrotreatment of Lignins: SERI, Golden, CO.
The aim of this research was the development of mild
hydrotreating processes to produce phenols from lignin for
methyl aryl ether synthesis to produce gasoline blending
agents. Batch and semicontinuous laboratory reactor experiments were performed with lignin and model compounds. Catalyst development was a primary goal of the
project; use of a more acidic support for the catalyst was
identified as a potentially valuable area of re~earch.'~J~'
Other Biomass Liquefaction Research

Centralized Analysis/Chemical Recovery: British
Columbia Research, Vancouver, British Columbia,
(125)Bakehi, N. N.; Furrer, R. M.; Sharma, R. K. In Proceedings of
the Seventh Canadian Bioenergy R&D Seminar, Hogan, E., Ed.; Energy,
Mines, and Resources Ministry: Ottawa, Canada, 1989; pp 687-692.
(126)Gevert, S.B. In Energy from Biomass and Wastes X f i Klass,
D. L., Ed.; Institute of Gas Technology: Chicngo, 1988;pp 948-974.
(127)Gevert, S. B.; Otterstedt, J-E. In Energy from Biomass and
Wastes X Klaes, D. L. Ed.; Institute of Gas Technology: Chicago, 1987;
pp 845-854.
(128)Gevert, S. B.; Otterstedt J-E. Biomass 1987,13,105-115.
11291 Gevert. S. B.: Otterstedt J-E. Biomass 1987.14.173-183.
(130)Otters&dt,-J-E.; Gevert, S. B.; Sterte, J. Prepr. Pap.-Am.
Chem. Soc., Diu. Pet. Chem. 1987,32(3),692-694.
(131)Otteretedt J-E.; Gevert, S.B.; Sterta, J. Fluid Catalytic Cracking; ACS Symposium Series No. 375; American Chemical Society:
Washington, DC, 1988,Chapter 17.
(132)Gevert, S. B. Determination of Oxygen in Organic Materials.
Preaented at the Pittaburgh Conference on Analytical Chemistry and
Applied Spsctroecopy, Atlantic City, NJ, March 1986; Paper 53.
(133)Gevert, S. B. Upgrading of Directly Liquefied Biomass to
Transportation Fuels. Ph.D. thesis, Chalmers University of Technology,
Gothenburg, Sweden, 1987.
(134)Gevert, S. B.; Andersson, A.; JBrAs, S. G.;Sandquist, S. Prepr.
Pap.-Am. Chem. Soc., Div. Fuel Chem. 1988, 39(4),913-919.
(135)Gevert, 8. b.; Otterstedt, J-E.;Maseoth, F. E. Appl. Catal. 1987,
31,119-131.
(136)Ratcliff, M. A.; Johnson, D. K.; Poeey, F. L:; Chum, H. L. Ninth
Symposium on Biotechnology for Fuels and Chemicals; Humana Press:
Clifton, NJ, 1987;pp 151-160.
(137)Ratcliff, M. A.; Johneon, D. K.; Posey, F. L.;Maholland, M. A.;
Cowley, S.W.; Chum, H. L. In Research in Thermochemical Biomass
Conversion; Bridgwater, A. V., Kuester, J. L., Eds.; Elsevier Applied
Science: New York, 1988; pp 941-955.
Energy & Fuels, Vol. 5, No.3, 1991 407
Canada. British Columbia Research conducted centralized analytical studies of liquid products, byproducta, and
wastes produced from direct conversion research at other
facilities in Canada and the USA. The product analysis
included standard physical properties, as well as more
detailed and specific studies such as analysis of polycyclic
aromatic hydrocarbons by gas chromatography/mass
spectrometry, identification and quantification of chemicals in biomass oils, and use of nuclear magnetic resonance
to characterize products.lM
Research was also under way on methods for recovery
of chemicals from biomass-derived oils and from waste
aqueous phases associated with the processes. One program studied the recovery of levoglucosan, and a second
program studied the recovery of industrial chemicals such
as hydroxyacetaldehyde, hydroxyacetone, formic acid,
acetic acid, and mixed calcium formate, acetate, and
propionate (for road d e i ~ e r ) . ' ~ ~ J ~
Oil Product Analysis: PNL, Richland, WA. Other
supporting research completed at PNL involved analysis
of biomass liquefaction product oils. Essentially two
projects were involved; one dealt with detailed analysis of
pyrolysate condensates from various process systems and
the second was a chemical analysis of oils produced by
high-pressure liquefaction of several types of nonwoody
biomass. The pyrolysate study identified a continuum of
chemical functional types produced as a function of pyrolysis temperature. Biological activity of the pyrolysates
was also correlated with temperature of formation and
attributed primarily to the formation of polycyclic aromatic
hydrocarbons at higher temperatures. Flash pyrolysis oils
produced at temperatures around 500 "C were found to
have immeasurably low activity as mutagens or tumorigens
whereas pyrolysis tars formed at higher temperatures were
progressively more car~inogenic.'~~J~~
Oil compositions formed from nonwoody biomass were
found to have many similarities to the wood-derived oils.
Nitrogen incorporation into the oils resulting from nitrogen
in the feedstock was identified as a major difference. Fatty
acids and fatty-acid-derived hydrocarbons were also
identified in some of the oils.la
Pyrolysis Vapor Analysis: SERI, Golden, CO.
Direct MB/MS sampling of the vapors allowed real time
analysis of complex gas-phase species, Le., the pyrolysis
products and revaporized pyrolysis or liquefaction oils.
