Accepted Manuscript

Co-pyrolysis of bamboo residual with waste tire over dual catalytic stage of CaO and
co-modified HZSM-5

Jia Wang, Zhaoping Zhong, Kuan Ding, Bo Zhang, Aidong Deng, Min Min, Paul Chen,
Roger Ruan

PII: S0360-5442(17)30904-0
DOI: 10.1016/j.energy.2017.05.146
Reference: EGY 10954

To appear in: Energy

Received Date: 26 December 2016

Revised Date: 24 April 2017
Accepted Date: 23 May 2017

Please cite this article as: Wang J, Zhong Z, Ding K, Zhang B, Deng A, Min M, Chen P, Ruan R, Co-
pyrolysis of bamboo residual with waste tire over dual catalytic stage of CaO and co-modified HZSM-5,
Energy (2017), doi: 10.1016/j.energy.2017.05.146.

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 ACCEPTED MANUSCRIPT

1 Co-pyrolysis of bamboo residual with waste tire over dual

2 catalytic stage of CaO and co-modified HZSM-5
a c c
3 Jia Wanga, Zhaoping Zhonga*, Kuan Dinga, Bo Zhang , Aidong Dengb, Min Min , Paul Chen , Roger

4 Ruan c

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a
5 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast

6 University, No.2 Sipailou, Xuanwu District, Nanjing, Jiangsu 210096, China

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b
7 National Engineering Research Center of Turbo-generator Vibratio, Southeast University, Nanjing

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8 210096, Jiangsu Province, China
c
9 Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of

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10 Minnesota, 1390 Eckles Ave., St. Paul, MN 55108, USA

11
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12 _____________________

13 * Corresponding author. Tel./fax: +86 25 83794700.

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14 E-mail address: zhangbo8848@yeah.net, zzhong@seu.edu.cn (Z. Zhong).

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16
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17 AB STRACT

18 Experiments for an upgraded liquid oil production via fast co-pyrolysis of bamboo
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19 residual and waste tire over two catalytic beds of CaO and HZSM-5 were conducted,
20 and the effect of CaO to HZSM-5 mass ratio on pyrolytic products distribution was
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21 investigated and analyzed. Furthermore, a novel modification method for enhancing

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22 the catalytic performance of HZSM-5 by an integrated alkali treatment and

23 hydrothermal process was carried out, and the influence of co-modified HZSM-5 on
24 products distribution was also studied. Experimental results revealed that the catalytic
25 fast co-pyrolysis of bamboo residual and waste tire increased the relative contents of
26 aromatics and olefins. Simultaneously, a use of dual catalytic stage of CaO and
27 HZSM-5 further facilitated the relative contents of aromatics and olefins significantly,
28 and inhibited the formation of undesirables like acids. A maximum yield of
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29 hydrocarbons could be reached at HZSM-5 to CaO mass ratio of 3:2. Furthermore, the
30 co-modified HZSM-5 promoted the relative contents of aromatics and olefins
31 compared with the fresh ones, which showed great promise for upgrading the quality
32 of liquid oil.

33 Keywords

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34 Catalytic fast co-pyrolysis;
35 Bamboo residual;

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36 Waste tire;
37 Dual catalytic stage;

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38 Upgraded liquid oil production.
39

40

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List of acronyms and abbreviations
CaO Calcium Oxide CFP Catalytic Fast Pyrolysis
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CO2 Carbon Dioxide Co-CFP Catalytic Fast Co-pyrolysis

Catalytic Fast Co-pyrolysis
CaCO3 Calcium Carbonate Co-DCFP
over Dual Catalytic Stage
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Catalytic Fast Pyrolysis over

CH4 Methane DCFP
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Dual Catalytic Stage

Non-catalytic Fast
NaOH Sodium Hydroxide Co-NCFP
Co-pyrolysis
BR Bamboo Residual WTE Waste-to-Energy
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Hydrogen to Carbon Molar

WPs Waste Plastics H/C
Ratio
WT Waste Tire HZ-5 Fresh HZSM-5
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WCO Waste Cooking Oil 4MHZ-5 Co-modified HZSM-5 for 4h

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Ammonia-Temperature
XRD X-ray Diffraction NH3-TPD
Programmed Desorption
Fourier Transform
Peak Area of a Certain Kind
FTIR Infrared Ph
of Aromatics or Olefins
Spectroscopy
Total Peak Area of Aromatics
HCs Hydrocarbons ΣPh
or Olefins
Selectivity of Aromatics or
UPs Undesired Products Sh
Olefins
Value-Added
VACs PET Polyethylene Terephthalate
Chemicals
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Pyrolyzer- Gas
Ethylene Diamine Chromatography
EDTA Py-GC/MS
Tetraacetic Acid Coupled with Mass
Spectrophotometry
Chemical Vapor Benzene, Toluene, p-Xylene,
CVD BTXEN
Deposition Ethylbenzene, Naphthalene
Fluid Catalytic
FCC
Cracking

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41 Introduction

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Bamboo, as a typical kind of plant in Poaceae grass group, which is a vital cash

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42

43 crop in mountainous areas of China. As the biggest bamboo products supplier, the
44 annual output value of bamboo industry is $14.5 billion based on the statistical data
45
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derived from the last 10 years, and China Bamboo Industry Development Plan has
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46 announced that the overall value of output will increase to $48 billion by 2020 [1].
47 However, the dramatic development of bamboo industry leads to a sustained growth
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48 of bamboo residual (BR). Therefore, from the perspective of waste-to-energy (WTE),

