Journal Pre-proofs

Upgrading of biomass fast pyrolysis oil over a moving bed of coal char

Junjie Zhang, Guangyong Wang, Shaoping Xu

PII: S2588-9133(20)30010-7
DOI: https://doi.org/10.1016/j.crcon.2020.09.001
Reference: CRCON 75

To appear in: Carbon Resources Conversion

Received Date: 8 July 2020

Revised Date: 20 September 2020
Accepted Date: 26 September 2020

Please cite this article as: J. Zhang, G. Wang, S. Xu, Upgrading of biomass fast pyrolysis oil over a moving bed
of coal char, Carbon Resources Conversion (2020), doi: https://doi.org/10.1016/j.crcon.2020.09.001

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover
page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version
will undergo additional copyediting, typesetting and review before it is published in its final form, but we are
providing this version to give early visibility of the article. Please note that, during the production process, errors
may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2020 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd.
 1 Upgrading of biomass fast pyrolysis oil over a moving bed of coal char

2 Junjie Zhanga, b, Guangyong Wanga, *, Shaoping Xub

3 a State Key Laboratory of Industrial Vent Gas Reuse, National Center of C1 Chemical Engineering

4 Research, Southwest Research & Design Institute of Chemical Industry, No.393 Jichang Road,

5 Chengdu 610225, China

6 b State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of

7 Technology, No.2 Linggong Road, Dalian 116024, China

8 * Corresponding author: wanggy313@163.com

9 Abstract: Fast pyrolysis of sawdust (SD) and upgrading of the derived bio-oil* (water-free basis)

10 over Shenmu bituminous coal char (SMC) were conducted in an integrated free fall pyrolyzer and

11 moving bed upgrading reactor. The water soluble and heavy bio-oil* (THF soluble) yields

12 decrease and the content of light bio-oil* (CH2Cl2 soluble) increases significantly compared that

13 without SMC despite the decrease of light bio-oil* yield. Chemical analyses of the light bio-oil*

14 were performed using GC-MS and 1H-NMR techniques. The results show that during

15 volatiles-char interaction, the SMC plays important roles in deoxygenation and denitrogenation.

16 The role of SMC in the upgrading process was explored by BET, FT-IR and XRD

17 characterization. The porous structure provides reaction active sites for the bio-oil upgrading.

18 After volatiles-char interaction, the specific surface area of SMC decreases significantly and the

19 carbon crystallite size increases. With increasing the char updating rate from 1 g/min to 4 g/min,

20 the relatively fresh SMC surface leads to the increased active sites, the conversion of heavy

21 bio-oil* is slightly promoted and the removal effects of heteroatoms (O, N) compounds in the light

22 bio-oil* are enhanced. The changes in SMC specific surface area and microcrystalline size are

23 weakened accordingly.

1
24 Keywords: Biomass; Fast pyrolysis; Bio-oil upgrading; Char; Volatiles-char interaction;

25 1. Introduction

26 Along with the world’s population grows and the crude oil reserve is depleting, the need of

27 alternative energy source in a sustainable and environmentally conscious manner, such as

28 biomass, is becoming a pressing task [1, 2]. Currently, the pyrolysis of biomass to produce bio-oil

29 as fuels and chemicals has been received considerable attention [3-5]. However, the bio-oil

30 contains extremely high oxygen, rendering it acidic, instable and resulting in its lower heating

31 value compared with the conventional fuel [6]. The bio-oil requires, therefore, further upgrading

32 in order to be used directly as feedstock in the existing refinery plant.

33 Recently, catalytic hydrogenation and cracking of bio-oil to remove its oxygen-containing

34 functional groups have been widely studied [7-11]. Nevertheless, the measures using the catalysts,

35 including molecular sieve, metal and other transition metal catalysts, are still challenged by tough

36 experimental conditions and easy deactivation of the catalysts by oil coking. As an alternative,

37 char is considered to be one of the most potential tar upgrading catalysts [12-15]. Gilbert et al.

38 [16] investigated the effect of pinewood char on the biomass tar upgrading at different

39 temperatures in a single-stage fixed bed reactor. They found that the heavy component content of

40 biomass pyrolysis tar decreased to 8.33% in presence of char at 700 °C. Boroson et al. [17]

41 investigated the influence of volatiles-char interaction on tar conversion in a two-stage fixed bed

42 quartz reactor, in which the volatiles generated from wood pyrolysis in the upper bed could pass

43 through the char produced from the same biomass pyrolysis in the lower bed. It was found that

44 biomass tar was reactive in the presence of char at temperatures as low as 400 oC, leading to the

45 reduction of the oxygen content of tar. Sun et al. [18] studied the upgrading of biomass tar in a

2
46 two-stage fixed bed reactor by passing the volatiles through a biomass or coal char bed in the

47 upper part of the reactor. The results suggested that biomass char promoted the decomposition of

48 most oxygenated compounds in the tar at the char bed temperatures of 500 oC and 600 oC.

49 Different coal chars also lowered the heavy tar yield at 550 oC. Han et al. [19] found that the coal

50 pyrolysis with a succedent secondary upgrading over a layer of coal char in a two-stage fixed bed

51 reactor at 600 oC resulted in lower total tar yield and higher non-condensable gas yield, but the

52 light tar component was obviously increased. They further revealed that both pore structures and

53 ash of char had effect on the tar catalytic conversion during volatiles-char interaction [20]. In most

54 of the cases, as mentioned above, a two-stage fixed bed reactor consisting of one reactor for

55 pyrolysis and the other packed with char for volatiles upgrading was used. As the volatiles-char

56 interaction can cause significant changes to the char porous structures and surficial functional

57 groups [21-23], it is reasonable to say that the char samples at varied layer of the fixed bed are

58 different. To understand the tar upgrading based on analyses of the char samples, a continous tar

59 upgrading reactor is a better choice. However, little is currently known in this area, especially the

60 effects of consecutive char on the forming and upgrading of hot biomass pyrolysis oil under

61 moderate conditions.

