Biomass and Bioenerg~ Vol. 13, Nos l/2. pp.

25-37, 1997
i; 1997 Published by Elsevier Science Ltd. All rights reserved
Pergamon Printed in Great Britain
PII: so!461-%34(!n)ooo21-4 0961-9534/97 $17.00 + 0.00

SEPARATION OF PHENOLS FROM EUCALYPTUS

WOOD TAR

CARLOS AMEN-CHEN*, HOOSHANGPAKDEL~ AND CHRISTIAN Rout

*Department of Chemical Engineering, Universite Lava], Ste-Foy, QuCbec, Canada GIK 7P4
tlnstitut Pyrovac Inc., 1560 Avenue du Part Beauvoir, Sillery, Qutbec, Canada GIT 2M4

(Received 20 March 1996; accepted 3 Muy 1997)

Abstract-Isolation of phenols from Eucalyptus wood pyrolysis tar was carried out with the objective of
recovering valuable pure phenols, such as phenol, cresols, guaiacol, Cmethylguaiacol, catechol and
syringol. The approach included a primary conversion of the raw wood tar into a lighter oil. Phenolic
compounds were further separated from the oil by liquid-liquid extraction using aikali and organic
solvents. GC/MS analysis of acetyl-derivatized phenolic compounds was used to evaluate the separation
method. The primary conversion allowed the isolation of a lighter oil containing the desirable compounds
without causing major chemical changes in the distilled oil. Liquid-liquid extraction by alkali and organic
solvents essentially yielded a phenolic fraction. Removal of phenols was more efficient under highIy
alkaline conditions. An evaluation of the analytical procedure for the determination of phenols was also
undertaken. 0 1997 Published by Elsevier Science Ltd

Keywords-Phenols; wood; tar; Eucalyptus; extraction; separation; analysis; pyrolysis; vacuum

I. INTRODUCTION In some countries, wood carbonization is still

an important industry. In Brazil, for example,
Wood represents an abundant renewable source
more than 40 million tons of wood are
of readily available energy on combustion. On
carbonized annually to produce charcoal for the
the other hand, thermal decomposition reac-
production of steel. The economics of either
tions in the absence of oxygen enable the
carbonization or fast wood pyrolysis processes
recovery of solid and liquid fuels as welI as
may be improved by the recovery of valuable
valuable fine chemical by-products.
compounds. However, chemical recovery costs,
Wood pyrolysis under atmospheric pressure
purity of the final compounds and the
with long vapour residence time is called
end-market have to be considered in all cases.
carbonization. Wood carbonization produces
For flash or vacuum pyrolysis processes, higher
three main products: charcoal; liquids; and gas
liquid yields are obtained in comparison with
with yields 37-50% char, 4-l 1% wood tar,
carbonization kilns, which may further improve
30-36% aqueous phase and l&29% by weight
the process economics.
of non-condensable gases. The liquids usually
Phenols derived from biomass pyrolysis oils
separate into an aqueous and oil phase. The
are valuable and useful chemicals. They have
latter is also called wood tar. Wood tar is a
both germicidal activity and anti-diarrhea1
complex and unstable mixture of many com-
properties.4 They can also be used as intermedi-
pounds, including phenols. In the past, isolation
ates in the synthesis of pharmaceutical prod-
of wood chemicals on an industrial scale has
ucts,5 for the production of adhesiveCB and the
been performed for few compounds, such as
synthesis of specialty polymers. Various labora-
methanol, acetic acid, acetone and mixtures of
tory- and bench-scale separations of phenols
phenols (e.g. wood creosote). These have been
from wood pyrolysis oils have been reported in
displaced by the rapid growth of the petroehem-
the literature using solvent elution chromatog-
ical industry over the last decades and wood tar
raphy, liquid-liquid extraction and fractional
has been used as a low-value fuel substitute.
distillation.
Preparative liquid chromatographic separ-
Author to whom correspondence shoul,d be addressed.
(Tel: (418) 656 7406; Fax: (418) 656 2091; e-mail: ation of wood vacuum pyrolysis oils at the
croy(a gch.ulaval.ca) laboratory- and bench-scale has been studied
25
26 CARLOS AMEN-CHEN et al.