49 some efforts should be urgently made to converting BR into liquid oil or value-added
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50 chemicals [2-5].
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51 Note that there are various BR management techniques including combustion,

52 WTE, and carbonization. However, excessive quantities of gaseous products like CO2
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53 or CH4 will inevitably be produced via combustion and carbonization, which

54 contribute to serious environmental risks. Conversely, WTE via catalytic fast
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55 pyrolysis (CFP) could be used as a preferable way in terms of energy conversion and
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56 waste management [6-9]. During a typical CFP process, quality of the obtained liquid
57 products can be upgraded by the presence of moderate heterogeneous catalysts, which
58 shows great promise to the improved compatibility with crude oil as refinery
59 feedstocks, thus further procedures for upgrading may be minimized or avoided [2,
60 10-13].
61 Among the catalysts applied in the CFP of biomass, HZSM-5 has been recognized
62 to be one of the most efficient catalysts [14]. However, HZSM-5 was beneficial for
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63 the rearrangements of small pyrolytic molecules, but was prominently constrained for
64 the bulky ones as a function of diffusional limitations [15]. In this sense, the
65 diffusional constrains could be improved by the formation of an intracrystalline
66 micro-mesopore system. Various routes, including templating methods and
67 modifications like zeolitization of mesoporous materials and synthesis of nanosized

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68 zeolite crystals, were conducted and studied [15]. Among them, desilication by NaOH
69 leaching has been illustrated as one of the most effective methods [16]. While alkali

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70 treatment shows less selectivity towards the removal of acid sites [17-19]. Therefore,
71 in order to regulate acid sites and enhance hydrothermal stability, hydro-thermal

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72 treatment (dealumination) at moderate temperature has been used as a common
73 procedure [20]. Therefore, modifying HZSM-5 successively by NaOH leaching and

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74 hydrothermal treatment may obtain more significant effects on catalytic performance.
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75 On the other hand, it has been reported that CaO can be utilized as a prominent
76 candidate for tar cracking in gasification of biomass [21]. Simultaneously, due to its
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77 excellent deoxygenation, the use of CaO in catalytic upgrading of pyrolytic liquid oil
78 to achieve high contents of desirables has been investigated [22-25]. Wang et al. [25]
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79 conducted Fourier transform infrared spectroscopy (TGA–FTIR) to investigate the

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80 effects of CaO on the formation characteristics and composition of pyrolytic organic

81 vapors of corncob, and it was found that CaO dominated a high selectivity towards
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82 deacidification and formation of hydrocarbons. Sun et al. [24] analyzed the effects of
83 Fe contents on fast pyrolysis of biomass with Fe/CaO catalysts by Py-GC/MS
experiments, and it was concluded that carbon yields of light phenols and aromatics
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84

85 were increased while the yields of acids, aldehydes and ketones were significantly
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86 decreased. Therefore, in this regard, a dual catalytic stage system, which is formed by
87 two catalytic beds (i.e., HZSM-5 and CaO), might be used as a substitute to further
88 facilitate the catalytic upgrading of liquid oil.
89 Despite the catalysts are of crucial importance in the process of CFP, the
90 hydrogen-deficiency essence of biomass also largely limits an upgraded liquid oil
91 production [11, 26, 27]. A parameter named H/C molar ratio was used to evaluate the
92 hydrogen-containing degree, which was defined as follows:
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H - 2O - 3N - 2S
93 H / C= (1)
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94 Where C, H, O, N and S are the mole percentages of carbon, hydrogen, oxygen,

95 nitrogen and sulfur in samples, respectively. Note that the very low H/C ratio of
96 biomass (0~0.3) is responsible for the restriction of converting biomass into high

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97 quality liquid products. Therefore, one distinct approach to solve the
98 hydrogen-deficiency disadvantage is to catalytic fast co-pyrolysis (co-CFP) of

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99 biomass with other hydrogen-rich materials like waste plastics (WPs) or waste
100 cooking oil (WCO) [26, 28, 29]. However, at the best of our knowledge, co-CFP of

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101 bamboo residual (BR) and waste tire (WT) over a dual catalytic stage system
102 (co-DCFP) of CaO and zeolites (fresh and co-modified HZSM-5) has not been

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103 reported yet.
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104 In this contribution, in order to further upgrade the quality of liquid products and
105 enhance the catalytic performance of HZSM-5, experiments for co-DCFP of BR and
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106 WT were conducted by an analytical Py-GC/MS. Simultaneously, the effects of BR to

107 WT mass ratio (i.e, H/C ratio) and CaO to HZSM-5 mass ratio on pyrolytic products
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108 distribution, were studied in depth. In addition, successive desilication (NaOH

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109 leaching) and dealumination (hydrothermal treatment) was applied to modify the
110 HZSM-5 zeolites, and the influence of co-modification on the yields of aromatics and
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111 olefins was discussed in detail.

