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J Joei 2016 08 004
J Joei 2016 08 004
PII: S1743-9671(16)30287-2
DOI: 10.1016/j.joei.2016.08.004
Reference: JOEI 261
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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4 Heilongjiang, PR China)
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6 Abstract
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7 To better understand pyrolysis mechanism and further develop selective pyrolysis
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9 components (cellulose, hemicellulose and lignin) were investigated and compared by
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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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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
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.
26 1. Introduction
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
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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
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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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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
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
51 contributions from the three main components [15,16]. It is well known that the
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
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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
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59 of the pyrolytic volatile products, which revealed the effects of pyrolysis temperature
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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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67 behavior of the three components under the same pyrolysis conditions [21,23-25].
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69 mechanism of the main components for further enhancing the volatile products yields
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77 The experimental results obtained in the present work will provide valuable assistance
79 2. Experimental section
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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,
89 structure. The moisture content, ash content and volatile matter (VM) content were
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91 and the fixed carbon (FC) fraction was calculated by subtraction. The ultimate
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.
101 and lignin were investigated by thermo-gravimetric (TG) analysis and derivative
104 environment (N2, 20 mL/min) from room temperature to 900 ℃ at a heating rate of
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105 5 ℃/min.
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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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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 Ybiochar 100% (1)
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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).
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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
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
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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.
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
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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
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
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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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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.
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.
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
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
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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236 with increasing pyrolysis temperature (>400 ℃), and then dropped. It is explained
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238 cellulose molecule, is the major product obtained at the condition of medium
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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%,
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,
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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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
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
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.
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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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289 8.93–28.09%). This result could be attributed to the weak bond strengths in the
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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
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
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.%),
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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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
340
6.38–22.71 MJ/kg). It is because bio-gas phase for all the three components was
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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
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
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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
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355 three components, cellulose was responsible for the formation of bio-oil products, and
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356 hemiellulose was the major contributor for bio-gas products. Moreover, the bio-gas
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357 yields from pyrolysis of the three main components had the same trend as increasing
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
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361 content. Lignin pyrolysis generated the highest CH4 characterized by the largest HHV,
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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
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365
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
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
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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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460 Fig. 3. Cellulose, hemicellulose and lignin TG-DTG experimental curves at 5 ℃/min.
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461 Fig. 4. Bio-oil yields obtained from cellulose, hemicellulose and lignin at the experimental
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463 Fig. 5. Distribution of bio-oil compounds classes obtained from cellulose, hemicellulose
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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
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466 pyrolysis temperatures of 300–700 ℃.
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467 Fig. 7. Composition analysis of bio-gas obtained from cellulose, hemicellulose and lignin
469 Fig. 8. The higher heating value of bio-gas obtained from cellulose, hemicellulose and
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Table 1.
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Moisture 3.31 3.96 3.42
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Ash - 5.59 3.85
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FC 2.04 11.03 25.50
C
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43.08 42.14 61.81
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H 6.40 6.22 5.63
Table 2.
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2970–2860 (m) C-Hn stretching Alkyl, aliphatic, aromatic
1730–1700 (m), Ketone, carbonyl,
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C=O stretching
1580–1520 (m) ester, ethanol
1643 (m) C=C Benzene stretching ring
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1601 (w), 1512 (w) C=C stretching Aromatic skeletal mode
1417 (m)
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C-H deformation Alkyl
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1282 (s), 1253 (s) C-O stretching Acid
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1170 (s), 1067 (s), 896 (s) C-O-C stretching vibration Pyranose ring
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deformation
850–700 (m) C-H Aromatic hydrogen
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Area (%)
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Groups Compounds
300℃ 400℃ 450℃ 500℃ 550℃ 600℃ 700℃
Levoglucosenone - 11.17 - - - - -
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1,6-Anhydro-.beta.-D-glucopyranose(levoglucosan) 14.45 36.48 37.05 34.13 25.31 20.45 6.00
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Saccharides
1,4:3,6-Dianhydro-.alpha.-d-glucopyranose - - 8.41 6.02 6.12 6.35 4.80
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D-Allose 49.71 8.77 - - - - -
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Furfural 8.53 6.33 5.96 5.87 6.10 5.50 5.71
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3-Furaldehyde 3.02 2.48 1.99 1.35 0.67 1.44 1.54
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4-Methyl-5H-furan-2-one - - 1.45 - 1.49 - 1.48
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5-Methyl-2-furaldehyde 1.82 1.33 0.98 0.71 1.14 0.66 0.75
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2-Furanmethanol 10.52 6.12 5.73 5.09 4.76 5.85 4.31
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Total 25.35 22.47 22.45 20.53 21.80 23.68 22.56
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1-Hydroxy-2-propanone - 0.79 1.42 1.84 5.28 8.13 16.08
