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Synergetic effect of co-pyrolysis of cellulose and PP over an allsilica mesoporous catalyst MCM-41 using TG-FTIR and Py-GC-MS Junjie Xue, Jiankun Zhuo, Mi Liu, Yongchao Chi, Dahu Zhang, and Qiang Yao Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b01651 • Publication Date (Web): 27 Jul 2017 Downloaded from http://pubs.acs.org on July 28, 2017

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Synergetic effect of co-pyrolysis of cellulose and PP over an all-silica mesoporous catalyst MCM-41 using TG-FTIR and Py-GC-MS Xue Junjie, Zhuo jiankun*, Liu Mi, Chi Yongchao, Zhang Dahu, Yao Qiang Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084, China

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Abstract Biomass is one of the promising alternative materials to solve the energy and

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environment crisis. Fast pyrolysis is one of the most economical and commercially

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realizable technology to convert the biomass to useable fuels and chemicals. To

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improve the liquid products, co-pyrolysis with propylene (PP) over a mesoporous

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catalyst MCM-41 was studied in this paper. TG-FTIR and Py-GC-MS were used as

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the main analysis methods to study the mass loss and the detailed products of the

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co-pyrolysis. The mass loss, main functional groups and identified products of

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pyrolysis of cellulose, PP and their mixture were analyzed and discussed. All the TG,

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FTIR and Py-GC-MS data show there is no significant synergism between the

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cellulose and PP when simply mixing them, though the C/H eff of the mixture

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increases from 0 to 1.3. However, the addition of MCM-41 bring significant

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synergism. The TG and DTG data show the co-pyrolysis with MCM-41 shifts the

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decomposition of PP to lower temperature, which provides more overlap between

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cellulose and PP in the range of 300-400°C. According to the FTIR spectra, there are

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also CO, CO2 and carbonyl produced in the peak supposed for pyrolysis of PP for the

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mixture together with MCM-41, which indicates the intermolecular synergetic

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reaction. Furthermore, the results from Py-GC/MS show olefins (43.9%), oxygenated

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compounds (24.8%, mainly alcohols) and aromatic (17.8%) are the main products of

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co-pyrolysis of cellulose and PP in the presence of MCM-41, while the oxygenated

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compounds (82.2%, mainly saccharides), olefins (4.7%) and aromatic (1.1%) will be

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the main products without catalyst. The olefins and alcohols are much more than the

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calculated value, which are the main result of synergism. The alcohols are mainly

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produced from the radical from cracking of PP combines with the hydroxyl radical

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produced from decomposition of cellulose. While the olefins are produced from

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interaction reaction (carbenium ion reaction and β-scission) between the primary

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products of the cellulose and hydrocarbon pool reaction of primary products of

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cellulose and PP. The results of this study enhance the understanding of co-pyrolysis

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of cellulose and PP in the presence of MCM-41 and provide the possible pathway of

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modifying the special pyrolysis products in catalytic pyrolysis of biomass with

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polymers.

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Keywords: Co-pyrolysis, cellulose, PP, catalyst, synergism

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1. Introduction Today, energy and environment problems have become one of the major problem

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of the survival and development of human society.1 Biomass is an important part of

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renewable energy, which can provide abundant carbon. What’s more, biomass will

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trap and use the CO2 by photosynthesis when they grow up. These advantages make

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biomass one of the promising alternative materials to solve the energy and

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environment crisis. As a result, realizing the high efficiency of biomass conversion is

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now an important development strategy of most country around the world.2

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Pyrolysis is one of the effective ways to convert the biomass to liquid fuel and

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chemicals. Fast pyrolysis is one of the most economical and commercially realizable

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technology by rapid heating the biomass for bio-oil under no oxygen, which has few

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limitation of raw material, high throughput and high reaction rate. 3-5 However, the

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liquid fuel has high oxygen contents (10-40 wt%), low calorific value (16-19 MJ/kg,

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about half that of crude oil ) and strong acidity (pH from 2 to 4). 6 As a result, the

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liquid fuel cannot be used directly. 6 In 1986, Chen et al. put forward the concept of

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effective hydrogen to carbon ratio (Eq. (1)) to estimate if the raw material is able to be

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converted to hydrocarbon chemicals economically.