Most conversion routes could be adequately described by
a combination of the major solid-phase and gas-phase
pathways:
the two classes of carbohydrate primary pyrolysis
pathways, transglycosylationand alkali-catalyzedglycosidic
fission;
the two classes of lignin primary pyrolysis pathways, the
prompt formation of alkenyl methoxyphenols (such as
(138)McKinley, J. Biomass Liquefaction: Centralized Analysis; Final
Report, DSS File No. 232-4-6192;
Energy, Mines and Reeources Ministry
Ottawa, Canada, 1988.
(139)Longley, C. In Proceedings of the R&D Contractors Meeting on
Biomass Liquefaction; Hogan, E., Ed.; Energy, Mines, and Resources
(140)Oehr, K. In Proceedings of the R&D Contractors Meeting on
Biomass Liquefaction; Hogan, E., Ed.; Energy, Mines, and Resources
(141)Elliott, D.C."Analysis and Comparison of Biomaes Pyrolysis/
Gasification Condenaates". Final Report PNL-5943;Pacific Northwest
Laboratory: Richland, WA, 1986.
(142)Elliott, D.C. In Pyrolysis Oils from Biomass: Producing, Analyzing, and Upgrading; Soltes, E. J., Milne, T. A., Eds., ACS Symposium
Series No.376;American Chemical Society: Washington, DC, 1988; pp
55-65.
(143)Elliott, D.C.; Sealock, L. J., Jr.; Butner, R. S . Prepr. Pap.-Am.
Chem. Soc., Diu. Fuel Chem. 1987,32(2),186-194.
coniferyl alcohol) and the later formation of low-molecular-weight aromatics (such as guaiacol); and
the four zones of gas-phase processes, primary product
preservation below 500 "C, slight cracking of thermally
labile species from 500 to 600 OC, secondary reactions from
600 to 750 "C forming simple phenols, and tertiary reactions from 750 to lo00 "C forming polycyclic aromatics.
Over 50 different samples of biomass and RDF were
pyrolyzed and analyzed by the MB/MS scanning over the
mass ranges of 10-250. Multivariate analysis of this very
extensive data set was used to determine that there were
13 factors that explained over 90% of the variance in the
data. Interpretation of the data resulted in the identification of six major chemical compound classes to explain
the 13 factors.
To determine the effect of process variables, a statistically designed set of experiments was conducted to look
at the effects on the six compound classes identified in the
feedstock screening tests. Empirical equations were fitted
to the data and used to generate parametric plots showing
the effect of different variables.1m*14-1M
International Energy Agency Thermochemical
Round Robin Analysis. The first IEA Thermochemical
Round Robin was organized as part of an IEA Voluntary
Standards Activity. The objective of the study was to
determine the variability associated with the measurement
of carbon, hydrogen, oxygen, and water in biomass oils
using those techniques normally employed at each laboratory. Two biomass oil samples were distributed to 15
laboratories in November 1988. One sample was a lowoxygen-content condensed oil (PERC TR-12 oil from the
Albany facility), and the second was a primary oil (fast
pyrolysis oil from University of Waterloo) with a high
oxygen and water content.
The precision for carbon was excellent, whereas both the
hydrogen and oxygen values were more variable. The
water content was quite variable, and it had a strong influence on the carbon and hydrogen estimates (on a dry
basis) which in turn had a significant effect on the H/C
ratio of the biomass oil. The coefficients of variation for
the H/C ratios of the two oils were markedly different in
that the PERC oil had a value of 5%, which was in the
range anticipated, while that of the Waterloo oil was
19.5%.14'
Chemical Mechanisms Studies: PNL, Richland,
WA. Research on chemical mechanisms of biomass component conversion to oil has continued as part of the Basic
Energy Sciences Program of the U.S.DOE. Experimental
conditions focused on aqueous processing in neutral or
base-catalpd conditions. Conversion of cellulose pyrolysis
products to aromatics in the presence of alkali was well
documented. Acidic processing conditions have been
identified as existing in both alkali-catalyzed and uncatalyzed experiments; the pH is higher (4-5) in the alkali-catalyzedsystems compared with 2-3 in the uncatalyzed
systems.1qg162
(144) Evans, R. J.; Milne, T. A. Energy Fuels 1987,1,123-137.
(145) Evans, R. J.; Milne, T. A. Energy Fuels 1987, 1,311-319.
(146) Evans, R. J.; Milne, T. A. In Research in Thermochemical
Applied Science: new York, 1988; pp 264-279.
(147) Overend, R.P.; McKinley, J. W.; Eltiott, D. C. Readta of the IEA
Round Robin on the Ultimate h a l y s i s of Two Biomass Pyrolysis Oils.
Presented at the American Chemical Society National Meeting, Boston,
April 22-27, 1990.
(148) Samuels, W.D.;Nelson, D. A.; Hallen, R. T. Tetrahedron Lett.
1986, 27,3091.
(149) Nelson, D.A.; Samuels, W. D.; Hallen, R. T. Energy Fuels 1987,
1, 239.
(150) Nelson, D. A.; Hallen, R. T. J . Anal. Appl. Pyrolysis 1987, 12,
11.
Reviews
Other Studies. Results of several other, more basic