previously in this laboratory.0 A relatively good preliminary feasibility study showed a pro-
fractionation was achieved using six types of duction cost of half that of the commercial
solvents. Purity of over 90% of 2(3H)-furanone phenol.
and 4-hydroxy-3-methoxybenzaldehyde Fractional distillation has been applied
(vanillin) was obtained by thin-layer chroma- mainly for the analysis of wood pyrolysis and
tography on one of the fractions collected after liquefaction oils. Elliott distilled a wood
a preparative chromatographic step. However, liquefaction oil under vacuum into seven
high consumption of solvents and silica gel solid fractions, which allowed the direct analysis of
phase regeneration problems affected the pro- the volatile fractions by gas chromatography. It
cess economic feasibility. It is believed that was found that the distillates were more stable
sequential elution solid chromatographic tech- than the whole oil, and could be stored for
niques could become economical if applied as a subsequent analyses without noticeable changes
final purification step of a phenolic fraction in composition. In that study, distillation was
rather than as a preparative separation of the applied as a preparative step for qualitative
whole pyrolysis oil. evaluation of the oil rather than as a separation
Conflicting results have been reported on technique of some desired compounds. Adjaye
aqueous alkaline extraction of phenols from et LZ/.,~ analyzed different families of com-
wood pyrolysis oils. Faix et al., Maggi and pounds in fractions collected up to 250C after
Delmon, and Galceran and Eek found that vacuum distillation at 0.17 kPa abs. of an aspen
aqueous alkaline extraction of phenols was not wood-derived liquefaction oil. They could not,
very selective and it was shown that various however, obtain a clear separation of families of
compounds were distributed in different frac- compounds. They also reported that the yields
tions. These authors also reported a consider- of phenols in the distillates were directly
able loss of products and the formation of proportional to the distillation temperature,
precipitates during the extraction. No analysis although they did not quantify individual
of the precipitates was reported. On the other phenols in the distillates. Goheen et al.,
hand, efficient separations of different families distilled a Kraft black liquor pyrolysis oil into
of compounds, including phenols, have been three fractions at a maximum temperature of
reported by other researchers.4 I6 Moreover, the 125C and 2.0 kPa abs. pressure; the second
oils used as feedstocks were obtained under fraction contained 52% by weight of guaiacol.
different pyrolysis operating conditions, which However, they found some loss of guaiacol after
render the panorama even more complex. the separation, but no explanation was given for
Bench-scale separations of phenols by liquid- this observation. Pepper and Fleming,2 distilled
liquid extraction were carried out earlier. a hydrogenolytic lignin oil to a maximum
Gallivan and Matschei obtained a phenolic temperature of 240C at 0.2 kPa abs. pressure.
fraction from a wood pyrolysis oil by an The authors reported a continuous production
aqueous alkaline extraction, followed by acidifi- of low boiling point products during the
cation of the aqueous phase. The phenols were separation. It was suggested that structural
recovered by organic solvent extraction. The changes occurred in the bulk of the oil and
biomass-derived phenols could replace 25-75% produced some water during distillation.
of commercial phenol used in the production of Schuchardt et al., 2 distilled a hydrogenolytic
adhesives. However, no evaluation of the lignin oil as a preparative step for the recovery
performance of the adhesive produced with this of monomeric phenols. Neither loss of phenols
blend was reported. Chum and Black6 isolated nor production of water or low boiling point
a phenolic/neutral fraction from the fast products were reported. Yatagai et a1.,22
pyrolysis of pine sawdust-derived oil that can be obtained very high pitch yields in the range
used as a feedstock for the formulation of 48865% by weight of wood tars from different
adhesives. The authors used a series of wood species after atmospheric distillation. An
liquid-liquid extractions based on the acidic aqueous phase was obtained at a temperature
properties of phenols and their derivatives. The below 180C with 1430% yield, while an oil
authors concluded that approximately 50% of phase was recovered at a temperature range of
the petroleum-based phenol adhesives could be 180-230C with 7.2-30% yield by weight. The
produced from sawdust pyrolysis oils. Their yields of total phenols were low and the
product performance was comparable with distillates were composed mainly of light
Cascophen 313@ adhesive brand. A further carboxylic acids. The quantification of phenols
 Separation of phenols from Eucaly~fus wood tar 21