112 2. Materials and Methods

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113 2.1 Feedstocks preparation

114 BR was collected from Huzhou, Zhejiang province, China. Prior to the experiment,
115 BR was grinded into powder with a size smaller than 100 mesh, and then was dried at
116 108 oC for 12h. Simultaneously, WT was obtained from Nanjing, Jiangsu province,
117 China. Similar pretreatments were conducted and the ultimate analysis of WT and BR
118 was carried out by Vario EL II elemental analyzer (Germany), and the results were
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119 presented in Tab.1. Note that the H/C ratios for WT and BR were 0.79 and 0.18,
120 respectively. Furthermore, CaO was purchased from Nanjing Chemical Reagent Co.
121 Ltd., and HZSM-5 zeolites were provided by the Catalyst Plant of Nankai University,
122 Tianjin, China.

123 2.2 Co-modification treatment

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124 The co-modification treatment with NaOH leaching and hydrothermal process of

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125 HZSM-5 zeolites could be summarized as follows: (I) 10g HZSM-5 zeolites were put
126 into the 200 mL NaOH solution with a concentration of 0.2 M, and then the mixed

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127 liquid was stirred with magnetic stirring apparatus at 323 K for 4h; (II) Quickly
128 cooled down the slurry, then filtered and washed thoroughly until a neutral solution
129
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could be reached, then dried at 375 K for 12h in a drying oven. (III) NH4NO3 solution
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130 with a concentration of 1 M was used to carry out the ammonia exchanges, and after
131 that, a muffle furnace was utilized to calcine the samples at 823 K for 4h. (IV) The
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132 NaOH leaching modified HZSM-5 zeolites were applied to conduct the hydro-thermal
133 treatment at 773 K for 4h, and then the integrated modified HZSM-5 zeolites could be
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134 obtained. Note that the specific hydro-thermal treatment process could be found
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135 elsewhere in our previous work [20]. Hereafter, the parent unmodified HZSM-5
136 zeolites and the co-modified ones were labeled as HZ-5 and 4MHZ-5, respectively.
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137 2.3 Characterizations

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138 The pore characteristics and surface features of the HZSM-5 samples were carried
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139 out by a Belsorp-Max adsorption instrument with N2 at 77K. BET and Langmuir
140 methods were utilized to calculate the specific surface area, and t-plot method was
141 used to determine the microporous volumes and specific surface area. XRD patterns
142 were conducted by Bruker D8 Focus using CuKα radiation with a step of 0.02 at a
143 current of 40mA and a voltage of 40 kV. The scanning range of 2θ was from 5o to 50o
144 with a 10 min-1 scanning rate. NH3-TPD was conducted by FineSorb 3010 automatic
145 temperature programmed chemical adsorption equipment to analyze the acidity
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146 performances of various samples. For a typical run, 100 mg specimens were
147 introduced in a U-shaped quartz cell and the temperature was fixed at 873 K with a
148 He steam for 1h, and then cooled down to 423 K. Finally, the samples were saturated
149 by some NH3 gas, then the NH3-TPD was conducted with a fixed heating rate of 15
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150 C/min from 150 to 650 oC.

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151 2.4 Experimental methods

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152 Note that a CDS Pyroprobe 5200 pyrolyzer was used to carry out the CFP
153 experiments (Fig. S1). The probe was heated by platinum resistance, and an

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154 open-ended quartz tube was applied to place the feedstocks. Specifically, taking the
155 co-DCFP for instance, the specimens were placed in the order shown as follows:
156
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quartz wool, HZSM-5 (1mg), quartz wool, CaO (1mg), quartz wool, mixture of BR
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157 and WT (1 mg), quartz wool, CaO (1mg), quartz wool, HZSM-5 (1mg), quartz wool,
158 which could be seen in Fig. 1. Moreover, for each experiment, the pyrolyzer was
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159 initially kept at 80 oC, and then was heated at 2000 oC/s to a final temperature of 600
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160 C based on our previous work (Fig. S2). Helium with a purity of 99.999% and a
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161 stable flow of 1.0 mL/min was chosen as carrier gas, which was obtained from
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162 Nanjing Maikesi Nanfen Special Gas Co., Ltd.

163 A gas chromatography/mass spectrometry (GC/MS, 7890A/5975C, Agilent) was
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164 applied to identify the pyrolytic organic volatile matters, and the injector and interface
165 temperature was respectively fixed at 275 oC and 300 oC. Simultaneously, the GC
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166 separation was conducted by a capillary column (HP-5MS, 0.25mm×0.25um×30m),

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167 and the split ratio was kept at 1:80. Furthermore, the NIST MS library was used to
168 discriminate and analyze the chromatographic peaks. Despite the pyrolytic products
169 could not be gathered during each Py-GC/MS experiment, the total mass of feedstock
170 samples (i.e., BR and WT) and catalysts (i.e., HZ-5 and CaO) were accurately kept at
171 fixed values, thus a semi-quantitative method via analyzing the peak areas of
172 pyrolytic volatile matters was used [11]. Note that each experiment was conducted in
173 triplicate for reducing experimental errors, and the mean values were investigated and
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174 discussed.

175 2.5 Evaluation method

176 In this paper, the selectivity of aromatics or olefins was defined, which could be
177 shown as follows:

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Ph
178 Sh = (2)
∑ Ph

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179 where Ph is the peak area of a certain kind of aromatics or olefins. ΣPh is the total
180 peak area of aromatics or olefins.

