Pyrolysis of Wood-Biomass For Bio-Oil A Critical Review-2
Pyrolysis of Wood-Biomass For Bio-Oil A Critical Review-2
Pyrolysis of Wood-Biomass For Bio-Oil A Critical Review-2
3, 2006 857
Table 7. Typical Properties of Wood Pyrolysis Bio-oil and Heavy Table 8. Typical Properties of Bio-oil, Compared to Those of Light
Fuel Oila and Heavy Fuel Oila
Value BioTherm light heavy
property bio-oil fuel oil fuel oil
physical property bio-oil heavy fuel oil
heat of combustion
moisture content (wt %) 15-30 0.1
BTU/lb 7100 18200 17600
pH 2.5
MJ/L 19.5 36.9 39.4
specific gravity 1.2 0.94
viscosity (centistokes)
elemental composition (wt %)
at 50°C 7 4 50
C 54-58 85
at 80°C 4 2 41
H 5.5-7.0 11
ash content (wt %) <0.02 <0.01 0.03
O 35-40 1.0
sulfur content (wt %) trace 0.15-0.5 0.5-3
N 0-0.2 0.3
nitrogen content (wt %) trace 0 0.3
ash 0-0.2 0.1
pour point (°C) -33 -15 -18
HHV (MJ/kg) 16-19 40
turbine emissions (g/MJ)
viscosity, at 500 °C (cP) 40-100 180
NOx <0.7 1.4 N/A
solids (wt %) 0.2-1.0 1
SOx 0 0.28 N/A
distillation residue (wt %) up to 50 1
a Data taken from ref 106.
a Data taken from ref 59 with permission from the American Chemical
Society.
8.1. Chemical Nature of Bio-oil. Wood pyrolysis causes
bond cleavage and produces fragments of the original polymers
of three key biomass building blocks: cellulose, hemicellulose, (cellulose, hemicellulose, and lignin). Most of the original
and lignin, as previously discussed. Perfect reproduction of all oxygen is retained in the fragments that collectively comprise
the bio-oil processing conditions can produce varying bio-oils, bio-oil. A small amount of CO2 and CO is formed, along with
because the feed composition (biomass or wood) influences the a substantial amount of water. Bio-oil contains 45-50 wt %
nature of the final product. The physical properties of bio-oils oxygen,68 but the oxygen content is dependent on the bio-oil’s
are well-described in the literature.59,70 The lower heating value water content. Proximate analysis of the bio-oil gives a chemical
(LHV) of bio-oils is only 40-45 wt % of that exhibited by formula of CH1.9O0.7, which corresponds to ∼46 wt % oxygen
hydrocarbon fuels.59 The LHV of bio-oils on a volume basis is (versus ∼42 wt % oxygen in wood). The difference in oxygen
∼60% of the heating value of hydrocarbon oils,59 because of content present in the feed versus that in the bio-oil is related
the high oxygen content, the presence of water, and the higher to the oxygen content in the gases and the amount present as
bio-oil density. A typical heating value of bio-oil is ∼17 MJ/ water in the oil. Oxygen is present in most of the more than
kg. Bio-oil is miscible with ethanol and methanol but immiscible 300 compounds that have been identified in bio-oil.11 The
with hydrocarbons. Bio-oil can be stored, pumped, and trans- compounds found in bio-oil have been classified into the
ported in a manner similar to that of petroleum-based products following five broad categories:63 (1) hydroxyaldehydes, (2)
and can be combusted directly in boilers, gas turbines, and slow- hydroxyketones, (3) sugars and dehydrosugars, (4) carboxylic
and medium-speed diesel engines for heat and power applica- acids, and (5) phenolic compounds.
tions.59 Basic data for bio-oils and conventional petroleum fuels The phenolic compounds are present as monomeric units and
are compared in Table 7,59 whereas typical properties of bio- oligomers derived from the coniferyl and syringyl building
oil, light oil, and heavy oils are compared in Table 8. blocks of lignin. Oligomer molecular weights range from several
858 Energy & Fuels, Vol. 20, No. 3, 2006 Mohan et al.
(4) The kinematic viscosity at 40 °C is accurate for (1) Pyrolysis liquids produced from industrially important
homogeneous pyrolysis liquids. The Newtonian behavior should biomass feedstocks should be included.