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H − 2O Hൗ Ceff = C

(1)

The research indicates the raw material with a H/Ceff value of 1~2 can be

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converted to petroleum products. While the raw material with a H/Ceff value lower

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than 1 will produce more coke, which will deactivate the catalyst, and fail to produce


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high quality liquid fuel.7 The H/Ceff value of lignocellulosic biomass is between 0~0.3,

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which means lignocellulosic biomass is lack of hydrogen. 8 Some researchers studied

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the co-pyrolysis of biomass with high H/Ceff value material like alcohols (methanol

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and butanol). The results show co-pyrolysis increases the yield of petroleum

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chemicals and decreases yield of the unwanted coke. 9-10

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Waste plastics are much cheaper material with high H/Ceff value, like the two most

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commonly used plastics polyethylene (PE) and polypropylene (PP) with very high

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H/Ceff value being 2. Besides, waste plastics are abundant. The global production of

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plastic has reached about 322 million tons in 2015 and has increased by 3.5% over

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2014.11 The polymeric wastes may take up to billions of years to degrade naturally

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and result in environmental impact, which is concerned by the public.12-13 To recycle

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the waste plastics and reuse them is of significance. In addition, biomass and plastics

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are main components of municipal solid waste (MSW), like the package in food

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industry, which are difficult to be separated.14 In conclusion, co-pyrolysis of biomass

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and plastics is promising to effectively convert the biomass and waste plastics to

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valuable liquid fuels and chemicals.15

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Several researches concerning co-pyrolysis of biomass and plastics has been

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reported.16-18 Some researchers found there is no noticeable cross reaction products

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between pine and plastics or their decomposition products when co-pyrolysis without

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catalyst.16 But other researchers reported the yield of bio-oil increased when

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co-pyrolysis of pine and plastic. 15 And alcohol will increase in the bio-oil product if

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co-pyrolysis of cellulose and PP. 19


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Furthermore, the addition of proper catalyst is expected to reduce decomposition

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temperature, to promote decomposition speed, and to modify the products. 20 The

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mechanism for the improvements is the presence of the catalyst may change the

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reaction path and the activation energy. 17-18, 21-23 For example, the addition of a

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catalyst in polymer pyrolysis processes helps the hydrogen transfer reaction due to the

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presence of acid active centers inside the catalyst.24 And there will be significant

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synergism. The effective and most used catalyst is zeolite HZSM-5, with which the

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yield of petrochemical product will be enhanced, and more aromatic compounds and

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olefin will be produced.2, 17-18

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However, due to the bulky nature of the polyolefin, especially the larger molecules

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with branched structure like PP, the pore structure (pore size: 5.1 × 5.5 Å, internal

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pore space: 6.4 Å) of the HZSM-5 is not big enough for the entrance and diffusion of

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the reactant molecules, and the catalyst activity will be limited. 1, 13, 25 Besides, the

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high acidity of the HZSM-5 leads to the excessive cracking of the cellulose and

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plastics, which results in the carbon deposit and deactivation of the catalyst.26

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Research found catalyst with bigger pore size will improve the diffusion limitation,

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and the bigger plastic molecules can access the inner active site. 1 That means the

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catalyst will be more effective only when its structure is accessible for the plastic

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molecules. 24-25

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MCM-41 is a silica catalyst with mesoporous pore size (2-50 nm), which is more

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effective to catalyze reactions involving high volume molecules with non-ignorable

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steric hindrance, and which will improve the limitation of the HZSM-5. 13, 24, 27


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Besides, MCM-41 can also decrease the content of unwanted carboxylic acids and

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carbonyl functionalities and increasing the quantity of desirable hydrocarbons, which

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will upgrade the bio-oil. 27 It is promising to study the co-pyrolysis of cellulose and

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polymer together with MCM-41, which may improve the products. However, there is

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little knowledge about the co-pyrolysis of cellulose and PP in the presence of

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MCM-41.

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This study will focus on the synergetic effect of co-pyrolysis of cellulose and PP

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over an all-silica MCM-41 catalyst, aiming at improving the products distribution and

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giving more information about the mechanism of co-pyrolysis of cellulose and PP

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over MCM-41 by analysis the pyrolytic kinetic data and the yield and distribution of

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the pyrolysis products.

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2. Material and methods 2.1 Cellulose, Polypropylene (PP) and MCM-41 The cellulose was bought from Alfa Aesar company, whose chemical formular is

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[C6H10O5]n. The polypropylene (PP) was bought from Shanghai YangLi mechanical

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and electrical technology company, whose chemical formular is [C3H6]n. The catalyst

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MCM-41 was bought from the Catalyst Factory of Nankai University, which is made

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from silicon. All of the sample and the catalyst are fine powder.

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2.2 TG-FTIR Experiment To analyze the pyrolysis products and measure the weight change of the sample at the same time, the thermogravimetric analyzer (STA449F3, Netzsch, Germany) was


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connected to a FTIR spectrometer (VERTEX70V, Bruker, Germany) using thermal

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insulation pipeline, which was made from teflon. The temperature of the pipeline and

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the FTIR sample chamber were kept at 200 oC. About 11 mg sample and

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corresponding MCM-41 was put in the Al2O3 sample cup. The mass ratio of MCM-41

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to sample is 10:1. Argon was used as protecting gas. And the gas flow is 60 ml/min.

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The heating procedure started from room temperature and ended at 1000oC at the

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heating rate of 20oC/min. For the FTIR experiment, the scanning was performed in

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the range of 650~4000 cm-1 at the resolution of 4cm-1 and repeated for 16 times.

