Accepted Manuscript

Volatile production from pyrolysis of cellulose, hemicellulose and lignin

Chenxi Zhao, Enchen Jiang, Aihui Chen

PII: S1743-9671(16)30287-2
DOI: 10.1016/j.joei.2016.08.004
Reference: JOEI 261

To appear in: Journal of the Energy Institute

Received Date: 6 June 2016

Revised Date: 16 August 2016
Accepted Date: 31 August 2016

Please cite this article as: C. Zhao, E. Jiang, A. Chen, Volatile production from pyrolysis of cellulose,
hemicellulose and lignin, Journal of the Energy Institute (2016), doi: 10.1016/j.joei.2016.08.004.

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 ACCEPTED MANUSCRIPT

1 Volatile production from pyrolysis of cellulose, hemicellulose and lignin

2 Chenxi Zhao, Enchen Jiang*, Aihui Chen

3 (Department of Engineering, Northeast Agricultural University, Harbin 150030,

4 Heilongjiang, PR China)

5 *Corresponding author. Tel.: 18745111509, e-mail: Jiangenchen2016@outlook.com

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6 Abstract

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7 To better understand pyrolysis mechanism and further develop selective pyrolysis

8 technology, characteristics of volatile products in the pyrolysis of three main

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9 components (cellulose, hemicellulose and lignin) were investigated and compared by

10 amplifying experiments in a tube furnace at 300–700 ℃. Distribution of volatile

11

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products (including bio-oil and bio-gas), the influence of temperature and
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12 contributions of each single component were discussed in depth. It was found that, for

13 each sample pyrolysis, pyrolysis temperature and their own chemical structures
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14 played an important role in the yields, composition of bio-oil and bio-gas. The
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15 optimal temperatures for production of bio-oil from cellulose, hemicellulose and

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16 lignin focused at 500 ℃, 450 ℃ and 600 ℃, respectively, and cellulose made greater

17 contribution to bio-oil formation, and hemiellulose was the major contributor for
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18 bio-gas. Moreover, the more bio-gases from the three components generated at the

19 higher temperature, but compositions of volatile products were different depending on

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20 their unique chemical structures. In the three components, cellulose produced the
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21 highest CO, hemicellulose owned the highest CO2, and lignin generated the highest

22 CH4 characterized by the largest HHV. As for bio-oil, cellulose bio-oil displayed

23 unique saccharides and higher furans, hemicellulose bio-oil contained higher acids

24 and ketones, while phenols were the dominant composition of lignin bio-oil.

25 Keywords: Pyrolysis; Cellulose; Hemicellulose; Lignin; Bio-oil; Bio-gas

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26 1. Introduction

27 Lignocellulosic biomass is a promising alternative to petroleum for production of

28 fuels and chemicals. It takes the most important advantages in terms of renewable

29 resource, low cost and essentially nil emissions of carbon dioxide for utilization of

30 biomass resources. In this sense, pyrolysis technology, one of the promising

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31 thermochemical routes in biomass conversion, could satisfy the growing interest on

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32 the production of bio-fuels and chemicals [1]. However, like all other renewable

33 technologies, biomass pyrolysis is also facing many technical challenges. For example,

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34 the liquid fuels (bio-oils) obtained from pyrolysis of biomass are usually

35 multicomponent mixtures characterized by high acidity, high water content, or store

36
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instability, which limit its large-scale application [2-6]. Thus more detailed
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37 information is necessary for pyrolysis processes to make best of biomass.
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38 The bio-oils are main volatile products from biomass pyrolysis, which could be

39 potential fuels for diesel engines, gas turbines and boilers, and cooking, and also
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40 could be used as raw materials for the production of resin, pharmaceutical product and
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41 hydrocarbons by appropriate treatments [7-9]. Some chemicals with high demand,

42 such as methanol, acetic acid, acetone and particularly phenols, also could be obtained
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43 from bio-oils [10,11]. The pyrolytic gases are the other essential volatile products, and

44 composed of CO2, CO, CH4 and H2, together with high heating value of 10-14 MJ/kg,
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45 which could be good fuels for power generation and cooking. The knowledge on
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46 formation mechanism of bio-oil and bio-gas is the basis and essentially important for

47 a better utilization of biomass resources.

48 So far, selective pyrolysis has been carried on improving the properties of bio-oil

49 or bio-gas by increasing the product selectivity [12-14]. Many studies indicated that

50 the production of volatile matter corresponds to the summation of the individual

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51 contributions from the three main components [15,16]. It is well known that the

52 lignocellulosic biomass mainly consists of cellulose, hemicellulose and lignin, their

53 structure properties have a great impact on the pyrolysis characteristics. Moreover, the

54 distinctive chemical structures of the three main components can lead to great

55 differences in the thermochemical characteristics, which will subject to dehydration,

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56 depolymerization, bond cleavage and reformation within different temperature range

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57 [17-19]. Lu et al. [20] used analytical pyrolysis gas chromatography/mass

58 spectrometry (Py-GC/MS) instrument for pyrolysis of cellulose and on-line analysis

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59 of the pyrolytic volatile products, which revealed the effects of pyrolysis temperature

60 on the product distribution, and the formation characteristics of important products.

61
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Peng et al. [21] investigated the structural characteristics of hemicellulose by FTIR,
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62 the thermal characteristics and main volatile products by TGA and Py-GC/MS. Liu et
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63 al. also studied degradation mechanisms of lignin using GC-MS [22]. It is obvious

64 that previous works on the pyrolysis mechanism of cellulose, hemicellulose and lignin
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65 ordinarily used Py-GC/MS, TG-FTIR and TG-MS to investigate pyrolysis

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66 characteristics, and paid little attention to a comparative study on the pyrolysis

67 behavior of the three components under the same pyrolysis conditions [21,23-25].
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68 Thus, it is urgently needed to further investigate and compare the pyrolysis

69 mechanism of the main components for further enhancing the volatile products yields
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70 or the selectivity of the target chemicals.

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71 Based on knowledge of thermal stabilities of three main biomass components

72 (cellulose, hemicellulose and lignin) using thermo-gravimetric analyzer, the objective

73 of present work was to further analyze pyrolysis characteristics of the three

74 components by amplifying experiments in a tube furnace. The distribution of

75 pyrolysis products, respective composition of bio-oil and bio-gas, the influence of

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76 temperature and contributions of each single component were analyzed thoroughly.

77 The experimental results obtained in the present work will provide valuable assistance

78 in further development of selective pyrolysis technology.