studies of the pyrolysis of biomass were reported at a
symposium, Production, Analysis and Upgrading of Pyrolysis Oils from Biomass, at the national meeting of the
American Chemical Society, April 5-10, 1987, in Denver,
CO. These results were reported in the Preprints of the
Fuel Chemistry Division (American Chemical Society:
Washington, DC, 1987), Vol. 32, No. 2. Among these results is a study of the products of low-temperature (250
"C) pyrolysis of biomass (Degroot et al., pp 36-43); chemistry of secondary reactions in pyrolysis (Boroson et al.,
pp 51-58); coliquefaction of lignin and coal (Altieri and
Coughlin, pp 117-128); pyrolytic reactions in supercritical
solvents (Simkovic et al., pp 12s132; Townsend and Klein,
pp 133-142); particle size and moisture effects on pyrolysis
(Kelbon et al., pp 44-50); alkaline degradation of saccharides to organic acids (Krochta et al., pp 148-156);
pyrolysis products from municipal solid waste components
(Helt and Agrawal, pp 82-89); the melting-like characteristic of pyrolyzing biomass (Lede et al., pp 59-67); and
zeolitic cracking of pyrolysis liquids and related compounds
in a fluidized bed (Chen et al., pp 264-275). The last five
of these can also be found in expanded form in Pyrolysis
Oils from Biomass: Producing, Analyzing, and Upgrading; ACS Symposium Series No. 376; American Chemical
Society: Washington, DC, 1988.
Technoeconomic Assessments
IEA Working Group: Canada, Finland, Sweden,
USA. A major emphasis of the IEA Working Group has
been the technoeconomic assessment of the biomass liquefaction processes under development in the laboratories
in the participating countries. The original assessment,
completed in 1984,153concluded the following:
High thermal efficiencies were obtainable by these
biomass liquefaction processes.
Flash pyrolysis was the most promising process for the
production of a fuel oil for combustion purposes.
The process costs are highly sensitive to feedstock cost.
Technical uncertainties because of the early state of
development made comparisons impossible for upgrading
processes. Further research was recommended for the
processes and processing equipment, especially for the
primary oil upgrading step.
During the second stage of the IEA project, a more
detailed assessment of the biomass liquefaction process was
undertaken including primary liquefaction, upgrading of
the primary oil by hydrotreating, and final refining of the
upgraded oil to market p r o d u ~ t s . ~ J " JThat
~ ~ study concluded the following:
The high efficiencies and the feedstock cost sensitivities
found in the first stage were reaffirmed.
Flash pyrolysis was identified as the most economical
(151)Theander, 0.;Nelson, D. A. Adu. Corbohydr. Chem. 1988, 46,
273-326.
(152) Nelson, D.A.;Hallen, R. T.; Theander, 0.In Pyrolysis Oils from
Biomass: Producing, Analyzing, and Upgrading; Soltes, E. J., M h e , T.
A., ME.;
ACS Symposium Series No. 376; American Chemical Society:
Washington, DC, 1988; pp 113-118.
(153) McKeough, P.; Nissili, M.; Solantausta, Y.; Beckman, D.;
Ostman, A.; Bergholm, A.; Kannel, A. 'Techno-Economic Assessment of
Selected Biomass Liquefaction Processes. IEA Cooperative Project D1,
Biomass Liquefaction Teat Facility Project";Final Report, DOE/NBM1062-Vol. 5; National Technical Information Service: Springfield, VA,
1988.
(154) Elliott, D.C.; Baker, E. G.; Beckman, D.; Solantaueta, Y.; Tulenheimo, V.; Gevert, B.; Hdmell, C.; btman, A.; KjellsMm, B. B t o m s
1990,22(1-4), 251-270.
(155) Elliott, D.C.; Baker, E. G.; Beckman, D.; Solantaueta, Y.; Tulenheimo, V.; Ostman, A.; Gevert, B.; Hdmell, C.; KjehWm, B. In Energy
from Biomass and Waste XIII: Klaas. D. L.. Ed.: Institute of Gaa
Technology: Chicago, 1990; pp 743-768.
Reviews
process both for production of primary fuel oil and for
gasoline production.
Significant development and cost reduction potential
exists for both high-pressure liquefaction and flash pyre
lysis.
The upgrading step remains the less developed, more
uncertain step, with catalyst lifetime being the most important factor. Therefore, the Working Group recommended that future development of the flash pyrolysis
process be emphasized.
Economic Evaluation of Emerging Pyrolysis Processes: SA1 Corp., McLean, VA. A continuing effort
within the US. DOE, Thermochemical Conversion of
Biomass program, has been the SA1 economic evaluation
work. The SA1 group has evaluated the liquefaction
processes under development in the U S . from several
assumption bases. The first studylMof the Georgia Tech
Entrained Flow Pyrolysis process concluded (1)the production of oil product from wood seems to be cost competitive with current fuel oil selling prices (around $4.5/
million Btu); and (2) oil production costs are highly sensitive to feedstock cost and oil yield but less sensitive to
capital cost and byproduct char credit. The study recommended further development of the process and upgrading
procedures to produce high-quality liquid fuels.
A second effort by SAI was a comparison of the Georgia
Tech Entrained Flow process incorporating catalytic hydrotreating for gasoline production and the ablative pyrolysis system from SERI with their zeolite cracking upgrading process. That studylS7concluded the following:
Entrained flow pyrolysis with catalytic hydrotreating
maximized gasoline yield and had a higher thermal efficiency.
Ablative pyrolysis with zeolitic cracking had a lower
capital requirement but also a lower yield and efficiency.
Current costs for the gasoline product were around
$2/gal but future potential developments could reduce
costs to under $l/gal for both processes. The study recommended further development of both process types. In
a second version, the evaluation was further refined,lMbut
the conclusions were unchanged.
A final analysis by SA1 compared direct liquefaction
costs with indirect liquefaction (methanol from biomass
gasification)costs. On an energy basis, the methanol costs
were similar to the direct liquefaction gasoline product cost
in the present case, but the direct liquefactiontechnologies
exhibited much greater potential for cost reduction based
on potential process devel~pments.'~~
Technoeconomic Assessments: Aston University,
Birmingham, UK. A process simulation with an integral
cost estimation computer model was developed for the
production of liquid fuels from biomass by direct and
indirect thermochemical conversion routes.lmJsl The
(156) Wan, E. I. Proceedings of the 1985 Biomass Thermochemical
Conversion Contractors' Meeting; Pacific Northwest Laboratory: Richland, WA, 1986; PNL-SA-13571; pp 167-192.
(157) Wan, E. I.; Fraeer, M. D.; Kwartang, I. K. Proceedings of the
1987 Biomass Thermochemical Conversion Contractors' Meeting; Pacific
Northwest Laboratory: Richland, WA, 1987; P?SA-l5482;,pp 115-140.
(158) Wan, E. I.; Fraser, M. D. Thermochemtcal Conversion Program
Annual Review Meeting; Solar Energy Research Institute: Golden, CO,
1988, SERI/CP-231-3355; pp 111-120.
(159) Wan, E. I.; Fraeer, M. D. In Research in Thermochemical
(160) Bridgwater, A. V.; Double, J. M. In Research in Thermochemical
(161) Bridgwater, A. V.; Double, J. M. Non-Waste Technology; VTT
Symp. 102; Technical Research Centre: Ekpoo, Finland, 1989; Vol. 1, pp
127-144.
Energy & Fuels, Vol. 5, No.3, 1991 409
conversion process covered all stages from biomass reception, storage and handling,through conversion, product
synthesis, and refining. Feedstocks included wood, straw,
and prepared MSW; products included methanol, fuel
alcohol, gasoline (via two routes), and diesel. The model
also included biochemical conversion processes for ethanol
production.
The model was based on mass and energy balance over
significant process steps that could be sequentially combined to give an overall process based on logical rules.
Each process step also included a capital cost estimation
model. On completion of a mass and energy balance for
a complete process, the total capital cost was estimated
by summing process step costs, and the product cost was
then estimated. In addition, various detailed energy
balance and cost estimates were also produced. A major
feature of this model was that a consistent comparison of
technologies could be undertaken to aid in determining
preferred processes, feeds, or products.
Technoeconomic assessments of smaller scale plants to
produce pyrolysis liquids and char slurries were also carried
out to compare alternative technologies, feedstocks, and
products from 1to 10 ton/h scale units.182 The work was
extended to cover environmental and social costs and
benefits in the context of the EEC Leben projects to
provide more robust justification for early implementation
of those technologies."
In addition, a comprehensive world-wide database of
thermochemical biomass conversion activities was assembled.'MJa About 650 activities were identified and information collated on the technical and commercial status
of each one.
Future Directions for the Technology

