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Bioresource Technology 179 (2015) 98–103

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Study on the preparation of wood vinegar from biomass residues


by carbonization process
Qiaomei Wu, Shouyu Zhang ⇑, Baoxin Hou, Hongjun Zheng, Wenxiang Deng, Dahai Liu, Wenjiao Tang
School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

h i g h l i g h t s

 Cotton stalk was used to produce wood vinegar by carbonization process.


 The highest yield of the refined wood vinegar reaches 25% at 350 °C.
 The main organic components in the wood vinegars are acids, phenols and ketones.
 The presence of potassium restrains the formation of ketones.

a r t i c l e i n f o a b s t r a c t

Article history: In the paper, the production of wood vinegar from Chinese fir sawdust (FS), cotton stalk (CS) and bamboo
Received 25 September 2014 sawdust (BS) by carbonization process was addressed. The wood vinegar yield was investigated and the
Received in revised form 7 December 2014 organic compounds contained were determined by gas chromatography and mass spectrometry. It was
Accepted 8 December 2014
found that the refined wood vinegar yield of FS increased firstly and then decreased with increasing
Available online 13 December 2014
carbonization temperature and the highest yield reached about 25% in 350–450 °C. The relative contents
of acids and ketones from FS decreased and that of phenols increased with increasing temperature. The
Keywords:
relative contents of acids and phenols in the wood vinegars produced from the samples were in the order
Chinese fir sawdust
Cotton stalk
of BS > CS > FS and that of ketones reversed. KCl solution treatment caused a decrease in the relative
Bamboo sawdust contents of the phenols and ketones, but an increase in that of the acids in FS wood vinegar.
Wood vinegar Ó 2014 Elsevier Ltd. All rights reserved.
Carbonization

1. Introduction compositions. It is reported that the high concentration of the


organic acids in the WV exhibited the high antimicrobial activity
Wood vinegar (WV) or Pyroligneous acid (PA) is an acidic (Ma et al., 2011) and the phenolic compounds showed significant
reddish-brown aqueous liquid. It is obtained by clarifying the antioxidant activity, and demonstrated dosage dependency (Loo
liquid product of the carbonization process of woods or wood et al., 2007, 2008). Wood vinegar contains lots of very complicated
residues from wood processing industry, tree branches, bamboo, organic components and over 200 compounds have been found in
crop straw, fruit shell and other biomaterials (Wei et al., 2010). the wood vinegar obtained from different resources (Guillén et al.,
WV is often used as insect repellent, odor remover, wood preserva- 2001). In China, there have been some researches only on the
tive, soil or foliar fertilizer and plant growth promoter or inhibitor, organic components contained in the wood vinegars obtained
animal feed additive, coagulant in NR sheets’ preparation. Until directly from the charcoal kiln or WV Company. The wood vinegars
now, lots of the products have been applied in a wide variety of are produced from Mongolian oak, birch, apple tree and pear by
markets (Wu et al., 2014; Shiny and Remadevi, 2014; Mu et al., carbonization process.
2004; Ferreira et al., 2005; Baimark and Niamsa, 2009). Based on the heating rate, pyrolysis process can be divided into
The properties and utilizations of wood vinegar have been three modes: fast, intermediate and slow. As a kind of pyrolysis
widely researched and the utilization is closely related to its technology with low heating rate, carbonization process has been
widely used in the conversion process of agricultural and forestry
residues into high added-value products (Xiong et al., 2014).
⇑ Corresponding author at: School of Energy and Power Engineering, University of During the carbonization process, the raw material is heated up
Shanghai for Science and Technology, 516 Jungong Road, Shanghai 200093, China. in oxygen-free environment and volatile matters emits from the
Tel.: +86 18939950839; fax: +86 21 65711123. parent materials and the three-phase matters of charcoal, liquid
E-mail address: zhangsy-guo@163.com (S. Zhang).