62 In this study, to reach a better understanding on the volatiles-char interaction at a steady state, a

63 coal char was prepared in the present work firstly considering the yield of low-rank coal char is

64 relatively high compared to that derived from biomass because of the higher fixed carbon level in

65 coal in addition to the potential catalytic activity. And then fast pyrolysis of a woody biomass in a

66 free fall reactor and upgrading of the derived bio-oil over the coal char in a moving bed reactor

67 down-stream the free fall reactor were performed. The effects of char updating rate on the product

3
68 distribution and bio-oil quality were investigated. The evolution of coal char structure was

69 characterized by Brunauer-Emmett-Teller (BET), X-ray powder diffractions (XRD) and Fourier

70 transform infrared (FT-IR) analyses.

71 2. Experimental

72 2.1. Biomass sample and coal char preparation

73 The biomass feedstock for pyrolysis in the free fall reactor is sawdust (SD) from Dalian, China.

74 The air-dried sample was pulverized and sieved to obtain a fraction with uniform particle sizes

75 between 0.25 and 0.38 mm. The sample was oven-dried at 105 oC for 4 h before experiments.

76 The coal char used in the moving bed reactor was produced by pyrolyzing Shenmu bituminous

77 coal (SM, from Shanxi, China) in an electrically heated rotary kiln. About 300 g of the oven-dried

78 SM was pre-loaded in the kiln. The kiln was then heated up at 10 °C/min to 800 °C and held at

79 this temperature for 60 min. Finally, the kiln was cooled down to room temperature. The char

80 sample collected was sieved to get the fraction of the particle sizes of 0.38~0.83 mm, which was

81 named as SMC. Table 1 shows the proximate and ultimate analyses of SD and SMC. The

82 compositions of SMC ash are listed in Table 2.

83 2.2. Experimental apparatus and methods

84 Experiments were carried out in an integrated pyrolysis and upgrading reaction system, as

85 shown in Fig. 1, consisting of a free fall reactor for biomass pyrolysis and a countercurrent

86 moving bed reactor for the biomass pyrolysis oil upgrading. The free fall reactor is a modification

87 of the one employed in our previous work [24]. It is composed of a feeding unit, a drop tube and a

88 gas-solid separation system, and all of them are made of 316L stainless steel. Biomass is fed into

89 the drop tube by a screw feeder in which a churn-dasher is set to avoid the bridging of biomass.

4
 90 The drop tube with an i.d. of 26 mm and a heating length of 1900 mm is heated by six independent

91 electrical heaters. At the bottom of the drop tube, volatiles and pyrolyzed char are separated in the

92 gas-solid separator. The moving bed reactor is composed of a hopper and an upgrading reactor

93 tube. The upgrading reactor tube with 26 mm i.d. and 370 mm length is heated by an electric

94 heater. The SMC was used as the bed material of the upgrading reactor. It was maintained 10 cm

95 in height and its updating rate was controlled by adjusting the rotation speed of the rotary valve,

96 thus the residence time of SMC could be controlled and a steady state char bed could be formed

97 inside the upgrading reactor. The residence times of SMC corresponding to different updating

98 rates were determined through a series of cold state tests. The ratio of the added char mass to the

99 updating rate was the corresponding char residence time. In the system, a K-type thermocouple is

100 inserted in the middle of each heater closing to the outer wall of the reactor tube. The temperature

101 signals at different heights inner the reactor tubes are monitored and recorded as well by a

102 computer.

103 Prior to test, a stream of nitrogen gas of 400 mL/min was introduced into the system at the top

104 of the free fall reactor tube to insure the system was air-free. Under the nitrogen flow, the reactors

105 were heated up to the prescribed temperatures, i.e. 560 °C for the free fall reactor and 500 °C for

106 the moving bed reactor loaded with the SMC. Then the SD particles were fed into the free fall

107 reactor at a rate of 120 g/h. Meanwhile, the char bed of the upgrading reactor started to move at a

108 preset rate. During the experiment, the pressure of the reactor was controlled at atmospheric

109 pressure by a vacuum pump at the system terminal. With the help of the vacuum pump, the

110 volatiles from the free fall reactor were countercurrently passed through the moving char bed,

111 where the biomass derived bio-oil was upgraded. The product gas was then passed through four

5
112 condensers in series to capture the liquid products in the gas. To ensure a complete collection of

113 liquid products, the first condenser was cooled by ice water and the other three by glycol of -15

114 oC. In the first three collection bottles there was each 100 mL dichloromethane (CH2Cl2) to absorb

115 the oil entrained in the gas. A cotton filter was used to capture the remained aerosol in the

116 non-condensable gas. The product gas was further moved to a wet gas meter to measure its total

117 volume and analyzed by GC in every 10 min. Every experimental run was kept for about 2 h at a

118 steady state without intervals. After each experiment, CH2Cl2 was used to wash the connecting

119 pipelines and liquid product collectors. The recovered liquid was placed in a separating funnel.

120 Then stratification occurred, giving the upper water phase and the lower oil phase. Water content

121 in the water phase was determined by azeotropic distillation with toluene. The content of water

122 soluble matter was also obtained. The bio-oil component was considered in a water-free basis and

123 denoted as bio-oil*. The CH2Cl2 soluble matter (light bio-oil*) was recovered by evaporating the

124 CH2Cl2 in the oil phase under vacuum at 28 oC in a rotary evaporator. After that, tetrahydrofuran

125 (THF) was used to wash the entire pipelines and collectors which had been washed by CH2Cl2.

126 The heavy bio-oil* was recovered by evaporating THF under vacuum at 35 oC in the rotary

127 evaporator. The sum of water soluble, CH2Cl2 soluble and THF soluble mass was defined as the

128 bio-oil* output. The fast pyrolysis char and the used SMC were collected and weighed.

129 2.3. Product characterization

130 2.3.1 Product gas analysis

131 The product gas was off-line analyzed by a GC7890II gas chromatograph equipped with TCD

132 and FID detectors. In this paper, the light hydrocarbon gases C2H4, C2H6, C3H6 and C3H8 are

133 overall shown as C2+ hydrocarbons.