In recent years the development of alternative sources
of liquid fuels has slowed dramatically as research funding
sources have been reduced in response to the apparent
oversupply of petroleum and resultant lower prices.
However, the interlude will undoubtedly be short before
more price shocks are seen in the market because of the
continually increasing demand and diminishing supply of
oil.
During the period just before this review's time frame,
North American and Scandanavian research support was
strong, and as a result the main research efforts were found
in Canada, Finland, Sweden, and the USA. Now the major
funding for future research efforts is found in the European
Community. Without major shifts in government funding
of research in the USA and Canada, in a few years the next
review of the state-of-the-art of biomass liquefaction could
be dominated by the work being initiated under the EC
JOULE ~ r 0 g r a m . lBiomass
~~
liquefaction provides one
alternative to petroleum as a source of both liquid fuels
and chemicals. The research described in this article has
as its collective goal the development of processes for the
economical production of these valuable products.
The research has shown that reactor systems can be
designed to efficiently produce liquid products from
biomass. The chemical compositions of the liquids have
been studied in detail. Upgrading processes have been
(162) Bridgwater, A. V. Proceedings of the 25th IECEC; American
Institute of Chemical Engineers: New York, 1990; Vol. 5, pp 107-112.
(163) Graasi, G.; Bridgwater, A. V. Proceedings of the 25th IECEC;
American Institute of Chemical Engineers: New York, 1990; Vol. 5, pp
126-1 30.
(164) Bridgwater, A. V.; Double, J. M.; Bridge, S. A. In Research in
Thermochemical Biomss Conuersion; Bridgwater, A. V., Kueeter, J. L.,
Eds.; Eleevier Applied Science: New York, 1988; pp 46-60.
(165) Bridgwater, A. V. Biomass 1990,22(1-4), 279-292.
identified to further transform these liquids into directly