http://dx.doi.org/10.1016/j.biortech.2014.12.026
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
Q. Wu et al. / Bioresource Technology 179 (2015) 98–103 99

products, and fuel gas are produced. As a high application value slight and could be neglected. The samples were dried at 105 °C
product, WV can be obtained by clarifying from the liquid prod- for 2 h in a thermostatic air-blower-driven drying oven (DXG-
ucts. During the process, the final carbonization temperature 9073B-1, Fuma Laboratory Instrument Co., Shanghai, Temperature
employed plays a notable role in the distribution of the three- precision 1 °C). Then, the dried materials with the particle size of
phase products (Kwapinski et al., 2010; Angın, 2013). 0.5–3 mm were prepared using a grinding machine (FW-400A,
The production and characterization of wood vinegar from rub- Zhongxing Weiye Instrument Co., Beijing).
berwood was studied by Ratanapisit et al. (2009) and it was found FS sample was immersed in KCl solution with a concentration of
that the optimum condition of pyrolysis was obtained at the heat- 20% in the ratio of 20 ml/g biomass for 12 h, then filtered and dried
ing rate of 1.4 °C/min to the final temperature of 550 °C with a WV in an oven at 60 °C for 24 h. The dried samples were placed in the
yield of 27.45%. The main ingredient contained in the WV was ace- dry airtight container for the subsequent carbonization experi-
tic acid and included the high content of methanol compared to the ment. The charcoal powder (60.5 mm) was prepared by Xiong
WV produced from other woods. Moreover, Sßensöz (2003) also et al. (2014) from FS carbonized under the final carbonization tem-
found that there was an obvious difference in the ingredients of perature of 550 °C.
the wood vinegar produced from different raw materials and under
different process conditions. However, there have been very few 2.2. Methods
papers reported about WV preparation and the influence of prepar-
ing condition and feedstock on the yields and compositions of the 2.2.1. Biomass carbonization
resultant wood vinegar. As illustrated in Fig. 1, the carbonization processes of the sam-
In the paper, as agricultural and forestry residues, Chinese fir ples were carried out in a vertical quartz tube reactor with the
sawdust, cotton stalk and bamboo sawdust were chosen as the body length of 970 mm and the internal diameter of 35 mm. There
raw materials for the wood vinegar production. Because that the was a quartz frit used as a gas distributor in the center section of
wood residue including the fir sawdust is the main biomaterials the tube reactor. The tube reactor was heated by an electric furnace
for the production of the wood vinegar (Wei et al., 2010), Chinese (temperature precision 1 °C) based on the designed procedure.
fir sawdust was chosen as main research object. The experiment During every run, about 90 g sample was loaded on the quartz frit.
was conducted on a vertical tubular carbonization reactor and A flow of dry nitrogen (99.999%, 200 ml/min) was purged into the
the organic constituents of the resultant wood vinegar were ana- tube reactor to provide an inert atmosphere. A gas chromatograph
lyzed and determined. Thus, the effect of carbonization tempera- (GC2014, Japan SHIMADZU Company) was used to test the oxygen
ture and feedstock type on the yields and organic constituents of in the outlet gas. When there was no O2 determined in the outlet
the resultant wood vinegar could be investigated in detail. Further- gas, the reactor was heated from room temperature to the
more, Chinese fir sawdust was pretreated by KCl solution and the designed final temperature at 10 °C/min and held at the tempera-
resultant sample was carbonized in order to investigate the effect ture for 30 min to ensure complete pyrolysis. The final carboniza-
of the presence of potassium on the compositions of the resultant tion temperature range was designed from 250 °C to 550 °C. At
wood vinegar. The aim of the research was to provide a theoretical the end of each run, the reactor was cooled down in nitrogen atmo-
basis for the further development and utilization of WV. sphere to room temperature and the liquid in the condenser was
collected. The collected liquid product is considered as the crude
2. Methods wood vinegar in the research. The yield of the crude wood vinegar
could be obtained by calculating the increase in weight of the
2.1. Materials condenser. Each experiment under the same temperature was
repeated three times in order to obtain adequate liquid and ensure
Three agricultural and forestry residue samples, Chinese fir the yield accuracy. The product yield was the average value of the
sawdust (FS), cotton stalk (CS) and bamboo sawdust (BS) were cho- three trials.
sen as the raw materials for the investigation. Their proximate and
ultimate analyses are shown in Table 1 and their ash analyses are 2.2.2. Crude WV refining
listed in Table 2. The ash constituents of FS could not be deter- According to the refining process shown in the literature (Wei
mined due to its very low ash yield as shown in Table 1. Thus, et al, 2010), the crude wood vinegars prepared under the different
the influence of the mineral matters contained in the biomass is carbonization temperature and from different raw materials were

Table 1
Proximate and ultimate analyses of the samples.