79 2. Experimental section

80 2.1. Materials and characterization

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81 The three main components (cellulose, hemicellulose and lignin) were provided

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82 by Sigma-Aldrich Co., Ltd. Cellulose is in the form of white microcrystalline powders,

83 lignin is alkali lignin in brown powders, and xylan has been widely used as a

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84 representative component of hemicellulose in pyrolysis process, because commercial

85 hemicellulose can hardly be purchased. Here, xylan is in the form of yellow powders,

86 and was used as hemicellulose.

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87 Prior to any pyrolysis, fundamental analysis of the three components was
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88 conducted, including measurement of composition, heating value and chemical

89 structure. The moisture content, ash content and volatile matter (VM) content were
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90 detected according to ASTM E871-82, D1102-84 and E872-82 methods, respectively,

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91 and the fixed carbon (FC) fraction was calculated by subtraction. The ultimate

92 analysis for C, H, N and S content was performed using an elemental analyzer

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93 (EA3000), and O content was calculated by subtraction. The higher heating value

94 (HHV) of samples was measured by an oxygen bomb calorimeter (YX-ZR 9302). The
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95 chemical structures of the three components were analyzed by FTIR (Spectrum One,
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96 USA) using a KBr disk contained 1% ground samples, the spectra were recorded in

97 the range of 400–4000 cm-1, and each spectrum was the result of 10 times scans with

98 4 cm-1 resolution.

99 In order to evaluate the effectiveness of thermal control of biomass components

100 during tube furnace pyrolysis, the thermo-decomposition of cellulose, hemicellulose

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101 and lignin were investigated by thermo-gravimetric (TG) analysis and derivative

102 thermo-gravimetric (DTG) analysis using a STA449C Jupiter thermo-gravimetric

103 analyzer; and 8 mg of samples were heated at atmospheric pressure in inert

104 environment (N2, 20 mL/min) from room temperature to 900 ℃ at a heating rate of

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105 5 ℃/min.

106 2.2. Pyrolysis measurements

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107 Pyrolysis of samples was conducted using tubular reactor for a target

temperature of 300, 400, 450, 500, 550, 600 or 700 ℃, the details are shown in Fig. 1.

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108

109 The reactor includes four main parts: nitrogen input section, temperature control

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110 system, liquid collection system and gas collection system, respectively. In each test,
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111 25 g of samples were placed in room temperature region of quartz tube in advance.

112 Once the temperature inside the reactor was heated to a target temperature at a rate of
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113 10 ℃/min by temperature controller, the samples were pushed to reaction region of
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114 quartz tube, and the reactor was kept at the constant temperature for 20 min to

115 complete pyrolysis. During all the pyrolysis experiments, carrier gas (99.99% N2) was
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116 continuously supplied at a flow rate of 80 mL/min to keep an inert circumstance and
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117 purge pyrolytic vapors from the reactor. The pyrolytic volatiles were passed through

118 the two ice-water condensers; condensable bio-gases were collected in the form of
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119 liquid (called bio-oil), non-condensable gases (called bio-gas) were sampled into air
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120 collection bags; while the solid residue (called bio-char) remained in the reactor. The

121 pyrolysis product yields were calculated using the following equations:

M0
122 Ybiochar  100% (1)
M

123 Ybio gas 

M 1
100% (2)
M
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124 Ybiooil  1  Ybiochar  Ybio gas (3)

125 where M is the initial weight of each component, M0 and M1 represent bio-char and

126 each bio-gas mass, respectively, M1 is converted by volume fraction of each bio-gas

127 composition and cumulative volume of overall bio-gas (on the standard condition: 1

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128 mol=24.45 L).

129 2.3. Analytical methods

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130 The detailed composition of bio-oil was analyzed by an Agilent 6890 GC-MS

with a HP-35 capillary column. Before the analysis, the bio-oil was dissolved by

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131

132 isopropanol solvent (1:9, v/v), because isopropanol was better to absorb condensed

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133 liquid products for GC-MS analysis in the tests. The analysis started at the column
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134 temperature of 45 ℃ for five minutes, then heated up to 320 ℃ by a heating rate of

135 10 ℃/min and held for ten minutes; the temperature of inlet was 300 ℃; the carrier gas
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136 flow (He) was 1 mL/min without splitting; electron impact (EI) of mass spectrometry

137 was 70 eV, scanning mass range was 33–750 amu.

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138 The composition of bio-gas was analyzed by an Agilent 7890A gas

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139 chromatography with a thermal conductivity detector (TCD) and hydrogen

140 flame ionization detector (FID) attached directly to the sampling point. The
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141 temperature of the chromatographic column, TCD and FID was 250 ℃, 200 ℃ and
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142 300 ℃, respectively. The flow rate of practical gas (air) and tail gas blowing (N2) of
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143 TCD was 20 mL/min and 5 mL/min, respectively, and the flow rate of fuel gas (H2)

144 and practical gas (air) of FID was 60 mL/min and 300 mL/min, respectively. HHV of

145 bio-gas was calculated using the following equations:

n
146 q   qi  i (4)
i 1

147 where qi and wi represent HHV and volume fraction of each bio-gas composition,
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148 respectively.

149 3. Results and discussion

150 3.1. Materials properties

151 The characterization data in Table 1 depicted a similar moisture content of the

152 three main components (3.31–3.96 wt.%), thus before the pyrolysis experiments, all

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153 samples have been placed in oven at 45 ℃ for drying 24 h until the mass no longer

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154 change, which is for minimizing the impact of water content on pyrolysis procedure.

155 Seen from the three biomass components, the ash content of hemicellulose and lignin

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156 was higher than that of cellulose sample (respectively 3.85 wt.% and 5.59 wt.%), and

157 the high mass concentration of ash could promote bio-char yields since inorganic

158
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elements in the ash are known to catalyze the formation of solid product during
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159 pyrolysis [26]. Moreover, based on comparable in volatile matter and fixed carbon,
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160 the yields of pyrolytic products can be predicted to be significantly different in the

161 three main components. Cellulose contained the highest volatile matter (94.65 wt.%)
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162 can be expected to reap the highest yields of volatile products, and that of
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163 hemicellulose ranked after it. The higher fixed carbon content of lignin can lead to the

164 higher bio-char yields.

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165 It is observed that the three main components showed similar hydrogen content

166 (5.63–6.40 wt.%), and pronounced differences were recorded in terms of C, O and N
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167 fractions among cellulose, hemicellulose, lignin samples. In particular, the highest C
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168 and N fraction were detected for lignin (61.81 wt.% and 1.72 wt.% respectively), this

169 was probably to determine the lower HHV (see Table 1). And O concentration of

170 cellulose and hemicellulose was greater amounts (respectively 41.40 wt.% and 46.71

171 wt.%).