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181 3. Results and discussion

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182 3.1 Effect of catalysts on fast pyrolysis of BR
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183 In this section, experiments for single CFP of BR individually over CaO and HZ-5,
184 as well as over dual catalytic stage system were conducted, and the experimental
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185 results were illustrated in Fig. 2. Furthermore, in order to evaluate the effect of
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186 catalysts on products distribution, some non-catalytic fast pyrolysis (non-CFP)

187 experiments were carried out for comparison and the corresponding results were also
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188 presented in Fig. 2. Note that the obtained pyrolytic volatile matters were classified
189 into four groups shown as followings: CO2, hydrocarbons (mainly aromatics and
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190 olefins, HCs), value-added chemicals (phenols and furans, VACs), and undesired
products (acids and ketones, UPs). As could be observed from Fig. 2, the products
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191

192 distribution of non-CFP were dominated by VACs and UPs, which was in good
193 agreement with previous works [1]. Simultaneously, there were no any aromatics
194 detected and only a small fraction of olefins with a relative content of 1.212% were
195 achieved in the non-catalytic run. Therefore, some efforts should be urgently made to
196 promote the production of HCs as to produce gasoline like components.
197 For the single CFP of BR over CaO, as shown in Fig. 2, an additive of CaO
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198 facilitated the yields of CO2, VACs and HCs, and suppressed the formation of UPs.
199 For instance, compared with the non-CFP, the relative contents of HCs and VACs
200 attained an increment of 2.734% and 4.471%, respectively. This was as a function of
201 the excellent deacidification of CaO during the thermal cracking process of bioenergy
202 through three reaction pathways: catalytic cracking, neutralization, and thermal

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203 cracking [25]. More specifically, acids could be converted into H2O and calcium
204 carboxylate through neutralization as shown in reaction (I), and the calcium

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205 carboxylate would further be decomposed to CaCO3 and ketones under the
206 temperature of 400~500 oC. Simultaneously, it was reported that thermal cracking

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207 reaction, i.e., reaction (III), would boost the conversion of acids catalyzed by CaO to
208 CO2 and hydrocarbons, which could be clearly reflected in Fig. 2 as the yields of CO2

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209 and HCs increased by the presence of CaO. Furthermore, CO2 derived from reaction
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210 (III) could react with CaO, which contributed the chemical equilibrium to the
211 direction of deacidification and hydrocarbons formation, as could be seen in reaction
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212 (IV).

213 CaO + 2R − COOH → ( RCOO )2 Ca + H 2 O (I)

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214 ( RCOO )2 Ca → CaCO3 + R − COR (II)

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215 R − COOH 

CaO
→ CO 2 + RH (III)

CaO + R − COOH → CaCO3 + RH

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216 (IV)

217 With respect to the single HZ-5 catalytic run, it could be found that the relative
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218 content of HCs exhibited a dramatic increase (16.721%) by comparison with the
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219 single CaO catalytic run, while the VACs yield was 19.153% lower than that of CFP
220 over CaO. Therefore, HZ-5 zeolites with the MFI structure could be recognized as a
221 promising candicate for the upgrading of liquid oil. During the thermal catalytic
222 cracking process of BR, HCs, especially the aromatics, could be formed by multiple
223 chemical reactions, such as cracking, dehydration, decarboxylation and aromatization
224 [30]. However, coke will inevitably occur during the catalytic process and thus lead to
225 deactivation due to pore blockage, and this has been the dominating restriction for
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226 thermal conversion of bioenergy with zeolites. Therefore, in this regard, we

227 performed CFP of BR over dual catalytic stage of CaO and HZ-5 (DCFP) to upgrade
228 the liquid fuel and improve the catalytic ability of HZ-5, and the results were also
229 exhibited in Fig. 2.
230 As could be indicated in Fig. 2, the relative contents of CO2 and HCs obtained from

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231 DCFP over CaO and HZ-5 (mass ratio: 1:1) reached the maximum values compared
232 with those of single CFP, while the relative content of UPs tended to markedly

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233 decrease, which reflected that dual catalytic stage dominated the superiority for
234 promoting the target products and effectively suppressing the formation of

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235 undesirables like acids. This might be attributed to the distinct deoxygenation and
236 aromatization as aforementioned. Furthermore, it was of interest to find that the

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237 relative content of VACs for various catalysts was in the order of CaO > HZ-5+CaO >
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238 HZ-5, which proved that dual catalytic stage not only accelerated the productivity of
239 HCs, but also possessed a moderate selectivity towards VACs, thus it might be used as
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240 a potential development trend in the field of liquid oil upgrading.

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241 3.2 Effect of BR to WT mass ratio on products distribution

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242 As has been noted, the hydrogen-deficient essence of BR with a low H/C of 0.18
243 largely inhibited the quality of liquid oil. In this sense, experiments for catalytic fast
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244 co-pyrolysis of BR and WT over dual catalytic stage (co-DCFP) of CaO and HZ-5
245 were carried out, and the results were performed in Fig. 3. As illustrated, compared
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246 with DCFP of BR alone, the relative content of HCs was 22.772% but increased to
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247 52.441% and 67.454% as the BR/WT mass ratio was kept at 3:2 and 1:1, respectively.
248 Similar experimental results have been reported by other literatures [31, 32]. Uçar et
249 al. [32] carried out co-pyrolysis of pine nut shells (PNS) and scrap tires (ST), and it
250 was observed that the highest yield of light and heavy naphtha were obtained at
251 PNS/ST mass ratio of 1:1. This was attributed to the relatively high H/C ratio in WT,
252 which facilitated the hydrocarbon pool for the production of aromatics and olefins.
253 Zhang et al. concluded that H/C ratio played a vital role in the HCS yield during the
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254 CFP process, and the deactivation rate of HZSM-5 would be suppressed with H/C
255 ratio increasing [33]. Fig. 4 exhibits the proposed reaction mechanism of co-DCFP of
256 BR and WT via hydrocarbon pool. As shown in Fig. 4, WT acts as hydrogen donor to
257 the hydrocarbon pool, which favors co-DCFP reaction towards the formation of
258 aromatics and olefins. In addition, oxygenates obtained from BR pyrolysis with high