was done only for the fraction boiling in the selected phenols. During the course of this
range ISO-230C. Therefore, the data reported investigation, phenolic compounds, such as
by these authors did not cover the entire range phenol, cresols, guaiacol, 4-methylguaiacol,
of wood tar phenols. catechol and syringol were quantified before
Flash distillation has also been used for wood and after each separation step in order to
tar characterization. It has been reported that evaluate the performance of the fractionation
this type of distillation yields more distillate process.
than in batch mode.X,4 According to Bagaev,2
this is due to a lower vapour residence time in
2. EXPERIMENTAL
the still which prevents secondary reactions
involving low molecular weight compounds in 2.1. Sample .speciJcation
the tar. Distillate yields of 59% by weight at
The wood tar used in this work was
275C and 13.3 kPa abs. by flash operation was
commercially produced by ACESITA, Brazil,
obtained in comparison with 33.4% by weight
during carbonization of Eucalyptus crops in
at 240C and 2 kPa abs. using batch distillation.
beehive kilns under an oxygen-poor atmos-
Similarly, Kiprianov ef af.,24 reported distillate
pheric pressure at about 400C. Details about
yield of 85.6% by weight at 280C and 22.6 kPa.
the facility operation can be found elsewhere.
In both studies, linear correlations were found
About 201 of the ACESITA raw wood tar were
between the yield of distillate and the operating
shipped to our laboratories 1 year prior to the
temperature. However, there was no quantifi-
beginning of this work and kept in a cold, dark
cation of individual phenols in the distillate
room at 10C in tightly-closed glass bottles.
reported in the cited studies.
Distillation of wood tar at the bench scale has
2.2. Chemical reagents and solvents
recently been carried out by Carazza et a[.,
who isolated methoxyphenolics by two consecu- Standard samples of phenol (CAS 108-95-2)
tive distillations under reduced pressure. The o-cresol (CAS 95-48-7), m-cresol (CAS 108-39-
equipment consisted of a boiler attached to a 4), p-cresol (CAS 106-44-5), 2,5-xylenol (CAS
four-plate column and a mechanical pump to 95-87-4), guaiacol (CAS 90-05-l), 4-methylguai-
establish the vacuum. The homogenization of acol (CAS 93-51-6) catechol (CAS 120-80-9)
the mixture in the boiler was accomplished with and syringol (CAS 91-10-l) were purchased
a centrifugal pump. The first distillation was from Aldrich Chemical Co, MI, U.S.A. with
performed at 9.3 kPa abs. and a maximum 98% purity or higher. HPLC-quality ethyl
temperature of 3OOC, which yielded about 17% acetate (CAS 141-78-6) and anthracene (CAS
by weight of aqueous phase, 27% oil phase and 120-12-7) (Baker grade) were from J. T. Baker,
5 1Oh pitch. The oil phase was further distilled Phillipsburg, NJ, U.S.A., sodium hydroxide
with the same equipment at 1.3 kPa pressure (CAS 1310-73-Z) (99.5%) in pellets was from
and a maximum temperature of 340C at the Fisher Scientific, Fair Lawn, NJ, U.S.A. and
top of the column, which yielded 85% of sulfuric acid (CAS 7664-93-9) (95-98%, ACS
distillates. During the second distillation, 95 grade) was from Omega Chemicals, Levis, PQ,
samples were collected and analyzed and Canada. All the reagents were used as received
approximately 80% of the distillates were without further purification.
identified. Syringol was concentrated to 60% by
weight in one of those fractions. In general, 2.3. Primary converter
syringol and its derivatives were collected in The primary converter (see Fig. 1) was a
fractions with concentrations ranging from 40 0.41 m high x 0.25 m I.D. stainless steel insu-
to 60% by weight. lated cylindrical vessel equipped with an
The objective of the present study is to agitator and a 0.20 m high basket installed at
investigate the possibility of isolating valuable the bottom of the heating chamber. The wood
phenols from raw wood tar at a laboratory scale tar was fed through a 0.95 cm I.D. piping
with a potential application at a higher scale. connected to a 500 ml Pyrex graduated cylinder.
Our approach involved the application of a The feed rate was controlled by a SS-8BW-TW
primary raw wood tar conversion into a lighter Nupro valve (Nupro Co, Willoughby, OH,
oil by a flash-like distillation method under U.S.A.) at 10-20 ml/min. The agitator consisted
vacuum. The distilled oil was further subjected of 22 screws arranged in a cross-like configur-
to liquid-liquid extraction to separate some ation and attached to a 1.6 cm diameter shaft
28 CARLOSAMEN-CHENet al.

powered by an electric motor (Robbins and 10-l cylinder and later analyzed by gas
Myers, Cheshire, CN, U.S.A.) at 6 rev/min. chromatography.
The volatiles were condensed in a series of An Edwards E2M-I8 high vacuum pump
four 33 x 5 cm I.D. Pyrex traps maintained at (Edwards Co, Sussex, U.K.) was used for setting
different temperatures: the first at room the system under vacuum.
temperature; the second at approximately 0C
in a bath of ethylene glycol-water; and the 2.4. Liquid-liquid extracsion of phenols from
last two traps were submerged in a bath of primary oil
dry ice-acetone at - 60 to - 70C. The The procedure consisted of four main steps:
non-condensable gases were stored in a (1) the wood tar-derived oil containing the

