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Studies of the co-pyrolysis of oil shale and wheat straw
Bin Chen, Xiangxin Han, Mao Mu, and Xiumin Jiang
Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 30 May 2017
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Page 1 of 31 Energy & Fuels

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4 1 Studies of the co-pyrolysis of oil shale and wheat straw
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6 2 Bin Chen, Xiangxin Han∗, Mao Mu, Xiumin Jiang
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9 3 Institute of Thermal Energy Engineering, School of Mechanical Engineering,
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11 4 Shanghai Jiao Tong University, Shanghai 200240, China
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14 5 Abstract
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16 6 The co-pyrolysis characteristics of oil shale-biomass blends were investigated by
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19 7 open-system pyrolysis with a thermogravimetric analysis-mass spectrometry (TG-MS)
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21 8 analyzer and closed-system pyrolysis with a fixed-bed reactor, respectively. The on-line
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24 9 Gasmet fourier transform infrared (FTIR) spectrometer and gas chromatography-mass
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26 10 spectrometry (GC-MS) were employed for analyzing the gas and liquid products which
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29 11 were generated from the closed-system pyrolysis. In addition, Gaussian program was also
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31 12 employed for the calculation of quantum chemistry. According to the results, one
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34 13 important reaction mode of the oil shale-biomass interactions can be described as
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36 14 “biogas-kerogen” reaction, which means the combination of kerogen and some free
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39 15 radicals volatilized from the biomass in the temperature range of 180-400 oC. During the
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41 16 co-pyrolysis, oil shale influences the distribution of the oxygen content in the biomass
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44 17 products, causing the increase of CO2 and CO in gas products and the reduction of
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46 18 oxygen-containing compounds like alcohols, aldehydes, lipids and ethers in liquid
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49 19 products. The results will be useful for improving the quality of shale oil in industrial
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51 20 utilization of oil shale in the future.
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54 21 Keywords: Oil shale; biomass; co-pyrolysis; TG-MS; GC-MS.
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58 *
To whom correspondence should be addressed. E-mail: hanxiangxin@sjtu.edu.cn
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4 22 1. Introduction
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6 23 The limited reserves of conventional fossil fuels and the increasing demand of energy
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9 24 have raised a wide research about alternative energy sources in the world. Oil shale, a
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11 25 sedimentary rock with organic matter called kerogen, has a great potential for future
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14 26 applications because of its large reserves [1-2]. According to the calculation based on the
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16 27 in-situ oil shale [3-5], the amount of shale oil has exceeded conventional crude oil reserves
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19 28 in the world. Because of the large reserves, it has been considered as one of the most
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21 29 important potential substitute resources for petroleum [5-7]. Moreover, as a renewable
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24 30 energy, biomass has also attracted more and more attentions of many researchers because
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26 31 of its availability in large quantities in many regions and big potential to play an important
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29 32 role in the energy field [8-10].
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31 33 During the retorting, the kerogen in oil shale is first converted into critical organic
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34 34 intermediates (i.e. pyrolytic bitumen) around the temperature of 350 oC [11], releasing
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36 35 some small molecular substances such as moisture, interlayer water and CO2. When
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39 36 temperature continues to rise, the bitumen is further decomposed and evaporated,
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41 37 generating gases, shale oil and coke in the temperature range of 400-550 oC.
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44 Gases
o
45 ~350 C
46 Kerogen Bitumen Shale oil
47 o
400-550 C
48 Coke
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50 39 For the pyrolysis of most kinds of biomass, bio-oil, synthetic gases and semicoke are
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53 40 usually formed before 400 oC [12]. Unlike shale oil, bio-oil is lighter and contains more
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55 41 oxygenated compounds.