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259 activation also accelerate the chain scission of pyrolytic organic vapors in the thermal
260 conversion of WT [26]. Therefore, compared with DCFP of BR alone, a significant

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261 increased HCs could be obtained by co-DCFP of BR and WT.
262 On the other hand, the relative content of VACs decreased at first and then

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263 increased within the studied BR to WT mass ratio region, and the minimum yield of
264 17.023% could be obtained at 1:1, which was in consistent with other works [32, 34].

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265 Martinez et al. conducted the co-pyrolysis of pine wood chips with scrap tires, and it
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266 was observed that an addition of waste tires to the biomass decreased the amount of
267 aldehydes, ketones and phenolic compounds [34]. For instance, furans were
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268 consumed via Diels–Alder cycloaddition reaction during the co-DCFP process. Chen
269 and Huber reported that co-feeding furans with olefins significantly promoted the
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270 selectivity of aromatics, and the maximum selectivity of xylene could be reached
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271 when propylene was utilized [35]. During the co-DCFP of BR and WT, olefins were
272 produced by WT pyrolysis, which facilitated the Diels-Alder reaction towards the
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273 formation of aromatics. Similarly, the relative content of UPs performed the same
274 tendency with the minimum yield of 5.931% occurring at 1:1. Bertero et al. conducted
the thermal and catalytic conversion of ketones over equilibrium FCC catalyst, and
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275

276 experimental results revealed that aromatics with a selectivity of 70% were the main
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277 hydrocarbon products [36]. Therefore, ketones might be employed for the formation
278 of aromatics during the co-DCFP as the decreased yield was associated with an
279 increase in aromatics. Moreover, it was of interest to find that the relative content of
280 alcohols presented a remarkable variation, thus it could be concluded that co-DCFP of
281 BR and WT attributed to this phenomenon.
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282 3.3 Effect of HZ-5 to CaO mass ratio on products distribution

283 Fig. 5 exhibits the products distribution obtained from co-DCFP with various HZ-5
284 to CaO mass ratios. Herein, non-catalytic fast co-pyrolysis (co-NCFP) of BR and WT
285 was also carried out in order to make a comparison, and the experimental results were

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286 shown in Fig. 5. It could be observed that HCs, especially the olefins, played a pivotal
287 role in pyrolytic organic products distribution. Simultaneously, compared with single

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288 co-CFP of BR and WT over CaO or HZ-5, co-DCFP integrated with CaO and HZ-5
289 gave a positive contribution to promoting the production of olefins and aromatics, as

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290 well as inhibiting the yield of UPs. Furthermore, as indicated in Fig. 5, a HZ-5/CaO
291 mass ratio of 4:1 contributed to the productivity of aromatics as the maximum relative

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292 content could be reached, and compared with the co-NCFP, the relative content
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293 obtained a dramatic increment of 19.561%. Simultaneously, the yield of olefins
294 presented deviation when the HZ-5/CaO mass ratio exceeded certain limitation.
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295 Specifically, at the mass ratio of 1:4, the relative content of olefins was 45.523% but
296 increased to 54.274% as the mass ratio was raised to 2:3. However, further enhanced
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297 it to 3:2 and 4:1 decreased the relative content to 49.708% and 44.193%, respectively.
Therefore, a mass ratio of 2:3 formed the optimum reaction condition for olefins.
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298

299 However, when taken the relative content of HCs (i.e., aromatics + olefins) into
300 consideration, the maximum value of 73.583% could be obtained at mass ratio of 3:2.
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301 In terms of VACs, as illustrated in Fig. 5, the relative content of VACs tended to
302 decrease at first and then increase as the HZ-5/CaO mass ratios varied from 1:4 to 4:1,
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303 and the minimum value of 12.083% could be gained at 3:2. Simultaneously, compared
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304 with the co-NCFP, the formation of UPs was sharply suppressed, and similarly, the
305 minimum relative content of UPs with a value 2.163% could also be reached at 3:2.
306 Furthermore, the relative content of alcohols fluctuated widely, and the maximum
307 value of 9.518% could also be attained under the mass ratio of 3:2.
308 It should be noted that the aromatics derived from co-DCFP of BR and WT mainly
309 were BTXEN, i.e., benzene, toluene, p-xylene, ethylbenzene, naphthalene and its
310 derivatives. While the dominated components of olefins were D-limonene,
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311 1,3-pentadiene, and 2-butene, respectively. Fig. 6 presents the selectivities of

312 aromatics and olefins. As indicated in Fig. 6a, it was apparently to find that toluene
313 and p-xylene dominated the products distribution, and followed by naphthalene and
314 its derivatives. Similar results were also found by Song et al. [37]. In addition, the
315 selectivity of toluene decreased at first and then increased with a minimum value

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316 occurring at 2:3. Conversely, the selectivity of naphthalene and its derivatives was
317 inclined to present an opposite trend with a maximum value of 17.803% under the

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318 same condition. Simultaneously, the selectivity of p-xylene decreased gradually as the
319 HZ-5/CaO mass ratio increased, and a similar tendency could be observed with

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320 respect to ethylbenzene. However, the selectivity of benzene fluctuated slightly as the
321 maximum value of 10.308% achieved at 4:1.