6
134 2.3.2 Bio-oil* analysis

135 The analysis of the CH2Cl2 soluble of the produced bio-oil* was performed by GC-MS using an

136 Agilent-5975C gas chromatograph equipped with a HP-5MS capillary column (30 m×0.25

137 mm×0.25 μm). Helium was used as the carrier gas. The operation conditions of the mass

138 spectrometer were as follows: electron impact mode, 70 eV; ion source temperature, 230 oC;

139 quadruple spectrometer temperature, 150 °C. The injector temperature was 320 oC and the column

140 temperature was programmed to start at 50 oC for 3min, and then heated up to 300 oC at a heating

141 rate of 5 oC/min and held for 10min. Chemical compounds corresponding to each peak in the

142 chromatogram were identified by using NIST98 mass spectral database.

143 1H-NMR (400 MHz) spectra of the CH2Cl2 soluble was obtained with a Varian Inova 400

144 spectrometer at an operating temperature of 25 oC. The samples were prepared by dissolving the

145 CH2Cl2 soluble in CDCl3, using TMS of g/mL as an internal reference.

146 2.3.3 Coal char characterization

147 The specific surface area, pore volume and pore size of the fresh and spent SMC were measured

148 by N2 adsorption at -196 oC using a JWBK-122W analyzer. The samples were degassed at 150 °C

149 for 2 h prior to N2 adsorption. The Brunauer-Emmett-Teller (BET) method was used to calculate

150 the specific surface area (SBET). The total pore volume (Vt) was calculated by the equilibrium

151 adsorption amount of nitrogen when the relative pressure (P/Po) is close to 1.00. The micropore

152 volume (Vmic) and pore size distribution were determined by HK and BJH method, respectively.

153 The functional groups of the SMC were analyzed using an EQUINOX55 Fourier transform

154 infrared (FT-IR) spectrometer. All spectra were obtained at a resolution of 4 cm-1 in the

155 wavenumber range of 500~4000 cm-1.

7
156 X-ray diffraction (XRD) patterns were characterized using an X-ray diffractometer

157 (D/Max-2400, Rigaku) with a Cu Kα radiation (λ=0.154 nm, 40 kV, 100 mA). The scan angle was

158 ranging from 10 o~50o with a step size of 4 °/min.

159 2.4. Calculating method of product yields

160 The fast pyrolysis product yields of SD are based on dry ash-free basis (daf), and the calculation
161 methods are as follows:

mC H Cl soluble
YC H Cl soluble
= 2 2
 100% (1)
2 2
m(1 - A)

mWater soluble
YWater soluble =  100% (2)
m( 1 - A )

mTHF soluble
YTHF soluble   100% (3)
m( 1  A )

YBio-oil* = YC H 2 Cl2 soluble + YWater soluble + YTHF soluble (4)

mWater
YWater =  100% (5)
m( 1 - A )

162 where YC H 2 Cl2 soluble , YWater soluble , YTHF soluble , YBio-oil* and YWater is the product yield (%) of

163 CH2Cl2 soluble, water soluble, THF soluble, bio-oil* and water, respectively; mC H 2 Cl2 soluble ,

164 mWater soluble , mTHF soluble and m Water is the product mass (g) of CH2Cl2 soluble, water soluble,

165 THF soluble and water, respectively; m is the dry basis raw material mass (g); A is the ash content
166 of dry basis raw material (wt.%).

mgas
Ygas = 100% (6)
m( 1- A )

mgas =mj (7)

PVg xjM j
mj = (8)
RT

167 where YGas is the gas product yield (%); mgas is the total mass (g) of the gas product；mj, xj and Mj is

168 the mass (g), volume fraction (vol.%) and molar mass (g/mol) of the component j in the gas
169 product, respectively; P is the gas product pressure, namely atmospheric pressure (101.3 kPa); Vg

8
170 is the total gas volume (L); R is the gas constant of 8.314 J·mol-1·K-1; T represents the temperature
171 (K).
172 ωlight bio-oil* and ωchar is the light bio-oil* content (%) and change of coal char mass (%) before
173 and after reacting with volatiles respectively, which can be calculated by Eqs. (9) and (10):

YC H Cl
light tar = 2 2 soluble
 100% (9)
YBio oil*

mspent, char - mfresh, char

char =  100% (10)
mfresh, char
174 where mspent, char and mfresh, char is the coal char mass (g) after and before reacting with volatiles.

175 3. Result and discussion

176 3.1. Product distribution passed through the coal char bed

177 The biomass pyrolysis volatiles from the free fall reactor were upgraded over the moving bed

178 with SMC as the bed material. The updating rates of SMC were 1, 2 and 4 g/min, corresponding to

179 the char residence time of 60, 30 and 15 min, and denoted as SMC-1, SMC-2 and SMC-4,

180 respectively. For comparison, product distribution without SMC loading in the upgrading reactor

181 was also provided.

182 As shown in Fig. 2, secondary reactions of volatiles happened over SMC. Compared that

183 without SMC, the bio-oil* yield is lower and the gas and water yields are higher in the presence of

184 SMC. Moreover, the bio-oil* yield decreases and the gas and water yields increase with the

185 increase of the char updating rate. These data indicate that the upgrading led to the destruction of

186 bio-oil*. During volatiles-char interaction, the secondary reactions of bio-oil*, i.e. decomposition

187 and polymerization reactions could occur, resulting in the decreased bio-oil* yield. And the higher

188 char updating rate means the more active sites of SMC provided, thus the destruction of the

189 bio-oil* was enhanced. As a result, the formation of gas and water were increased.