be checked for extractive-rich liquids, using a closed-cup (2) Water, solids, homogeneity, viscosity, stability, water
rotaviscotester. insolubles, average molecular weight, and GC/MS should be
(5) Stability tests should be performed each time, in exactly included as analyses.
the same manner. If the weight loss is >0.1 wt % during the (3) Detailed and clear instructions on the handling, pretreat-
test, the results should be excluded. Stability testing is recom- ment, and analysis of needed reference samples should be
mended for comparison of pyrolysis liquids from one specific provided.
process. The best comparisons can be obtained when the
differences in the water contents of the samples are small. The 9. Methods of Bio-oil Preparation
viscosity is measured at 40 °C, where the measuring error is
smaller. Fast pyrolysis is the leading method for producing liquid
(6) The sample size for elemental analysis should be as large biofuels.83-86 The advantages include low production costs, high
as possible, and analyses should be performed at least in thermal efficiency, low fossil fuel input, and CO2 neutrality.
triplicate. Pyrolysis to a liquid offers the possibility of decoupling (time,
(7) Ethanol (or methanol) can be used for the solids place, and scale), easy handling of the liquids, and more-
determination of white-wood pyrolysis liquids. For new feed- consistent quality, compared to any solid biomass. A liquid
stocks, such as bark and forest residue, the solubility of the intermediate is produced for a variety of applications by fast
liquid should be checked using solvents of different polarity. pyrolysis. The typical yields obtained by different modes of
(8) Definitions and reliable determination methods for “water pyrolysis of wood are presented in Table 11.
insolubles” and “pyrolytic lignin” are necessary. (83) Oasmaa, A.; Kuoppala, E.; Gust, S.; Solantausta, Y. Energy Fuels
(9) It might be necessary to calibrate the gas and liquid 2003, 17 (1), 1-12.
chromatographic systems, using standard solutions of known (84) Oasmaa, A.; Kuoppala, E.; Solantausta, Y. Energy Fuels 2003, 17
amounts of compounds during chemical characterization. (2), 433-443.
(85) Oasmaa, A.; Kuoppala, E. Energy Fuels 2003, 17 (4), 1075-1084.
The following measures were recommended for future round- (86) Oasmaa, A.; Kuoppala, E.; Selin, J.-F.; Gust, S.; Solantausta, Y.
robin studies.26,82 Energy Fuels 2004, 18, 1578-1583.
860 Energy & Fuels, Vol. 20, No. 3, 2006 Mohan et al.
Table 11. Typical Product Yields (Dry Wood Basis) Obtained by Different Modes of Pyrolysis of Wooda
Product Yield (%)
process liquid char gas
fast pyrolysis (moderate temperature and short residence time) 75 12 13
carbonization (low temperature and long residence time) 30 35 35
gasification (high temperature and long residence time) 5 10 85
a Data taken from ref 25 with permission from Elsevier.
Several fast pyrolysis processes have been developed. Ex- radiation, and reaction heat for the process to proceed to
amples include the Tech-Air process,12 Waterloo fast pyrolysis,87 completion. The heat of reaction for the fast pyrolysis process
Ensyn rapid thermal pyrolysis,88 Georgia Tech entrained flow is marginally endothermic. It has been well-documented19 that
pyrolysis,89 NREL vortex ablative pyrolysis,90 Pyrovac vacuum heat fluxes of 50 W/cm2 are required to achieve true fast
pyrolysis,27,28,91-105 and Dynamotive’s fluidized bed.106 A fast pyrolysis. The two important modes of heat transfer in fast
pyrolysis process includes drying the feed to a water content pyrolysis are conduction and convection. Depending on the
of typically <10% (although up to 15% can be acceptable), to reactor configuration, each one can be optimized or a contribu-
reduce the water content in the product oil (http://www- tion from both can be achieved. In a circulating fluidized bed,
.pyne.co.uk). The feed must be ground (to ∼2 mm, in the case the majority of the heat transfer is achieved from the hot
of fluidized-bed reactors) to give sufficiently small particles to circulating sand, typically at a sand-to-feed ratio of 20-25. This
ensure rapid heat transfer and reaction (http://www.pyne.co.uk). requires an effective sand reheating system. On the other hand,
After pyrolysis, the solids (char) must be separated and the in a conventional fluidized bed, sand requires an external heat
vapors and aerosol are quenched. The liquid bio-oil then is source, which can be obtained from char in an integrated system.