172 The FTIR spectra of cellulose, hemicellulose and lignin are shown in Fig. 2. The
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173 typical functional groups and the FIIR signal with the possible compounds are listed

174 in Table 2 for a reference [27]. It can be observed that the three components of

175 biomass likely consisted of acids, alkenes, esters, aromatics, ketones and alcohol, with

176 different oxygen-containing functional groups, for example, O-H (3600–3000 cm-1),

177 C=O (1730–1700 cm-1, 1580–1520 cm-1), and C–O–(H) (~1282 cm-1), etc. Seen from

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178 Fig. 2, cellulose and hemicellulose presented a similar transmission peak, which

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179 means that some similar functional groups were obtained in them. Still, the highest

180 FTIR absorbance of O-H and C-O was found in cellulose, while hemicellulose

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181 contained higher C=O compounds. Compared with cellulose and hemicellulose, a big

182 difference was found in the region of 1800–700 cm-1 for lignin’s FTIR spectra. A

183
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group of complex IR absorbance of lignin was showed, indicating that lignin might be
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184 rich of methoxyl-O-CH3, C-O-C stretching and C=C stretching (aromatic ring)
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185 containing compounds.

186 Fig. 3 gathered TG-DTG curves of the three components, great differences were
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187 found among the pyrolysis behaviors of the three components. Hemicellulose started
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188 its decomposition easily, and the weight loss mainly happened at 203–386 ℃. It got

189 the maximum mass loss rate at 295 ℃, and there was 13% solid residue left at
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190 900 ℃. Cellulose pyrolysis was focused at a higher temperature range (286–426 ℃)
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191 with the maximum weight loss rate (23.28 %/min) attained at 335 ℃, and the final
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192 solid residue was only 4% because most of cellulose have volatilized. Among the

193 three components, cellulose and hemicellulose presented much huger weight loss

194 mass, while lignin was the most difficult one to decompose. The major decomposition

195 of lignin happened in a wide range of temperature from 215 ℃ to 585 ℃, which

196 acquired maximum weight loss rate at the temperature of 385 ℃, the solid residue

197 left from lignin pyrolysis reached up to 34%. The differences in the inherent
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198 structures and chemical nature of the three components possibly account for the

199 different behaviors observed [28]. Cellulose is consisted of a long polymer of glucose

200 without branches, its structure is in a good order, and the thermal stability is high.

201 Different to cellulose, hemicellulose is consisted of various saccharides (xylose,

202 mannose, glucose, galactose, etc.), and rich of branches, random, amorphous structure

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203 appear, which is easy to remove from the main stem and degrade to micromolecular

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204 volatiles at low temperatures. Lignin is full of aromatic rings with various branches

205 (see in Fig. 2); the activity of the chemical bonds in lignin covered an extremely wide

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206 range, which led to the degradation of lignin occurring in a wide temperature range.

207 3.2. Bio-oil

208 3.2.1. Bio-oil yields

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209 The yields of the bio-oil products in the pyrolysis processes mainly depended on
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210 the raw material and the reaction temperature. The bio-oil yields from pyrolysis of the

211 three components in the temperature range of 300–700 ℃, are reported in Fig. 4.
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212 Seen from Fig. 4, the yields of bio-oil production from pyrolysis of the three
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213 components showed the similar pattern that firstly presented an increase, and then

214 decreased, while cellulose, hemicellulose and lignin gained respective maximum of
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215 the bio-oil yields at different temperatures. Among the three components, cellulose

always yielded more bio-oil (47.77–64.70%) in the temperature range of 400–700 ℃.

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216
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217 In particular, the highest yield was obtained from cellulose pyrolysis, which is located

218 at 500 ℃. At lower temperature (300–450 ℃), hemicellulose yielded more bio-oil

219 than lignin (hemicellulose: 28.62–41.44% and lignin: 18.13–34.31%), and the highest

220 bio-oil yield is located at 450 ℃. On the other side, the more bio-oil yield was

221 obtained from lignin in the pyrolysis temperature range of 550–600 ℃ (hemicellulose:

222 32.62–36.99% and lignin: 37.03–39.73%), the maximum of bio-oil yields was
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223 acquired at 600 ℃. It can be explained by above mentioned thermal stabilities of the

224 three components.

225 3.2.2. Bio-oil composition analysis

226 The bio-oils are aqueous mixtures made up of a large number of compounds

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227 representing various chemicals species derived from the complex conversion network.

228 Fig. 5 shows the composition of bio-oils obtained from the three components, which

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229 are grouped according to chemical types, and the details are listed in Table 3–5. The

230 pyrolysis temperature took a significant effect on the composition of bio-oils from the

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231 pyrolysis of each sample.

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232 Cellulose derived bio-oil mainly consisted of saccharides, furans and ketones.
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233 With pyrolysis temperature rising, the content of saccharides constantly reduced from

234 64.16% to 10.80%. At 300 ℃, the content of D-Allose took up 78% of the group, and
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235 the content of dehydrated carbohydrates (mainly levoglucosan) significantly raised

236 with increasing pyrolysis temperature (>400 ℃), and then dropped. It is explained
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237 levoglucosan formed by the breakage and rearrangement of chemical bond in

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238 cellulose molecule, is the major product obtained at the condition of medium

temperatures, but heat stability is weak, which is easy to be degraded at higher

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239

240 temperature; little influence of pyrolysis temperature on the content of furans (mainly
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241 furfurals, furanones and furfuralcohols) was appeared, kept 20–26%. Along with
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242 increasing content of ketones and acids, respectively 2.15–29.98% and 1.43–16.83%,

243 1-Hydroxy-2-propanone and propanoic acid started to be the dominant ingredient of

244 corresponding groups.

245 Acids and ketones were the main ingredients of the bio-oil from hemicellulose

246 pyrolysis. Seen from Table 4, at 300 ℃, acids could be the major ingredient of bio-oil,

247 formed by the breakage of abundant carboxyls at initial stage of hemicellulose

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248 pyrolysis, especially acetic acid glacial, according for 86% of the group; and along

249 with the decreasing content of acids influenced by pyrolysis temperature, from

250 83.48% to 31.64%, the content of acetic acid glacial reduced to 22.78%. In addition,

251 higher pyrolysis temperature promoted more species and higher content of ketones

252 (from 12.91% to 35.63%), especially cyclopentenones increased rapidly from 7.26%

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253 to 30.53%, the formation of acetophenones was at 600–700 ℃. Similarly to ketones,

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254 aromatic acids were formed at higher temperature. In the rest of the groups, phenol

255 was the main ingredient of phenols, and the content increased to 8.30% with the

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256 increasing content of group at 300–700 ℃, furans (mainly furfural) kept relatively

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257 stable, and the content of alcohols still was low. The alkenes and thickening rings
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258 were observed at 500–700 ℃.