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2.3 Py-GC/MS Experiment

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To get more information of the primary reaction products, the fast pyrolyzer

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(5200HP, CDS, USA) was connected to the gas chromatograph-mass spectrometer

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(Clarus 560S, PerkinElmer, USA). Sample was put in the quartz tube, which can be

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inserted in the pyrolyzer. About 0.1 mg sample (cellulose, PP, and their mixture (1:1

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in weight)) was put in the center of the quartz tube first, then every 0.5 mg MCM-41

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was put in the both ends of the quartz tube. At last, the silica wool was used at both

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end of the quartz tube to avoid the solid powder being blew out of the tube. The

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prepared tube was inserted in the pyrolyzer, which will heat from room temperature to

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650 oC at 20 oC/ms and the temperature will be kept at 650 oC for 30 s. All the volatile

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products were analyzed on-line using the GC-MS part. The TR-35 MS capillary

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column (30m×0.25mm×0.25μm) was used. High purity (99.999%) Helium was

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used as carrier gas, whose flow rate was 1mL/min. The split ratio was 1:80. The

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heating procedure of the GC column was firstly kept at 40 oC for 4 min, then heated to


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180 oC at heating rate of 4 oC/min, afterwards, heated to 280 oC at 10 oC/min and kept

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at 280 oC for 4 min. The temperature of all the connection line and the injection port

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was kept at 280 oC to avoid condensation of the products. For the MS part, the

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electron, whose energy is 70 eV, was used to activate the products and get the

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expected ion. Qualitative analysis of the pyrolysis products was based on the NIST

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library, Wiley library and publications. 19-20, 25, 34-35

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3. Results and discussion 3.1 TG and DTG analysis Without catalyst MCM-41: The TG and DTG curves of pyrolysis of cellulose, PP

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and their mixture under argon atmosphere are shown as Figure 1a and 1b. The

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characteristic pyrolysis parameters of cellulose, PP and their mixture are shown as

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Table 1. According to the results, the cellulose mainly decomposes in the range of

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300-388 oC, and the max mass loss rate appears at 354 oC (Figure 1b). While the PP

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mainly decomposes at higher temperature in the period of 411-501 oC, and the max

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decomposing rate appears at 473 oC (Figure 1b). For the co-pyrolysis of cellulose and

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PP, there are two pyrolysis stages according to the DTG curve (Figure 1b). The first

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stage starts from 306oC and ends at 370 oC, and the weight loss ratio of this stage is

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about 28.5 wt%. While the second stage took place in the period of 419-505 oC, and

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the weight loss ratio in this range is 60.7 wt%. The weight loss ratio of the second

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stage is 2.1 times of the first one. The max weight lose rate of these two stages appear

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at 350 oC and 475 oC, respectively. According to the results of the pyrolysis

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temperature period and max weight loss ratio of the mixture, they are very close to the


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temperature when they decompose individually, which suggests there is no significant

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synergistic effect between the co-pyrolysis of cellulose and PP. Similar results for the

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TG behavior have been reported by other researchers. 18, 28-29

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With MCM-41: Notably, the pyrolysis temperature of PP is reduced with the

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appearance of MCM-41. According to the results, the pyrolysis temperature of PP is

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reduced significantly from 411-501 oC to 277-491oC. However, the pyrolysis

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temperature of cellulose is still in the similar range of 302-392oC (Table 1). That

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means there will be a wider overlap region between their pyrolysis temperature

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(Figure 1b), which is a great advantage for the synergistic reaction. The co-pyrolysis

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results show the first pyrolysis stage is strengthened with a weight loss ratio being

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36.0 wt%. And the weight loss ratio of second stage is 50.2 wt%. They are all

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calculated by normalization, which is regardless of the catalyst weight. The weight

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loss ratio of the second stage is 1.4 times of the first one. All these data show that

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there is really significant synergistic reaction in the co-pyrolysis of cellulose and PP

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when the MCM-41 is added, which strengthens the reaction in the lower temperature.

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Marcilla et al. reported the maximum mass loss temperature decreased by 110 oC

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when loaded 16 wt% of the MCM-41. And their data revealed a reduction in the

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activation energy of the catalytic decomposition. 24 Other researchers have also

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reported the consistent results of the synergism of the catalytic co-pyrolysis. 12, 24, 30

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3.2 Products analysis by on-line FTIR

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3.2.1 Products from pyrolysis of cellulose, PP and their mixture


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Products with lower molecular weight, like CO2, CO and other oxygenated

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chemicals, can be measured using mid-infrared (FTIR) spectrum. From the

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information of the FTIR, possible reaction mechanism of the pyrolysis of cellulose,

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PP, and their mixture can be speculated. 19, 28-29, 31-33 The wavenumber-to-compound

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information are shown as Table 2.

