biomass and bioenergy 34 (2010) 1059–1063

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Short communication

Rice husk bio-oil upgrading by means of phase separation

and the production of esters from the water phase, and
novolac resins from the insoluble phase

Junming Xu*, Jianchun Jiang, Wei Lv, Weidi Dai, Yunjuan Sun
Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab, For Biomass Chemical Utilization;
Key and Open Lab. on Forest Chemical Engineering, SFA, Nanjing 210042, China

article info abstract

Article history: A new method of utilization of original bio-oil was developed in this paper. The procedure
Received 26 December 2007 chosen was based on the fractionation of the bio-oils with water into water soluble and
Received in revised form insoluble fractions. After oxidizing the aldehydes to acids by hydrogen peroxide, water
22 January 2010 soluble fraction was used to obtain upgraded bio-oil (light oil) with ethanol through reac-
Accepted 22 January 2010 tive rectification. The yield of light oil was 20.6% (account to original bio-oil) and the
Available online 21 March 2010 components of upgraded bio-oil were characterized by HPLC and FT-IR. The analysis
showed that the main components were ethyl acetate, ethyl formate, methyl acetate and
Keywords: methyl formate. Using water insoluble fractions as starting materials in synthesis of
Oryza sativa novolac resins was also studied. The water insoluble fraction was used as a substitute of
Bio-oil phenol at different ratio to prepare novolac resins. Main properties of obtained resin such
Pyrolysis as cure time and soft point were characterized. The novolac property of resins was
Upgrading determined by DSC.
Reactive rectification ª 2010 Elsevier Ltd. All rights reserved.
Novolac resins

1. Introduction carbohydrates and lignin-derived substances. Because the

Thermochemical processes are thought to have great promise
as a means for efficiently and economically converting
biomass into higher value fuels. It is attractive because solid
biomass and wastes, which are difficult and costly to manage,
can be readily converted to liquid products. These liquids have
advantages in transport, storage, combustion, retrofitting
and flexibility in production and marketing. However, the
chemical composition of biomass-based pyrolysis oils is
complicated, comprising mainly water, carboxylic acids,
compositions and properties of the bio-oils differ considerably
from those of petroleum-based fuel oils, these bio-oils are
acidic, viscous, reactive and thermally unstable. Due to its
special properties, many problems arise in their handling and
utilization. For possible future use as replacements for
hydrocarbon chemical feed stocks and fuels, the oils will
require considerable upgrading to improve its characteristics.
Currently, the most used upgrading techniques are hydro-
deoxygenation [1,2] and catalytic cracking of pyrolysis vapors
[3]. However, the yield of upgraded oils is generally low

* Corresponding author.
E-mail address: lang811023@163.com (J. Xu).
0961-9534/$ – see front matter ª 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.01.040
1060 biomass and bioenergy 34 (2010) 1059–1063

because of the high yields of char, coke and tar. These unde-
Table 1 – Fraction quantity of original bio-oil.
sired products, which are deposited on the catalyst and cause
its deactivation, make a periodical or continual regeneration Bio-oil g1 Water insoluble Water soluble H2O from
fractions g1 fractions g1 bio-oil g1
necessary.
In this work, in order to avoid the problems in hydro- 232 73.0 82.4 76.6
deoxygenation and catalytic cracking of bio-oil, we aim to find
another method that would utilize pyrolysis oils. Among the
obtained on a MAGNA-IR 550 spectrophotometer. Gas
compositions in pyrolysis oil, it could be divided into water
chromatography–mass spectrometry (Agilent 6890N/5973N)
soluble and insoluble fractions according to the hydrophilic
was conducted to analyze the composition of bio-oil.
and hydrophobic properties. The water soluble fractions
The separation was realized on a column of HP-5,
contained formic acid, acetic acid, ketones etc. These frac-
30 m  0.25 mm  0.25 um. HPLC analysis was carried out on
tions were originated from cellulose and hemicelluloses with
LC-10A (Shimadzu, UV detector: SPD-10A 210 nm, solvent:
good water solubility and low boiling point. Water insoluble
methanol:H2O ¼ 40:60). The dynamic viscosity was measured
fractions contained phenolic compounds originated from
with SYP-IA viscometers (GB/T265-88), and gross calorific value
lignin. These fractions were of hydrophobic with high boiling
was measured using IKA-C200 calorimetric bomb (ASTM
point. Therefore, by adding pyrolysis oil into a sufficient
D4809). The water content was determined by the Karl Fischer
amount of water, water soluble and insoluble fractions were
titration (ASTM D1744, GB11146-89), which was performed by
obtained. Upgraded oil (light oil) was obtained using water
using KF-412A Titrino. The acidity was evaluated by a PHS-25C
soluble fractions and ethanol as starting materials through
precision pH-meter from the Shanghai KangYi Instrument
reactive rectification and solid acid as the catalyst. Water
Factory. Cure time and soft point of phenol novolac resin were
insoluble fractions were attempted to produce phenol novolac
tested according to standards (HG 5-1338-80 and GB/T 4507-
resin as a phenol substitute for it was rich in mixture of
1999). Other materials used were of technical grade.
phenolic compounds. Characterization of upgraded oils and
phenol novolac resin was also examined.
2.2. Experimental setup and procedure