collected. Free moisture in the biomass feed should not be Slow pyrolysis produces ∼30% liquid, ∼35% char, and ∼35%
removed entirely, because it assists in high heat transfer upon gas, whereas in fast pyrolysis, the liquid, char, and gas contents
rapid conversion to steam. This assists in rupturing the biomass can be 75%, 12%, and 13% respectively.91 The total heat
particle structure, thereby enhancing pyrolysis. required to obtain a bio-oil yield of 62% (including radiation
9.1. Heat-Transfer Requirements. High heat-transfer rates and exhaust gas losses) is ∼2.5 MJ/kg of bio-oil produced107
are required to heat the feed particles quickly. The heat required for a prepared feedstock. The net heat required from an external
for pyrolysis is the total amount to provide all the sensible, fuel source, such as natural gas, is only 1.0 MJ/kg of bio-oil
produced. This applies when produced non-condensable gases
(87) Scott, D. C.; Piskorz, J.; Radlein, D. Ind. Eng. Chem., Process Des. are directly injected into the reactor burner. This represents
DeV. 1985, 24, 581.
(88) Graham, R. G.; Freel, B. A.; Bergougnou, M. A. The production of approximately 5% of the total calorific value of the bio-oil being
pyrolysis Liquids, Gas and char from wood and cellulose by fast pyrolysis. produced.107
In Research in Thermodynamical Biomass ConVersion; Bridgwater, A. V.,
Kuester, J. L., Eds.; Elsevier Applied Science: London, 1988; pp 629-
641. 10. Bio-oil Production from Various Feedstocks
(89) Kovac, R. J.; Gorton, C. W.; O’Neil, D. J. Presented at the
Thermochemical Conversion Program Annual Meeting, Solar Energy It is difficult to divide bio-oil feedstocks into different
Research Institute, Golden, CO, 1988, Paper No. SERI/CP-231-3355; pp categories, because such classifications are dependent on the
5-20.
(90) Diebold, J.; Scahill, J. Production of Primary Pyrolysis Oils in a
species, age, portion of the plant selected, and many other
Vortex Reactor. In Pyrolysis Oils from Biomass: Producing, Analyzing, variables. We have selected some very general feedstock
and Upgrading; Soltes, E. J., Milne, T. A., Eds.; ACS Symposium Series categories. Readers may compare the difference in bio-oil
No. 376; American Chemical Society: Washington, DC, 1988; pp 31-40. properties obtained from these different feedstock groups. These
(91) Bridgwater, A. V., Ed. Progress in Thermochemical Biomass
ConVersion, Volume 2; Blackwell Science: London, 2001. categories are bark, wood, agricultural wastes/residues, nuts and
(92) Murwanashyaka, J. N.; Pakdel, H.; Roy, C. J. Anal. Appl. Pyrolysis seeds, algae, grasses, forestry residues, cellulose and lignin, and
2001, 60, 219-231. miscellaneous.
(93) Murwanashyaka, J. N.; Pakdel, H.; Roy, C. Sep. Purif. Technol.
2001, 24, 155-165. 10.1. Bio-oil from Bark. Bark is removed from wood in
(94) Garcia-Perez, M.; Chaala, A.; Roy, C. J. Anal. Appl. Pyrolysis 2002, lumber manufacture and in many papermaking processes. Thus,
65, 111-136. bark is often available where wood is not prepared for the
(95) Garcia-Perez, M.; Chaala, A.; Roy, C. Fuel 2002, 81 (7), 893-
907. generation of secondary products, such as bio-oil. Furthermore,
(96) Ba, T.; Chaala, A.; Garcia-Perez, M.; Roy, C. Energy Fuels 2004, bark has different heat-transfer characteristics, different moisture
18 (1), 188-201. contents, and, in most cases, a higher lignin content than the
(97) Ba, T.; Chaala, A.; Garcia-Perez, M.; Rodrigue, D.; Roy, C. Energy underlying wood. These differences must be considered when
Fuels 2004, 18 (3), 704-712.
(98) Darmstadt, H.; Garcia-Perez, M.; Adnot, A.; Chaala, A.; Kretschmer, the fast pyrolysis of bark to bio-oil is undertaken. It is possible
D.; Roy, C. Energy Fuels 2004, 18 (5), 1291-1301. that the pyrolytic lignin fraction from various bark feeds may
(99) Chaala, A.; Ba, T.; Garcia-Perez, M.; Roy, C. Energy Fuels 2004, exhibit different properties than the pyrolytic lignin fraction from
18 (5), 1535-1542.