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4 250-400 oC
Biomass Bio-oil +Gases +coke
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6 42
7 43 Co-pyrolysis system has been employed by many researchers for investigating the
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10 44 interaction between two kinds of fuels, such as coal and biomass [13-18]. Unfortunately,
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45 the pyrolysis characteristics of oil shale-biomass blends were rarely researched, although
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15 46 some researchers have explored the individual pyrolysis process of oil shale and biomass
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47 [11, 19]. Compared with coal, oil shale contains more aliphatic hydrocarbons such as
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20 48 longer straight chains and less aromatic hydrocarbons [20]. In addition, the thermal
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49 conversion process of “kerogen → bitumen” in oil shale occurs almost in the same
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25 50 temperature range where biomass decomposes. So, it is very desirable to research the
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51 co-pyrolytic behavior of these two fuels. Usually, pyrolysis process of carbonaceous
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30 52 materials could be considered as an independent process to produce various fuels [21], and
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53 the yields and quality of shale oil are limited due to its own H/C ratio. The existence of
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35 54 biomass might influence or even improve the quality of shale oil.
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38 55 In this paper, thermal behavior during the co-pyrolysis of oil shale and wheat straw
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40 56 (S-W, for short) were analyzed by a thermogravimetric analysis-mass spectrometry
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43 57 (TG-MS), which was used to analyze the generating hydrocarbon in this process.
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45 58 Moreover, gas chromatography-mass spectrometry (GC-MS) and gas analyzers (Gasmet
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48 59 FTIR and MRU GmbH Vario Plus analyzer) were also employed in closed-system
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50 60 pyrolysis experiments to analyze the obtained oil and gases. The results could be utilized
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53 61 to forecast the pyrolytic behavior of oil shale and biomass blends for proper design of the
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55 62 industrial thermal conversion system.
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4 63 2. Experimental
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6 64 2.1 Oil shale and biomass samples
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9 65 The oil shale sample used in this study was collected from Dachengzi mine located in
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11 66 Huadian, China. Also, wheat straw, which was obtained from a cropland in the Northeast
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14 67 of China, was used as the biomass sample. All the samples were first air-dried, crushed
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16 68 and sieved to a grain size of ≤3mm. Following those, proximate and ultimate analysis was
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19 69 determined according to national standards of China. The obtained data and heating values
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21 70 of both samples are given in Table 1. It is noteworthy that the wheat straw used in this
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24 71 experiment was taken directly from the cropland and contained some dirt and dust, so its
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26 72 ash content was higher than normal biomass. The atomic ratio of H/C is 1.58 in wheat
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29 73 straw and 1.77 in oil shale. The blending ratio of oil shale vs. wheat straw (S:W) in this
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31 74 study was specified as 1:0, 3:1, 1:1, 1:3, 0:1, respectively.
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34 75 2.2 Closed-system Pyrolysis
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36 76 This work used a stainless-steel cylindrical retort (100 mm in height, 70 mm in
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39 77 internal diameter) to hold oil shale and straw blends. About 24 g (error ratio < 1%) S-W
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41 78 blends in different blending ratios were electrically heated from room temperature to the
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44 79 final temperature of 520 oC at an average heating rate of 10 oC min-1. During the pyrolysis,
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46 80 argon was used as the purge gas at a flow rate of 0.3 L min-1. At the end of the heating
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49 81 process, all the samples were held for about 20 min at 520 oC. The liquid products were
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51 82 collected in a series of cold containers that were immersed in a mixture of ice and water.
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54 83 The evolved gases were injected into the gas analyzers (Gasmet FTIR and Vario Plus gas
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84 analyzer) for online analyzing. The yield of non-condensable gases were calculated and
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4 85 analyzed by overall material balance and gas analyzers. The schematic diagram of the
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6 86 pyrolysis system was shown in the authors’ previous research [22].
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9 87 2.3 Products analysis
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11 88 2.3.1 Gas analysis
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14 89 The gases exhausted from the closed-system were continuously introduced into an
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16 90 on-line Gasmet DX-4000 FTIR spectrometer (8 cm-1 resolution), which was composed of
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19 91 sampling and measuring units for gas sampling, filtration and continuous analysis. First,
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21 92 the argon spectrum was recorded and chosen as a background spectrum. And then the
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24 93 exhausted gases were measured by the FTIR analyzer at 180 oC and 1.046 bar. Finally the
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26 94 obtained spectra and the concentration of the gases were handled and further determined
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29 95 by Calcmet Software 2005 in a computer which was connected to the FTIR analyzer via
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31 96 RS232. Among the emitted gases, CO, C1-C4 and NOx were investigated in this equipment
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34 97 and CO2 and H2 were detected and analyzed by MRU GmbH Vario Plus analyzer.