Samples Proximate analysis (wt%, ad) Ultimate analysis (wt%, ar)


M A V FC C H O N S
CS 4.25 3.78 72.11 19.86 46.19 3.09 38.82 0.84 0.39
BS 2.85 2.04 78.97 16.14 47.14 3.26 41.01 0.73 0.27
FS 2.13 1.64 80.67 15.56 50.60 2.62 36.69 0.91 0.03

M = moisture; A = ash; V = volatile yield; FC = fixed carbon yield; ad = air-dried basis; ar = as received basis.

Table 2
Ash analyses of the samples.

Samples wt/%
SiO2/% Al2O3/% Fe2O3/% CaO/% MgO/% TiO2/% SO3/% K2O/% Na2O/% P2O5/%
CS 11.69 1.75 1.13 30.8 13.88 1.39 6.3 18.86 10.03 4.07
BS 37.04 1.51 2.99 11.67 3.15 1.8 6.15 27.6 3.67 4.39
100 Q. Wu et al. / Bioresource Technology 179 (2015) 98–103

1 by 3 ml ether for six times. The ether left in the liquid was removed
by water-bath heating at 40 °C. The concentrated wood vinegar
N2 2 was dried using anhydrous magnesium sulfate powder for
GC–MS analysis.

3
10 2.2.4. GC–MS analyzing
4 The analysis of the organic components contained in the refined
WV was carried out using the combination of gas chromatography
and mass spectrometry (GC–MS, Agilent 7890A-5975C, America).
5 N2 (99.999%) was used as carrier gas with a constant flow rate of
1.0 ml/min. The separation was performed using a HP-INNOWAX
6 (30 m  0.25 mm  0.25 lm). The injection port temperature was
designed as 260 °C. The column temperature was maintained at
9 50 °C for 3 min and then programmed to increase to 250 °C at a
heating rate of 4.0 °C/min and held at the temperature for
7 15 min. The split injection was conducted at a split rate of 20:1.
8
The mass spectroscopic conditions were given as follows: electron
impact source, electron energy 70 eV, ion source temperature
Fig. 1. Schematic diagram of the carbonization apparatus. 1. Thermocouple; 2. 230 °C, mass scanning range 20–500 amu/s. The compounds were
quartz tube reactor; 3. vertical electric furnace; 4. feedstock; 5. quartz frits; 6.
identified by the comparison of the retention time and mass spec-
volatile products; 7. crude WV; 8. ice-bath trap; 9. gas; 10. temperature controller.
tra with the library data of mass spectra (NIST2011). The relative
contents of the compounds were determined by the corresponding
stood for 1 month. Then, there appeared three layers in the crude peak areas.
wood vinegars: a thin layer of oil on the top, a thick layer in the
middle, and a thin layer of ropy wood tar in the bottom. The middle 3. Results and discussion
layer was siphoned off and then the liquid was mixed with the
charcoal powders in the charcoal–liquid ratio of 5% (w/w). The 3.1. Effect of carbonization temperature on FSWV yield
mixtures were stirred for 10 min and then stood for 72 h to ensure
the removal of the wood tar residues. The supernatant was FS consists of celluloses, hemicelluloses and lignins with the
decanted carefully and the remaining liquid was filtrated using content of 47.40%, 10.65% and 32.94%, respectively (Zhang et al.,
Syringe Filter (Nylon, diameter of 13 mm, aperture of 0.45 lm). 2004). Fig. 2 shows the yields of the crude and refined WV pro-
Then the refined wood vinegar was obtained and labeled as FSWV, duced from FS under the different carbonization temperature. As
BSWV and CSWV, respectively. FSKWV-350 means the wood vine- shown from the figure, the crude FSWV yield increases with the
gar produced from KCl solution treated FS at the carbonization increasing carbonization temperature. The increase in the crude
temperature of 350 °C. The both yields of the crude and refined FSWV yield with the increasing carbonization temperature is
wood vinegar were calculated based on the weight of the samples mainly attributable to the degradation of hemicelluloses, celluloses
loaded in the quartz tube during every run. and lignins contained in the feedstock. When the temperature rises
from 300 °C to 350 °C, the crude FSWV yield increases quickly from
2.2.3. Sample preparing for gas chromatographic and mass 19.8 to 43.2 wt.%. The sharp increase in the crude FSWV yield is
spectrometric (GC–MS) analysis mainly caused by the cellulose and lignin decomposition because
According to the methods from the literature (Wei et al, 2010), they are the major constituents contained in FS. The research of
10 ml of the refined wood vinegar was subjected to the extraction Wang et al. (2008) indicated that the temperature corresponding