(100) Pakdel, H.; Roy, C. Bioresour. Technol. 1996, 58, 83-88. wood or other forms of plant biomass. It should be noted that
(101) Pakdel, H. et al. Phenolic Compounds from Vacuum Pyrolysis of wood and its bark are often copyrolyzed.
Biomass, Bio-oil Production & Utilization. In Proceedings of the 2nd EU- The development of the vacuum pyrolysis process was an
Canada Workshop on Thermal Bioenergy, February 1996; pp 124-131.
(102) Amen-Chen, C.; Riedl, B.; Wang, X.-M.; Roy, C. Holzforschung important contribution that was made by Roy and co-
2002, 56 (2), 167-175. workers27,28,92-105 at Universite Laval, Canada. Vacuum py-
(103) Amen-Chen, C.; Riedl, B.; Roy, C. Holzforschung 2002, 56 (3), rolysis is typically performed at a temperature of 450 °C, under
273-280. a pressure of <20 kPa. This enables the production of very large
(104) Amen-Chen, C.; Riedl, B.; Wang, X.-M.; Roy, C. Holzforschung
2002, 56 (3), 281-288.
(105) Amen-Chen, C.; Pakdel, H.; Roy, C. Biomass Bioenergy 1997, 13 (107) Fast pyrolysis of bagasse to produce biooil fuel for power
(1-2), 25-37. generation. Presented by Dynamotive Energy Systems Corporation at the
(106) http://dynamotive.com/biooil/whatisbiooil.html. 2001 Sugar Conference.
Pyrolysis of Wood/Biomass for Bio-Oil: A ReView Energy & Fuels, Vol. 20, No. 3, 2006 861
Table 12. Physicochemical Properties of the Upper Layer, Bottom Table 13. Elemental Compositions of Bio-oil from the Vacuum
Layer, and the Whole Bio-oil from Softwood Bark Vacuum Pyrolysis of Bark: Whole Bio-oil, the Water-Soluble Fraction, and
Pyrolysisa Water-Insoluble Fractiona
Value S+ C/H molar
sample C H N ash + O ratio
upper bottom whole
property layer layer bio-oil water-insoluble fraction, WIF 72.7 7.1 0.7 19.5 0.85
water-soluble fraction, WSF 51.7 6.3 1.2 40.8 0.68
water content (wt %) 3.5 14.6 13.0 whole bio-oil 62.6 7.0 1.1 29.3 0.74
density at 28 °C (kg/m3) 1089 1222 1188
kinematic viscosity (cSt) a Data taken from ref 97 with permission from the American Chemical
at 50 °C 88 66 62 Society.
at 80 °C 14 11 11
at 90 °C 21 15 15 Table 14. Molecular Weight Distribution (MWD) of the
gross calorific value, anhydrous basis (MJ/kg) 34.3 26.4 27.9 Water-Insoluble Fraction (WIF) of Bio-oils from Vacuum Pyrolysisa
methanol insoluble materials, MTM (wt %) 1.30 0.6 0.7
solid content, CH2Cl2 insoluble (wt %) 0.28 0.58 0.55 Molecular Weight
Conradson carbon residue, CCR (wt %) 14.3 22.2 20.5 weight number
pH 3.03 2.98 3.00
average, average, polydispersity,
acidity (NaOH g/100 g oil) 3.51 5.00 4.77
elemental analysis, anhydrous basis (wt %) lignin Mw Mn Mw/Mn
C 74.1 61.3 62.3 WIF (softwood bark residues) 1163 577 2.0
H 8.5 6.5 7.00 Biomass Technology Group (BTG) 1317 592 2.2
N 0.3 0.6 1.1 (mixed softwood)
S 0.05 0.07 0.07 MWL (spruce) 5720 3270 1.8
ash 0.1 0.3 0.3 a
oxygen content (by difference) 17.0 31.3 29.0 Data taken from ref 97 with permission from the American Chemical
Society.