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36 98 2.3.2 Oil analysis
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39 99 The derived liquid products were not only consisted of oil but also aqueous phase.
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41 100 Thus they were separated by simultaneous distillation extraction. The compositions of
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44 101 blending-oil were analyzed using a GC-MS instrument with the model of Agilent 6890N
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46 102 GC/5973N MS. The temperature of injection port and detector in GC was 280 oC. The
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49 103 flow rate of helium was 3.0 mL/min, and the split ratio was 100:1. First, the temperature
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51 104 of GC was kept in 45 oC for 4 min, and then heated to 280 oC at a rate of 3 oC min-1. The
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54 105 MS detection was operated under the temperature of 230 oC, electron energy of 70 eV, and
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106 electron impact mode with the scanning range of 15-500 u. The corresponding peaks in
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4 107 mass spectra were identified through a comparison with the mass spectral data library of
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6 108 the NIST 02 (National Institute of Standards and Technology). The product distributions in
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9 109 blending-oil were analyzed semi-quantitatively by calculating from the peak areas divided
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11 110 by the total ion chromatogram (TIC).
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14 111 2.4 Open-system pyrolysis with TG-MS
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16 112 TG analysis was performed in a Mettle-Toledo TGA/DSC1/1600 TG analyzer
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19 113 coupled to a mass spectrometer (LF-PTM mass analyzer). The co-pyrolysis experiment
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21 114 was carried out in the temperature ranging from 30 to 850 oC at a heating rate of 10
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24 115 C/min. About 16 mg (error ratio < 1%) blending samples were weighted for each
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26 116 experiment. Argon was employed as the carrier gas to transport the products from
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29 117 pyrolysis oven to the MS detector (flow rate of 40 ml/min). The detection charge-mass
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31 118 ratio range of the MS is from 1 to 200 amu (atomic mass unit), with a scan rate of 0.2-60
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34 119 s/amu.
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36 120 In order to research the co-pyrolysis characteristics of the blends, the experimental
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39 121 curves were compared with the theoretical ones from the additive model that assumed that
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41 122 there are no interactions between two kinds of samples during the heating [21]. So, the
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44 123 calculated points of theoretical curves are the sum of the values of individual samples with
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46 124 proportional to their blending mass ratio as:
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49 125 Xadd = X1×R1 +X2×(1 – R1) (1)
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51 126 Xadd is the calculated value from the additive model, X1,2 represents the experimental value
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54 127 of wheat straw and oil shale separately, and R1 is the blending mass ratio of them.
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128 2.5 Kinetic analysis of TG experiments
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4 129 Under the open-system pyrolysis, non-isothermal kinetic analysis of mass loss is
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6 130 complex because the decomposition of oil shale and wheat straw represents many
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9 131 reactions in parallel and series [23]. Therefore, the kinetic parameters computed from the
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11 132 TG experiments are about the overall reactions, rather than individual reactions. In
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14 133 addition, the calculated activation energy should be apparent activation energy. The
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16 134 pyrolysis kinetic equation of the samples should be written as follows, according to the
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19 135 reaction rate theory:
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21 136
=    (2)
22  

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24 137 where
the ratio of actual mass loss to total mass loss at a given stage of the reaction; m0,
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26 138 mt, and  are the initial, the actual, and the final mass of the sample, respectively.
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29 139


= ×   (1 −
) (3)
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31 140 where A pre-exponential factor, min-1; E activation energy, kJ/mol; R universal gas
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34 141 constant, kJ/(mol K); T particle temperature at time t, K; n reaction order; t time of
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36 142 combustion process, min.
