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Evidence of interactions in microwave-assisted Co-Pyrolysis of different varieties of

coals

B. Rajasekhar Reddy, R. Vinu

PII: S1743-9671(20)30200-2
DOI: https://doi.org/10.1016/j.joei.2020.11.006
Reference: JOEI 827

To appear in: Journal of the Energy Institute

Received Date: 15 July 2020

Revised Date: 3 November 2020
Accepted Date: 10 November 2020

Please cite this article as: B.R. Reddy, R. Vinu, Evidence of interactions in microwave-assisted
Co-Pyrolysis of different varieties of coals, Journal of the Energy Institute (2020), doi: https://
doi.org/10.1016/j.joei.2020.11.006.

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Graphical Abstract

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1 Evidence of Interactions in Microwave-Assisted Co-Pyrolysis of Different

2 Varieties of Coals

3 B. Rajasekhar Reddy* and R. Vinu*

4 Department of Chemical Engineering and National Center for Combustion Research and

5 Development, Indian Institute of Technology Madras, Chennai-600036, India.

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*
Corresponding Authors. E-mail (R.V.): vinu@smail.iitm.ac.in. Phone: +91-44-22574187.
E-mail (B.R.R.): rajasekharreddy104@gmail.com.
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 7 Abstract

8 In this study, microwave-assisted co-pyrolysis of blends of Indonesian coal (IC), with

9 Indian medium ash coal (MAC), Indian high ash coal (HAC) and coking coal (CC) was

10 performed to evaluate the product yield and quality of the pyrolysis tar, and to understand the

11 interactions during co-pyrolysis. The tar yields from pyrolysis of individual coals, viz., IC,

12 HAC, MAC and CC were 26 ± 3 wt.%, 14 ± 2 wt.%, 12 ± 2 wt.% and 11 ± 2 wt.%,

13 respectively. In co-pyrolysis, tar yields decreased with decrease in IC fraction in the mixture.

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14 Importantly, the experimental yields of products were similar to that calculated using the

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15 mixture rule. However, interactions were evident in the gas and char yields from pyrolysis of

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IC-rich mixtures, and the deviation from calculated values was in the range of 3-5 wt.%.

17 Pyrolysis tar from IC predominantly contained phenols, whereas tars from HAC, MAC, and
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18 CC contained aromatic hydrocarbons, phenolics and aliphatic hydrocarbons. The interactions
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19 were evidenced in the form of enhanced selectivity to naphthalene derivatives and

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20 polyaromatic hydrocarbons with a concomitant reduction in the selectivity to simple phenols

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21 in the coal tar. Interactions were predominant in equal composition and IC-rich mixtures of
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22 IC:HAC, IC:MAC and IC:CC, which is due to the early formation of char via decomposition

23 of IC. Hydrogen and methane constituted a major fraction of pyrolysis gases from MAC,

24 HAC and CC and their blends, while the pyrolysis gas from IC was rich in H2 and CO2.

25 Higher heating values of coal chars varied in the range of 21-27 MJ kg-1.

26 Keywords: Microwave pyrolysis; Indonesian coal; high ash coal; medium ash coal; coking

27 coal; coal tar

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28 1. Introduction

29 Coal blending is a process of mixing two or more coals of different ranks or

30 reactivities. Coals differ a lot in their reactivity due to their petrographic and chemical

31 composition. Moreover, there is a high possibility that a particular coal mined from a colliery

32 can be a mix of different ranks/types. Generally, less reactive low rank coals are blended with

33 more reactive high rank coals in order to enhance their conversion in any thermochemical

34 process. Coal blending is commonly preferred in gasification and combustion processes in

35 order to reduce the ash content, sulfur content, and to increase the combustible matter [1]. In

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36 coke making, it is imperative to blend high quality coking coals with locally available coals

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37 in order to strike a balance in the use of locally available coals with high-cost metallurgical

38
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coking coals [2]. In the past decade, there has been an increase in utilization of coal blends by
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39 the Indian power industry. Typically, Indonesian coals are blended with Indian coals due to
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40 high ash content and inadequate supply of the latter [3]. Coal blending alters the process
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41 parameters, product quality, and the efficiency of the thermochemical process.