a Data taken from ref 96 with permission from the American Chemical
Table 15. Bio-oil Yield from Pyrolysis of Beech Trunkbarks, as a Table 16. Char Yields from Beech Trunkbark Pyrolysis as a
Function of Temperature and Heating Ratesa Function of Temperature and Heating Ratea
temperature Bio-oil Yield (wt %, daf basis)b temperature Char Yield (wt %, daf basis)b
range (°C) 2 °C/s 5 °C/s 10 °C/s 20 °C/s 40 °C/s 100 °C/s range (°C) 2 °C/s 5 °C/s 10 °C/s 20 °C/s 40 °C/s 100 °C/s
25-277 24.2 27.4 27.8 28.5 29.1 31.0 25-277 58.6 53.7 51.0 48.7 46.5 43.2
25-327 26.1 28.8 29.9 30.8 31.4 33.7 25-327 53.2 49.0 45.8 44.6 43.1 39.6
25-377 27.4 29.9 31.5 32.0 33.2 35.1 25-377 48.8 43.2 42.0 41.1 38.9 35.8
25-427 27.8 30.7 32.2 32.9 33.7 35.8 25-427 47.1 41.4 40.2 39.2 37.0 34.2
25-477 27.5 30.1 31.7 31.0 32.1 34.0 25-477 43.2 37.8 34.6 33.7 32.0 30.2
25-527 26.7 29.6 29.8 30.4 31.0 32.6 25-527 41.9 36.4 33.5 32.6 31.3 28.9
a Data taken from ref 108 with permission from Elsevier. b The term a Data taken from ref 108 with permission from Elsevier. b The term
daf represents dry ash free basis. daf represents dry ash free.
Table 18. Product Yields from the Stepwise Pyrolysis of Birch birch bark followed a similar trend. The most active zone was
(Birch Bark and Birch Sapwood), as a Function of Increasing observed to be within the range of 275-350 °C. Guaiacol
Temperaturea
derivatives result at low temperatures, followed by syringol
stepwise Yield (wt %, Anhydrous Feed Basis) derivatives. Their transformation to pyrocatechols occurs at high
pyrolysis (°C) solid residue pyrolysis oil gas water phenols temperatures. The evolution of phenols was determined to occur
1. 25-200 93.96 6.02 0.02 5.91 0.00 in the following order: methylguaiacol, ethylguaiacol, guaiacol,
2. 200-275 70.46 18.14 5.36 6.19 0.40 propenylsyringol, phenol, and catechol. The maximum rate of
3. 275-350 37.85 27.28 5.33 6.95 2.18 evolution was observed at 275-350 °C. Phenols were converted
4. 350-450 25.67 9.47 2.71 0.70 1.83
5. 450-550 23.25 1.48 0.94 0.41 0.01 sequentially into catechols by demethylation of the methoxy
cumulative 25.25 62.39 14.36 20.16 4.42 groups at 350-450 °C. The pyrolysis is almost complete at 450
(steps 1-5) °C. The total phenolic yields obtained by stepwise and one-
one-step, 25-500 24.79 63.43 11.78 19.79 2.51 step pyrolysis were 4.43 and 2.51 wt %, respectively, on an
a Data taken from refs 92 and 93 with permission from Elsevier. anhydrous feed basis.
Murwanashyaka et al.93 also conducted a vacuum pyrolysis
fixed-bed gasification. A wood layer was exposed to thermal on 116 kg of a mixture of birch bark (Betula papyrifere) (ca.
radiation by means of a stainless steel mesh screen, whose sides 46%) and birch sapwood (ca. 54%). Syringol was separated from
were wrapped on two titanium rods (the uniform heated zone the pyrolytic oil. The total pressure inside the reactor was <3
is ∼2.6 cm in the axial direction of the reactor). Aluminum kPa, the final temperature was 500 °C, and the heating rate was
supports connected the sample holder to a precision (0.1 mg) 100 °C/min. The pyrolysis was held at a temperature of 500 °C
balance. A continuous nitrogen flow at ambient temperature (1 for at least 30 min. The pyrolytic oil obtained was stored at 4
× 10-3 m3/min, nominal velocity of 3.0 cm/s; residence time °C to prevent aging. The products yields included 53.9%
of 14 s) established an inert environment, reduced the residence condensates (i.e., 45.9% anhydrous pyrolysis oil and 8% of
time of vapors inside the reactor, and cooled both the gas-phase miscible reaction water), 24.0% gas, and 22.1% wood charcoal
environment during pyrolysis and the solid residue after (on a weight-percent feedstock moisture-free basis). The mass
complete devolatilization. Liquid yields (water and tars) increase
balance accounted for 96.8% of the feed. Steam distillation of
from ∼40% to ∼55% of dry wood mass with increasing
the oil recovered the phenols at various steam/pyrolysis oil
temperature. Approximately 90 product species were identified.