259 Observed from Table 5, the main compound of bio-oil from lignin pyrolysis were
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260 phenols. The content of phenols was gradually increased until the temperature reached

261 600 ℃, which provided the maximum fraction (83.24%). At 300 ℃, it mainly
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262 consisted of 4-Ethyl-2-methoxyphenol, Guaiacol, 2,6-Dimethoxyphenol,

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263 4-Ethylphenol and 2-Methoxy-4-methylphenol, representing 84% of the group, and

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264 the types of phenolic compounds increased affected by increasing temperature. Of

265 phenols, the content of alkylated phenols (mainly phenol, p-cresol, and 4-ethylphenol)
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266 significantly rose, due to the deep cracking of the lignin and secondary reactions of
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267 the primary products such as guaiacol [29]. Moreover, it showed that obtained acids

268 were mainly long chain and macromolecular compounds such as petroselic acid,

269 palmitic acid and linoleic acid, which was gained from fracture of ether bond and side

270 chain in lignin samples, reducing with an increase in pyrolysis temperature, from

271 18.79% to 4.69%. 2,3-Dihydrobenzofuran represented trend of furans throughout the

272 pyrolysis process, first reduced, then rose quickly; ketones (mainly acetosyringone)
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273 and esters were falling, especially ester compounds did not existed at 700 ℃.

274 Overall, bio-oils derived from pyrolysis of the three components have a large

275 number of oxygen containing reactive functional groups and a complete

276 characterization of pyrolytic bio-oil is hardly. By results reported in Fig. 5 and Table

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277 3–5, the bio-oil derived by cellulose presented the unique saccharides, especially

278 levoglucosan; cellulose and lignin derived bio-oils showed the highest concentration

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279 of acids and phenols, respectively mainly acetic acid and phenol.

280 3.3. Bio-gas

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281 3.3.1. Bio-gas yields

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282 The bio-gas products yields from pyrolysis of the three components in the

temperature range of 300–700 ℃ are reported in Fig. 6. The bio-gas yields increased
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283

284 with increasing temperature for all samples, this is probably because pyrolysis became
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285 more active as the pyrolysis temperature increasing, and more organic compounds

286 were converted into non-condensable gases [30]. Furthermore, as it is seen from Fig.
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287 6, hemicellulose always produced more bio-gases than cellulose and lignin
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288 (respectively cellulose: 5.37–39.96%, hemicellulose: 13.12–46.04%, lignin:

289 8.93–28.09%). This result could be attributed to the weak bond strengths in the
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290 chemical structures of hemicellulose, and hemicellulose was easier to degrade to

micromolecular volatiles influenced by the temperature.

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291

Combining with the analysis of Fig. 4 and Fig. 6, the reason of decreasing of
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292

293 bio-oil yields and more significant increasing of bio-gas yields at higher pyrolysis

294 temperatures was believed to be the formation of secondary cracking reactions of the

295 pyrolysis vapors. On the other hand, catalysis of hot bio-char also made a contribution

296 for an increase in gaseous products [31].

297 3.3.2. Bio-gas composition analysis

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298 The bio-gas products analyzed by gas chromatography include CO, CO2, H2 and

299 some light hydrocarbon (CH4, C2H4 and C2H6), are plotted in Fig. 7. The influence of

300 pyrolysis temperature on bio-gas composition was significant.

301 Bio-gas production from pyrolysis of cellulose presented the highest volume

302 contents of CO2 and CO, which exceed 62 vol.% of the total gaseous products. With

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303 an increase in the pyrolysis temperature, CO2 content decreased from 62.0 vol.% to

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304 28.0 vol.%, CO content first increased from 37.0 vol.% at 300 ℃ to the largest value

305 of 45.9 vol.% at 500 ℃, then decreased to the smallest value of 34.2 vol.% at 700 ℃.

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306 The contents of H2, CH4 and light hydrocarbons C2 (including C2H4 and C2H6) were

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307 very low, and kept increasing trend (H2: 0.4–20.9 vol.%, CH4: 0.6–15.2 vol.% and C2:
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308 ~1 vol.%). In the three components, the concentration of CO2 derived from

309 hemicellulose was always higher, accounting for above 38 vol.% of the total gaseous
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310 products, while CO2 content rapidly decreased from 70.2 vol.% to 38.5 vol.% with

311 temperature increasing, CO content gradually increased from 29.0 vol.% at 300 ℃ to
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312 the largest value of 35.5 vol.% at 500 ℃, followed by a decrease to 25.0 vol.% at
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313 700 ℃. Similarly, the contents of H2, CH4 and C2 continued to increase, while they
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314 were still low. For lignin, the volume contents of CO2 and CO in bio-gas products

315 were very high at lower temperature, accounting for 95.4 vol.% of the total gas
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316 volume at 300 ℃, as the pyrolysis temperature increased from 300 ℃ to 700 ℃, CO2
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317 content rapidly decreased from 60.7 vol.% to 28.0 vol.%, CO content first decreased

318 from 34.7 vol.% at 300 ℃ to 21.0 vol.% at 400 ℃, then gradually increased to 26.8

319 vol.% at 700 ℃, while the volume contents of CH4, H2 and C2 continued to increase,

320 particularly, CH4 content showed a noticeable increasing trend (4.6–42.0 vol.%),

321 being the dominant composition above 450 ℃.

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322 Through the comparison of bio-gas products by pyrolysis of the three

323 components (seen from Fig. 7), some similar points could be observed. The

324 generation temperature of CO2 and CO was low, primarily formed by extrusion of

325 carbonyl groups and carboxyl groups. CO content remained stable in the whole

326 temperature range, one of reasons was formed by the secondary cracking of pyrolytic

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327 vapors, and another was due to incomplete oxidation reaction between

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328 high-temperature bio-char and oxygen generated in the pyrolysis. H2 was released out

329 at a higher temperature (>400 ℃), it is because H2 mainly came from the cracking and

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330 deformation of C=C and C–H, which needed more energy. In addition, the releasing

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331 of C2 was generally very low for each sample.
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332 It can be observed that cellulose obtained the highest CO, due to the higher

333 carbonyl content in it. Hemicellulose displayed the highest CO2, because of the higher
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334 carboxyl content. Lignin owned the highest CH4, it might be attributed to the higher

335 content of aromatic rings and O-CH3 functional groups in the origin lignin sample.
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336 For cellulose and hemicellulose, the releasing of H2 was significant.