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Without MCM-41: The FTIR spectra of the products from the first mass loss peak

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(mainly from cellulose pyrolysis) and second mass loss peak (mainly from PP

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pyrolysis) are shown as Figure 2a and Figure 2b. According to Figure 2a, there are

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obvious several peaks in the FTIR spectra, which are the information about CO2, CO

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and other oxygenated chemicals (Table 1). The spectrum of the mixture (PP:

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cellulose=1:1 wt%) from the first mass loss is almost the same as the pure cellulose.

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Moreover, the products from the mixture of cellulose and PP is also almost the same

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as the pure PP for the second mass loss peak. That means there is no significant

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synergetic reaction between cellulose and PP without MCM-41 (Figure 2).

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With MCM-41: For the first mass loss peak, which is mainly come from pyrolysis

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of cellulose, the enhancement in the intensity of the bands in the cellulose together

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with MCM-41 sample reflects all of the products increase apparently, except alcohols,

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which means the MCM-41 promotes the further cracking of the cellulose (Figure 2).

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For the cellulose and PP together with MCM-41, carboxyl compound (1179 cm-1) and

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alcohols (1110 cm-1) disappear. Compared to the cellulose, the carbonyl (1742 cm-1),

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furan (749 cm-1) and hydrocarbon compounds decrease apparently. While small

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molecular like CO2 and CO increase significantly. Notably, there are two new peaks


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(2183 cm-1 and 2113 cm-1) in both of the two samples with MCM-41 in the first mass

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loss peak, which is attributed to the alkyne bond “C≡C” or conjugated dienes

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“C=C-C=C”. For the second mass loss peak, the yield of alkanes and olefins decrease

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slightly for both of the two samples when the MCM-41 added in (Figure 2b). Besides,

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there is one more peak (2881 cm-1) in both of two samples with MCM-41 in the

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second mass loss peak, which is attributed to the methyne bond “C-H”. The results

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suggest the MCM-41 may promote the dehydrogenation and produce more

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unsaturated products in the pyrolysis of cellulose or/and PP. Furthermore, MCM-41

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will strengthen the deoxidized reaction (Figure 2) in the co-pyrolysis of cellulose and

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PP, which results in the increase of CO2 and CO.

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3.2.2 Main change of the products along with pyrolysis temperature

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Main products like furan compound (749 cm-1), alcohols (1110 cm-1), carboxyl

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compound (1179 cm-1), carbonyl compound (1742 cm-1), CO (2352 cm-1), CO2 (2755

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cm-1) and hydrocarbon compounds (2806 cm-1) are investigated here to study how the

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products of cellulose, PP and their mixture change along with the increasing of the

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pyrolysis temperature, which is one of the evidence of pyrolysis evolvement.

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Products from Cellulose: According to Figure 3a, the main products of pyrolysis

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of cellulose are carbonyl compounds, carboxylic compounds, alcohols, furans,

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hydrocarbons, CO and CO2. The peak appears at 354oC, which is consistent with the

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TGA result (3.1 TG and DTG analysis). The height of the peak of CO2 is half of that

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of carbonyl compound. For the results of the cellulose with MCM-41, the catalyst

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does not change the type of the products (Figure 3b). The yield of carboxylic


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compounds is promoted in the main peak. Notably, there is still a lot of CO2 produced

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in the higher temperature period (Figure 3b). It suggests the MCM-41 promotes the

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decarboxylation and results in producing more carboxylic compounds and CO2 in a

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very broad temperature range (300-700 oC).

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Products from PP: The product of PP is much simpler than that of cellulose,

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which has only one neat peak of hydrocarbon compounds at 2806 cm-1 (Figure 4).

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The peak of the hydrocarbon compounds appear at 483 oC without MCM-41, and at

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392 oC with MCM-41. The height of the latter one is higher. That means the MCM-41

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catalyze the decomposition of PP at lower temperature and produce more hydrocarbon.

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Elena et al. reported the FTIR spectra of pyrolysis of the PP under 315 oC, 360 oC and

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465 oC. They also found the decomposition of the PP is prevailing at 465 oC. 29

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Products from Mixture of cellulose and PP: The pyrolysis products of mixture of

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cellulose and PP changing following the pyrolysis temperature are shown as Figure 5a

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(without MCM-41) and Figure 5b (with MCM-41). According to Figure 5, there are

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mainly two peaks for the mixture. The first peak, including carbonyls, carboxyls,

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alcohols, furans, hydrocarbons, CO and CO2, is at 350 oC, which mainly come from

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decomposition of cellulose. While the second peak happens at 479 oC, including

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mainly hydrocarbon produced from pyrolysis of PP. Notably, there are also CO and

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CO2 produced in the second peak, which is probably produced from the synergistic

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reaction between cellulose and PP by decarboxylation and decarbonylation. In the

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presence of MCM-41, the first peak is at 334 oC, which is a little lower than that of

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without MCM-41. Less carbonyls and more CO2 are produced when adding PP to the


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cellulose (Figure 5). The second peak is very low compared to the first peak, which is

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at 456 oC. The yield of hydrocarbon decrease obviously in the second peak. The

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results suggest the MCM-41 catalyst the decomposition of mixture of cellulose and

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PP at lower temperature and enhance the yield of carbonyls, carboxyls, alcohols and

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furans. Moreover, it also means the synergetic reaction between the cellulose and PP

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decomposition that enhances the deoxygenation reaction will be strengthened when

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providing MCM-41. More details of the production distribution will be discussed in

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the following Py-GC-MS results analysis.