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39 143 This work used the Coats-Redfern method to obtain the parameters. Since the
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41 144 pyrolysis behaviors and reaction ranges of wheat straw and oil shale are quite different,
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44 145 the kinetic parameters and the reaction order were calculated in two stages. The reaction
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46 146 order is presumed to lead to the best linear plot, corresponding to the maximum
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48  ()
49 147 correlation coefficient value. A computational procedure was designed to plot ln [ 
]
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51  ()"
148 or ln [ ] versus 1/T for the reaction order values ranging from 0 to 2 at a step of
52 ()
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54 149 0.1. And then the optimum order, values of E and A in every region were obtained. The
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150 corresponding results are shown in Table 3 and Fig. 1-f.
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4 151 2.6 Gaussian analysis of “biogas-kerogen” reaction
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6 152 In order to further analyze the “biogas-kerogen” reaction discussed above and find
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9 153 “pure kerogen” conversion pathways and the corresponding energy barrier, two simple
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11 154 models were constructed and analyzed using the transition state theory (TST) of quantum
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14 155 chemistry with Gaussian09 package. Detailed introductions of this method were given in
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16 156 the authors’ previous research [20]. To decrease the calculate amount, the model and some
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19 157 corresponding parameters were simplified and calculated based on the following
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21 158 assumptions:
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24 159 1) The influences of the other parts in the kerogen matrix are not considered in the
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26 160 course of the calculated reactions.
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29 161 2) Oxygen–bridge bond (R1–O–R2) was used in this paper, and two straight carbon
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31 162 chains were chosen as the other two structures Ri connecting the oxygen atom.
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34 163 3) This paper concentrated mainly on the effect of H radical on the rupture bond,
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36 164 and whether H radical exists was taken as the only difference between
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39 165 “biogas-kerogen” and “pure kerogen” reactions. So the authors only calculated
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41 166 and displayed the first step of the cracking reaction pathways.
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44 167 3. Results and discussion
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46 168 3.1 TG-MS Analysis
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49 169 3.1.1 TG/DTG characteristics
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51 170 In Table 1, compared with oil shale, wheat straw contains a higher proportion of
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54 171 oxygen, leading to a higher thermal sensitivity of the straw and lower H/Ceff ratio
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172 (hydrogen to carbon effective ratio) [24-25].
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4 173 Fig.1a and 1b show the experimental TG and DTG curves of oil shale and wheat
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6 174 straw samples. The pyrolysis parameters of oil shale and wheat straw are displayed in
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9 175 Table 2. The striking differences of pyrolysis parameters like Tv, Tmax and Ts are attributed
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11 176 to the different molecular structure between oil shale and wheat straw [26]. The molecular
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14 177 structure of wheat straw is constituted with lignin, cellulose and hemicellulose, which are
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16 178 linked together with weak ether bonds (R-O-R) [27]. The bonds would decompose at
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19 179 relative low temperature (295.65-392.74 oC). However, in oil shale, the relatively stable
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21 180 phase, which comprises many long-straight hydrocarbons containing C-C bonds with
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24 181 higher bond energy than R-O-R [28], is more resistant to heat. As shown in Figs. 1a and
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26 182 1b, the mass loss process of both two samples can be roughly divided into three
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29 183 temperature stages: <180 oC, 180-600 oC and 600-850 oC. The first stage (<180 oC, L1)
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31 184 corresponds to the moisture-evaporating region; the second (180 oC-600 oC, L2) is the
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34 185 pyrolytic degradation of organic matter; and the third stage (600-850 oC , L3) is mainly
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36 186 ascribed to the decomposition of minerals. In Table 2, the mass loss of L1 was just about
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39 187 2.2 % of original sample mass, which was assigned as the moisture contents of two
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41 188 samples. The mass loss of L2 was 39.01% and 32.43 % for wheat straw and oil shale,
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44 189 respectively, accounting for 85.49 % and 77.40 % of the total mass losses. For wheat straw,
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46 190 both the hemicellulose and cellulose, and part of the lignin decomposed in L2 [29]. For oil
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49 191 shale, the kerogen was first converted to bitumen in the temperature range of 180-350 oC
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51 192 and then further decomposed to shale oil, non-condensable gases and char in the
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54 193 temperature range of 350-600 oC. The mass losses of L3 were only 4.34 % and 7.28 %,
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194 which mainly comes from the decomposition of lignin (for wheat straw), some minerals
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4 195 (mainly for oil shale), and organic residues [29].