2. Experimental section
2.1. General
The bio-oil studied was obtained by fast pyrolysis of biomass in
the fluidized bed of 2 m  70 mm, with two screw feeders, two
cyclones, a condenser, and an electric heater, and the specific
operation conditions were illustrated in the literature [4]. The
feedstock of pyrolysis was rice husks, and the bio-oil was held
in a refrigerator for 4 month before its upgrading. Thermal
analysis: Thermal analysis was carried out with Pyris Diamond
(PerkinElmer) differential scanning calorimeter (DSC). A 5–
10 mg sample was sealed in a medium pressure capsule pan
and scanning temperature range from 25 to 280  C was
employed for thermal characterization. The sample crucibles
were heated at 10  C min1. IR spectra (max in cm1) were
The procedure chosen was based on the fractionation of the
bio-oils with water into water soluble and insoluble fractions.
Water soluble fraction was used to obtain upgraded bio-oil
(light oil) through reactive rectification and the water insol-
uble fraction was used as a substitute of phenol at different
ratio to prepare novolac resins.
2.2.1. Fractionation of original bio-oil
In a typical operation, 200 mL bio-oil (232.0 g) was added
slowly as drops in 200 g H2O with constant stirring at room
temperature (293 K). The fraction quantity of original bio-oil
was given in Table 1. Main components of bio-oil and insol-
uble fractions were given in Table 2.
From Table 2, it was determined that there was a complex
mixture of phenolic compounds in original bio-oil. Moreover,
after separation of original bio-oil, fraction quantity of

Table 2 – Corresponding compositions of bio-oil and insoluble fractions.

Original bio-oil Insoluble fractions

Composition wt% Composition wt%

Phenol,-3-methyl- 1.980 Phenol,-3-methyl- 2.598

Phenol, -2-methoxy- 5.038 Phenol, -2-methoxy- 7.644
Phenol, -4-ethyl- 4.272 Phenol, -4-ethyl- 3.869
Phenol,-2-methoxy-4-methyl- 3.367 Phenol,-2-methoxy-4-methyl- 4.259
1,2- Benzenediol,-3-methyl- 1.277 1,2- Benzenediol,-3-methyl- 1.602
Hydroquinone 1.610 Hydroquinone 0.928
Phenol,-4-ethyl-2-methoxy- 1.857 Phenol,-4-ethyl-2- methoxy- 2.823
1,2- Benzenediol, -4-methyl- 2.372 1,2- Benzenediol, -4-methyl- 2.473
2-methoxy-4-vinylphenol 2.663 2-methoxy-4-vinylphenol 2.196
Vanillin 3.479 Vanillin 4.251
Phenol,-2-methoxy-4-(1-propenyl)- 4.061 Phenol,-2-methoxy-4-(1-propenyl)- 6.501
4-Hydroxy-2-methoxycinnamaldehyde 3.798 4-Hydroxy-2-methoxycinnamaldehyde 5.930
 biomass and bioenergy 34 (2010) 1059–1063 1061

Table 3 – Effects of different catalysts on results of

reactive rectification.
Solid acid catalyst Yield of light
oil, wt%

Adding H2O2 No H2O2

SO2
4 /ZrO2 18.2 3.5
SO2
4 /TiO2 16.4 2.6
SO2
4 /ZrO2-MCM-41 20.6 2.9
No catalyst 1.5 No Ratio