/
rl ..... 01
_.-----~._.,

~~....__.___ .,_......-- ,b
:
8
0
0000 !.I: 0000
0
iii

8
,@

1. Graduated Cylinder. 7. Vacuum Pumps.

2. Agitator. 8. Gas Storage Cylinder.
3. Receiving Basket 9. Pressure Gauge.
4. Arrangement of the Agitator Blades. 10. Microcomputer
5. Primary Converter. 11. Manual Valves.
6. Distillation Traps
Fig. I. Schematic diagram of the primary converter.
 Separation of phenols from Eucnl~vptuswood tar 29

1:l by weight ratio of

feedstock/Ethyl acetate

NaOH I:1 by weight ratio of

NaOH/ organic solution

5-stage alkaline extraction

Acidification to pH 6,
Ethyl acetate extraction,
0.51 by weight ratio of
Discarded
EtOAc/ Aqueous solution
4-stage ethyl acetate extraction
-l

Fig. 2. Liquid-liquid extraction of phenols from primary oil

desired phenols was dissolved in ethyl acetate;
(2) an aqueous alkaline solution was added to
extract phenols by converting them into
water-soluble phenolate ions; (3) phenols were
regenerated by acidification of the aqueous layer
with sulfuric acid; and (4) a phenolic-rich
fraction was recovered by ethyl acetate extrac-
tion of the acidic aqueous layer. The procedure
was performed at room temperature.
The detailed procedure was as follows: an
accurate amount of primary oil weighing
between 2 and 6 g was dissolved in ethyl acetate
at a 1 : 1 weight ratio to improve the flowability
and to decrease the density of the original oil.
The solution was mixed with an aqueous
sodium hydroxide solution in a 1 : 1 ratio by
weight in a 125 ml separatory funnel. The
phases could be clearly distinguished at this
ratio. The funnel was shaken and phases were
separated on standing and pH was measured.
The alkaline extraction of the solvent phase was
repeated five times with fresh alkali solution. An
aliquot of the aqueous phases was taken in each
stage to determine the phenolic composition in
the extract. The combined aqueous phases were
collected in a 125 ml separatory funnel and the

Table 1. Properties of Eucalyprus raw wood tar produced by ACESITA

Pronertv Value
% Water (%w/w on as received wood tar basis) 15.9Gl6.76
Density @ 20C (g/ml) 1.13
Insolubles in methanol (%w/w on as received wood tar basis) 5.48
Elemental composition (moisture-free basis)
% c 65.64
% H 6.38
%N 0.63
% 0 (by difference) 27.35
30 CARLOS AMEN-CHEN Ed al.

Table 2. Amount of selected phenolic compounds in the The carbonate content of the sample was
ACESITA raw wood tar
assumed to be negligible. Oxygen content was
%w/w on an as-received raw
calculated by difference. Sulphur content was
Compounds wood tar basis
not analyzed.
Phenol 0.3
o-Cresol 0.1
m-Cresol 0.2 2.6. Determination of water in wood tar and
p-Cresol 0.1
primary oil
2,5-Xylenol <0.05
Cuaiacol I.0 A Mettler DL 18 Karl Fisher automatic
4-Methylguaiacol 1.0
Catechol 1.3
titrator was used for the determination of water
Syringol 2.5 in the wood tar and distillates. The Karl Fisher
reagent was pyridine-free Hydranal-Composite
5 (Riedel-de Haen, NY, U.S.A.). The titration
solvent was a mixture of glass-distilled methanol
phenols were regenerated by acidifying the
and dichloromethane (1 : 1 by volume). About
solution with a solution of sulfuric acid 50% by
40-80 mg of sample were injected with a 1 ml
weight to a pH near 6. It has been observed that
disposable syringe. The reported results are the
phenols were better extracted from the aqueous
average of three analyses. The water determi-
phase at a pH below 7.26.27Ethyl acetate was
nation method has been evaluated earlier in this
used as the organic solvent to recover the
laboratory.30
phenols from the aqueous phase. -An earlier
study has shown that ketones and esters are
good solvents for the removal of phenols from 2.7. GCIMS analysis of the oil fractions
water.2X Ethyl acetate in particular, has been A HP-5890 gas chromatograph equipped
used for the extraction of wood tar phenols with with split/splitless injector and a HP-7673
optimum results.29 The extraction was repeated automatic sampler were used. The split ratio
four times with a 0.5 : 1 solvent/aqueous phase was varied from I : 10 to 1 : 200 depending on
weight ratio. Aliquots were taken from the ethyl the sample concentration. The injector was
acetate layer in the same manner as in the maintained at 290C and helium (Ultra High
alkaline extraction to analyze the phenolic Purity grade, ProdAir, Canada) was used as the
content of the extracts and to determine the carrier gas with a flow rate of about 1 ml/min.
number of stages required. The GC was equipped with a 30 m x 0.25 mm
The extraction procedure was carried out 1.D Hewlett Packard HP-5MS capillary column
using NaOH solutions of 2 , 0.3 and 0.05 M to with 0.25 mm film thickness. The oven tempera-
determine the effect of pH on the recovery of ture program was 50C for 2 min, heated at
phenols. A scheme of the liquid-liquid extrac- SC/min to 2OOC, then at 30C/min to 290C
tion procedure is shown in Fig. 2. and held at 290C for 5 min. The end of the
column was directly introduced into the ion
2.5. Elemental analysis of the raw wood tar source of a HP 5970 mass selective detector
The elemental analysis of the raw wood tar (MSD) with electron impact ionization mode.
was performed on a LECO model CHN-600 The mass spectrometer conditions were as
Elemental Analyser (LECO Co, MI, U.S.A.) follows: transfer line 270C; ion source 250C;
following the manufacturers method of analy- and electron energy 70 eV. The data acquisition
sis. The samples were accurately weighted in the was done with a HP-UX chemstation software
IO&150 mg range. The results reported here are using a HP-UNIX computer and NBS mass
the average of four analyses. spectra library database.