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6 196 As can be seen in Figs. 1c-1e, the major pyrolysis temperature range of the S-W
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9 197 blends is around 180-400 oC and 400-550 oC. The theoretical curves of TG and DTG were
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11 198 drawn according to equation (1). By comparing DTG curves between theoretical and
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14 199 experimental results, it can be seen that the theoretical curves in the temperature range of
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16 200 400-850 oC was similar to the experimental curves. However, in 180-400 oC, DTG
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19 201 experimental curves of all blends were higher than the calculated curves, which means the
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21 202 mass loss rate around 180-400 oC is higher in the experimental co-pyrolysis.
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23 203 3.1.2 Kinetic analysis of co-pyrolysis
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25 204 As shown in Table 3, in the temperature range of 180-400 oC, oil shale needs less
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205 activation energy (46.06 kJ/mol) than wheat straw (92.77 kJ/mol) and the experimental
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30 206 activation energy of each S-W blend is higher than their theoretical activation energy. But
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207 in 400-550 oC, the activation energy of oil shale reaction is higher, and the theoretical
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35 208 activation energy is higher than the experimental activation energy in all the blends. These
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38 209 results show that, with the increasing mass ratio of wheat straw, the co-pyrolysis increases
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40 210 the activation energy of the reaction in low pyrolytic temperature (<400 oC). However, it
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43 211 will reduce the activation energy in the higher temperature of 400-550 oC. Fig. 1f shows
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45 212 the differences of the activation energy between the experimental and theoretical results.
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48 213 The maximum difference corresponds to the blending ratio of S:W=3:1 in the stage of
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50 214 180-400 oC, and corresponds to S:W=1:1 in the temperature range of 400-550 oC.
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53 215 3.1.3 MS analysis
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55 216 The curves of the released volatile products from different S-W blends are shown in Fig.
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58 217 2. The peak areas of different m/z in different blends were calculated and displayed in Fig.
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4 218 3. In addition, the NIST database was referred in the m/z identification. It can be seen
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6 219 from Figs. 2a-2c that there are two peaks around 180-400oC and 400-550oC,
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9 220 corresponding to the major decompositions of biomass and oil shale, respectively. The
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11 221 parameter m/z of 15, 16, 17, 18, 27, 29 and 44 represented CH4, H2O, C2H4, C2H6 and
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14 222 CO2, respectively. It is clearly detected that wheat straw produces more oxygen-containing
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16 223 gases like H2O and CO2 than oil shale, resulting from its own higher oxygen content. CH4
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19 224 peaks of these two samples are roughly equal.
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21 225 The curves in Fig. 2c and 2d indicate that oxygen-containing compounds such as
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24 226 alcohols, aldehydes, lipids and ethers (m/z=31, 45, 37) are usually produced before 400 oC.
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26 227 And Fig. 3 shows that almost all the experimental peak areas of oxygen-containing
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29 228 compounds are less than theoretical values. For the aliphatic hydrocarbons (m/z=43, 57,
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31 229 71), the difference between experimental and theoretical curves of –C3H7 and –C4H9 is
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34 230 small, but the experimental value of –C5H11 is higher than its theoretical values.
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36 231 3.2 Closed-system pyrolysis analysis
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39 232 For oil shale and wheat straw, the yield of their retorting products is obviously different
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41 233 because the biomass usually produces more gas and less char than oil shale [3, 30]. Fig. 4
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44 234 shows the change of four kinds of products with different blending ratios. It can be seen
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46 235 that Dachengzi oil shale (S:W=1:0) generated more oil than wheat straw (S:W=0:1) in this
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49 236 paper. With the increasing ratio of wheat straw, oil and semi-coke increased a little, while
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51 237 gas and water decreased.
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54 238 3.2.1 Analysis of gases
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239 This paper focused on the yields of non-condensative gases like H2, H2O, CO, CO2,
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4 240 NO2 and some light hydrocarbons including CH4, C2H4, C2H6, C3H8. During the
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6 241 closed-system pyrolysis, gases were detected and analyzed using Gasmet FTIR and Vario
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9 242 Plus analyzer.