70 90
Crude WV yield
65 85
Refined WV yield
60 Refined WV percent in crude WV
80
Percent of Refined WV in crude WV /%

55
75
50

45 70
WV yield /%

40 65
35
60
30
55
25
20 50

15 45
10
40
5
35
200 300 400 500 600
Carbonization temperature /oC

Fig. 2. Effect of carbonization temperature on WV yield of FS.


Q. Wu et al. / Bioresource Technology 179 (2015) 98–103 101

Acids Aldehydes in Fig. 3, the organic compounds contained in FSWV indentified by


30 Phenols Alcohols
Ketones Esters
GC–MS mainly consist of acids, phenols, ketones, aldehydes, alco-
hols and esters. Of these matters, the components with higher con-
25
tent are acids, phenols and ketones. However, the relative contents
of aldehydes, alcohols and esters are lower and have no obviously
20
regular change with the carbonization temperature. Only at 550 °C,
Relative content/%

the relative content of the alcohols increases notably and reaches


15 9.04%. Of the alcohols, the compound with the highest content of
6.6% is tetrahydrofurfuryl alcohol may due to the decomposition
10 of the celluloses under high carbonization temperature. The glyco-
sidic linkages as well as some C–C bonds in the pyranose rings of
5 celluloses rupture and the molecular fragments are dehydrated
to form tetrahydrofurfuryl alcohol (Shafizadeh et al., 1971).
0 The relative content of the acids decreases from 19.31% to 6.64%
200 300 400 500 600 with the carbonization temperature increasing from 250 °C to
o
Temperature / C
550 °C. The highest content (19.31%) of the acids is obtained at
Fig. 3. Effect of carbonization temperature on the organic compositions of FSWV. 250 °C and decreases sharply to 9.96% at 350 °C. The ratio of the
acids to the total organic compounds in the refined wood vinegar
decreases with increasing temperature may be owing to the large
24 BSWV amount of volatile matters emitting in the temperature rang of
22 CSWV 250–350 °C. The breakage of the acetyl groups in hemicelluloses
FSWV and celluloses is contributed to the higher content of the acids at
20
FSKWV low temperature (Wang et al., 2009).
18
The content of the ketones is at relatively high level but
Relative content /%