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2-Methylcyclopentanone - - 0.30 0.41 - 0.54 -
Ketones
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3-Methyl-2-cyclopenten-1-one - - - 0.22 0.36 1.49 2.73
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2-(Vinyloxy)ethanol - - - - 0.44 1.79 2.21
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4-Methyl-1-hepten-4-ol 2.15 1.68 0.86 0.54 0.41 - -
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1-Methylcycloheptanol 2.43 1.34 0.84 0.25 - - -
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cis-1,2-Cyclohexanediol - - - 0.52 0.71 0.77 0.52
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5-Methyl-2(3H)-furanone - - 1.38 1.20 - - -
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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
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Total 1.43 8.76 9.84 9.94 10.13 11.56 16.83
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2-Methylcrotonaldehyde - - - 0.16 0.22 0.23 1.23
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Formaldehyde diisopropyl acetal - 1.11 2.73 3.81 4.32 3.13 2.07
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Total - 1.11 2.73 7.50 4.54 3.36 3.30
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Phenols 4-Methylphenol - - 0.35 0.43 0.45 0.44 0.52
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Maltol - - 0.79 0.65 0.62 0.56 -
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Area (%)
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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
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Propanoic acid 12.05 13.03 14.10 8.80 8.66 6.78 6.74
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Acids (E)-2-Methyl-2-butenoic acid - 1.57 1.10 - - - -
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4-Hydroxy-benzoic acid - - - - - 1.36 1.23
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Total 83.48 52.70 46.32 31.66 31.76 31.80 31.64
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2-Hydroxy-3-methyl-2-cyclopenten-1-one 3.07 4.12 4.65 3.96 3.42 2.20 1.00
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2,3,4,5-Tetramethyl-2-cyclopenten-1-one - - - 0.25 0.36 0.52 0.95
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4-Hydroxy-3-methylacetophenone - - - - - 1.06 0.56
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4-Hydroxy-2-methylacetophenone - - - - - 1.27 0.93
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2-Methyl-furan - - - 1.32 2.96 3.15 4.03
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Furfural 2.53 4.33 4.96 5.87 6.10 5.50 5.71
Phthalan - - - - - - 2.54
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Total 2.53 14.17 14.99 12.67 12.27 12.17 12.49
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2-Methyl-phenol - - - 4.65 3.78 2.70 1.63
Phenols
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4-Methyl-phenol - - - 2.33 3.65 4.56 6.21
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Total - 3.06 5.38 12.60 15.63 16.47 16.14
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1,3-Dimethoxy-2-propanol - 1.71 1.83 - - - -
1,1'-Oxybis-2-propanol 1.08 - - - - - -
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Alcohols
(E)-3-Methyl-2-penten-4-yn-1-ol - - - 1.34 1.32 1.29 1.28
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4-Methyl-cyclohexanol - - - 0.87 1.23 1.26 1.29
1,3-Cycloheptadiene - - - 1.42 - - -
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2-Methyl-1-naphthalenol - - - - - 1.35 0.72
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Total - - - 9.09 5.31 3.01 1.53
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Table 5.
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Composition analysis of bio-oil obtained from lignin.
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Area (%)
Groups Compounds
300℃ 400℃ 450℃ 500℃ 550℃ 600℃ 700℃
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Phenol - 3.93 6.92 9.00 10.71 11.20 12.97
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o-Cresol - 1.21 1.45 1.60 1.63 2.19 3.98
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Guaiacol 9.28 7.40 6.77 5.71 4.93 4.61 2.01
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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
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4-Methylcatechol - - - - - 2.24 2.97
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4-Hydroxy-3-methoxystyrene 3.35 2.96 3.53 5.50 5.48 6.33 3.02
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2,6-Dimethoxyphenol 7.45 6.23 6.18 5.47 4.73 3.62 -
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3,4-Dimethoxyphenol - 0.79 1.57 1.58 1.58 - -
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Total 52.63 62.03 69.44 73.34 76.06 83.24 79.56
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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
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Petroselic acid 10.11 9.16 7.76 6.79 3.26 - -
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Total 14.00 7.84 7.24 6.22 5.51 5.14 12.07
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Acetovanillone - 0.56 0.78 0.93 1.11 1.76 0.77
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Acetosyringone 7.25 6.92 4.50 4.31 3.78 3.77 2.91
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Total 10.79 10.61 7.75 6.48 5.89 5.82 3.68
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Esters
Methyl petroselinate 3.07 2.70 2.19 1.27 0.95 - -
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Total 3.78 3.36 2.80 1.84 1.47 0.53 -
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1. Nitrogen bottle; 2. Reducing valve; 3. Nitrogen flowmeter; 4. Temperature controller; 5.
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Quartz tube; 6. Thermocouple; 7. Pyrolysis furnace; 8. Ice water condenser; 9. Mixed gas
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Transmittance (%)
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4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )
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Fig. 2. FTIR spectra of the three main components in biomass.
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100 DTG
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Cellulose
80 -6
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-10
-1
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TG (%)
-14
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TG -22
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0 -26
0 100 200 300 400 500 600 700 800 900
Temperature (°C)
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DTG (% •min )
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295°C
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0 100 200 300 400 500 600 700 800 900
Temperature (°C)
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110 0.0
100
-0.5
90 Lignin
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PT DTG (% •min )
-1.0
-1
70
TG (%)
-1.5
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-2.0
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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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50
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Bio-oil yields (wt.%)
30
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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
Saccharides
Cellulose Furans
Ketones
60 Alcohols
Esters
Acids
Aldehydes
50 Phenols
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Area (% )
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300 350 400 450 500 550 600 650 700
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Temperature (ºC)
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Acids
Ketones
Furans
Phenols
Alcohols
70 Others
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Area (% )
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300 350 400 450 500 550 600 650 700
Temperature (ºC)
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Acids
80 Furans
Ketones
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70 Lignin
60
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Area (% )
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300 350 400 450 500 550 600 650 700
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Fig. 5. Distribution of bio-oil compounds classes obtained from cellulose, hemicellulose and
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40
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Bio-gas yields (wt.%) 30
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300 400 450 500 550 600 700
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Fig. 6. Bio-gas yields obtained from cellulose, hemicellulose and lignin at the experimental
CO
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Cellulose CO
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CH
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40
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Bio-gas concentration
30
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300 350 400 450 500 550 600 650 700
Temperature (ºC)
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CO
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Bio-gas concentration
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300 350 400 450 500 550 600 650 700
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Temperature (ºC)
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CO
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60 Lignin CO
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C
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Bio-gas concentration
30
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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
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HHV (MJ/kg) 15
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300 400 450 500 550 600 700
Temperature (°C)
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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
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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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