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11 243 The obtained gas curves were integrated to get the volumetric productions, as shown in
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14 244 Fig. 5. The main gas products of wheat straw are CO2, CO and CH4, while CO2, NO2, and
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16 245 H2 are the main compounds of gas products from retorting oil shale. As the ratio of wheat
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19 246 straw increases, CO2 and CO both increase obviously. Moreover, the curves of CO2 and
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21 247 CO are convex rather than straight, which means the blends release more CO2 and CO in
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24 248 co-pyrolysis.
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26 249 3.2.2 Analysis of liquid products
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29 250 Fig. 6 shows the distributions of carbon chains with different length in the liquid
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31 251 products. It can be seen from Fig. 6a that bio-oil is lighter than shale oil. The liquid
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34 252 products of the wheat straw are mainly concentrated from C2-C10, while those of shale oil
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36 253 are mainly concentrated from C6-C21. It is noted that C2-C5 are composed primarily of
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39 254 oxygen-containing compounds like alcohols, esters and ethers, etc. C5 and C10 have the
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41 255 highest amount in the liquid products of wheat straw and oil shale, respectively. It also can
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44 256 be clearly seen from Fig. 6b that the experimental average length of carbon chains in the
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46 257 blends is longer than the theoretical value. Fig. 7 shows the difference of the distribution
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49 258 of carbon chains between the experimental and theoretical values. It can be seen that
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51 259 during the co-pyrolysis, the light compounds (<C8) reduced and the medium contents
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54 260 (C9-C20) increased in the blending-oil. Moreover, the heavy contents (>C20) changed a
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261 little. These indicate that the co-pyrolysis might restrain the generation of light
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4 262 components and promote the transformation of medium components during the heating.
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6 263 The compositional distribution of the blending oil is summarized and shown in Fig. 8. In
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9 264 bio-oil (S:W=0:1, shown in Fig. 8a), oxygen-containing compounds are the major
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11 265 components. Shale oil (S:W=1:0) contains more aliphatic hydrocarbons. Moreover, shale
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14 266 oil also contains more heteroatomic hydrocarbons than bio-oil. The difference between the
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16 267 experimental and theoretical values of different S-W blends was analyzed and displayed in
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19 268 Fig. 8b, from which it can be found that during the co-pyrolysis, oxygen-containing
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21 269 compounds decreased in the liquid products. The reduced oxygen might be transferred to
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24 270 gaseous products in the pyrolysis stage of 180-400 oC, resulting in the increase of CO2 and
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26 271 CO. In addition, by comparing the distributions of the compositions in different oils in
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29 272 Figs. 8a-8b, the oil produced by the blends of S:W=3:1 has the highest quality because of
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31 273 its relatively less heteroatomic hydrocarbons and oxygen-containing compounds.
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33 274 3.3 Interaction analysis of co-pyrolysis
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35 275 Through the analysis of TG experiments, it can be concluded that the co-pyrolysis
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38 276 has little effects in the pyrolytic temperature range, but accelerates the mass loss rate of
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o
40 277 the blends in 290-400 C, which mainly corresponds to the decomposition of
41
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43 278 hemicellulose and cellulose in wheat straw and the conversion of “kerogen → bitumen” in
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45 279 oil shale. These results indicate that one of the co-pyrolysis effects is leading to more
46
47
48 280 volatiles in low temperature stage of 290-400 oC. In addition, the H/C molar ratios of
49
50 281 blending oils were shown in Fig. 6c, indicating that the experimental values in the
51
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53 282 blending oils are higher than theoretical values. As discussed above, the conversion of
54
55 283 “kerogen → bitumen” in oil shale is almost simultaneous with the decomposition of
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58 284 hemicellulose and cellulose in wheat straw. In this stage, some free radicals such as -H and
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4 285 -CnHm (hydrocarbon free radicals) released from the biomass might be absorbed by
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6 286 kerogen during its transformation to critical intermediate in 180-400 oC. And then the
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9 287 higher H/C molar ratio bitumen decomposes in the temperature range of 400-600oC,
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11 288 producing more H2 and saturated hydrocarbon gases. It could be concluded and inferred
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14 289 that one kind of oil shale-biomass interactions is the “biogas-kerogen” reaction—the
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16 290 combination of kerogen and the free radicals volatilized from the biomass. And then wheat
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19 291 straw might play a synergistic role during the co-pyrolysis with oil shale. The existence of
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21 292 the H and hydrocarbon free radicals also prevents the recombination and cross-linking
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24 293 reactions of free radicals like benzene or other unsaturated hydrocarbons [31-32].