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337 Furthermore, observing bio-gas yields and composition can confirm heating

338 value of bio-gas products, is shown in Fig. 8. As the pyrolysis temperature increased,
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339 HHV of bio-gas products from pyrolysis of the three components increased

(respectively cellulose: 4.99–14.76 MJ/kg, hemicellulose: 3.95–13.99 MJ/kg, lignin:

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340

6.38–22.71 MJ/kg). It is because bio-gas phase for all the three components was
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341

342 mainly made up of CO2 and CO with low calorific value at low temperature, with an

343 increase of pyrolysis temperature, more and more bio-gases with high heating value

344 (i.e., not CO2), primarily CH4, were formed. Among the three components, HHV of

345 lignin derived bio-gas products was always the largest, due to the presence of massive

346 CH4 took responsible of the highest HHV.

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347 4. Conclusions

348 The characteristics of volatile products from pyrolysis of the three main

349 components (cellulose, hemicellulose and lignin) highly were dependent on pyrolysis

350 conditions and their own chemical structures. The pyrolysis temperature played an

351 important role in yields and composition of volatile products (bio-oil and bio-gas)

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352 from each sample pyrolysis. The optimal temperatures for bio-oil products from

RI
353 cellulose, hemicellulose and lignin were found to be 500 ℃, 450 ℃ and 600 ℃, with

354 maximum bio-oil yields of 64.70%, 41.44% and 39.73%, respectively. Among the

SC
355 three components, cellulose was responsible for the formation of bio-oil products, and

U
356 hemiellulose was the major contributor for bio-gas products. Moreover, the bio-gas
AN
357 yields from pyrolysis of the three main components had the same trend as increasing

358 temperature, while compositions of bio-gas products were different depending on

M

359 diverse samples. Cellulose pyrolysis produced the highest CO, due to higher carbonyl

360 content. Hemicellulose pyrolysis owned the highest CO2 formed by higher carboxyl
D

361 content. Lignin pyrolysis generated the highest CH4 characterized by the largest HHV,
TE

362 due to higher aromatic rings and methoxyl groups.

363 In addition, significant differences in the composition of bio-oil from pyrolysis of

EP

364 each component were drawn from GC-MS results. Cellulose bio-oil displayed unique

saccharides, and more furans, hemicellulose bio-oil mainly contained more acids and
C

365

ketones, and the dominant compositions of lignin bio-oil were phenols.

AC

366

367 Further investigations will be carried out in order to probe the interactions among

368 the three components and to evaluate characterization of volatile production from

369 pyrolysis of biomass. As a result, it can be concluded that the properties of pyrolysis

370 products of a real biomass are predictably described using a ternary model mixture

371 characterized by the three biomass components in biomass, application of products

 ACCEPTED MANUSCRIPT

372 are related favorably with the precursors used for pyrolysis.

373 Acknowledgements

374 This work was supported by the National Natural Science Foundation of China

375 (51576071) and Transformational Fund of Agricultural Scientific and Technological

376 Achievements of China (2014GB2E000048).

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377 References

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421 [17] B. Peters, Prediction of pyrolysis of pistachio shells based on its components
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422 hemicellulose, cellulose and lignin, Fuel Processing Technology 92 (2011)

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427 Technology 71 (2001) 187–195.

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428 [20] Q. Lu, X.C. Yang, C.Q. Dong, Influence of pyrolysis temperature and time on the

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430 and Applied Pyrolysis 92 (2011) 430–438.

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433 [22] C. Liu, J. Hu, H.Y. Zhang, R. Xiao, Thermal conversion of lignin to phenols:
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434 Relevance between chemical structure and pyrolysis behaviors, Fuel (2016) (in press).

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436 polysaccharides extracted from hardwood: Cellulose and hemicellulose, Carbohydrate

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437 Polymers 82 (2010) 39–45.

438 [24] D.K. Shen, S. Gu, The mechanism for thermal decomposition of cellulose and its
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439 main products, Bioresource Technology 100 (2009) 6496–6504.

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441 Donnison, The effect of alkali metals on combustion and pyrolysis of

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442 Lolium and Festuca grasses, switchgrass and willow, Fuel 86 (2007) 1560–1569.

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444 biomass from natural lake blooms with lignocellulosic biomass, Bioresource

445 Technology 102 (2011) 11018–11026.

446 [27] H.P. Yang, R. Yan, H.P. Chen, D.H. Lee, C.G. Zheng, Characteristics of
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447 hemicellulose, cellulose and lignin pyrolysis, Fuel 86 (2007) 1781–1788.

448 [28] P. McKendry, Energy production from biomass (part 1): Overview of biomass,

449 Bioresource Technology 83 (2002) 37–46.

450 [29] J. Murwanashyake, H. Pakdel, C. Roy, Step-wise and one-step vacuum pyrolysis

451 of birch-derived biomass to monitor the evolution of phenols, Journal of Analytical

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452 and Applied Pyrolysis 60 (2001) 219–231.

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453 [30] C.F. Palma, Modeling of tar formation and evolution for biomass gasification: a

454 review, Applied Energy 111 (2013) 129–141.

SC
455 [31] P. Gilbert, C. Ryu, V. Sharifi, J. Swithenbank, Tar reduction in pyrolysis vapours

456 from biomass over a hot char bed, Bioresource Technology 100 (2009) 6045–6051.

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457 Figure Captions:

458 Fig. 1. Schematic diagram of tube furnace pyrolysis reactor.

459 Fig. 2. FTIR spectra of the three main components in biomass.

460 Fig. 3. Cellulose, hemicellulose and lignin TG-DTG experimental curves at 5 ℃/min.

PT
461 Fig. 4. Bio-oil yields obtained from cellulose, hemicellulose and lignin at the experimental

462 pyrolysis temperatures of 300–700 ℃.

RI
463 Fig. 5. Distribution of bio-oil compounds classes obtained from cellulose, hemicellulose

SC
464 and lignin at the experimental pyrolysis temperatures of 300–700 ℃.

465 Fig. 6. Bio-gas yields obtained from cellulose, hemicellulose and lignin at the experimental

U
466 pyrolysis temperatures of 300–700 ℃.
AN
467 Fig. 7. Composition analysis of bio-gas obtained from cellulose, hemicellulose and lignin

468 at the experimental pyrolysis temperatures of 300–700 ℃.

M

469 Fig. 8. The higher heating value of bio-gas obtained from cellulose, hemicellulose and
D

470 lignin at the experimental pyrolysis temperatures of 300–700 ℃.

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Table 1.

Physico-chemical properties of the feed-stocks.