16
decreases gradually with the increasing carbonization tempera-
14 ture. However, the content of the phenols increases as the temper-
12 ature increases and reaches the highest content of 24.35% at
10 450 °C. The phenols are formed due to the decomposition of the
lignins with cross-linked structures of various hydroxyl- and meth-
8
oxy-substituted phenylpropane units (Evans and Milne, 1987)
6
occurring in the large temperature range of 250–550 °C (Wang
4 et al., 2008). The higher the carbonization temperature is, the more
2 vigorous the decomposition is. The maximum weight loss of lignin
0 during the carbonization occurs at 450 °C (Wang et al., 2008). Thus,
Acids Phenols Ketones Aldehydes Alcohols Esters the content of the phenols produced at 450 °C is much higher than
that at 350 °C.
Fig. 4. Effect of the feedstock type on the organic components of WV. In sum, the above analyses indicate that the highest content of
the acids contained in FSWV can be produced at the carbonization
temperature of 250 °C and the higher content of phenols can be
to the maximum weight loss of cellulose is around 333 °C. Thus, obtained at 350–450 °C.
lots of the volatile matters emits from the parent material in the
temperature range of 300–350 °C. 3.3. Effect of feedstock type on the organic components of the resultant
However, the yield of the refined WV increases until the car- WV
bonization temperature of 350 °C and then decreases. The highest
yield of the refined WV reaches 25% during the carbonization tem- Based on the above yield and organic composition analyses of
perature range of 350–450 °C. When above 450 °C, the yield FSWV, the carbonization temperature of 350 °C is chosen for the
decreases to 21.22%. The decrease may due to the secondary deg- wood vinegar production from cotton stalk and bamboo sawdust.
radation of some ingredients contained in the refined WV under As seen from the Fig. 4, the main organic components of the
higher carbonization temperature because they are thermally three wood vinegars produced from FS, BS and CS all include acids,
unstable products (Demiral and Ayan, 2011). phenols and ketones. In particular, the high relative content of the
The variation in the percent of the refined WV in the crude WV alcohols contained in BSWV and CSWV can be observed. The rela-
under the different carbonization temperature is given in Fig. 2. tive contents of the acids and phenols contained in the three wood
The refined WV percent decreases sharply from 79% to 59% as vinegars are in the order of BSWV > CSWV > FSWV and that of
the temperature ranged from 250 °C to 300 °C and remains nearly ketones is FSWV > CSWV > BSWV. The result also indicates the
constant from 300 °C to 350 °C and then decreases from 59% to 39% highest content acids and phenols contained in BSWV and the
as the temperature increases to 550 °C. Considering the high yield highest content ketones contained in FSWV. The alcohols are the
of the wood tar produced under the carbonization temperature typical compounds in CSWV.
above 350 °C, the temperature of 350 °C is suitable for WV The main compounds in the acids, phenols and ketones con-
preparation. tained in the refined WV are listed in Table 3. The table indicates
that the acetic acid and propionic acid are the main compounds
3.2. Effect of carbonization temperature on the organic compositions of in the acids and acetic acid content is the highest of them. It was
FSWV reported that acetic acid and propionic acid is mainly derived from
the thermal decomposition of hemicelluloses (Demirbas, 2007).
The relative contents of the main organic components con- The relative concentrations of the hemicelluloses in the three res-
tained in the refined wood vinegars produced from FS under differ- idues are in the order of BS (23.59%) > CS (14.82%) > FS (10.65%)
ent carbonization temperature are given in Fig. 3. As demonstrated (Dong and Xiong, 2014; Jiang et al., 2015; Zhang et al., 2004).
102 Q. Wu et al. / Bioresource Technology 179 (2015) 98–103

Table 3
Main compounds of the acids, phenols and ketones contained in the refined wood vinegar (relative content P1%).

Organic compounds Relative content %


BSWV CSWV FSWV FSKWV
Acids
Acetic acid 10.1887 7.6456 4.0346 8.381
Propionic acid 2.4254 1.5694 1.1683 1.0267
3-Methoxy-4-hydroxyphenyl acetic acid – – 1.2097 1.3011
Phenols
2-Methoxy phenol 2.5099 3.1398 3.969 5.1693
2,6-Dimethoxyphenol 5.7586 3.9201 <1 <1
2-Methoxy-4-methylphenol 1.0296 1.5745 3.8925 2.225
4-Ethyl-2-methoxyphenol <1 1.1249 2.1088 1.4598
1,2-Benzenediol 1.0539 1.1764 1.6167 2.0651
Trans-2-methoxy-4-propenylphenol <1 <1 2.3306 –
5-tert-Butylpyrogallol 1.2779 1.5772 <1 –
2,6-Dimethoxy-4-(2-propenyl)phenol 1.6688 1.9942 – –
4-Ethylphenol 1.8406 <1 – –
3-Methoxy-2-benzenediol 1.2321 1.0086 – –
Phenol 1.1466 <1 <1 –
2-Methylphenol 1.1466 <1 – –
Ketones
2,3-Dimethyl-2-cyclopentene-1-one 1.9792 4.6179 5.6855 3.4955
Hydroxyacetone 1.8177 2.3165 2.8544 2.495
Methyl cyclopentenolone 1.9792 2.4401 2.7957 2.0602
(4-Hydroxy-3-methoxyphenyl)acetone <1 1.0328 1.8058 2.1303
1-Hydroxy-2-butanone 1.8808 1.2343 <1 –