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3.3 Products analysis by Py-GC/MS

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The GC-MS curves of the cellulose, PP and their mixture decomposes at 650 oC

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for 30s are shown as Figure 6 and Figure 7. According to related researches, 19-20, 25,

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34-35

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PP and their mixture is shown as Table 3 and Table 4. About one hundred compounds

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were analyzed here. They were divided into alkenes, olefins, aromatics, oxygenated

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groups first. Then the remaining compounds are put to the “else” group. More

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information is in the supplementary data.

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3.3.1 Cellulose, PP and their mixture without catalyst MCM-41

NIST and Wiley library, the main identified pyrolysis products of the cellulose,

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The main pyrolysis product of cellulose is oxygenated chemicals, which takes up

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90.4% of all the products (Table 3). Wherein, carbohydrate is the maximum product,

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which accounts for 85.7% of all the products. The rest are ketones, alcohols, acids,

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esters and epoxides, which takes up 2.0%, 1.5%, 0.42%, 0.70% and 0.07%,

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respectively (Table 4). Furthermore, 1, 6-anhydro-Beta-D-glucopyranose is the main


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monomer product of pyrolysis of cellulose, which accounts for 84.4% of all the

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products (supplementary data). For the PP, olefins, aromatics and alkanes are the main

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products, which account for 49.2%, 12.5% and 2.7%, respectively (Table 3). When

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adding PP to the cellulose, though the C/H eff increases from 0 to be 1.3, the

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oxygenated chemicals only decrease from 90.4% to 82.2%, which is much higher the

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calculated value.

303 304 305 306 307

The calculated value is obtained from Eq. (2), Calculated value = 50%*Cellulose Value+ 50%*PP Value

(2)

In Eq. (2), Cellulose Value is the yield when using pure cellulose, and PP Value is the yield when using pure PP. Furthermore, according to the distribution of the oxygenated chemicals (Table 4),

308

the adding of the PP does not change the products significantly. It means the simple

309

mixing is not able to improve the products as expected. The FTIR data also show the

310

consistent results (3.2.1 Products from pyrolysis of cellulose, PP and their mixture).

311

Similar results have been reported by other researchers.19

312

3.3.2 Cellulose, PP and their mixture, with catalyst MCM-41

313 314

When put catalyst MCM-41 in the sample, the pyrolysis products of cellulose, PP and their mixture changed significantly.

315

According to Figure 8, oxygenated chemicals are still the main products of

316

pyrolysis of cellulose together with MCM-41, which account for 57.2% of all the

317

products. However, the distribution of the oxygenated chemicals changes significantly.

318

First, the saccharides decrease sharply from 85.7% to 10.1%. Besides, remarkable


Page 15 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

319

amount (34.9%) of furans are produced. It suggests the MCM-41 promotes the

320

opening ring reaction of the saccharides, which also results in the increase of other

321

oxygenated chemicals like alcohol, acid, esters, ketone and epoxides (Table 4). In

322

addition, compared to the pure cellulose, other products of high value like aromatics,

323

olefins and alkanes also increase significantly, which take up 15.7%, 4.9%, and 0.52%

324

of all the products, respectively. This result is also consistent with the front FTIR

325

result, where C=C increases significantly.

326

As for the PP and MCM-41, the olefins and aromatics are the main products,

327

which accounts for 36.2% and 34.0% of all the products. Compared to the pure PP,

328

more aromatics and less olefins are produced, which means the MCM-41 motivates

329

the cyclization of the olefins or other product to form aromatics.

330

When mixing PP with cellulose together with MCM-41, the pyrolysis products

331

change significantly. The oxygenated chemicals reduce significantly from 57.2% to

332

23.7%, while the olefins increase from 4.9% to 43.9%. And the yield of aromatic

333

hydrocarbons and alkanes are 17.8% and 2.4%. Compared to the calculated value, the

334

mixture of cellulose and PP co-pyrolysis with MCM-41 strengthens the conversion of

335

oxygenated chemicals to olefins, which notes a very significant synergism. Besides,

336

the yield of “else” group reduces significantly to be half of the calculated value,

337

which means the reactions are directed positively in some extent with the presence of

338

MCM-41. Y.-H. Lin also found the MCM-41 helps to produce more olefinic products.