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322 With regard to the selectivities of olefins, it could be concluded from Fig. 6b that
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323 the selectivity of D-limonene was the most prominent among the three main
324 constitutes, and the selectivity increased at first and then decreased with HZ-5/CaO
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325 mass ratio increasing. Similarly, previous studies with respect to the pyrolysis of WT
326 illustrated that the high yield of D-limonene was attributed to the thermal conversion
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327 of natural rubber (NR) [37, 38]. It was worth noting that D-limonene was also largely
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328 used in the field of food industry due to its antimicrobial activity [39, 40]. Zahi et al.
329 [41] developed a novel antimicrobial delivery system via encapsulating D-limonene
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330 into an organogel-based nanoemulsion, and it was found that the encapsulation of
331 D-limonene made a significant contribution to the increment of antimicrobial activity.
Moreover, a similar trend for the selectivity of 1,3-pentadiene could be observed, and
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332

333 the maximum value of 29.913% occurred at 3:2. However, the selectivity of 2-butene
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334 varied inversely with a minimum value of 10.243% attaining at 2:3.

335 3.4 Effect of co-modified HZ-5 on products distribution

336 As aforementioned, the microporous essence (i.e., porous properties) and acidic
337 properties of HZ-5 catalysts inhibited the mass transfer and diffusion, which resulted
338 in the constraints of catalytic performance, and thus it seemed that some efforts
 ACCEPTED MANUSCRIPT

339 should be urgently made to improve the catalytic properties by moderate modification
340 methods. Note that in our previous work, a series of modified treatments for HZ-5
341 zeolites, such as EDTA dealumination, chemical vapor deposition (CVD), and
342 hydrothermal process had already been done and noteworthy achievements were
343 obtained [10, 20, 42, 43]. Nevertheless, given that the modification process for

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344 integrating the porous properties and acidic properties of HZ-5 has not been
345 conducted, and at the best of our knowledge, there are rare reports related to this

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346 creative modification method. In this section, an innovative modification combined
347 successive desilication and dealumination to form a micro-mesopore hierarchical

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348 system, was carried out by sodium hydroxide leaching and subsequent hydrothermal
349 process, and the specific treatment process could be seen at section 2.2.

U
350 The pore volume features and surface area were carried out by N2
AN
351 adsorption-desorption isotherms, and the calculated results were shown in Tab. 2. As
352 indicated, both the external surface areas and mesopore volumes of co-modified
M

353 zeolites (labelled as 4MHZ-5) increased significantly compared with the fresh ones,
354 while the micropore volume decreased due to the conversion of micropores to
D

355 mesopores. Thus a micro-mesopore hierarchical system could be obtained, which

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356 might show great promise for decreasing the diffusional constrains and advancing the
357 catalytic properties.
EP

358 Fig. 7 shows the XRD patterns and NH3-TPD results of fresh and co-modified
359 HZ-5 zeolites. As described in Fig. 7a, compared with fresh zeolites, the crystal
structure of 4MHZ-5 zeolite was not damaged as a consequence of the characteristic
C

360

361 diffraction peaks were still kept, and the results were in consistency with other works
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362 [44, 45]. Simultaneously, as could be observed in Fig. 7b, the strong acid sites of
363 4MHZ-5 zeolites decreased in comparison with the parent ones, while the weak acid
364 sites were inclined to increase. The underlying reason for this phenomenon was that
365 not only the NaOH treatment led to the removal of Si-OH bonds inside the zeolites,
366 but also the hydrothermal process resulted in the dealumination [20, 46].
367 In order to investigate whether an enhanced catalytic performance of co-modified
368 HZ-5 zeolites could be reached, some experiments for co-DCFP of BR and WT over
 ACCEPTED MANUSCRIPT

369 4MHZ-5 zeolites and CaO (mass ratio was 1:1) were conducted, and the specific
370 pyrolytic products were performed in Tab. 3. As exhibited in Tab. 3, it was of crucial
371 importance to find that the relative content of aromatics increased dramatically from
372 21.418% to 33.324% by comparison with the fresh HZ-5 co-DCFP run, and toluene
373 and p-xylene were still the main focus of aromatics production. Namchot et al. carried

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374 out the catalytic pyrolysis of waste tire over HY/MCM-41 core-shell composite, and it
375 was reported that the synthesized micro-and mesoporous core-shell structure

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376 facilitated the transformation of the bulky aromatics to valuable aromatics [47].
377 Simultaneously, the relative content of olefins achieved from co-DCFP over 4MHZ-5

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378 increased by 2.561% compared with that of parent HZ-5. Conversely, the
379 productivities of VACs and UPs drastically declined when 4MHZ-5 was utilized, and

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380 light phenols, such as phenol and 3-methyl-phenol, were the main components, which
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381 reflected that an integrated modification of HZ-5 showed prominent promise for
382 further facilitating the shape selectivity of aromatics and olefins, as well as boosting
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383 the ability of deoxygenation, and thus an improved catalytic performance could be
384 achieved. Therefore, co-modification of HZ-5 by NaOH leaching and hydrothermal
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385 treatment might be used as a prevalent method for upgrading the liquid oil quality.
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386 3.5 Future perspective

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387 In summary, co-DCFP of BR and WT over CaO and 4MHZ-5 significantly spurred
388 the production of aromatics, especially the BTX. Generally, benzene can be alkylated
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389 with olefins to produce alkylbenzenes for the formation of polystyrenes, and it also
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390 can be utilized as feedstocks to synthesize polyurethanes and polycarbonates.