ratios. A volatile fraction (14.9 wt %, based on the total feed
GC/MS identification of 40 compounds from the pyrolysis
oil) was recovered at a steam:oil ratio of 27. The distillate
liquid, corresponding to 40%-43% of the organic fraction (tars),
analyzed by GC/MS after acetylation contained 21.3 wt % of
demonstrated that this analysis reflects the combined thermal
phenolic compounds. The distillate was then vacuum-distilled
responses of holocellulose and lignin. The holocellulose leads
at 0.7 kPa. Sixteen sub-fractions were recovered. The steam-
to the formation of furans and carbohydrates, whereas the lignin
distilled fractions were observed to be chemically and thermally
generates phenolics. The high number of liquid compounds
stable, when subjected to further purification. The 2,6-dimethoxy-
quantified represents a significant advance in the current state
phenol (syringol)-rich fraction was separated and purified.
of the art. This analytical approach can be used to improve
Syringol was obtained in a purity of 92.3 wt %.
reactor development/optimization and to formulate detailed
reaction mechanisms. Syringols and guaiacols, originating from Amen-Chen et al.105 isolated phenol, cresols, guaiacol,
primary degradation of lignin, reach their maximum levels in 4-methylguaiacol, catechol, and syringol from Eucalyptus wood
the bio-oils during pyrolyses at ∼477-527 °C. In contrast, pyrolysis tar. The approach included a primary conversion of
secondary degradations continuously increase production of the raw wood tar into lighter oil. Phenolic compounds were
phenols with increasing temperature. Conventional pyrolysis and further separated from the oil by liquid-liquid extraction, using
fast pyrolysis exhibit enhanced levoglucosan and hydroxy- aqueous alkali and organic solvents. GC/MS analysis of acetyl-
acetaldehyde formation at faster heating rates with lower yields derivatized phenolic compounds was used to evaluate the
of carboxylic acids. separation method. The primary conversion allowed the isolation
Both stepwise and one-step vacuum pyrolyses of birch- of lighter oil without causing major chemical changes in the
derived biomass (birch bark and birch sapwood) were conducted original wood tar. Liquid-liquid extraction by alkali and organic
by Murwanashyaka et al.,92 to monitor the evolution of phenols. solvents produced a phenolic fraction. Removal of phenols was
The feedstock was shredded to fibrous particles with the longest efficient under highly alkaline conditions.
dimension ranging between 5 mm and 20 mm. Before pyrolysis, Few papers have discussed pyrolysis under irregular heating
the sample was split into two parts. One portion was pyrolyzed rates. Demirbas55 pyrolyzed beech wood in the absence of
in one step and the second was pyrolyzed in stepwise modes oxygen in a stainless steel horizontal cylindrical reactor inserted
under a 0.7 kPa vacuum. Dry ice in limonene condensers were vertically into an electrically heated furnace. Irregular heating
used to trap the pyrolysis vapors at -72 °C. A stepwise pyrolysis rates were used from 25 °C to 502 °C. The average heating
of the birch feed was performed by increaing the temperature rate was higher than 6 °C/s from 60 s to 90 s for three samples
from 25 °C to 550 °C. After heating to a selected temperature with particle sizes of <0.063 mm, 0.060 mm, and >0.150 mm.
and holding for 1 h, the reactor was cooled to room temperature The average temperature increase was low, from 170 s to 350
and kept under nitrogen until the next step. Before each s. The temperature increase was highly regular, in periods of
subsequent temperature step, the liquids formed in the previous 450-600 s. The time to complete pyrolysis decreased when
step were collected. The residual solids were weighed and placed the particle size increased from <0.063 mm to >0.150 mm and
back into the reactor for further pyrolysis. Table 18 lists the then increased as the particle size increased. The completion
different pyrolysis steps and product yields obtained. time was lower (445 s) at 397 °C for >0.150 mm particle size.