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26 294 In previous research [33], Li et al. have proven that calcite and limestone could
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29 295 decrease the acid in bio-oil and increase CO and CO2 in gas during the fast pyrolysis.
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31 296 Coincidentally, Dachengzi oil shale also contains much calcite [34]. Combining with the
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34 297 results of GC-MS and TG-MS/Gas analyzer in liquid and gas analysis, it can be concluded
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36 298 that oil shale might act as a catalyst and play a similar role of calcite during the
37
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39 299 decomposition of wheat straw, promoting the cracking of C-O and the generation of CO2
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41 300 and CO. So, synergy effect inhibits the conversion of oxygen-containing compounds in
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44 301 blending oil and promotes the generation of CO2 and CO in gas during the co-pyrolysis.
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46 302 The conversion history of the S-W blends was further summarized and shown in Fig.
47
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49 303 9. During the co-pyrolysis, wheat straw was decomposed first in the temperature range of
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51 304 200-400oC, with the re-integration of kerogen to bitumen. In this stage, the volatile
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54 305 components which were released from the biomass provided H and other hydrocarbon free
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306 radicals for the re-integration process of kerogen → bitumen, increasing the H/C ratio in
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4 307 bitumen. At the same time, more oxygen contents were transferred from liquid products to
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6 308 gas products, increasing the amount of CO2 and CO, and reducing the oxygen content in
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9 309 liquid product. With the temperature increasing, more hydrocarbon gases like CH4, C2H4
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11 310 and C2H6, and saturated and unsaturated hydrocarbon components were generated.
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13 311 3.4 Results of Gaussian analysis
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15 312 The results in this section cannot make a full comparison of two reactions because of
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313 the complex reactions and limited calculation conditions. But some crucial conclusions
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20 314 could be achieved.
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315 Fig. 10 shows two reaction pathways of the rupture of bridge bond and the
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25 316 corresponding reaction rate constant. It can clearly be seen that the energy barrier height is
26
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317 reduced significantly (from 367.40 to 164.02 kJ/mol) on account of the appearance of H
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30 318 free radical.
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32
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319 The reaction rate constants were calculated as the following equation:
34
%&  (∗ -.
35 320 k(T) = +, (− ) (4)
' (* (& /
36
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38 321 where kB is Boltzmanns constant, 1.381×10-23 m2·kg·s-2·K-1; T is reaction temperature,
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40 322 K; h is Plank constant, 6.626×10-34 m2·kg·s-1; Q*, QA, QB represents the partition functions
41
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43 323 of transition state, reactants A and B, respectively, which can be obtained from the output
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45 324 file of GaussView; R is universal gas constant, kJ/(mol K); and Ea is activation energy,
46
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48 325 kJ/mol. Fig. 11 shows the reaction rate constants over the temperature range of 300-1800
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50 326 K. The higher reaction rate constant at each temperature point also indicates that the
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53 327 “biogas-kerogen” reaction with H free radicals is easier to happen.
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55 328 4. Conclusions
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58 329 In this paper, co-pyrolysis of oil shale with wheat straw was performed in closed and
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4 330 open system, respectively. Combining with different blending ratios, the synergy effect of
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6 331 the two samples was discovered and discussed. With the mixing of oil shale and wheat
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9 332 straw, the activation energy of the blends decreases during 180-400 oC, but increases
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11 333 during 400-550 oC. With the wheat straw proportion increasing, the yields of gas and
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14 334 water increase while the oil and semi-coke become less.