339

20

340

lot (Table 4 and Figure 9). First, the saccharides continue decreasing from 10.1% to

In addition, the distribution of the produced oxygenated chemicals also improve a


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

341

4.9%. Second, the furan reduces from 34.9% to 3.5%, while the alcohol increases

342

from 7.5% to 49.3%. Third, the esters, which will improve the stability of the oil, also

343

increase from 9.5% to 17.5%. It suggests the addition of PP promotes the reactions,

344

which produce non-cyclic chemicals like alcohols, aldehydes and esters instead of

345

cyclic chemicals like furans, epoxide and phenol. Deepak, et al (2015) also reported

346

the alcohol was one of the cellulose-PP interaction product, which is involving

347

hydroxyl radical abstraction from cellulose, chain fission, β-scission and

348

intramolecular hydrogen abstraction from PP. 19 The other synthesis pathway is

349

involved by the hydrocarbon pool mechanism, where the furans will be consumed and

350

olefins will be produced. 8-9

351

3.3.3 Proposed reaction pathway

352

As shown as Figure 10, after taking all the results of TG-FTIR and GC-MS into

353

consideration, the possible reaction pathway of the co-pyrolysis of cellulose and PP

354

together with MCM-41 is summarized. The products are formed through series of

355

complicated reactions, which can be classified into three types, including

356

decomposition of cellulose, decomposition of PP, and intermolecular reactions

357

between cellulose, PP and their intermediate products. The well-known reaction

358

mechanisms, such as radical reaction mechanism, hydrocarbon pool, carbenium ion

359

reaction, β-scission and Diels-Alder reaction, 9-10, 36-37 will be involved during the

360

catalytic pyrolysis process with MCM-41.

361

The main product of pyrolysis of cellulose is oxygenated chemicals, where

362

saccharides occupied 85.6% of all identified oxygenated products (Table 4), which


Page 16 of 34

Page 17 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

363

was marked as path 1 in Figure 1016. While olefins, aromatics and alkanes are the

364

main products of decomposition of PP (path 6, 7, 8). 17, 25, 36 When simply mixing the

365

cellulose and PP without catalysts, there is no significant synergism between the

366

pyrolysis, which still mainly produces saccharides, olefins, aromatics and alkanes.

367

However, the adding of MCM-41 change the products significantly. Pyrolysis of

368

cellulose together with MCM-41 produces olefins, aromatics and alkanes, apart from

369

oxygenated chemicals (path 9 and path 11). 35-36 Furthermore, the furans are the major

370

products of oxygenated chemicals. It suggests the path 1 is restrained while the path 2

371

is strengthened. For the PP together with MCM-41, the catalyst strengthen the

372

reaction to form more aromatics (path 8).

373

Notably, olefins will be the major product of co-pyrolysis of cellulose and PP

374

together with MCM-41. At the same time, alcohols become the main product of the

375

oxygenated chemicals. It shows the path 3, 4, 5, 9 and 10 are strengthened, which are

376

mainly the synergetic reactions between cellulose and PP. Path 3, 4 and 5 describe the

377

radical from cracking of PP combines with the hydroxyl radical produced from

378

decomposition of cellulose (Figure 10). 19, 36 Path 9 is the cross reaction (carbenium

379

ion reaction and β-scission) between the intermediate products of the cellulose.17 And

380

Path 10 is the cross reaction of intermediate product of cellulose and PP based on the

381

hydrocarbon pool mechanism. 1-2, 8-9, 17, 36

382

However, different from the HZSM-5, the yield of aromatic compounds is less

383

than the calculated value. Shantanu Kelkar(2015) also reported mesoporous catalyst,

384

which lacks of microporous and macroporous structure, will reduce the yield of


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

385

aromatic compounds. 35 It also suggests the mechanism of the co-pyrolysis in presence

386

of MCM-41 is different from that with HZSM-5. It is believed that all-silica MCM-41

387

catalyst has no acidic sites, while HZSM-5 has both weak acid site and strong acid

388

site, which can promote the yield of aromatic compounds. In this study, all-silica

389

MCM-41 shows large surface area (756 m2/g) because of mesoporous structures, and

390

the average pore size was 3.2 nm, which partly compensates its weaker acid property.

391

12, 30

392

products to produce more olefinic products. Besides, the MCM-41 may help cellulose

393

produce more free radical and motivate the chain end scission of PP to produce more

394

olefin.