Table 3. Recovery of standard phenols after acetyl derivatization without purification and concentration
Compound Amount* (mg) Average (mg) Theoretical value (mg) SD (mg) Coefficient of variation (X)

Phenol 1.62 1.49 I.52 1.54 1.62 f 0.12 * 7.8

Guaiacol 1.58 1.51 I .66 1.58 1.60 * 0.08 + 5.1
Methylguaiacol 1.59 1.60 1.69 1.63 1.59 f 0.08 + 4.9
Catechol 1.58 1.46 1.58 1.54 I.51 * 0.07 * 4.5
Syringol 1.60 1.49 1.48 1.52 1.60 _+O.ll + 7.2
*Measured by CC.
Separation of phenols from Eucalyptus wood tar 31

2.8. Derivatization and puriJcation of samples

before GC/MS analysis
The samples analyzed were acetylated, based
on the method used by Thring et al., and
purified following the procedure described
hereafter. A known amount of sample between
50 and 500 mg depending on the phenolic
concentration of the sample was weighed in an
analytical balance in a 4-ml vial. An excess of
acetic anhydride reagent (CAS 108-24-7) (Ana-
Chemia, ACS grade) and two drops of pyridine
(CAS 110-86-l) (AnaChemia, 99.0%) as reac-
tion catalyst were then added. The vial was
heated in a water bath at 60C for 90 min, then
cooled to room temperature. The derivatized
solution was transferred onto a small glass
column containing approximately 0.8 gm of
silica gel (CAS 112926-00-S) (Aldrich, 70-230
mesh, pore size 60 A) and eluted with 15 ml of
a solution of 20% by volume of glass-distilled
CHzClz in n-hexane (CAS 110-54-3) (BDH,
ACS grade, Toronto, ON, Canada). The
solution was concentrated by evaporation under
a flow of N, and a predetermined amount of
internal standard solution (anthracene in ethyl
acetate) was added with a 50-ml analytical
syringe (Hamilton Co, Reno, NA, U.S.A.). The
synthetic mixture of phenols used for determi-
nation of GC/MS response factors was deriva-
tized without purification.

2.9. Ident$cation and quantljication of deriva-

tized phenols
Four standard mixtures of phenols were
prepared with different concentration and
analyzed. The integration results were verified
to ensure correct compound identification and
integration by the computer program. All
samples were duplicated.
Under the GC conditions used in this work,
guaiacol and syringol peaks overlapped with
other compounds. Single ion chromatograms
with characteristic fragments of m/z = 124 and
154 were used for quantifying guaiacol and
syringol, respectively. The other phenols were
quantified with their total ion current peaks.

3. RESULTS AND DISCUSSION

3.1. Raw wood tar characterization

The as received raw wood tar was dark with
an acidic smell and good flowability. Table 1
shows some properties of the ACESITA raw
wood tar. The methanol insolubles are believed
32 CARLOS ASPEN-CHEN er al.