Materials Cellulose Hemicellulose Lignin

Proximate analysis (wt.%)

PT
Moisture 3.31 3.96 3.42

RI
Ash - 5.59 3.85

VM 94.65 79.42 67.23

SC
FC 2.04 11.03 25.50

Ultimate analysis (wt.%)

C
U
43.08 42.14 61.81
AN
H 6.40 6.22 5.63

O 46.71 41.40 23.57

M

N 0.50 0.69 1.72

D

HHV (MJ/kg) 17.28 16.81 25.51

TE
C EP
AC
 ACCEPTED MANUSCRIPT

Table 2.

The main functional groups of the three components in biomass.

Wavenumber (cm-1) Functional groups Compounds

3600–3000 (s) O-H stretching Acid, methanol

PT
2970–2860 (m) C-Hn stretching Alkyl, aliphatic, aromatic
1730–1700 (m), Ketone, carbonyl,

RI
C=O stretching
1580–1520 (m) ester, ethanol
1643 (m) C=C Benzene stretching ring

SC
1601 (w), 1512 (w) C=C stretching Aromatic skeletal mode

1460–1425 (s) O-CH3 Methoxyl-O-CH3

1417 (m)
U
C-H deformation Alkyl
AN
1282 (s), 1253 (s) C-O stretching Acid
M

1262 (s) C-O-C stretching Aryl-alkyl ether linkage

1217 (s) C-O stretching Phenol

D

1170 (s), 1067 (s), 896 (s) C-O-C stretching vibration Pyranose ring
TE

1108 (m) O-H association C-OH

C-O stretching and C-O
1040 (w) C-OH (ethanol)
EP

deformation
850–700 (m) C-H Aromatic hydrogen
C

700–400 (w) C-C stretching -

AC
 PT
Table 3.

Composition analysis of bio-oil obtained from cellulose.

RI
Area (%)

SC
Groups Compounds
300℃ 400℃ 450℃ 500℃ 550℃ 600℃ 700℃

Levoglucosenone - 11.17 - - - - -

U
1,6-Anhydro-.beta.-D-glucopyranose(levoglucosan) 14.45 36.48 37.05 34.13 25.31 20.45 6.00

AN
Saccharides
1,4:3,6-Dianhydro-.alpha.-d-glucopyranose - - 8.41 6.02 6.12 6.35 4.80

M
D-Allose 49.71 8.77 - - - - -

Total 64.16 56.42 45.46 40.15 31.43 26.80 10.80

D
Furfural 8.53 6.33 5.96 5.87 6.10 5.50 5.71
TE
3-Furaldehyde 3.02 2.48 1.99 1.35 0.67 1.44 1.54

5-(Hydroxymethyl)-2-furancarboxaldehyde - 1.64 1.75 1.84 1.84 2.01 2.12

EP
Furans
1-(2-Furanyl)ethanone - - - - 1.47 1.77 1.66

2,2-Dimethyl-3(2H)-furanone - - 1.24 1.25 1.11 0.81 -

C

2(5H)-Furanone - 0.46 1.53 1.58 2.10 2.77 3.74

AC
 PT
3-Furanmethanol - 1.13 - - 1.12 1.33 1.25

5-Methyl-2(5H)furanone - 1.35 - 1.38 - 1.54 -

RI
4-Methyl-5H-furan-2-one - - 1.45 - 1.49 - 1.48

SC
5-Methyl-2-furaldehyde 1.82 1.33 0.98 0.71 1.14 0.66 0.75

Furyl hydroxymethyl ketone 1.46 1.63 1.82 1.46 - - -

U
2-Furanmethanol 10.52 6.12 5.73 5.09 4.76 5.85 4.31

AN
Total 25.35 22.47 22.45 20.53 21.80 23.68 22.56

1-Hydroxy-2-butanone - 0.80 1.10 1.16 0.89 2.28 5.81

M
1-Hydroxy-2-propanone - 0.79 1.42 1.84 5.28 8.13 16.08

D
2-Methylcyclopentanone - - 0.30 0.41 - 0.54 -

Ketones
TE
3-Methyl-2-cyclopenten-1-one - - - 0.22 0.36 1.49 2.73

3-Methyl-1,2-cyclopentanedione - 1.53 1.19 1.56 1.35 0.75 0.77

EP

1,2-Cyclopentanedione - 1.41 1.43 1.38 1.23 1.23 1.23

2-Hydroxy-3-methyl-2-cyclopenten-1-one - - 1.55 1.19 1.20 1.06 0.87

C

2-Methyl-2-cyclopenten-1-one 2.15 1.85 1.69 1.54 1.47 1.16 1.28

AC
 PT
3,5-Dihydroxy-2-methyl-4H-pyran-4-one - - 1.63 3.49 2.21 1.99 1.21

Total 2.15 6.38 10.31 12.79 13.99 18.63 29.98

RI
2-(Vinyloxy)ethanol - - - - 0.44 1.79 2.21

SC
4-Methyl-1-hepten-4-ol 2.15 1.68 0.86 0.54 0.41 - -

Alcohols Glycidol - - - - 1.24 2.25 4.34

U
1-Methylcycloheptanol 2.43 1.34 0.84 0.25 - - -

AN
cis-1,2-Cyclohexanediol - - - 0.52 0.71 0.77 0.52

Total 4.58 3.02 1.70 1.31 2.80 4.81 7.07

M
5-Methyl-2(3H)-furanone - - 1.38 1.20 - - -

D
Triisopropyl orthoformate 1.27 0.52 0.36 - 14.14 7.66 5.05

Esters TE
Methyl 2-furoate 0.92 0.96 0.85 0.93 0.76 0.85 0.74

Methyl4-methyl-2-pentenoate - - 1.86 1.58 - - -

EP

2-Hexenoic acid, methyl ester - - 1.51 2.55 - - -

Total 2.19 1.48 5.96 6.26 14.90 8.51 5.79

C

Acids Propanoic acid - 6.30 6.29 6.30 7.01 8.35 12.53

AC
 PT
3,4-Dihydroxy-3-cyclobutene-1,2-dione 1.43 2.46 2.42 2.44 3.12 3.21 4.30

Heptanoic acid - - 1.33 1.20 - - -

RI
Total 1.43 8.76 9.84 9.94 10.13 11.56 16.83

SC
2-Methylcrotonaldehyde - - - 0.16 0.22 0.23 1.23

Aldehydes Heptanal - - - 3.53 - - -

U
Formaldehyde diisopropyl acetal - 1.11 2.73 3.81 4.32 3.13 2.07

AN
Total - 1.11 2.73 7.50 4.54 3.36 3.30

Phenol 0.14 0.36 0.41 0.44 0.58 1.65 3.67

M
Phenols 4-Methylphenol - - 0.35 0.43 0.45 0.44 0.52

D
Maltol - - 0.79 0.65 0.62 0.56 -

Total TE 0.14 0.36 1.55 1.52 1.65 2.65 4.19

C EP
AC
 PT
Table 4.