The highest content of the hemicelluloses contained in BS contrib- the phenols and ketones decreases, that of the acids increases
ute to the highest content of the acids contained in BSWV and the and that of alcohols doubles approximately compared to the corre-
lowest content of the acids contained in FSWV. sponding components in FSWV. The main compounds contained in
The phenols, the typical carbonization products of lignins, are FSKWV-350 are listed in Table 3. The data presents a decrease in
generated from the dehydration reaction of hydroxy groups in pro- the content of almost all the main compounds of ketones, a
pane side chains followed by the cleavage of ether linkages among decrease in that of the phenol compounds and guaiacol derivatives
the lignin units (Amen-Chen et al., 2001). The guaiacols and their and an increase in the content of acetic acid. The results indicate
derivatives are the main compounds contained in FSWV and the that the presence of KCl promotes the carbonization of FS to form
higher content of the syringols are found in CSWV and BSWV as acetic acid and alcohols, while inhibits the formation of ketones
shown in Table 3. It can be deduced that the lignins contained in and phenols. In sum, based on the above analyses on the content
FS is composed of guaiacyl units and those of CS and BS consists of the ketones contained in the three wood vinegars, the presence
of syringyl units. The ether linkages among syringyl units are easier of potassium shows a certain inhibition effect on the formation of
to be broken than that among guaiacyl units during the carboniza- ketones during the carbonization process.
tion process (Jakab et al., 1997). Furthermore, the products derived
from guaiacyl unit are easily dehydrogenated and accumulated in 4. Conclusion
char residues (Fengel and Shao, 1985). Thus, the higher content
of the phenols contained in CSWV and BSWV is observed than that The yield of the crude WV increases with the increasing carbon-
of FSWV. The decomposition of lignins is influenced by the oxygen ization temperature and that of the refined WV increases firstly
content and the reaction activity of the lignins with higher oxygen then decreases. The refined wood vinegar yield of 25% can be
content is higher (Fengel and Shao, 1985). The ultimate analyses obtained in the carbonization temperature range of 350–450 °C.
are given in Table 1. The table indicates that the oxygen content The relative contents of the acids and ketones contained in FSWV
of the three biomasses is in the order of BS > CS > FS. Thus the phe- decrease and that of the phenols increases with the increasing
nols concentration in the three wood vinegars is in the order of temperature. The typical components with high content are the
BSWV > CSWV > FSWV. acids and phenols in BSWV, the ketones in FSWV and alcohols in
As shown in Fig. 4, the relative content of the ketones in the CSWV, respectively. The presence of potassium has a certain nega-
three refined wood vinegars is in the order of FSWV > CSWV > tive effect on the formation of ketones in WV.
BSWV. The main ketone compounds include 2,3-dimethyl-2-cyclo-
pentene-1-one, hydroxyacetone and methyl cyclopentenolone, Acknowledgement
et al. The large difference exists in the relative content of 2,
3-dimethyl-2-cyclopentene-1-one contained in the three wood This work was financially supported by the National Program
vinegars. The difference may be caused by the minerals presenting on Key Basic Research Project (973 Program) of China (No.
in the raw materials. Table 2 indicates that the high content potas- 2012CB214900).
sium oxide in BS ash is observed while there is almost no potas-
sium oxide determined in FS ash. The presence of potassium
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