190 The information about the evolution of small molecule gases along with conversion of bio-oil*

191 is helpful to understand the relevant mechanism of bio-oil* destruction in the upgrading process.
9
192 As is shown in Fig. 3, the yields of H2, CO, CH4 and CO2 increase after the volatiles reacted with

193 SMC at the char updating rate of 1 g/min. All of them show an increasing trend with increasing

194 the char updating rate from 1 g/min to 4 g/min. The yield for C2+ hydrocarbons changes little in

195 the absence and presence of SMC. In the volatiles-char interaction, a complex reaction system was

196 formed by char and water, bio-oil*, H2, CO, CO2, CH4, which is characterized by the co-existence

197 of multi-component and multi-reaction. In this process, more H2 was mainly generated from the

198 bio-oil* polymerization and dehydrogenation reactions [25]. And the element O in the bio-oil*

199 was transmitted into pyrolysis gas in the form of CO and CO2. Besides, the water gas shift

200 reaction could also result in the change of H2, CO and CO2. It is usually thought that CH4 mainly

201 comes from the decomposition of aliphatic side chains of aromatic compounds and -OCH3 [26].

202 That is, the volatiles-char interaction facilitated the bio-oil* upgrading into small molecule gases

203 by deoxygenating and dealkylating. The variations of gas components yields indicate that the

204 reactivity of bio-oil* with char increased with increasing the char updating rate as mentioned

205 above.

206 Fig. 4 shows the yields of bio-oil* components and light bio-oil* content produced from the fast

207 pyrolysis of SD with and without the subsequent interaction with SMC. At the char updating rate

208 of 1g/min, all the bio-oil* components decrease after interacting with the SMC. The destruction of

209 the bio-oil* components are enhanced with increasing the char updating rate from 1 g/min to 4

210 g/min. Meanwhile, the light bio-oil* content increases a lot by introducing the SMC while the

211 content of the light bio-oil* remains almost constant with the increase of char updating rate over

212 1g/min further. The evolution of the raw as produced bio-oil over char is somewhat different from

213 the tar reforming process [27]. In general, the light bio-oil* and water soluble riched in the

10
214 relatively unstable oxygen-containing compounds could be easily cracked into non-condensable

215 gas and water by deoxygenation, confirmed by the increased gaseous products especially CO2 and

216 water yields in the presence of SMC. Compared with the light bio-oil*, the heavy bio-oil*

217 contains the larger aromatics and tended to adsorb on char surface and/or pore, followed by further

218 condensation-hydrogen elimination reactions into coke [25, 28]. As a result, the formation of H2

219 was improved, which is consistent with the significant increase in H2 yield after the volatiles

220 reacted with SMC. And the content of the light bio-oil* increased accordingly. This result

221 indicates that the quality of the bio-oil* was improved due to the selective volatiles upgrading

222 over the SMC. Nevertheless, the trend in the destruction of heavy bio-oil* over SMC is different

223 from that of light bio-oil* with the increase of char updating rate: the destruction trend of heavy

224 bio-oil* reduces obviously while the light bio-oil* shows an opposite trend. This result indicates

225 that the SMC was sufficient for the heavy bio-oil* adsorption and further conversion at the char

226 updating rate of 1g/min, due to the certain amount of heavy bio-oil* in the volatiles. Therefore, the

227 SMC showed insignificant effect on the further destruction of heavy bio-oil* by increasing char

228 updating rate. And the increment of H2 yield decreased accordingly as shown in Fig. 3. In

229 addition, it is speculated that the cracking capacity of the SMC on the light bio-oil* was enhanced

230 due to the increased active sites at higher char updating rates.

231 3.2. Bio-oil* variation after the upgrading reactor

232 To further investigate the influence of SMC on the upgrading of bio-oil, GC/MS analysis was

233 carried out to identify the chemical compositions of light bio-oil* and their relative abundances in

234 the absence and presence of SMC. According to the similarity of molecular structure, the detected

235 compounds in the light bio-oil* are divided into several categories, including benzenes, phenols,

11
236 naphthalenes and et al, as shown in Table 3. Phenol compounds are the main compositions in the

237 bio-oil*. These results indicate that the biomass pyrolysis oil contains much O-containing

238 compounds as depicted above.

239 From Table 3, it can be seen that as to the light bio-oil* from SD pyrolysis obtained with and

240 without SMC, the compound species have little difference, whereas the upgrading leads to the

241 compounds proportions change obviously in comparison with that without SMC. For example, the

242 content of catechols decreases significantly while the biphenyl is observed after the volatiles

243 reacted with SMC. In addition, the content of dihydronaphthalene is lower and the content of long

244 chain hydrocarbon is much higher than that in the absence of SMC. These trends are enhanced

245 with increasing char updating rate. During volatiles-char interaction, large amounts of active

246 intermediates could be produced as a result of the cracking of bio-oil*. In this process, the

247 newly-formed radicals could recombine to form biphenyl and long chain hydrocarbon. At the char

248 updating rate of 1g/min, the contents of O-containing compounds except for catechols show no

249 obvious change. The contents of catechols, phenols and aliphatic-O decrease while the contents of

250 naphthols and aromatic-O increase with the increase of char updating rate. Nevertheless, the total

251 content of O-containing compounds decreases evidently, as is shown in Fig. 5. These date reveal

252 that the ability of SMC to remove oxygen was improved by increasing char updating rate. As is

253 mentioned above, the SMC was sensitive to unstable oxygenated compounds and played a

254 deoxygenation role, capturing the oxygen in bio-oil* and leading to re-distribution of oxygen

255 during volatiles-char interaction. The oxygen was removed from bio-oil* with the formation of

256 CO2, CO and water. Meanwhile, the aromatic radical intermediates resulted from the cracking of

257 bio-oil* could combine to form newly aromatic compounds. This may be account for the

12
258 increased naphthols and aromatic-O. Compared with that without SMC, the proportions of

259 benzenes and naphthalenes decrease after the volatiles reacted with SMC at the char updating rate

260 of 1g/min. At the higher char updating rate, these variations exhibit opposite trend. These results

261 indicate that benzenes and naphthalenes aromatic hydrocarbons could be converted during

262 volatiles-char interaction. With increasing the char updating rate, the removal of hydroxyl and

263 alkyl side chains of bio-oil* over SMC involved the transformation of newly-formed active

264 intermediates into aromatic compounds, could lead to the increased benzenes and naphthalenes.