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16 335 The quantum chemical calculation further confirms that the cracking of bridge bonds
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19 336 in kerogen is more likely to happen in the presence of H free radical, which is provided by
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21 337 the decomposition of wheat straw. And then the “biogas-kerogen” reaction was put
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24 338 forward as an important kind of the oil shale-biomass interactions. On one hand, the
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26 339 mineral like calcite in oil shale makes the oxygen in biomass transfer from oil to gas,
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29 340 improving the quality of blending oil. On the other hand, the biomass provides H and
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31 341 other hydrocarbon free radicals in the re-integration process of kerogen, resulting in the
32
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34 342 reduction of energy barrier height, more saturated hydrocarbons and higher H/C ratio in
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36 343 shale oil.
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39 344 Acknowledgements
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41 345 This work was sponsored by Shanghai Pujiang Program of China (Grant No.
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44 346 15PJD018).
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54 388
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3 389 Table 1 Ultimate analysis and proximate analysis of oil shale and wheat straw
4 Ultimate analysis(mass%) Oil shale Wheat straw
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6 C 30.43 25.49
7 H 4.00 3.31
8 Od 8.78 15.72
9 N 0.63 0.52
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11 St 0.94 0.27
12 Proximate analysis(mass%)
13 Moisture 1.52 3.07
14 Ash 53.70 51.62
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16 Volatile matter 40.31 41.46
17 Fixed carbon 4.47 3.85
18 HHV(MJ/kg) 12.59 10.26
19 H/C molar ratio 1.58 1.56
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21 390 d- By difference; t-Total sulfur; HHV-high heat value
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3 392 Table 2 pyrolysis parameters of wheat straw and oil shale
4 Tv/oC Tmax/oC Ts/oC L1/% L2/% L3/% LT/%
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6 Wheat straw 295.65 348.27 392.74 2.28 39.01 4.34 45.63
7 Oil shale 438.14 476.31 521.44 2.19 32.43 7.28 41.90
8 393 Tv-precipitation temperature; Tmax- maximum mass loss temperature; Ts-final temperature; L1,L2 and L3-accumulative
9 394 mass loss in the temperature range of <180oC, 180-600oC, and >600oC, respectively; LT-total mass loss during TG-DTG
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11 395 experiments.
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3 396 Table 3 Pyrolysis kinetic parameters of the samples with different blending ratios
4 Blending Pyrolysis E/kJ mol-1 A/(min-1) Correlation coefficient n
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6 ratio stage E E* A A* C C* n n*
7 180-400 oC 92.77 7.25×107 0.983 2
S:W=0:1
8 400-550 oC 177.34 3.35×1012 0.945 1.9
9 180-400 oC 90.16 88.80 3.98×107 3.02×107 0.981 0.981 2
10 S:W=1:3
11 400-550 oC 207.33 211.68 3.51×1014 6.90×1014 0.971 0.974 1.7
12 180-400 oC 84.43 82.72 1.10×107 7.82×106 0.978 0.979 2
S:W=1:1
13 400-550 oC 230.75 235.23 1.54×1016 3.15×1016 0.977 0.980 1.7
14 180-400 oC 75.25 72.48 1.34×106 8.02×105 0.974 0.971 2
15 S:W=3:1
16 400-550 oC 247.15 249.57 2.25×1017 3.20×1017 0.981 0.983 1.7
17 180-400 oC 46.06 2.06×103 0.907 2
S:W=1:0
18 400-550 oC 260.07 1.76×1018 0.984 1.7
19 *
397 : Theoretical values which come from the theoretical TG/DTG results.
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21 398 The pyrolysis stages were selected according to the peaks around 180-400 oC and 400-550 oC in Fig. 1c-e.
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46 Fig. 1 Pyrolytic behavior of wheat straw and oil shale
47 and co-pyrolytic behavior of different blends
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32 c d
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36 oil shale & wheat straw blends.
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47 -S:W=0:1 - S:W=1:3 - S:W=1:1 - S:W=3:1 - S:W=1:0
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19 Fig. 5 Gas yield of S-W blends during the closed-system pyrolysis
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33 c Change of H/C atomic ratio in different S-W blends
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Fig. 6 Change of the liquid products from the co-pyrolysis of different S-W blends
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21 Fig. 8 Influence of blending ratios on the compositions of blending-oils
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