395

4. Conclusion

The MCM-41 may strengthens the β-scission of cellulose, PP and their primary

396

The co-pyrolysis of cellulose and PP in the presence of MCM-41 was studied

397

using TG-FTIR and Py-GC/MS in this paper. All the TG, FTIR and Py-GC-MS data

398

show there is no significant synergism between the cellulose and PP when simply

399

mixing them, though the C/H eff of the mixture increases to be 1.3. However, the

400

adding of MCM-41 bring significant synergism. The TG and DTG data show the

401

co-pyrolysis with MCM-41 shifts the decomposition of PP to lower temperature,

402

which provides more overlap between cellulose and PP. According to the FTIR

403

spectra, there are also CO, CO2 and carbonyl produced in the second peak (mainly

404

from PP) for the mixture together with MCM-41, which indicates the intermolecular

405

synergetic reaction. Furthermore, the results from Py-GC/MS show olefins, aromatic

406

and oxygenated compounds (mainly alcohols) are the main products of co-pyrolysis


Page 18 of 34

Page 19 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

407

of cellulose and PP in the presence of MCM-41. The olefins and alcohols are much

408

more than the calculated value, which are the main result of synergism. The alcohols

409

are mainly produced from the radical from cracking of PP combines with the hydroxyl

410

radical produced from decomposition of cellulose. While the olefins are produced

411

from interaction reaction (carbenium ion reaction and β-scission) between the primary

412

products of the cellulose and hydrocarbon pool reaction of primary products of

413

cellulose and PP.

414


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

415

Page 20 of 34

Table 1 Characteristic pyrolysis parameters of cellulose, PP and their mixture Decomposition

Weight loss ratio

Max mass loss

temperature range/°C

/ wt%

temperature/°C

Cell

300-388

80.7

354

Cell-MCM-41

302-392

52.2

347

PP

411 -501

95.9

473

PP-MCM-41

277-491

100.0

387

Cell-PP

306-370, 419-505

28.5, 60.7

350, 475

Cell-PP-MCM-41

302-387, 407-506

36.0, 50.2

347, 456

Feedstock

416 417

Table 2 Wavenumber to compounds of the pyrolysis products of cellulose, PP and

418

their mixture Wavenumber/cm-1

Compounds

3350~4000, 1260~2059

H2 O

2275~2390

CO2

2048~2143~2238

CO

1625~1858

Carbonyls

2666~3060

hydrocarbon

1067~1110

alcohols

1184

Carboxyl

747

furans

2848,2881,2918,2963,1375,1462

alkane

891,968,1648,3081

alkene

419 420


Page 21 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

421 422

Table 3 Main products from pyrolysis of cellulose, PP and their mixture at 650 oC for

423

30s (GC-MS)

424

Feedstock /% Cell Cell-MCM-41 Cell/PP Cell/PP-MCM-41 PP PP-MCM-41

H/C eff 0 0 1.3 1.3 2.0 2.0

Oxygenated 90.4 57.2 82.2 24.8 0 0

Olefins 0 4.9 4.7 43.9 49.2 36.2

Aromatics 0 15.7 1.1 17.8 12.5 34.0

Alkanes 0 0.52 0 2.4 2.7 5.4

Else 9.6 21.7 12.0 11.1 35.6 24.5

425 426

Table 4 Oxygenated chemicals of products from pyrolysis of cellulose, PP and their

427

mixture at 650 oC for 30s (GC-MS)

428

Feedstock /% H/C eff Alcohol Furans Acids Esters Saccharides Ketone Phenol Epoxide

Cell 0 1.5 0 0.42 0.70 85.7 2.0 0 0.07

Cell-MCM-41 0 7.5 34.9 5.8 9.5 10.1 17.9 4.1 10.0

Cell/PP 1.3 0.87 0 0.04 0.15 80.6 0.45 0.08 0.01

429 430


Cell/PP-MCM-41 1.3 49.3 3.5 6.2 17.5 4.9 13.9 0 0

Energy & Fuels

100

80

TG/%

60

40

Cell Cell/MCM-41 PP PP/MCM-41 Cell-PP Cell/PP/MCM-41

20

0 200

400

431

T/

432

(a)

600

0

DTG(%/min)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 34

-20

-40

Cell Cell/MCM-41 PP PP/MCM-41 Cell-PP Cell/PP/MCM--41

-60 200

400

433

T/

434

(b)

600

435

Figure 1 TG (a) and DTG (b) curve of pyrolysis of Cellulose, PP and their mixture

436

(mass ratio= 1:1) with MCM-41 (MCM-41 to sample mass ratio=10:1)


Page 23 of 34

0.5

Cell Cell/MCM-41 Cel/PP Cel/PP/MCM-41

A/a.u.

0.4

0.3

0.2

0.1

500

1000

1500

2000

2500

3000

3500

4000

3500

4000

Wavenumber/cm-1

437 438

(a) First mass loss peak PP PP/MCM-41 PP/Cell PP/Cel/MCM-41

2.0

1.5

A/a.u.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

1.0

0.5

0.0

500

1000

1500

2000

2500

3000

Wavenumber/cm-1

439 440

(b) Second mass loss peak

441

Figure 2 FTIR spectra of the first (a) and second (b) mass loss peak of pyrolysis of

442

cellulose, cellulose/MCM-41 (1:10), PP, PP/MCM-41 (1:10), cellulose/PP (1:1) and

443

cellulose/PP/MCM-41 (0.5:0.5:10)，herein the absorbance value of mixture is adjusted

444

using pure cellulose or PP.