Table 6. Raw wood tar primary conversion yields

Item %w/w on an as-received wood tar basis

Run No. 1 (230C) Run No. 2 (19OC) Run No. 3 (16OC)

Aqueous phase 22.40 22.40 23.30
Oil phase 61.10 50.77 41.40
Total distillates 83.50 73.17 64.70
Solid residue 14.53 24.34 32.50
Gases 0.59 0.32 0.02
Mass closure 98.70 97.88 97.30

to be heavy materials or some coke. The
elemental analysis and the water content were
found to be similar to other wood pyrolysis oils
reported in the literature.x3 However, the
concentration of some individual phenols (see
Table 2) were higher than that reported by
Scott32 for oils produced by different thermo-
chemical conversion methods. However, a
considerable amount of catechol was found in
this tar, which is not usually found in wood flash
pyrolysis oils, and is an indication of secondary
transformations of primary pheno1s.33
3.2. Evaluation of phenol derivatization pro-
cedure
Acetylation procedure was preferred as the
derivatization technique over silylation because
the former requires milder reaction conditions.3
Three different tests were conducted to assess
the influence of the nature of solvent and the
purification and concentration steps on the
analytical results using standard phenolic
solutions of known composition. Table 3 shows
the recovery of phenols after triplicate analysis
of authentic phenolic mixtures in ethyl acetate
solution. This mixture was prepared by taking
a 40 ,~l aliquot with a syringe from a stock
solution initially with 40 mg/ml of each phenol,
derivatizing and then diluting to 4 ml in a vial.
A predetermined amount of anthracene in ethyl
acetate was added for quantification. Results in
Table 3 show the quantification by GC/MS of
the compounds derivatized and analyzed with-
out purification. The procedure which involved
purification on silica gel and concentration
under N, flow was also evaluated and the results
are reported in Table 4. Derivatization and
purification of the same phenols in the aqueous
phase was also performed (the results are shown
in Table 5). Statistical value of the results was
expressed in terms of standard deviation and
coefficient of variation.34
The derivatized standard phenolic solution
in ethyl acetate was analyzed without purifi-
cation and showed standard deviations in the
range 47%. These results are in good
agreement with those reported by Thring et al.3
The standard deviation increased from 10% to

.--*... phenol
--B-- guaiacol
-A- creosol
-+- catechol
+- syringol

80 90 100 110 120 130

Temperature (C)

Fig. 3. Concentration of phenols in the multi-plate vacuum distillates of primary oil.

 Separation of phenols from Eucalypruswood tar 33

-+-- phenol
--m- guaiacol
+ creOso1
-V- catechol
--6 syfingol

Number of cross-current stages

Fig. 4. Alkaline extraction of phenols from primary oil at a pH of 11.3

23% as the derivatized phenols were purified on
silica gel and concentrated by evaporation
under nitrogen. Standard deviation of the
phenols after derivatization in the aqueous
phase followed by purification on silica gel and
concentration by N, varied between 2 and 15%,
with the exception of catechol which showed a
very high deviation of 62%. Comparison
between Table 3,4 indicates that the negative
deviations from the expected values observed
amongthe phenols were due essentially to losses
in the purification and concentration steps. No
significant differences were found with either
ethyl acetate or water as solvents for derivatiza-
tion. Results on phenolic yields presented in this
work included the derivatization and purifi-
cation steps. A second more polar solvent
consisting of a 1 : 1 CH& : n-hexane solution
by volume did not elute any additional
derivatized phenolic compound. Recovery of
phenols was lower after purification because of
their incomplete elution from the silica gel
column with the solvents used. On the other
hand, GC analysis of clean, purified mixtures
allows longer capillary column life.
3.3. Primary conversion of wood tar
The first step for the recovery of phenols
included a vacuum distillation performed in the
primary converter. The operational principle of
the primary converter was based on the
formation of a thin layer of wood tar inside the
apparatus by means of an agitator that swept
the bottom surface of the converter as the wood

-+-- phenol
a- guaiacol
--C creosol
-V - catechol
-.+ syringol
\
\

1 2 3 4 5
Number of cross-current stages
Fig. 5. Alkaline extraction of phenols from primary oil at a pH of 10.5
 CARLOSAMEN-CHEN et al.

-e phenol
-+ - guaiacol
--&- creosol
-v- catechol
//-- +- syringol
/ \
/ \
/ \
/
\
\

1 2 3 4 5
Number of cross-current stages

Fig. 6. Alkaline extraction of phenols from primary oil at a pH of 9.5.

tar was continuously fed. Thus, the temperature The distillates collected in the four traps were
gradient between the hot walls of the converter mixed and separated into two phases: a clear
and the layer of wood tar was reduced and and light phase with a strong acidic smell, which
possible secondary chemical reactions involving was mostly composed of water and designated
the targeted phenols were minimized. Appli- as primary aqueous phase; and a dark and
cation of vacuum to the system to remove the smoke smelling phase with a little amount of
vapours produced during the process and their water, designated as primary oil phase. Yields of
rapid condensation prevented further undesir- distillates, gases and pitch for the three runs are
able reactions. presented in Table 6.
Three primary conversion runs were con- The selected phenols were mainly recovered
ducted at a reduced pressure of about 0.40 kPa in the primary oil phase. The phenolic
abs and at temperatures of 230, 190 and 160C. concentration was low in the aqueous phase