265 Besides, the presence of SMC decreases the content of N-containing compounds. This means that

266 the volatiles-char interaction was beneficial to remove heteroatom N from the light bio-oil*,

267 leading to improve in bio-oil* quality.

268 The results of hydrogen distribution of the light bio-oil* obtained by 1H-NMR spectroscopy are

269 given in Table 4. 1H-NMR spectra can be divided into three main regions: aromatic, phenolic

270 (OH) and aliphatic, basing upon the chemical shifts of specific proton types [29, 30]. Aromatic

271 protons (HAr), phenolic (OH) protons (HHy) and aliphatic protons (HAl) exist in the ranges of

272 6.4~8.3, 4.3~6.4 and 0.5~4.3 ppm, respectively. For aromatic protons, the uncondensed and

273 condensed aromatic protons are presented as HArU and HArC, respectively. The uncondensed

274 aromatic protons are mainly mono-aromatic structures, and the condensed aromatic protons are

275 mainly di-aromatic structures. The aliphatic protons are divided into three species: Hα, Hβ and Hγ.

276 Hα is assigned to the CH3 groups in α position to the aromatic ring and CH-C(O), the CH-C(O)

277 means the protons in CHx groups bounding to O-containing groups. Hβ is the protons in β position

278 or further away from the aromatic ring and CH2 groups in the long chain saturated hydrocarbons.

279 Hγ is assigned to CH3 groups in γ position or further away from the aromatic ring and CH3 groups

13
280 in the long chain saturated hydrocarbons.

281 From Table 4, it can be seen that the light bio-oil* from SD pyrolysis mainly contains aliphatic

282 protons, indicating that most of aromatic rings in the light bio-oil* are substituted by alkyl. At the

283 same time, it is hence reasonable to conclude that the uncondensed aromatic compounds are much

284 more substituted than the condensed aromatic compounds, due to there are more mono-aromatic

285 structures than poly-aromatic structures as shown in Table 3, while the proportion of HArU is

286 nearly equal to HArC. From Table 4, it can also be seen that in the presence of SMC, the content

287 of aliphatic protons increases, while the phenolic (OH) protons decreases, which is in agreement

288 with the result that the reduction of phenol compounds determined by GC-MS. These imply that

289 the light bio-oil* reacted with SMC contains less amount of oxygen. In the upgrading process,

290 with the increase of char updating rate from 1g/min to 4g/min, the deoxygenation reaction was

291 enhanced, leading to a continuous decrease in phenolic (OH) protons.

292 3.3. Coal char changes by contacting with the volatiles

293 Fig. 6 shows the determined SMC weight increased ratio at different char updating rates. The

294 weight of SMC increases after interacting with the volatiles at the char updating rate of 1g/min.

295 The increased ratio decreases with increasing the char updating rate further. These data confirm

296 that the coke was formed from the bio-oil* polymerization at the experimental conditions. In the

297 upgrading process, the heavy component containing the larger aromatic ring systems had higher

298 tendency to form coke than the light component [31]. The condensation-hydrogen elimination

299 reactions proceeded along with the formation of aromatic precursors of coke [24]. Thus the

300 upgrading yielded much more H2 than that without SMC. This also provides a plausible

301 explanation to the higher conversion of heavy bio-oil* over SMC than that of light bio-oil* at the

14
302 char updating rate of 1 g/min. The change of heavy bio-oil* yield shows that the amount of coke

303 in the SMC structures decreases by increasing char updating rate. As a result, the increased ratio

304 of SMC weight decreased. This data was also corresponding to the variation of H2 yield.

305 Table 5 presents the porous structure characteristics of the SMC before and after reacting with

306 volatiles. Char itself exhibits some reaction activity being influenced by pore size, surface area of

307 char. The char has larger specific surface area that is conducive to the effective collision of

308 volatiles and active sites, which improve the activity accordingly. From Table 5, after interacting

309 with the volatiles, the specific surface area, microspore volume and total pore volume of SMC

310 decrease sharply and the average pore diameter increases in comparison with that of the fresh

311 SMC. This result shows that the porous structure of SMC provided reaction sites for the bio-oil

312 upgrading, and the volatiles-char interaction in turn caused significant change in the pore structure

313 parameters of SMC. During volatiles-char interaction, it is generally believed that the coke formed

314 from the polymerization of heavy bio-oil* components accumulated on the char surface and in the

315 pores, which could block the pores and cause loss of micropores, and this should be mainly

316 responsible for the reduction in specific surface area and the increase of average pore diameter

317 [32, 33]. With increasing the char updating rate, the effect of SMC on the secondary reactions of

318 bio-oil* was enhanced due to the increased active sites, while the further destruction of heavy

319 bio-oil* was small as indicated in Fig.4. Thus, the variations of surface area and pore volumes of

320 the SMC decreased.

321 To further investigate the function of SMC on the bio-oil upgrading, the FT-IR spectra of the

322 fresh and spent SMC are compared in Fig. 7. It can be seen that the SMC is carbonized more

323 completely, mainly containing carbon, as indicated in Table 1. Thus the SMC shows higher

15
324 aromaticity and lower polarity. The band at 3200~3600 cm-1 represents the O-H streching

325 vibration. The peaks in the range of 2840~3000 cm-1 are attributed to the stretching vibrations of

326 aliphatic C-H. In addition, the overlapping peaks which form an absorption band in the 960~1200

327 cm-1 region can be assigned to the stretching vibration peak of C-O-C and quartz Si-O-Si

328 anti-symmetric stretching vibration [22]. These peaks show no obvious change after the SMC

329 reacted with volatiles and no new absorption bands are found in the spent SMC. More specially,

330 there are no C=C skeleton stretching vibration peaks in the vicinity of 1500 and 1600 cm-1 and

331 C-H bending vibration peaks in the range of less than 1000 cm-1 of aromatic structures are found.

332 These observations show that the formed coke mainly contains the aromatics with little hydrogen

333 as a result of the highly polymerization of heavy component [34].