Composition analysis of bio-oil obtained from hemicellulose.

RI
Area (%)

SC
Groups Compounds
300℃ 400℃ 450℃ 500℃ 550℃ 600℃ 700℃

Acetic acid glacial 71.43 38.10 31.12 22.86 23.10 22.96 22.78

U
Propanoic acid 12.05 13.03 14.10 8.80 8.66 6.78 6.74

AN
Acids (E)-2-Methyl-2-butenoic acid - 1.57 1.10 - - - -

M
4-Hydroxy-benzoic acid - - - - - 1.36 1.23

3-Methylcinnamic acid - - - - - 0.70 0.89

D
Total 83.48 52.70 46.32 31.66 31.76 31.80 31.64

3-Hydroxy-2-butanone TE 5.65 3.26 2.98 2.60 2.16 1.58 1.30

4-Hydroxy-3-hexanone - 2.96 2.26 1.83 1.53 1.21 1.08

EP

Ketones 2-Cyclopenten-1-one - 4.96 5.64 6.47 6.95 7.39 8.02

2-Methyl-2-cyclopenten-1-one - 3.16 4.88 4.71 5.23 5.64 6.62

C

2-Cyclohexen-1-one - 1.23 1.16 1.23 1.12 1.11 1.11

AC
 PT
3-Methyl-2-cyclopenten-1-one - 1.55 2.51 2.60 2.79 2.89 3.39

2,3-Dimethyl-2-cyclopenten-1-one 4.19 7.12 7.40 8.12 8.92 8.24 9.44

RI
2-Hydroxy-3-methyl-2-cyclopenten-1-one 3.07 4.12 4.65 3.96 3.42 2.20 1.00

SC
2,3,4,5-Tetramethyl-2-cyclopenten-1-one - - - 0.25 0.36 0.52 0.95

4'-Methoxy-acetophenone - - - - - 0.89 1.23

U
4-Hydroxy-3-methylacetophenone - - - - - 1.06 0.56

AN
4-Hydroxy-2-methylacetophenone - - - - - 1.27 0.93

Total 12.91 28.36 31.48 31.77 32.48 34.00 35.63

M
2-Methyl-furan - - - 1.32 2.96 3.15 4.03

D
Furfural 2.53 4.33 4.96 5.87 6.10 5.50 5.71

2,5-Dimethyl-furan TE - 4.15 3.65 - - - -

Furans 2-Ethyl-furan - 2.52 2.62 2.12 1.59 1.36 -

EP

5-Methyl-2-furancarboxaldehyde - 1.22 2.10 3.36 1.62 1.16 0.21

5-(Hydroxymethyl)-2-furaldehyde - 1.95 1.66 - - - -

C

Phthalan - - - - - - 2.54
AC
 PT
Total 2.53 14.17 14.99 12.67 12.27 12.17 12.49

Phenol - 1.48 2.32 4.07 6.55 7.50 8.30

RI
2-Methyl-phenol - - - 4.65 3.78 2.70 1.63
Phenols

SC
4-Methyl-phenol - - - 2.33 3.65 4.56 6.21

4-Ethyl-2-methoxy-phenol - 1.58 3.06 1.55 1.65 1.71 -

U
Total - 3.06 5.38 12.60 15.63 16.47 16.14

AN
1,3-Dimethoxy-2-propanol - 1.71 1.83 - - - -

1,1'-Oxybis-2-propanol 1.08 - - - - - -

M
Alcohols
(E)-3-Methyl-2-penten-4-yn-1-ol - - - 1.34 1.32 1.29 1.28

D
4-Methyl-cyclohexanol - - - 0.87 1.23 1.26 1.29

Total TE 1.08 1.71 1.83 2.21 2.55 2.55 2.57

1,3-Cycloheptadiene - - - 1.42 - - -
EP

Bicyclo[4.2.0]octa-1,3,5-triene - - - 1.59 1.68 - -

Others
2,5-Dimethyl-2,4-hexadiene - - - 1.58 0.79 - -
C

1-(1-Cyclohexen-1-yl)-ethanone - - - 1.94 1.68 - -

AC
 PT
1-Ethenyl-4-methyl-benzene - - - 2.56 1.16 - -

1-Indanone - - - - - 1.66 0.81

RI
2-Methyl-1-naphthalenol - - - - - 1.35 0.72

SC
Total - - - 9.09 5.31 3.01 1.53

U
AN
M
D
TE
C EP
AC
 PT
Table 5.

RI
Composition analysis of bio-oil obtained from lignin.

SC
Area (%)
Groups Compounds
300℃ 400℃ 450℃ 500℃ 550℃ 600℃ 700℃

U
Phenol - 3.93 6.92 9.00 10.71 11.20 12.97

AN
o-Cresol - 1.21 1.45 1.60 1.63 2.19 3.98

p-Cresol - 3.32 4.09 5.12 6.59 7.56 9.35

M
Guaiacol 9.28 7.40 6.77 5.71 4.93 4.61 2.01

D
3,4-Dimethylphenol - - - 1.15 1.27 2.10 2.60
Phenols
4-Ethylphenol TE 7.35 9.00 10.50 12.57 14.06 14.66 15.93