Table 7. Phenols mass balance after liquid-liquid extraction

%w/w of the initial phenols in the primary oil
Compound PH Neutral layer (I) Ethyl acetate (2) Mass balance closure (1 + 2)
Phenol 11.3 66.0 66.0
10.5 35.5 39.8 75.3
9.5 55.5 32.3 87.8
o-Cresol 11.3 58.9 36.3 95.2
10.5 124.0 13.9 137.9
9.5 87.9 12.1 100.0
m-Cresol II.3 23.1 54. I 77.2
10.5 62.5 22.1 84.6
9.5 60.9 16.4 77.3
p-Cresol 11.3 44.9 67.6 112.5
10.5 80.2 16.3 96.5
9.5 78.9 9.5 88.4
Guaiacol 11.3 54.2 54.2
10.5 25.6 38.3 63.9
9.5 41.9 19.2 61.1
Methylguaiacol 11.3 19.5 44.4 63.9
10.5 51.9 16.2 68.1
9.5 47.6 11.5 59.1
Catechol 11.3 68.0 68.0
10.5 72.3 72.3
9.5 5.9 54.5 60.4
Syringol 11.3 71.1 71.1
10.5 19.0 61.7 80.7
9.5 44.4 53.7 98.1
 Separation of phenols from Eucahpfus wood tar 35

