FRACTIONATION OF WOOD TAR

F. CARAZZA*, M.E.A. REZENDE, V.M.D. PASA AND A. LESSA

Companhia A~os Especiais Itabira - ACES ITA
Avenida Afonso Pena, 4000-8Q andar - BH/MG - 30130 Brazil
* Dept. of Chemistry - Universidade Federal de Minas Gerais
Campus UFMG, Belo Horizonte, 31270, MG, Brazil

ABSTRACT
This work describes the results of a pilot-scale test in which
8 metric tons of wood tar were distilled into an aqueous
fraction, an oily fraction and pitch. The average yields were
18%, 30% and 52%, respectively. The oily fraction was distil-
led into 95 fractions, producing samples for application
development and other studies of concentration, separation and
purification. The fractions were analysed by HRGC-MS/C.
Although the work was done using a low-efficiency recti-
fication column, concentrations around 20% guaiacol or
creosol, 60% syringol and 50% ethyl syringol were easily ob-
tained.

INTRODUCTION
Wood tar is a complex mixture of hundreds of phenolic and non
phenolic chemical products, recovered in the process of wood
pyrolysis. Wood tar fractionation at a laboratory level has
been reported by different authors [1,2,3], aiming at
achieving a better knowledge of its chemical composition.
The existing wood tar fractionating plants are restricted
to the production of a few products, such as wood creosote
[4], maltol and cyclotene, not exploring the entire potential
of wood tar.
In Brazil, the present charcoal production for ironmaking
amounts to 10 million metric tons a year, what would allow for
the recovery of 4 million metric tons a year of wood tar. Due
to the high potential for the production of this raw material,
the processing of wood tar in Brazil is more likely to be made
economically feasible

1465

A. V. Bridgwater (ed.), Advances in Thermochemical Biomass Conversion

© Springer Science+Business Media Dordrecht 1993
 The recovery and fractionation of wood tar for the
production of chemical feedstock may bring about the following
benefits:

- financial resources for the modernization of the charcoal

production;
- adequate return on the investment in Eucalyptus forests,
assuring self-sufficiency in Eucalyptus charcoal for the
ironmaking industry;
- reduction of the emission of volatile organic compounds
(VOC), minimizing the current level of environmental impact;
- development of a renewable source of chemical feedstock.
Wood tar components, if produced at competitive prices, can
make fine chemicals and engineering polymer more
competitive.

ACES ITA, a Brazilian leading company in the production of

special steels, in the long run will be able to process
100,000 metric tons a year of Eucalyptus tar. A semi-indus-
trial plant for fractionation of wood tar will be implemented
in the next few years.
In the beginning, the plant will produce small amounts of
specialized chemical products with high commercial value. At a
later phase the range of products will be widened, seeking the
development of the market to absorb the production capacity of
ACES ITA.

MATERIALS AND METHODS

Eight thousand liters of Eucalyptus tar, recovered from the

carbonization retort at ACESITA, were distilled. The average
properties of this tar were as follows:

- Density (g/cu cm): 1.18

- Moisture (% w/w): 12.50
- Viscosity (SSF): 43.00
- Acidity (% HAc): 8.47
- Heating Value (KJ/Kg): 20900
Tar was distilled in 4 batches of 2,000 liters at a low
efficiency column, as shown on Figure 1. The mixture was sepa-
rated, at a first stage, into aqueous fraction (up to 110°C),
oily fraction(up to 300°C) and wood pitch. At a second stage
the crude oil was fractionated into 95 samples, weighing about
15 kg each.

The Distillation System

This consists of a 3,000 I boiler, coupled to a fractionation
column of 4 drilled plates. There is a vacuum system and a top
reflux system which may be actuated when it is considered con-
venient. Homogenization of the mixture throughout distillation
is accomplished through a centrifuge pump which recirculates
the material available on the bottom of the boiler.

1466
 -,
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P I LOT
I
I
~ I
Iu
II
I
I
I

,
I
I
r ilter

I
I
I
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coluam
I
I
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Figure 1: Distillation system used in the experiment

1467
 Temperature and pressure: In the primary fractionation of
wood tar, the temperature did not exceed 300°C and the
pressure applied was 70 mmHg.
In the secondary fractionation, in which the crude oil
produced during the first stage was processed, maximum top
temperature was 340°C while average pressure was 10 mmHg.
Top Reflux: This was used solely in the fractionation of
crude oil and was changed between the ratios of 3:1 and 7:1.
Analysis of the Samples: The analysis of crude oil was
carried out with a system HRGC-MS/C (GC-HP5890A coupled to an
MS-HP5987A). For the fractions HRGC was applied, correlating
the results with those of crude oil with the retention time of
synthetic standards.
GC operated with a 30 m x 0.32 mm internal diameter ca-
pillary column of the SE-54 type (methyl silicon). A flame io-
nization detector was also utilized (temperature: 225°C).
Samples were diluted (0.04 g - 10 ml CHC1 3 ) and injected
(1 ~l) - injector temperature: 250°C. After an isothermal pe-
riod of 1 min, the column temperature was increased from 80°C
to 170°C, at a rate of 3°C/min. Hydrogen was used as a drag-
ging gas at a flow rate of 1.5 ml/min.