Pyrocatechol 0.97 2.49 2.97 4.68 5.35 8.15 9.85

EP

2-Methoxy-4-methylphenol 6.15 5.39 5.19 4.95 4.31 3.67 -

p-Isopropylphenol - 1.32 2.33 1.85 1.41 1.68 2.25

C

3-Methoxy-2-benzenediol 2.29 4.32 4.09 1.02 3.13 3.43 3.72

AC
 PT
4-Ethyl-2-methoxyphenol 14.04 11.11 11.00 10.07 7.58 5.83 4.91

RI
4-Methylcatechol - - - - - 2.24 2.97

SC
4-Hydroxy-3-methoxystyrene 3.35 2.96 3.53 5.50 5.48 6.33 3.02

O-Methylorcinol 0.51 0.92 1.08 1.08 1.04 0.99 -

U
2,6-Dimethoxyphenol 7.45 6.23 6.18 5.47 4.73 3.62 -

AN
3,4-Dimethoxyphenol - 0.79 1.57 1.58 1.58 - -

4-Ethylresorcinol 1.26 1.63 1.77 1.99 2.25 4.98 6.01

M
Total 52.63 62.03 69.44 73.34 76.06 83.24 79.56

D
Vanillic acid - - - - 2.61 3.59 3.38

Acids
Palmitic acid

Linoleic acid
TE 4.85

2.93
3.31

2.47
2.61

2.40
2.93

2.04
3.84

-
1.69

-
-

1.30
EP
Petroselic acid 10.11 9.16 7.76 6.79 3.26 - -

Stearic acid 0.90 1.20 - 0.37 1.36 - -

C

Total 18.79 16.15 12.76 12.12 11.08 5.28 4.69

AC
 PT
Furans 2,3-Dihydrobenzofuran 14.00 7.84 7.24 6.22 5.51 5.14 12.07

RI
Total 14.00 7.84 7.24 6.22 5.51 5.14 12.07

SC
Acetovanillone - 0.56 0.78 0.93 1.11 1.76 0.77

Ketones 4-O-Methylphloracetophenone 3.54 3.13 2.47 1.24 1.00 0.30 -

U
Acetosyringone 7.25 6.92 4.50 4.31 3.78 3.77 2.91

AN
Total 10.79 10.61 7.75 6.48 5.89 5.82 3.68

Ethyl homovanillate 0.71 0.66 0.61 0.57 0.51 0.53 -

M
Esters
Methyl petroselinate 3.07 2.70 2.19 1.27 0.95 - -

D
Total 3.78 3.36 2.80 1.84 1.47 0.53 -

TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
SC
1. Nitrogen bottle; 2. Reducing valve; 3. Nitrogen flowmeter; 4. Temperature controller; 5.

U
Quartz tube; 6. Thermocouple; 7. Pyrolysis furnace; 8. Ice water condenser; 9. Mixed gas

flowmeter; 10. Air collection bag. AN

Fig. 1. Schematic diagram of tube furnace pyrolysis reactor.
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Cellulose Hemicellulose Lignin

80

70

PT
60

Transmittance (%)
50

RI
40

30

SC
20
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )

U
Fig. 2. FTIR spectra of the three main components in biomass.
AN
M
D
TE
C EP
AC
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100 DTG
-2
Cellulose

80 -6

PT DTG (% •min )
-10

-1
60
TG (%)

-14

40

RI
-18

20
TG -22

SC
335°C

0 -26
0 100 200 300 400 500 600 700 800 900

Temperature (°C)

U
100
AN -1.0

Hemicellulose
M
80

-2.5

DTG (% •min )
-1
60
D
TG (%)

-4.0
40
TE

-5.5
20

295°C
EP

0 -7.0
0 100 200 300 400 500 600 700 800 900

Temperature (°C)
C
AC
 ACCEPTED MANUSCRIPT

110 0.0

100

-0.5
90 Lignin

80

PT DTG (% •min )
-1.0

-1
70
TG (%)

-1.5
60

RI
50
-2.0

SC
40 385°C

30 -2.5
0 100 200 300 400 500 600 700 800 900

Temperature (°C)

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Fig. 3. Cellulose, hemicellulose and lignin TG-DTG experimental curves at 5 ℃/min.
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Cellulose Hemicellulose Lignin

60

50

PT
40
Bio-oil yields (wt.%)

30

RI
20

SC
10

0
300 400 450 500 550 600 700
Temperature (°C)

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Fig. 4. Bio-oil yields obtained from cellulose, hemicellulose and lignin at the experimental

pyrolysis temperatures of 300–700 ℃.

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Saccharides

Cellulose Furans
Ketones
60 Alcohols
Esters
Acids
Aldehydes
50 Phenols

PT
40
Area (% )

30

RI
20

SC
10

0
300 350 400 450 500 550 600 650 700

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Temperature (ºC)

80
AN Hemicellulose
Acids
Ketones
Furans
Phenols
Alcohols
70 Others
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60

50
Area (% )

40
TE

30

20
EP

10

0
300 350 400 450 500 550 600 650 700

Temperature (ºC)
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Phenols
Acids

80 Furans
Ketones
Esters
70 Lignin

60

PT
50
Area (% )

40

RI
30

20

SC
10

0
300 350 400 450 500 550 600 650 700

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Temperature (ºC)

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Fig. 5. Distribution of bio-oil compounds classes obtained from cellulose, hemicellulose and

lignin at the experimental pyrolysis temperatures of 300–700 ℃.

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Cellulose Hemicellulose Lignin

50

40

PT
Bio-gas yields (wt.%) 30

RI
20

10

SC
0
300 400 450 500 550 600 700

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Temperature (°C)

Fig. 6. Bio-gas yields obtained from cellulose, hemicellulose and lignin at the experimental

pyrolysis temperatures of 300–700 ℃.

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CO
2

Cellulose CO
60
CH
4

H
2

(vol.% )
C
2
50

40

PT
Bio-gas concentration

30

RI
20

10

SC
0
300 350 400 450 500 550 600 650 700
Temperature (ºC)

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70
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CO

CO
CH
2

H
60 2
M
(vol.% )

C
2

50
D

40
Bio-gas concentration

TE

30

20
EP

10

0
300 350 400 450 500 550 600 650 700
C

Temperature (ºC)
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CO
2
60 Lignin CO
CH
4

H
2

50

(vol.% )
C
2

40

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Bio-gas concentration

30

RI
20

10

SC
0
300 350 400 450 500 550 600 650 700
Temperature (ºC)

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Fig. 7. Composition analysis of bio-gas obtained from cellulose, hemicellulose and lignin at

the experimental pyrolysis temperatures of 300–700 ℃.

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Cellulose Hemicellulose Lignin

25

20

PT
HHV (MJ/kg) 15

RI
10

SC
0
300 400 450 500 550 600 700

Temperature (°C)

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Fig. 8. The higher heating value of bio-gas obtained from cellulose, hemicellulose and lignin
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at the experimental pyrolysis temperatures of 300–700 ℃.
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Highlights
 Pure cellulose, hemicellulose and lignin separately were pyrolyzed to produce

volatile products and compared by amplifying experiments in a tube furnace.

 Pyrolysis temperature and natural chemical structures played an important role on

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the yields and composition of products.

 Cellulose was the major contributor for bio-oil formation, hemiellulose generated

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more bio-gases, and lignin owned higher HHV bio-gas.

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 Cellulose bio-oil displayed unique saccharides (mainly levoglucosan),

hemicellulose bio-oil contained higher acids and ketones, and phenols were the

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dominant composition of lignin bio-oil.
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 Selective pyrolysis technology is expected to be further developed.
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