391 Simultaneously, toluene with a relative high octane number, which can be blended
392 into gasoline fuels, or applied to make toluene diisocyanate for the formation of
393 polyurethanes. With respect to p-xylene, similar to toluene, it can be used to enhance
394 the octane number of gasoline fuels. In addition, p-xylene also is a precursor to
395 produce terephthalic acid, which is then utilized to make polyethylene terephthalate
396 (PET). Due to the diversity of BTX aromatics, their market demands are expected to
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397 keep increasing, especially in p-xylene. On the other hand, limonene, as the typical
398 pyrolytic compound derived from pyrolysis of NR, which is a vital starting feedstock
399 in several industrial formulations including solvents, resins, or adhesives [38].
400 Additionally, D-limonene can also be used for fragrances and flavorants as a function
401 of the oranges smell. Therefore, co-DCFP of BR and WT could be used as a

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402 promising way for enhancing the production of BTX aromatics and olefins.

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403 4. Conclusions

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404 In this paper, experiments for co-DCFP of BR and WT over CaO and HZ-5 were
405 carried out by Py-GC/MS, and the HZ-5 zeolites modified by an integrated NaOH

U
406 leaching and hydrothermal treatment process were used to further upgrade the quality
of liquid oil. DCFP of BR indicated that the dual catalytic stage of CaO and HZ-5
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407

408 boosted the production of aromatics and olefins. Moreover, compared with DCFP of
409 BR alone, co-DCFP of BR and WT significantly increased the relative contents of
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410 aromatics and olefins, and a maximum relative content of HCs (67.454%), as well as
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411 the minimum relative content of UPs (5.931%), could be obtained when BR to WT
412 mass ratio was fixed at 1:1. Furthermore, the mass ratio of HZ-5 to CaO observably
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413 affected the products distribution of co-DCFP, and a mass ratio of 4:1 contributed to
414 the productivity of aromatics as the maximum yield could be reached. However, when
EP

415 taken the yield of HCs into consideration, the maximum value of 73.583% could be
416 achieved at mass ratio of 3:2. Finally, the 4MHZ-5 zeolites were used to conduct the
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417 co-DCFP experiments, and the relative content of aromatics increased dramatically
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418 from 21.418% to 33.324% by comparison with co-DCFP over fresh HZ-5 and CaO
419 (mass ratio: 1:1).

420 Acknowledgements

421 The authors are grateful for the National Key Basic Research Program of China
422 (973 Program) (No. 2013CB228106), the Scientific Research Foundation of Graduate
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423 School of Southeast University (YBJJ1646), the Fundamental Research Funds for the
424 Central Universities, as well as Scientific Innovation Research Program of College
425 Graduate in Jiangsu Province (KYLX16_0204).

426 Appendix A. Supplementary material

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427 Supplementary data associated with this article can be found.

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428 References

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523 biomass-derived feedstocks into olefins and aromatics with ZSM-5: the hydrogen to
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525 [34] Martínez JD, Veses A, Mastral AM, Murillo R, Navarro MV, Puy N, et al.
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539 and Applied Pyrolysis. 2016;120:314-20.

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550 technology. 2016;212:6-10.
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551 [43] Wang J, Zhong Z, Song Z, Ding K, Deng A. Modification and regeneration of
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553 Energy Conversion and Management. 2016;123:29-34.

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555 dehydration over alkali-modified H-ZSM-5; effect of temperature and water dilution
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556 on products distribution. Fuel. 2013;113:310-7.

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558 desilication of H-ZSM-5 by alkali treatment on catalytic performance in hexane

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562 compounds over hierarchical HZSM-5. RSC Adv. 2016;6(50):44313-20.

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565

566
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HZSM-5
CaO

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Quartz
tube Feedstocks

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Quartz wool

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567
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568 Fig. 1. Structure of quartz tube.

569
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50

Non-catalyst
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40 CaO only
HZ-5 only
Relative contents (%)

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HZ-5+CaO
30
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20

10
C
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0
CO2 HCs VACs UPs
570
571 Fig. 2. Products distribution of CFP of BR over various catalysts.
572
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50

40
Aromatics

Relative contents (%)

Olefins
VACs
30 Alcohols
UPs

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20

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10

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BR:WT=2:3 BR:WT=1:1 BR:WT=3:2
573
574 Fig. 3. Products distribution: effect of BR to WT mass ratio.