phenolic compounds was increased in water insoluble frac-

tions. Therefore, it was possible to use water insoluble
Fig. 1 – FT-IR spectra of original bio-oil and upgraded bio-
fractions as a phenol substitute in novolac production.
oils. (a) Raw bio-oil, (b) Upgraded oil (light oil).
2.2.2. Catalysts preparation
Ammonium water was added dropwise to the solution of zir-
conyl chloride or titanium sulfate, followed by stirring for 20 min temperature between 55 and 77  C and recovered ethanol was
at room temperature to obtain a homogeneous liquid gel system. obtained at the temperature between 78 and 79  C.
Thereafter the liquid gel was filtered, washed with distilled water,
dried at 373 K and milled to obtain solid product. The SO2 4 /ZrO2 2.2.4. Synthesis of phenolic resins
and SO24 /TiO 2 catalysts were prepared by impregnating the To a three-necked flask equipped with a mechanical stirrer,
obtained solid product with a sulfuric acid solution (1 M), fol- a condenser, a thermometer were charged 41 g of phenol,
lowed by drying at 383 K overnight and calcination at 823 K for 5 h. 34 mL of formaldehyde (37%), 5 g of water insoluble fractions,
SO2
4 /Zr-MCM-41 were prepared using 1 mol L
1
H2SO4 to and the mixture was adjusted by hydrochloric acid to pH ¼ 2.0,
infuse uncalcined Zr-MCM-41, followed by drying at 383 K then, heated at 90  C for 3 h. After completion of the poly-
overnight and calcination at 823 K for 5 h. Zr-MCM-41 was merization, removing water and excess formaldehyde under
synthesized according to literature [5] by hydrothermal vacuum distillation to form the novolac resins with cure time
method. The mole ratio of reactants was 0.05 Zr(SO4)2:0.67 75 s and soft point 81  C.
Na2SiO3:0.33 silica gel:0.20 CTMABr:102 H2O.

2.2.3. Upgrading of original bio-oil through reactive

3. Results and discussion
rectification
The reaction column has a diameter of 24 mm and was
3.1. Upgrading of bio-oil through reactive rectification
equipped with a conventional metal packing. The total packing
height was 800 mm and the column was operated at ambient
In the present work, we tried to separate the compounds in
pressure. Temperature measurement points were provided in
original bio-oil according to its hydrophilic and hydrophobic
the bottom and uppermost. In a typical experiment, the water
properties. By adding pyrolysis oil into a sufficient amount of
soluble fractions obtained from 200 mL bio-oil was charged in
the bottom with 100 mL of ethanol and 4 g of catalyst, and the
mixture was total refluxed at 70–75  C, then 60 mL of H2O2 (30%)
was added. After total refluxed for about 30 min, the temper-
ature at the head of the column was decreased to 50–55  C.
Under the temperature about 50–55  C, upgraded oil (light oil)
was obtained at the head of the reactive column. Distillate
having the slop cut distilled over from this reactive column at

Table 4 – Properties of raw bio-oil and upgraded oil (light

oil).
Properties Original oil Light oil

pH 2.82 7.06
Density (g cm3) 1.16 0.91
H2O content 33.0 0.52
Calorific value (kJ g1) 14.3 21.5
Dynamic viscosity 10.5 0.46
(mm2 s1)a
Appearance dark brown colorless Fig. 2 – HPLC of upgraded bio-oils. (a) light oil, (b) ethyl