The stepwise thermal decompositions of birch bark and birch Important variables affecting the yield are the biomass species,
sapwood under vacuum at low temperatures were less destruc- chemical and structural composition of the biomass, particle
tive.92 The evolution of pyrolysis oil and phenols during the size, temperature, heating rate, atmosphere, pressure, and reactor
stepwise vacuum pyrolysis of a mixture of birch sapwood and configuration.
864 Energy & Fuels, Vol. 20, No. 3, 2006 Mohan et al.
Table 19. Char Yields, Elemental Compositions, Surface Areas, Micropore Volumes, and N, C, and H Yields (Relative to the Amount of
Eucalyptus Sample) of Chars Obtained at Low (LHR) and High (HHR) Heating Ratesa
LHR Char HHR Char
property 600 °C 700 °C 800 °C 900 °C 800 °C 900 °C
char yield (wt %, dbb) 24.0 22.9 21.8 21.4 18.5 18.3
C 87.4 87.99 88.23 89.54 81.85 81.22
H 1.22 0.87 0.71 0.52 1.55 1.25
N 0.52 0.62 0.74 0.95 0.55 0.64
O 11.0 10.52 10.32 8.99 16.05 16.89
surface areac (m2/g) 570 588 589 362 528 539
micropore volume (mm3/g) 218 224 225 138 202 206
nitrogen yield (%) 44.6 50.7 57.6 72.6 36.4 41.8
carbon yield (%) 43.1 41.4 39.5 39.4 31.1 30.6
hydrogen yield (%) 4.8 3.2 2.5 1.8 4.7 3.7
a Data taken from ref 116 with permission from Elsevier. b Dry basis. c Surface areas were measured from the CO adsorption isotherm at 0 °C, using the
2
Dubinin-Radushkevich method.
than hardwoods. Steroids were present in trace amounts in Table 21. Properties of the Bio-oil Produced by Fast Pyrolysis from
tropical woods. Hybrid Poplar in the NREL (Run 175) Vortex Reactora
Paris et al.119 investigated the pyrolysis of spruce and pine Value
softwood in the temperature range of 25-1400 °C. The wood pyrolysis oil, pyrolysis oil,
sections were sandwiched between two alumina plates, to property dry basis wet basis
prevent warping, and placed in a Heraeus furnace that was empirical formula CH1.3O0.47 CH1.3O0.47 + 0.27H2O
equipped with a quartz tube that was continuously flushed with analysis
nitrogen to ensure a non-oxidizing atmosphere. A 2°C/min C 57.3 wt % 46.5 wt %
heating rate and the use of thin wood sections allow full H 6.3 wt % 7.2 wt %
O 36.2 wt % 46.1 wt %
preservation of the original cellular wood structure without the S 0.02 wt % 0.02 wt %
formation of cracks. Thermal degradation of the wood biopoly- N 0.18 wt % 0.15 wt %
mers and the evolution of the carbonaceous material’s molecular ash <0.01 wt % <0.01 wt %
and mesoscopic structure was studied by wide-angle X-ray moisture 0 wt % 18.9 wt %
high heating value, HHV 22.3 MJ/kg 18.7 MJ/kg
scattering, small-angle X-ray scattering, and Raman spectros- low heating value, LHV 21.2 MJ/kg 17.4 MJ/kg
copy. Formation of an isotropic and almost structureless material specific gravity ∼1.25 ∼1.15-1.2
occurs in a clear transition region between 307 °C and 347 °C. flash point 64 °C
Here, the cellulose microfibril crystal structure is completely potassium content 2.7 ppm
degraded. The scattering contrast, based on the density difference sodium content 7.2 ppm
calcium content 2.2 ppm
between cellulose microfibrils and polyoses/lignin, has fully chlorine content 7.9 ppm
disappeared. After this decomposition of the wood’s nanocom- aluminum content 2.6 ppm
posite structure, charring commences. Aromatic structures form titanium content <0.2 ppm
and a strongly increasing scattering signal, at small angles, vanadium content 0.002 ppm
manganese content 0.063 ppm
confirms the formation and growth of nanopores. Developing
a Data taken from ref 121 with permission from the American Chemical
graphene sheets show a slightly preferred orientation, with
respect to the oriented cellular structure of the wood. The unique Society.
cellulose microfibril orientation in the native wood cell wall
might affect the carbonaceous material. at 10 wt % of the pyrolysis oil. This methanol-modified biocrude
Stamatov et al.120 derived bio-oil via slow pyrolysis process was still a single-phase liquid and it met the ASTM No. 4 diesel
of two indigenous Australian tree species: red gum (Eucalyptus fuel specification for viscosity, even after 96 h of exposure at
camaldulensis) from the Murray basin in Victoria, and blue gum 90 °C.