334 Fig. 8 shows the XRD patterns of the fresh and spent SMC. The sharp peaks are attributed to

335 minerals in the ash of SMC as seen in Table 2. Compared to the XRD pattern of the fresh char, the

336 Fe3O4 peaks at 2θ=35.2°, 42.8° are observed in the spent SMC, indicating that the volatiles from

337 SD pyrolysis promoted the oxidation of α-Fe to Fe3O4. Carbon peak at 2θ≈25° (corresponding to

338 (002) band) can also be seen in the XRD patterns of the SMC before and after reacting with the

339 volatiles, which can illustrate how the carbon crystalline structure of SMC changes during

340 volatiles-char interaction. The (002) peak of carbon is attributed to the stacking structure of

341 aromatic layers. In general, soft and broad peaks in XRD pattern indicate the existence of

342 short-range order in the carbon structures, whereas sharp and narrow bands correspond to the

343 highly crystalline with high degree of long-range order. As shown in Fig. 8, the intensity of (002)

344 peak in the spent SMC shows an increasing trend in comparison with the fresh SMC. It can be

345 deduced that the order degree of SMC phase structure increased as a result of the ordered coke

16
346 formed from the heavy bio-oil* polymerization.

347 Structural parameters of the SMC including interlayer spacing d002 and average stacking height

348 Lc are obtained with the classic Bragg’s equation and Scherrer’s formula [35] and listed in Table

349 6. The d002 represents the interlayer spacing of the stacking structures of aromatic layers. The

350 increase of Lc results from crystallite growth and coalescence of crystallite. Table 6 shows that

351 d002 has no change but Lc increases after the SMC reacted with volatiles. And the increment of Lc

352 is decreased with increasing char updating rate. These results show that the microcrystalline size

353 of the SMC phase structure was increased by the polymerization and coke forming of the bio-oil*.

354 The coking degree of SMC decreased with the increase of char updating rate, and thus the

355 influence of the secondary reactions of volatiles on the SMC crystal structure was weakened.

356 4. Conclusion

357 In this paper, to reach a better understanding on the volatiles-char interaction at a steady state,

358 fast pyrolysis of SD in a free fall reactor and upgrading of the derived bio-oil over SMC in a

359 moving bed reactor down-stream the free fall reactor were performed. It was found that the SMC

360 had shown encouraging results for the bio-oil* upgrading. At the char updating rate of 1 g/min, the

361 upgrading improved the quality of the bio-oil* by decreasing the yields of water soluble and heavy

362 bio-oil* and increasing the content of light bio-oil*. And the derived light bio-oil* contained less

363 oxygen and nitrogen containing compounds. With increasing the char updating rate further, the

364 relatively fresh SMC surface led to the increased active sites, the conversion of heavy bio-oil* was

365 slightly promoted and the removal effects of heteroatoms (O, N) compounds in the light bio-oil*

366 were enhanced. It could effectively reduce the generation of heavy bio-oil* and regulate the

367 deoxygenation and denitrification degree of bio-oil* at the same time by adjusting the char

17
368 updating rate, so as to obtain the higher yield and quality bio-oil*. The analyses results of SMC

369 before and after reacting with volatiles showed that the porous structure provided reaction active

370 sites for the bio-oil upgrading. Meanwhile, the highly condensed coke formed from the

371 polymerization of the heavy bio-oil* blocked the pores, resulting in the specific surface area of

372 SMC decreased significantly. The amount of the coke in the SMC structures reduced with

373 increasing the char updating rate, and thus the variations of pore structure parameters of SMC

374 were weakened.

375 Acknowledgments

376 This work was financially supported by the National Key Research and Development Program

377 (No. 2016YFB0600304).

378 References

379 [1] F. Li, S.C. Srivatsa, S. Bhattacharya, A review on catalytic pyrolysis of microalgae to

380 high-quality bio-oil with low oxygeneous and nitrogenous compounds, Renewable & Sustainable

381 Energy Reviews, 108 (2019) 481-497.

382 [2] P.M. Mortensen, J.D. Grunwaldt, P.A. Jensen, K.G. Knudsenc, A.D.Jensen, A review of

383 catalytic upgrading of bio-oil to engine fuels, Applied Catalysis A General, 407 (2011) 1-19.

384 [3] M.W. Nolte, J. Zhang, B.H. Shanks, Ex situ hydrodeoxygenation in biomass pyrolysis using

385 molybdenum oxide and low pressure hydrogen, Green Chemistry, 18 (2015) 134-138.

386 [4] Z. Yang, J. Zhang, J. Huang, G. Qian, X. Duan, X. Zhou, In-Situ Catalytic Upgrading of Tar

387 and Coke during Biomass/Coal Co-Pyrolysis, Industrial & Engineering Chemistry Research,

388 (2020) accepted.

389 [5] G. Bharath, A. Hai, K. Rambabu, F. Banat, R. Jayaraman, H. Taher, J. Bastidas-Oyanedel,

18
390 M.T. Ashraf, J.E. Schmidt, Systematic production and characterization of pyrolysis-oil from date

391 tree wastes for bio-fuel applications, Biomass and Bioenergy, 135 (2020) 105523.

392 [6] Q. Lu, W.Z. Li, X.F. Zhu, Overview of fuel properties of biomass fast pyrolysis oils, Energy

393 Conversion & Management, 50 (2009) 1376-1383.

394 [7] P. Kaewpengkrow, D. Atong, V. Sricharoenchaikul, Effect of Pd, Ru, Ni and ceramic supports

395 on selective deoxygenation and hydrogenation of fast pyrolysis jatropha residue vapors,

396 Renewable Energy, 65 (2014) 92-101.

397 [8] Y. Zhao, L. Deng, B. Liao, Y.J. Fu, Aromatics Production via Catalytic Pyrolysis of Pyrolytic

398 Lignins from Bio-Oil, Energy Fuels, 24 (2010) 5735-5740.

399 [9] C. Hu, R. Xiao, H. Zhang, Ex-situ catalytic fast pyrolysis of biomass over HZSM-5 in a

400 two-stage fluidized-bed/fixed-bed combination reactor, Bioresource Technology, 243 (2017)

401 1133.