marketable fuels. Other methods are being studied for the
separation of useful chemic&. International cooperation
and exchange of information has played a paramount role
in the ability of the world research community in biomass
liquefaction to maximize its return on limited budgets.
However, there are significant developments that still lie
in the future because of the limited effort expended on the
research of these processes. These developments are
summarized below:
Large-scale demonstration of the liquefaction and upgrading processes, including the support systems such as
aqueous and gaseous byproduct handling. The operation
of the U.S. DOE Biomass Liquefaction Experimental Facility at Albany, OR, was a short-lived effort that remains,
10 years later, the largest scale attempt a t biomass highpressure liquefaction at a throughput of 18 kg of wood/h.
Larger versions of inefficient, slow pyrolysis process units,
which do not maximize liquids production, are in operation
in Europe, but scale-up of fast pyrolysis is still in the early
stages.
Completion of the refinery cycle to produce murketable
liquid fuels from biomass for testing and evaluation.
Although hydrocarbon fuels have been produced on the
bench-scale and octane measurements made with woodderived gasolines, complete testing and evaluation of the
fuels has yet to be achieved.
Demonstration of chemical separation technologies.
Chemicals separation from biomass liquids has been
studied both as a means of specialty chemical production
and also as a commodity chemical route. Actual separations remain in early development stages.
Determination of the compatibility of biomass liquefaction products with existing petroleum refinery systems.
The question of the scale of operation of biomass liquefaction is still debated. Incorporation of the biomass liquefaction product into the commercial liquid fuels production stream could occur at any of several points in the
Reviews
process. Siting of several biomass liquefaction points
feeding to a central upgrading plant which then sends its
product to a petroleum refinery is one concept to maximize
the economic advantages of scale.
Investigation of the potential for controlling the liquefaction process to maximize production of specific
products. Some research has been performed to determine
the effect of processing parameters on the chemical composition of the biomass liquefaction product. Continued
work in this area may lead to significant developments in
tailoring the liquefaction product for specific chemical or
fuel needs.
Development of biomass production systems that are
coordinated with the liquefaction process requirements
to maximize the overall efficiency of the solar energy
conversion process. Possible process advantages still remain to be explored in the area of optimization of the
biomass growing and harvesting process with the biomass
liquefaction process. Better coordination between researchers in each field is needed to identify options for
modifying either the liquefaction process or the biomass
production process to improve the overall system efficiency. Continued research on biomass liquefaction processes should address these issues in order that alternative
liquid fuels and chemicals will be available to meet future
needs.
Acknowledgment. The authors acknowledge the
support of their respective government agencies for the
International Energy Agency programs and the Bioenergy
Liquefaction Activity, specifically. The supporting government agencies are Energy, Mines and Resources, Canada; European Community Directorate for Research in
Science and Technology; Ministry of Trade and Industry,
Finland; National Committee for Nuclear and Alternative
Energy, Italy; Energy Technology Support Unit, UKAEA,
United Kingdom; and Department of Energy, United
States.