(Eucalyptus globulus) from the region of Mount Gambier, South Elliott122 studied pyrolysis oils obtained from three sources:
Australia. The bio-oil was blended with ethanol and burned in a hardwood (oak), a softwood (southern pine), and a high-
a circular jet spray at atmospheric pressure. Bio-oil flames were growth-rate herbaceous biomass (switch grass). All the bio-oils
shorter, wider, and brighter than diesel fuel flames under the were produced at ∼520 °C in a residence time of <1 s in the
same conditions. Adding flammable polar additives (e.g., Vortex flash pyrolysis reactor at the NREL in Golden, CO, using
ethanol) to bio-oil improved some of the undesired properties a feed particle size of 105-250 µm. The bio-oils were analyzed
of the fuel such as poor atomization, low calorific value, and and compared with others reported in the literature. The
high NOx emission from the flame. inorganic components include the alkali metals, which are
Diebold and Czernik121 studied the fast pyrolysis of hybrid distributed throughout the oil, in both the homogeneous oil phase
poplar in the vortex reactor (high heat transfer rate, moderate and the char.
temperature (450-550 °C), and a short (<1 s) vapor residence Nilson et al.123 pyrolyzed small (15-150 mg) samples from
time in the reactor) at the National Renewable Energy Labora- eight different birch (Betula) species at 550 °C and analyzed
tory (NREL). Vapor generation was followed immediately by the products using GC, direct injection with GC/FTIR/FID
hot gas filtration. The properties are listed in Table 21. Additives (where FID denotes flame ionization detection), and precon-
to reduce and stabilize the viscosity during storage were also centration with GC/MS. Aldehydes, acids, ketones, substituted
studied.121 Additives were selected on the basis of their cost furans, and methoxylated phenols were formed. The chromato-
and their potential to shed light on the relative importance of grams were similar for all eight wood species, both with direct
the several types of chemical reactions thought to contribute to injection and preconcentration. Larger amounts of products were
aging. These reactions include esterification, transesterification, formed in the molecular-weight range of 60-130 from birch
phenol/aldehyde condensation, aldol condensation, and etheri- wood than in similar studies on pine and spruces. Conifer
fication. Methanol and water were added in varying amounts pyrolysis oils had more peaks, with a molecular weight above
to the pyrolysis bio-oils as part of an extensive evaluation of 200 amu. A thermogravimatric study of the pyrolysis of three
these two additives. Ethanol, acetone, methyl isobutyl ketone, different types of wood (viz., forest wood, old furniture, and
and the methyl ester of soybean oil were also chosen as used pallets) using dynamic and isothermal techniques was
additives. These represent three chemical families that all reported.124 Both dynamic and isothermal pyrolyses were
demonstrated the ability to drastically reduce the aging rate of performed. Isothermal runs were conducted at two different
biocrude. The additives reduced the initial viscosity at 40 °C temperatures. The low-temperature range (225-325 °C) was
by half and also reduced the aging rate (viscosity increase) of chosen, where the main degradation processes of pyrolysis
hybrid poplar hot-gas-filtered pyrolysis oil by factors of 1:18, occur. The remaining residue pyrolyzed in the range of 700-
compared to original pure oil. Methanol was the best additive 900 °C. Five different heating rates were used in the dynamic
(119) Paris, O.; Zollfrank, C.; Zickler, G. A. Carbon 2005, 43 (1), 53- (122) Elliot, D. C. Biomass Bioenergy 1994, 7 (1-7), 179-185.
66. (123) Nilsson, M.; Ingemarsson, A.; Pedersen, J. R.; Olsson, J. O.
(120) Stamatov, V.; Honnery, D.; Soria, J. Renewable Energy 2005, in Chemosphere 1999, 38 (7), 1469-1479.
press. (124) Reina, J.; Velo, E.; Puigjaner, L. Thermochim. Acta 1998, 320
(121) Diebold, J.; Czernik, S. Energy Fuels 1997, 11, 1081-1091. (1-2), 161-167.