402 [10] V.K. Venkatakrishnan, W.N. Delgass, F.H. Ribeiro, R. Agrawal, Oxygen removal from intact

403 biomass to produce liquid fuel range hydrocarbons via fast-hydropyrolysis and vapor-phase

404 catalytic hydrodeoxygenation, Green Chemistry, 17 (2014) 178-183.

405 [11] J. Fermoso, H. Hernando, S. Jiménez-Sánchez, A.A. Lappas, E. Heracleous, P. Pizarro, J.M.

406 Coronadoa, D.P. Serrano, Bio-oil production by lignocellulose fast-pyrolysis: Isolating and

407 comparing the effects of indigenous versus external catalysts, Fuel Processing Technology, 167

408 (2017) 563-574.

409 [12] L. Jin, X. Bai, Y. Li, C. Dong, H. Hu, X. Li, In-situ catalytic upgrading of coal pyrolysis tar

410 on carbon-based catalyst in a fixed-bed reactor, Fuel Processing Technology, 147 (2016) 41-46.

411 [13] M. Wang, L. Jin, Y. Li, J. Wang, In situ catalytic upgrading of coal pyrolysis tar over

19
412 carbon-based catalysts coupled with CO2 reforming of methane, Energy & Fuels, 31 (2017)

413 9356-9362.

414 [14] S. Meesuk, J.P. Cao, K. Sato, Y. Ogawa, T. Takarada, The effects of temperature on product

415 yields and composition of bio-oils in hydropyrolysis of rice husk using nickel-loaded brown coal

416 char catalyst, Journal of Analytical & Applied Pyrolysis, 94 (2012) 238-245.

417 [15] H. Zhao, Q. Song, S. Liu, Y. Li, X. Wang, X.Shu, Study on catalytic co-pyrolysis of physical

418 mixture/staged pyrolysis characteristics of lignite and straw over an catalytic beds of char and its

419 mechanism, Energy Conversion & Management, 161 (2018) 13-26.

420 [16] P. Gilbert, C. Ryu, V. Sharifi, J. Swithenbank, Tar reduction in pyrolysis vapours from

421 biomass over a hot char bed, Bioresource Technology, 100 (2009) 6045.

422 [17] M.L. Boroson, J.B. Howard, J.P. Longwell, W.A. Peters, Heterogeneous cracking of wood

423 pyrolysis tars over fresh wood char surfaces, Energy Fuels, 3 (1989) 735-740.

424 [18] Q. Sun, S. Yu, F. Wang, J. Wang, Decomposition and gasification of pyrolysis volatiles from

425 pine wood through a bed of hot char, Fuel, 90 (2011) 1041-1048.

426 [19] J. Han, X. Wang, J. Yue, S. Gao, G. Xu, Catalytic upgrading of coal pyrolysis tar over

427 char-based catalysts, Fuel Processing Technology, 122 (2014) 98-106.

428 [20] J. Han, S. Liu, S. Shen, Catalytic cracking of in situ coal pyrolysis tar over char catalyst,

429 Modern Chemical Industry, 37 (2017) 62-65.

430 [21] D.Q. Fu, X.H. Li, W.Y. Li, J. Feng, Catalytic upgrading of coal pyrolysis products over

431 bio-char, Fuel Processing Technology, 176 (2018) 240-248.

432 [22] D. Feng, Y. Zhao, Y. Zhang, J. Gao, S. Sun, Changes of biochar physiochemical structures

433 during tar H2O and CO2, heterogeneous reforming with biochar, Fuel Processing Technology,

20
434 165 (2017) 72-79.

435 [23] Y. Song, Y. Zhao, X. Hu, L. Zhang, S. Sun, C. Li, Destruction of tar during volatile-char

436 interactions at low temperature, Fuel Processing Technology, 171 (2018) 215-222.

437 [24] J. Zhang, C. Quan, Y. Qiu, S. Xu, Effect of char on co-pyrolysis of biomass and coal in a free

438 fall reactor, Fuel Processing Technology, 135 (2015) 73-79.

439 [25] W.G. Appleby, J.W. Gibson, G.M. Good, Coke formation in catalytic cracking, Industrial &

440 Engineering Chemistry Process Design & Development, 1(1962) 102-110.

441 [26] K. Xie, Coal structure and its reactivity, Science Press, Beijing, 382 (2002).

442 [27] D. Feng, Y. Zhao, Y. Zhang, S. Sun, Effects of H2O and CO2 on the homogeneous

443 conversion and heterogeneous reforming of biomass tar over biochar, International Journal of

444 Hydrogen Energy, 42 (2017) 3070-13084.

445 [28] S. Li, S. Zhang, Z. Feng, Y. Yan, Coke formation in the catalytic cracking of bio-oil model

446 compounds, Environmental Progress & Sustainable Energy, 34 (2015) 240-247.

447 [29] M.J. Iglesias, M.J. Cuesta, I. Suárez-Ruiz, Structure of tars derived from low-temperature

448 pyrolysis of pure vitrinites: influence of rank and composition of vitrinites, Journal of Analytical

449 & Applied Pyrolysis, 58 (2001) 255-284.

450 [30] F. Ateş, A.E. Pütün, E. Pütün, Catalytic pyrolysis of perennial shrub, euphorbia rigida, in the

451 water vapour atmosphere, Journal of Analytical & Applied Pyrolysis, 73 (2005) 299-304.

452 [31] Y. Song, J. Xiang, S. Hu, D.M. Quyn, Y. Zhao, X. Hu, Y. Wang, C. Li, Importance of the

453 aromatic structures in volatiles to the in-situ destruction of nascent tar during the volatile-char

454 interactions, Fuel Processing Technology, 132 (2015) 31-38.