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575
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C EP

576
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577 Fig. 4. Proposed reaction mechanism of co-DCFP of BR and WT via hydrocarbon

578 pool.
579
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56

Non-catalyst
48 CaO only
HZ-5 only
Relative contents (%) HZ-5:CaO=1:4
40
HZ-5:CaO=2:3
32 HZ-5:CaO=3:2
HZ-5:CaO=4:1

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24

16

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8

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0
Aromatics Olefins VACs Alcohols UPs
580
581 Fig. 5. Products distribution: effect of HZ-5 to CaO mass ratio.

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582
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HZ-5:CaO=1:4
lene HZ-5:CaO=2:3
aphtha
N
M

e
ylen
p-X
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HZ-5:CaO=3:2
ene HZ-5:CaO=4:1
enz
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y lb
Eth

ene
Tolu
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e
zen
Ben
C

0 7 14 21 28 35 42
Selectivity (%)
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583
584 (a) Selectivities of aromatics
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ne
im one
D-L

en e HZ-5:CaO=1:4
tadi
Pen

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1 ,3 - HZ-5:CaO=2:3
HZ-5:CaO=3:2
HZ-5:CaO=4:1

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e
uten
2-B

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0 9 18 27 36 45 54
Selectivity (%)
585
586 (b) Selectivities of olefins

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587 Fig. 6. Selectivities of aromatics and olefins.
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588
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HZ-5
4MHZ-5
D
Intensity

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10 20 30 40 50

589 2θ (°)
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590 (a) XRD patterns.

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4MHZ-5
HZ-5

TCD signal (a.u.)

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200 250 300 350 400 450 500 550
o
591
Temperature ( C)

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592 (b) NH3-TPD results.
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593 Fig. 7. Characterization results of fresh and co-modified HZ-5 zeolites.
594
595 Table 1
Ultimate analysis of BR and WT.
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596
Ultimate analysis a (%) C H Ob N S
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BR 51.51 6.12 42.05 0.21 0.11

WT 90.38 6.3 0.56 0.65 2.11

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a
597 dry-ash free basis; b by difference

598
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599 Table 2
600 Pore structure features and surface areas of parent and co-modified zeolites.
SBET
C

Specimens Smicro (m2/g) Sexternal (m2/g) Vmicro (cm3/g) Vmeso (cm3/g)

(m2/g)
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HZ-5 291.915 50.824 342.721 0.091 0.082

4MHZ-5 262.831 120.309 383.142 0.071 0.291
601
602 Table 3
603 Products distribution obtained from co-DCFP over 4MHZ-5 and CaO.
C.Na R.Cb (%) M.Fc R.T.d (min)
Aromatics (sum) 33.324
Benzene 3.132 C6H 6 2.485
Toluene 10.251 C7H 8 3.645
Ethylbenzene 1.518 C8H10 5.202
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p-Xylene 12.177 C8H10 5.422
Benzene, 1-ethyl-4-methyl- 1.601 C9H12 7.256
Benzene, 1-methyl-3-(1-methylethyl)- 1.714 C10H14 8.521
Naphthalene 1.188 C10H8 11.73
Naphthalene, 1-methyl- 1.354 C11H10 13.756
Benzene, 1,1'-tetradecylidenebis- 0.386 C26H38 20.821
Olefins (sum) 48.588
2-Butene 11.873 C4H 8 1.599

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1,3-Pentadiene 11.782 C5H 8 1.827
Cyclohexene, 4-ethenyl- 1.441 C8H12 4.733
D-Limonene 17.066 C10H16 8.658

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Others 6.429 CxHy -
Phenols (sum) 8.068
Phenol 1.378 C6H6O 9.12

SC
Phenol, 3-methyl- 1.666 C7H8O 9.567
Phenol, 2-methoxy- 1.534 C7H8O2 9.728
2-Methoxy-4-vinylphenol 1.155 C9H10O2 13.942

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Phenol, 2,6-dimethoxy- 1.059 C8H10O3 14.584
AN
Phenol, 4-methoxy-3(methoxymethyl)- 0.456 C9H12O3 16.111
Phenol, 2-methoxy-6-(1-propenyl)- 0.581 C10H12O2 16.226
Phenol, 2,6-dimethoxy-4-(2-propenyl)- 0.239 C11H14O3 19.952
Furans (sum) 1.309
M

Benzofuran, 2,3-dihydro- 1.309 C8H8O 12.319

Ketones (sum) 2.723
D

3',5'-Dimethoxyacetophenone 1.815 C5H6O2 6.479

2-Propanone, 1-hydroxy- 0.908 C3H6O2 3.926
TE

Alcohols (sum) 4.835

3-Cyclohexen-1-ol, 1-methyl- 0.961 C7H12O 3.841
p-Menth-1(7)-en-9-ol 0.829 C10H18O 7.635
EP

2,4-Hexadien-1-ol 1.459 C6H10O 10.003

Estra-1,3,5(10)-trien-17πol 0.861 C18H24O 23.358
1-Heptatriacotanol 0.725 C37H76O 26.901
C

604 C.N a: Chemical Name; R.C b: Relative Content; M.F c: Molecular Formula; R.T. d: Retention
AC

605 Time.
606
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Highlights

Co-pyrolysis of bamboo residual and waste tire over CaO and HZSM-5 was
conducted.

Co-modification of HZSM-5 by NaOH leaching and hydrothermal process was
proposed.

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A dual catalytic stage bed of CaO and HZSM-5 facilitated the yield of aromatics.

Co-modified HZSM-5 zeolites showed significant selectivity towards aromatics.

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