Table 8. Phenol recovery after alkaline extraction of oil 3.4.2. Run No. 2. This extraction was
dissolved in different solvents with NaOH 5 M
performed at a pH of about 10.5 in order to
w/w% recovery of the initial phenols in the primary oil
determine the extractability of phenols by an
Compound EtOAc CH,CII MIBK
alkaline solution at a lower pH. Figure 5 shows
Phenol 70 72 84
o-Cresol 69 76 69
the results for this run.
rn-Cresol 81 86 96 3.4.3. Run No. 3. This extraction was
p-Cresol 72 78 57 performed at a pH of about 9.5 in an attempt
Guaiacol 90 98 107
4-Methylguaiacol 95 103 I08
to extract phenols under milder conditions and
Catechol II9 129 79 to correlate the phenol recovery with the
Syringol 94 102 116 extraction pH. The results are reported in Fig. 6.
It can be noticed from Fig. 4 that catechol
was completely extracted at a pH of 11.3 after
three stages. Extraction of the rest of the
after primary conversion. Guaiacol was the phenols required five stages. Catechol was
most abundant phenol in the aqueous phase extracted within four stages at a pH of 10.5 (see
with a concentration lower than 0.4% for the Fig. 5) whereas the other phenols were not
three runs. The aqueous phase was not completely removed. Thus, a pH of 10.5-l 1.5
considered for further study in this work. was suitable for the complete extraction of
Aqueous phase yield did not change within the catechol from the primary oil. Complete
temperature range studied, indicating that extraction of the other phenols requires more
dehydration reactions occurred either to the than five stages. No phenol could be completely
same extent or were negligible in the range of extracted from the primary oil at a pH of 9.5.
temperatures investigated. The total gases The acidity of phenols can be measured by
produced after the primary conversion were their dissociation constants. Catechol is the
very low (up to 0.6% w/w of the feedstock), most acidic phenol with a pKa = 9.40 and can
showing that there were no major cracking be easily extracted. On the other hand, phenol,
reactions. CO> and CO were the major gaseous guaiacol and 4-methylguaiacol have the same
products for all three runs with some light pKa = 10.0 and exhibited a similar extraction
hydrocarbons. The residue was completely yield under the alkaline extraction. Syringol is
soluble , in methanol, indicating that the probably more acid than phenol, guaiacol and
formation of heavy materials was avoided. 4-methylguaiacol due to the electron-withdraw-
Distillation of the primary oil under atmos- ing effect of the two methoxyl substituents.
pheric pressure to a temperature of 280C However, formation of the phenolate ion may
produced gases, increased threefold the initial be hindered by steric effects of the substituent
amount of water and left a methanol-insoluble groups.
residue. The selected phenols in this investigation are
Analysis of fractions collected after multi- very weak acids and complete neutralization is
plate vacuum distillation of the primary oil obtained at a pH of 1 1-12.35 Greminger et al.,
showed a fairly good separation between the indicated that distribution coefficients of pheno-
low boiling point phenols, such as phenol, lies towards the aqueous phase are favoured
cresols, guaiacol and the high boiling point under alkaline conditions of pH higher than 11.
phenols, such as catechol and syringol (see Ethyl acetate proved to be an excellent
Fig. 3). solvent for the extraction of phenols from the
aqueous phase despite its rather high solubility
3.4. Liquid-liquid extraction of phenols in water. Only two cross-current stages of
3.4.1. Run No. 1. Liquid-liquid extraction of extraction were necessary for the complete
phenols was performed on the primary conver- recovery of phenols from the aqueous phase at
sion oil obtained at 160C. This oil was a pH of about 6. Additional GC/MS analysis of
completely soluble in ethyl acetate and filtration the aqueous layers from the three runs after
of insoluble materials was not necessary. This ethyl acetate extraction confirmed this obser-
extraction was performed with an aqueous vation.
solution at a pH value of 11.3. Mass spectra of the major peaks in the ethyl
Results for the extraction of phenols from acetate extracts from the three runs revealed
the oil by alkaline solutions are plotted in that the compounds were almost all phenolics.
Fig. 4. Derivatized phenolic hydroxyl group was
36 CARLOS AMEN-CHEN et al.
mainly characterized by m/z = 43 fragment ion
of acetyl group. Light carboxylic acids could not
be detected. It is likely that light carboxylic
acids were mainly concentrated in the aqueous
phase after primary conversion and were absent
in the oil phase that was subjected to the
liquid-liquid extraction. Absence of relatively
stronger acid species due to their early removal
during primary conversion may facilitate phenol
extraction by combined alkaline-ethyl acetate
extraction.
Although ethyl acetate was used for liquid-
liquid extraction in this work, other organic
solvents, such as 4-methyl-2-pentanone (methyl-
isobutylketone or MIBK) and propyl acetate
are also suitable for the recovery of phenols.
Nevertheless, the choice of a solvent also
depends on economic considerations, which
were not evaluated in this work.
Extractions were also performed with a 5 M
NaOH aqueous solution by previously dissolv-
ing the oil in solvents such as methyl
isobutylketone (MIBK) and dichloromethane
(CH,Cl,). Three phases were formed after
addition of the alkaline solution: a lower
aqueous solution saturated with phenolates; an
intermediate solid layer consisting of phenolate
crystals; and an upper organic solvent layer. The
upper organic phase was separated by centrifu-
gation and designated as neutral phase. The pH
of the aqueous layer was 12-13. This phase
along with the solid layer were further acidified
and extracted with ethyl acetate as described in
the experimental procedure. Phenol recoveries
in the extract are presented in Table 8.
Compared with Table 7, recoveries after a single
stage alkaline extraction with a concentrated
NaOH solution were higher than by using five
stages of cross-current extraction with diluted
NaOH solutions( Table 8).
Additional work continues in our labora-
tories to further improve phenols solvent
extraction efficiency. Application of a NaOH
solution in a binary alcohol-water solvent will
be attempted. The synergistic effect of the
binary solvents on phenols extraction efficiency
may also be helpful for reducing the highly
alkaline conditions needed at this stage.
4. CONCLUSIONS
Heating under vacuum of a wood tar sample
allowed the separation of heavy materials
originally present in the raw wood tar, yielding
a light oil phase rich in phenols that was suitable
for further distillation and liquid-liquid extrac-
tion. The mild operating conditions allowed a
good recovery of the targeted phenols without
causing severe chemical changes in the original
wood tar.
Acetyl derivatization of phenols was con-
sidered a convenient analytical method for their
quantification. Derivatization yields were found
to be 93% or better on average and decreased
to a minimum of 80% when an additional
purification and concentration step was in-
cluded. Derivatization in water or ethyl acetate
solvents resulted in approximately the same
phenol derivatization yields except for catechol.
However, sample purification has to be
modified for complete phenols recovery.
Liquid-liquid extraction yielded a fraction
composed essentially of phenolic compounds.
However, incomplete extraction of the selected
compounds was achieved under a pH of 11. Due
to their weak acidities, a high pH value was
required for a complete extraction of phenols
from the oil matrix. Complete recovery of
phenols was achieved at a pH of 12-13 by using
a concentrated alkaline solution. The separation
of catechol from the primary oil was easier than
the rest of the selected phenols. At a pH as low
as 10.5, it was possible to completely extract this
compound, while the others were not com-
pletely removed. Full extraction of phenols
from the aqueous phase, previously neutralized
to a pH - 6, was accomplished within two
cross-current stages.
Acknowledgernen/s-This research was supported by Insti-
tut Pyrovac Inc., Quebec, Canada. The wood tar sample was
kindly provided by Companhia Aces Especiais itabira
ACESITA, Belo Horizonte, Brazil.
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