Energy & Fuels

0.10

furans alcohols carboxyls carbonyls CO CO2

Absorbtion /a.u.

0.08

0.06

hydrocarbon 0.04

0.02

0.00 200

400

600

800

o

Temperature / C

445 446

(a) Cellulose furans alcohols carboxyls carbonyls CO CO2

0.02

Absorbtion /a.u.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 34

hydrocarbon

0.01

0.00

200 447 448

400

600

800

o

Temperature / C (b) m(Cellulose)/m(MCM-41) =1:10

449

Figure 3 FTIR spectra of the main products (furans, alcohols, carboxyls, carbonyls,

450

CO, CO2 and hydrocarbon) of cellulose (a) and cellulose/MCM-41 (b) along with

451

increasing of the pyrolysis temperature


Page 25 of 34

0.20 0.15

PP/MCM-41 PP

0.10

A/a.u.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

0.05 0.00 -0.05 -0.10 200

400

600

800

Temperature/

452 453

Figure 4 FTIR spectra of the products (hydrocarbon compounds) of PP along with

454

increasing of the pyrolysis temperature


Energy & Fuels

0.10

Absorbtion /a.u.

0.08 0.06 0.04

furans alcohols carboxyls carbonyls CO CO2 hydrocarbon

0.02 0.00 -0.02 200

400

600

800

o

455

Temperature / C

456

(a) m(cellulose)/m(PP)=1:1

0.0100 furans alcohols carboxyls carbonyls CO CO2

0.0075

Absorbtion /a.u.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 34

0.0050

hydrocarbon

0.0025

0.0000

200

600

800

o

Temperature / C

457 458

400

(b) m(cellulose)/m(PP)/m(MCM-41) =0.5:0.5:10

459

Figure 5 FTIR spectra of the main products (furans, alcohols, carboxyls, carbonyls,

460

CO, CO2 and hydrocarbon) of the mixture (cellulose and PP) along with increasing of

461

the pyrolysis temperature


Page 27 of 34

9

1.4x10

Relative Abundance

cellulose

9

1.2x10

9

1.0x10

8

8.0x10

8

6.0x10

8

4.0x10

8

2.0x10

0.0 5

10

15

25

30

35

Time (min)

462 463

20

Figure 6 GC-MS data of products from pyrolysis of cellulose at 650 oC for 30s 9

4.70x10

9

3.76x10

9

2.82x10

9

1.88x10

8

Relative Abundance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

9.40x10

c b a 5

464

10

15

20

25

30

35

Time (min)

465

Figure 7 GC-MS data of products from pyrolysis of (a) cellulose/MCM-41(mass

466

ratio= 1:10), (b) PP/MCM-41(mass ratio= 1:10) and (c) Cellulose/PP/MCM-41 (mass

467

ratio= 1:1:20) at 650 oC for 30s

468


Energy & Fuels

60

cellulose/MCM-41 PP/MCM-41 cellulose/PP/MCM-41 calculated value

Area (%)

50 40 30 20 10 0 469

alkanes

olefins

aromatics oxygenated

else

470

Figure 8 Distribution of the products pyrolysis from cellulose/MCM-41, PP/MCM-41

471

and Cellulose/PP/MCM-41, herein calculated value is equal to 50% of the cellulose

472

value plus 50% of the PP value 50

cellulose/MCM-41 cellulose/PP/MCM-41

40

Selection (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 34

30

20

10

0

e 473

x id po

e

s l l e s es rs ide an no ids ster on ho d r r t e c e y o a u e h a f h e k ph eh et alc cc ald sa

474

Figure 9 Distribution of the oxygenated chemicals from cellulose/MCM-41 and

475

Cellulose/PP/MCM-41


Page 29 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

476 477

Figure 10 Reaction pathway of co-pyrolysis of cellulose and PP together with

478

MCM-41

479


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

480 481 482

Acknowledgments

483

The authors gratefully acknowledge the funding support by the National Natural

484

Science Foundation of China (No.51576111)，and the National Key Research Program

485

(No. 2016YFE0102500).

486


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Energy & Fuels

487 488 489

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Supporting Information: 1. Table S1 Main identified products from pyrolysis of cellulose at 650 oC for 30s (GC-MS) 2. Table S2 Main identified products from pyrolysis of cellulose, PP and their mixture together with catalyst at 650 oC for 30s (GC-MS) 3. Table S3 All the peaks from pyrolysis of cellulose, PP and Cellulose/PP at 650 oC for 30s (GC-MS) 4. Table S4 All the peaks from pyrolysis of cellulose/MCM-41, PP/MCM-41 and Cellulose/PP/MCM-41 at 650 oC for 30s (GC-MS)


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Synergetic effect of co-pyrolysis of cellulose and ... - ACS Publications

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