RESULTS AND DISCUSSION

Mass balances for the first phase are shown on TABLE 1.

TABLE 1
Mass Balance for Primary Fractionation of Eucalyptus sp Tar

B 1 B 2 B 3 B 4 Average
Aqueous Fraction (% ) 15.1 13.6 18.6 22.0 17.3
Crude Oil (% ) 30.1 30.8 31.3 15.2 26.9
Pitch (%) 48.8 49.8 46.1 59.2 50.9
Losses (% ) 6.0 5.8 4.0 3.6 4.9

Figure 2 shows a chromatogram of crude oil obtained in

primary fractionation, in which the prevalence of syringil
compounds can be seen (derived from 2.6 dimethoxyphenol).
Identification studies for this oil have been carried out
(5), allowing for a proposal of the approximate composition of
this mixture, as shown on Table 2.
In secondary fractionation, 95 samples of 15 kg each,
were obtained, and 15% of the initial mass were obtained as
residue (pitch).

1468
 It is believed that using equipment of great 7r efficiency
it should be possible to attain fractions with h~gher concen-
tration levels, chiefly for .syringol and its derived substan-
ces.

HRGC-IIS-C CItIIl»IATIlGIIM FOR £UCAl YPTUS TAlI OIL

\, lJ

•
.. l

Peak~

01 1,4-0illlethyl-furan 15 3-Methoxy-catecho I
02 Butyrolactone 16 4-Ethyl-guaYilcol
03 3,3-Dilllethyl Z-Butanane/Benzofuran/Z MethDaycarilonyl furan 17 Methyl-naphtalene
04 Phenol 18 4-Methyl-catechol
05 Cycl otene 19 Z,6-DilllethOllypheno 1
06 o-Cresol 20 3,4-Dillletho"Jphenal
07 a-p-Cresol 21 Propyl-guayacoI
08 &uaYicol ZZ Oilll!thyl-naphtalene
09 2,6-Xylenol 23 4-Methyl-2,6-dilllethOllyphenal
10 Maltol 24 1,2-Dilllethyl-4-allyl-naphtal-
11 2,4-0illl!thyl-phenol/3-ethyl-phenol 25 Di beozofuriln
12 4-Ethy I-pheno I/napllta lene 26 4-Etllyl-Z,6-dimethqllyphenOl
13 4~thyl-guayacol 27 4-Allyl-2,6-dilllethdxyphenol
14 3,4-Xylenol 28 4-Propyl-2,6-dilllethoilyphenol

Figure 2: HRGC-MS-C chromatogram for Eucalyptus crude oil.

1469
 TABLE 2
Approximate Composition of Eucalyptus crude oil

COMPONENT RETENTION TIME % (W/W)

Acetic Acid 2.61 0.63
Butyrolactone 2.66 1. 38
Phenol 3.39 2.22
Cyclotene 4.17 2.65
o - Cresol 4.66 1. 37
p,m - Cresol 5.09 4.10
Guaiacol 5.46 3.65
Maltol 6.00 1.21
2,4 Dimethylphenol 6.92 2.13
Ethyl phenol 7.51 1. 85
Methyl guaiacol 8.26 6.34
Ethyl guaiacol 11.16 5.84
2,6 Dimethoxyphenol 13.82 22.17
Propyl guaiacol 14.46 1.68
Methyl 2,6 dimethoxyphenol 17.55 17.36
Ethyl 2,6 dimethoxyphenol 20.68 10.16
Allyl 2,6 dimethoxyphenol 23.66 0.79
Propyl 2,6 dimethoxyphenol 23.92 4.64
TOTAL IDENTIFIED 90.14

* Data concerning HRGC-MS-C, under conditions indicated pre

viously.

Figure 3 shows the distillation curve for crude oil, as

well as the evolution of distilled mass and respective numbers
of fractions, with the increase of column top temperature.
The curve presents three steps, viz.:
- the first between 219 - 230·C, in which 8% of the mass were
distill~d (samples all - a24),with a predominance of phenols
and gual.acols;
- the second step on 240·C, in which 6% of the mass were
distilled (samples a28 - a36)' with a predominance of
methyl, ethyl and propyl deriveas of phenols and guaiacols;
- the third step presents 31% of the Initial mass, distilled
in ~ r~nge of 264 - 275·C ( samples a45 - a83 ), refers to
syrl.ngl.l components.
In the 95 samples submitted to HRGC it was possible to
identify approximately 80% of the mass of each fraction, based
upon available standards.
The distribution of maximum concentration levels of phe-
nolic, guaiacil and syringil components, in the fractions, are
shown on figure 4.