455 [32] S. Hosokai, K. Kumabe, M. Ohshita, K. Norinaga, C.Z. Li, J. Hayashi, Mechanism of

21
456 decomposition of aromatics over charcoal and necessary condition for maintaining its activity,

457 Fuel, 87 (2008) 2914-2922.

458 [33] Z. Chen, Y. Wang, D. Xu, X. Xu, Changes in char properties after catalytic reforming

459 volatiles from pyrolysis of brown coal, Journal of Fuel Chemistry and Technology, 45 (2017)

460 908-915.

461 [34] G. Chen, X. Zhang, Z. Mi, Effects of pressure on the coke and its precursors formation during

462 catalytic cracking of toluene over USY catalyst, Journal of fuel chemistry and technology, 35

463 (2007) 211-216.

464 [35] J. Hu, J. Shao, H. Yang, G. Lin, Y. Chen, X. Wang, W. Zhang, H. Chen, Co-gasification of

465 coal and biomass: synergy, characterization and reactivity of the residual char, Bioresource

466 Technology, 244 (2017) 1.

22
468 Table 1. Proximate and ultimate analyses of SD and SMC.

Proximate analysis (wt.%） Ultimate ananlysis (wt.%)

Samples
Mad Ad Vdaf Cdaf Hdaf Ndaf Odaf1) St,d
SD 10.97 0.37 86.02 50.03 6.23 0.13 43.43 0.18
SMC 0.54 15.94 3.67 94.94 1.03 1.09 1.93 0.84

469 1）by difference

23
471 Table 2. XRF analysis of SMC ash.

Component CaO SiO2 MgO Al2O3 K2O Na2O SO3 MnO Fe2O3 Others
Composition (wt.%, d) 27.05 10.50 2.44 3.85 0.19 0.87 9.75 1.22 43.20 0.93
472

24
474 Table 3. GC-MS analysis of CH2Cl2 soluble in the produced bio-oil*.

Relative content (area, %)

Category
without
SMC-1 SMC-2 SMC-4
SMC
Benzenes 13.62 11.47 11.82 12.71
Phenols 28.00 28.80 26.13 25.13
Catechols 36.08 33.69 30.51 23.47
Dihydronaphthalene 2.62 2.20 2.06 1.15
Naphthalenes 2.95 2.32 3.84 5.35
Naphthols 2.81 3.05 5.07 6.27
Fluorene 0.49 0.31 0.35 0.44
Biphenyl - 0.26 0.91 2.49
Anthracenes 0.29 0.32 0.41 0.45
Phenanthrene 0.27 0.34 0.32 0.45
Aromatic-O1) 6.50 6.56 7.73 9.93
Aliphatic-O2) 4.06 4.88 4.38 3.91
Long chain hydrocarbon 1.03 4.95 5.74 7.5
Compounds-N3) 0.54 0.31 0.17 0.15
others 0.74 0.54 0.56 0.6

475 1) Aromatic compounds containing complex oxygen; 2) Aliphatic compounds containing oxygen; 3) Compounds

476 containing nitrogen.

477

25
479 Table 4. Proton distribution of CH2Cl2 soluble in the produced bio-oil* (%).

Proton type (ppm) without SMC SMC-1 SMC-2 SMC-4

HAr (6.4-8.3) 27.97 27.34 27.74 28.55

HArU1) (6.4-7.2) 13.79 12.84 10.32 8.64
HArC1) (7.2-8.3) 14.18 14.5 17.42 19.91
HHy (4.3-6.4) 14.53 10.59 9.05 6.07
HAl (0.5-4.3) 57.5 62.07 63.21 65.38
Hγ2) (0.5-1.2) 7.81 9.11 9.66 10.35
Hβ2) (1.2-2.1) 16.7 19.66 20.49 21.94
Hα2) (2.1-4.3) 32.99 33.3 33.06 33.09
HAr/HAl 0.49 0.44 0.44 0.44
HArU/HArC 0.97 0.89 0.59 0.43

480 1) Percentage of the total amount of aromatic protons.

481 2) Percentage of the total amount of aliphatic protons.

482

26
484 Table 5. Pore textural characteristics of SMC before and after reacting with volatiles.

Samples SBET (m2/g) Vmic (cm3/g) Vt (cm3/g) Average pore diameter d (nm)

SMC 98.0 0.0414 0.079 3.21

SMC-1 0.3 0.0001 0.003 39.15

SMC-2 0.8 0.0003 0.006 30.09

SMC-4 1.2 0.0005 0.008 26.41

485

27
487 Table 6. Crystallite structural parameters of SMC before and after reacting with volatiles.

Samples 2θ002 (o) β002 (a.u.) d002 (nm) Lc (nm)

SMC 24.465 3.672 0.364 2.189

SMC-1 24.460 3.375 0.364 2.382
SMC-2 24.469 3.564 0.364 2.256
SMC-4 24.462 3.598 0.364 2.234

488

28
490 Figures

491 Fig. 1. Schematic diagram of the integrated pyrolysis and upgrading reaction system.

492 Fig. 2. Product distribution without and with SMC.

493 Fig. 3. Gas components yields without and with SMC.

494 Fig. 4. Bio-oil* components yields and light bio-oil* content without and with SMC.

495 Fig. 5. Change in weight of SMC after reacting with volatiles.

496 Fig. 6. FT-IR spectra of SMC before and after reacting with volatiles.

497 Fig. 7. XRD patterns of SMC before and after reacting with volatiles.

498 Junjie Zhang: Investigation, Conceptualization, Methodology, Experiments, Data curation,

499 Writing- Original draft preparation.
500 Guangyong Wang: Conceptualization, Methodology, Experiments, Editing.
501 Shaoping Xu: Experimental device, Writing-Reviewing and Editing.
502

503

504 Highlights:

505  Free fall pyrolyzer combined with moving bed reactor for bio-oil upgrading.

506  Volatiles-char interaction contributed to the increase of light bio-oil* content.

507  Char favored deoxygenation of bio-oil*, especially at higher char updating rate.

508  Catechols were more reactive with char than other oxygen-containing

509 compounds.

510

511

29