acetate b.p. 77.1 8C, (c) ethyl formate b.p. 54.6 8C, (d) methyl
a Measured at temperature of 30 C.
acetate b.p. 57.2 8C, (e) methyl formate b.p. 31.5 8C.
1062 biomass and bioenergy 34 (2010) 1059–1063
Table 5 – Effects of substitute ratio on novolac resins.
m(phenol): Cure Soft
m(insoluble fractions) time/s point/ C
20:1 70 84
10:1 71 85
5:1 73 86
4:1 77 83
3:1 76 90
water, it results in a phase separation. Then, water insoluble
fractions could be easily separated. For the ester (e.g., ethyl
formate, b.p. 54.6  C) has a lower boiling point than its corre-
sponding acid (e.g., formic acid, b.p. 100.7  C), so it was possible
to convert low-molecular-weight acids in water soluble frac-
tions into esters and separated by reactive rectification. There-
fore, separation of water soluble compounds from water phase
was realized, the converted esters and other low-molecular-
weight components could be separated from original bio-oil.
3.1.1. Catalytic activity of different acid catalysts on
upgrading of bio-oil
From the results of Table 3, it was indicated that H2O2
promoted the yield of upgraded oil (light oil), the yield of light
oil was increased because it converted aldehyde compounds
in to organic acids. Among the solid acid catalyst, SO2 4 /ZrO2-
MCM-41 gave higher yield of light oil and the catalyst could
easily be separated by filter after reaction. Then, it was
determined that SO2 4 /ZrO2-MCM-41 was of suitable catalyst
for reactive rectification.
3.1.2. Effect of reactive rectification on the properties of bio-oil
Some properties of upgraded bio-oils were changed in the
processing of reactive rectification catalyzed by SO2
4 /ZrO2-
MCM-41, its details were illustrated in Table 4.
From Table 4, the water content in the upgraded bio-oil
decreased remarkably from 33.0% to 0.52%. The pH value of
upgraded bio-oil catalyzed by SO24 /ZrO2-MCM-41 was allevi-
ated from 2.82 to 7.06. The dynamic viscosity was about one-
twenty of that of raw bio-oil, and gross calorific value
increased from 14.3 to 21.5 kJ g1.
Fig. 3 – DSC thermograms of novolacs (m(phenol):
m(insoluble fractions) [ 3:1, a: with 10 wt% hexamine; b:
without hexamine).
3.1.3. Characterization of upgraded oils
The IR spectrum of the original bio-oil and upgraded oil were
given in Fig. 1. Obviously the molecular structure of light oil
was changed compared with original bio-oil. The C–H
stretching vibrations between 2800 and 3000 cm1 and C–H
deformation vibrations between 1350 and 1475 cm1 indicate
the presence of alkanes. Moreover, there are C]O stretching
vibrations with absorbance between 1650 and 1750 cm1 and
C–O stretching vibrations with absorbance between 1100 and
1300 cm1, it was to indicate that light oil consisted of various
ester compounds.
We used HPLC to determine the main compounds in light
oil. From Fig. 2, the main components in light oil consist of
ethyl acetate (3.1 wt%), ethyl formate (65.3 wt%), methyl
acetate (3.4 wt%) and methyl formate (22.6 wt%). Methyl ester
was characterized in light oil because methanol was added in
the pyrolysis process to avoid the formation of coke and tar
deposition in system [4].
3.2. Synthesis of novolac resins
Novolac was widely used in the formation of molded pieces
and articles. Phenols and aldehydes are used as raw
materials usually as pure phenol and formaldehyde.
Because phenol was produced primarily from petroleum,
its price and availability were linked to that of petroleum.
Consequently, phenolic resins were relatively expensive. In
previous GC–MS analysis, it was determined that the
pyrolysis oils from biomass materials produce a complex
mixture of phenolic compounds, especially richer in water
insoluble fractions. Moreover, the bio-oil has many
compound with the groups such as C]O, CH2–OH, which
can modify the brittleness and increase the flexibility of the
resin. In our present work, the fraction of water insoluble
materials from original bio-oil was used as a phenol
substitute in novolac production. Results of the experi-
ments were given in Table 5 and novolac property of resin
determined by DSC was given in Fig. 3.
From Table 5, it was found out that by using of water insol-
uble fractions as a phenol substitute, it was possible to obtain
novolac resins with suitable cure time (60–90 s) and soft point
(80–90  C) used in the formation of molded pieces. However,
with the content of water insoluble fractions increasing, it was
difficult to obtained novolac resin with suitable cure time and
soft point. In our experiment, the maximum amount of insol-
uble fractions used as phenol substitute was about m(phe-
nol):m(insoluble fractions) ¼ 3:1. Fig. 3 showed the novolac
property of synthesized resin. It indicated that the resins
without curing agent did not show heat release of crosslink
reaction with the increase of temperature. Therefore, the
synthesized resin was novolac resin.
4. Conclusions
(1) A new procedure of utilization of original bio-oil was devel-
oped in this paper. Original bio-oil was added into water to
obtain water soluble and insoluble fractions. Water soluble
fractions were used to obtain upgraded oils by reactive
 biomass and bioenergy 34 (2010) 1059–1063
rectification. Water insoluble fraction was attempted to
produce phenol novolac resin as phenol substitute.
(2) The density of upgraded bio-oil (light oil) was reduced from
1.16 to 0.91 g cm3, water content of upgraded bio-oil
reduced from 33.0% to 0.52%, and the gross calorific
value increased from 14.3 to 21.5 MJ kg1, the pH of
upgraded bio-oil was also alleviated from 2.82 to 7.06.
(3) The results of HPLC and FT-IR analysis showed that the
ester reaction in the bio-oil was promoted by solid acid
catalysts and that the solid acid catalyst converted volatile
organic acids into esters.
(4) Synthesis of novolac resins using water insoluble fractions
and formaldehyde as starting materials was studied. The
novolac property of resins was determined by DSC.
Acknowledgment
The authors would like to thank the ‘‘863 plan’’(2009AA05Z437),
National Natural Science Foundation of China (30700634),
Jiangsu Natural Science Foundation (BK2009545) and the
1063
‘‘Commonweal research of CAF’’(200904008, CAFINT 2008C03)
for financial support during this investigation.
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