1470
 This can be inferred from the observation of figure 4,
which shows Gaussian type distributions for the concentra-
tions.
With more efficient systems, there should be smaller dis-
persion and higher levels of concentration of the desired pro-
ducts.

FRACTION No.

320

300
I I I
280
V
6" I ,,-', I~ ~I

I IJ
2SO
UJ
c: I I
d
:::l 240
l-
e(
c: I
( I
220

I I I
UJ
a..
~
UJ 200
I-
a.. I I I I I
II
0 180
I-
160
I I I I
140
I I
120
o
I' I I
10 20 30 «l 50
I I
60 70
I
80 90
DISTIllED MASS (%)

Figure 3: Distillation curve for Eucalyptus crude oil

1471
 20

I
~ 15
Z
0
~
a:
10

~
zW
U 5
Z
0
U
5 10 15 20 25 30 35 40 45 50
FRACTION No.
--- Phenol - - o-Cresol - p.rn Cresol -&- Ethyl phenol

25

~~ 20

Z
0 15

~
a: 10
~
W
U 5
Z
0
u J
0 50
0 5 10 15 20 25 30 35 40 45
FRACTION No.
- - Guayacol -+- Cr"""'" - Elhyl guayacol -e- Propyl guayacol

70

~~ 60

50
!
~ -.........
z ,,;"
0 40
~ i
a:
~
Z
W
U
30

20
.. i

Z
0
U
0
30 35 40 45 50 55 60 65 70 75
FRACTION No.
-+- IoIothyI syringoI _ Elhyl syringol .,.;r.. PYopyI syringol
- - Syringol

Figure 4: Distribution of wood tar components throughout the

fractions

1472
 CORCLUSIORS
Even though a low efficiency distillation system was used, it
was possible to separate chemical groups such as the
monomethoxylated phenols from dimethoxylated phenols.
The best separation results were obtained for the syrin-
gic compounds (maximum concentrations of 60 - 40% ), for these
are the components in greater quantity in crude oil.
The major achievement of the study was the production of
samples of larger volumes, with yields similar to those ob-
tained in the laboratory.
These samples are being used to study different
separation techniques to isolate constituents possible of
immediate marketing, such as maltol, cyclotene and the wood
creosote fraction.
The samples are also being used for market development
and the development of new applications. Some intermediate
substances for drugs have been synthesized from syringol
bearing fractions [6]
A literature review has indicated that there are good
possibilities for the development of applications such as
engineering plastics [7], phenolic resins [8] and carbon
materials [9].

RBFERBRCES
[1) Elder, T.J. and E.J. Soltes, Pyrolysis of Lignocellulosic
Materials. Phenolic Constituents of a Wood Pyrolitic Oil.
Wood and Fiber, 12(4), 1980, pp 217 - 226.
[2) Menard, H. et alIi, Caracterisation des Jus pyrolytiques
en Provenance de Differents Procedes de Conversion du
Bois. Departement de Chimie, Universite de Sherbrooke,
Sherbrooke, Canada.
[3] Yatagai, M. T. Takahashi and M.N. Sakita, By-products
from Wood Carbonization II. Mokuzai Gakkaishi, Vol 32,
No.8, pp 626-631, 1986.
[4] Ogata, N., T. Bata, Analysis of Beechwood Creosote By Gas
Chromatography - Hass Spectrometry and High - Performance
Liquid Chromatography Chemical Pathology and
Pharmacology, Vol 66 (3), 1989.
[5) Stuckenbruck, P., Estudos de Alcatroes Vegetais por
Cromatografia Gasosa de Alta Resolu~ao e seu acoplamento
a Espectrometria de Hassas: Analise do 61eo de Alcatrao
de Eucalyptus Citriodora. Masters Thesis - Universidade
Federal do Rio de Janeiro - Chemistry Institute, 1990.
[6) Carazza, F., M.O.S. Pereira, G.D.F. Silva and L.P. An-
drade. "Fine Chemicals with Trimethoxybenzoyl Group

1473
 Obtained from Wood Tar Eucalyptus", European Workshop on
Lignocellulosis and Pulp, Hamburg, 168, 207-212, 1991.
[7] Hatakeyama, H., S. Hirose and T. Hatakeyama. "High- Per-
formance Polymers from Lignin Degradation Products".
Lignin: Properties and Materials, ed. W.G. Glasser and S.
Sarkanen. American Chemical Society, Washington, DC
(1989).
[8] Lindberg, J.J., T.A. Kuusela and K. Levon. "Specialty Po-
lymers from Lignin". Lignin: Properties and Materials,
ed. W.G. Glasser and S. Sarkanen. American Chemical
Society, Washington, DC (1989).
[9] Otani, C., V.M.D. Pasa and F. Carazza. "The Structure and
Chemical Characteristics Variation of Wood Tar Pitch
During its Carbonization". Proceedings of the
International Symposium on Carbon, Tsukuba, Japan, 1990.

1474