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399

Energy & Fuels 1991,5, 399-410

The initial work of the IEA Working Group, which was

0 1991 American Chemical Society

400 Energy & Fuels, Vol. 5, No. 3, 1991

Fast Pyrolysis: University of Waterloo, Waterloo,

Vortex Ablative Pyrolysis: Solar Energy Research

Energy & Fuels, Vol. 5, No. 3, 1991 401

purge gas of 0.5 g of N2per gram of sawdust, and a feeding

402 Energy & Fuels, Vol. 5, No. 3, 1991

censed to several organizations in Europe, North America,

One attempt has been made at a unified treatment of

Energy & Fuekr, Vol. 5, No.3, 1991 403

(60)Vaneme, C.; Lemonnier, J. P.; Eugane, D.; Chomet, E.; Overend,

Thermochemical Biomcure Conversion;Bridgwater, A. V., Kueeter, J. L.,

Ede.; Elsevier Applied Science: New York, 1988; pp 843-853.

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(67) Boocock, D. G. B.; Allen, S. G.; Chowdhury, A.; Fruchtl, R. In

404 Energy & Fuels, Vol. 5, No. 3, 1991

High-pressure Liquefaction: Manoil/University of

Energy & Fuels, Vol. 5,No.3, 1991 405

Two-step Catalytic Hydrotreating of Pyrolysis

Oils: Pacific Northwest Laboratory (PNL),Richland,

WA. A two-step hydrotreating process was developed for

(9s) Elliott, D. C. In Research in Thermochemical Biomass Conuer-

eion; Bridgewater, A. V., Kuester, J. L., Eds.; Elsevier Applied Science:

Biomass Conuersion; Bridgwater, A. V., Kuester, J. L., Eds.; Elsevier

55.9 cm of the reactor was immersed in a salt bath so that

Thermochemrcal Bcomass Conversion; Bridgwater, A. V., Kueeter, J. L.,

406 Energy & Fuels, Vol. 5, No. 3, 1991

and shape of most of the identified compounds were small

copper chromite was an ineffectivehydrogenation catalyst

Other Biomass Liquefaction Research

Energy & Fuels, Vol. 5, No.3, 1991 407

408 Energy & Fuels, Vol. 5, No. 3, 1991

Other Studies. Results of several other, more basic

Energy & Fuels, Vol. 5, No.3, 1991 409

Future Directions for the Technology

410 Energy & Fuels, Vol. 5, No. 3, 1991

identified to further transform these liquids into directly

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