India is rich in high ash coals, which are not usually used due to their ineffective
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42

43 combustion leading to huge fly ash liberation and bottom ash deposits. In addition to the poor
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44 conversion and energy output, increased environmental concerns are also impacting the

45 utilization of high ash coals. Nevertheless, regained interest in coal-to-liquid technologies to

46 produce liquid transportation fuels and chemicals is an opportunity to utilize locally available

47 high ash coals. Therefore, it is essential to device alternate ways for the sustainable utilization

48 of these coals. Conversion of these coals into liquid hydrocarbon fuels is a viable and

49 practical option. Importantly, liquefaction of blends of low ash/high volatile matter coals such

50 as Indonesian coals with high ash/low volatile matter coals is promising due to the higher

51 production of coal tar, which is a source of high value chemicals. Although the production of

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52 hydrocarbons by Fischer Tropsch conversion of the syngas obtained via coal gasification is

53 an established technology [4], single step conversion of coal to liquids via pyrolysis

54 technology is an interesting and upcoming process. Pyrolysis involves subjecting the solid

55 fuels to moderate temperatures (500–800 °C) in non-oxidative environment to produce high

56 quality tar, gases and char [5]. Importantly, pyrolysis is the primary step in combustion and

57 gasification processes. Therefore, a fundamental understanding of the pyrolysis of blends of

58 high volatile and low volatile matter containing coals is vital for the deployment of this

59 technology.

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60 Conventional heating involves conduction, convection and radiation, while

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61 microwave heating involves non-contact energy transfer. Microwave-assisted pyrolysis has

62
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been recognized as an efficient, rapid, selective, and easily controllable process for the
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63 conversion of solid and liquid feedstocks [6–11]. The generation of localized microplasma
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64 hotspots ensures fast pyrolysis of the sample. This results in faster escape of the pyrolysis
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65 vapors to the gas phase, and effective control of secondary cracking reactions, which

66 improves the tar yield [12].

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67 Microwave pyrolysis of coals of different origins has been reported in the literature
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68 [9–11,13–21]. The dielectric loss tangent of coal is low, which leads to its poor microwave

69 absorbing capability [22]. In order to obtain high heating rates, it is imperative to use

70 susceptors such as activated carbon, graphite, pyrolysis char, SiC, and other similar materials.

71 Reddy and Vinu [9,10], and Reddy et al. [11] studied the microwave pyrolysis of Indian

72 coals, coking coals and Indonesian coals, and reported the effect of coal particle size, coal-to-

73 susceptor ratio, microwave power and type of coals on tar yield and tar composition.

74 Microwave pyrolysis tar was rich in polyaromatics, whereas analytical pyrolysis tar was rich

75 in monoaromatics for the same type of coal. Zhang et al. [18] have studied the microwave

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76 pyrolysis of low rank American brown coal, and the effect of feedstock mass (20-50 g),

77 reaction temperature (500-750 0C) and isothermal heating time (10-30 min) on tar yield. They

78 observed that tar yields increase initially, and then decreased with increasing feedstock mass,

79 reaction temperature and isothermal heating time.

80 Liu et al. [13] studied the microwave-assisted pyrolysis of low rank coal using metal

81 catalysts to obtain high quality products. Metals such as K, Ca, and Fe were impregnated into

82 coal to enhance the microwave absorbing efficiency and catalyze the reactions. The results

83 demonstrated that catalytic pyrolysis reactions generated high yields of syngas (CO + H2),

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84 mainly with Ca and Fe catalysts. Abdelsayed et al. [14,23] studied the microwave pyrolysis

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85 of low rank American coals and compared the results with conventional pyrolysis, and

86
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showed that microwave pyrolysis results in higher gas yields and lower tar yields compared
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87 to conventional pyrolysis. In methane ambience, both char and tar yields increased due to
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88 carbon deposition and hydrogenation reactions.

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89 A few studies have evaluated the effect of blending different varieties of coals on their
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90 coking and combustion behavior [24–26]. Wang et al. [24] studied the combustion
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91 characteristics of coal blends using thermogravimetry, and showed that the additive behavior

92 is not followed, and that the apparent activation energies of combustion of the blends at low

93 temperatures were higher than that at high temperatures. Krzesińska et al. [26] evaluated the

94 dynamic thermo-mechanical behavior of coal blends, and found variations in temperature of

95 maximum fluidity, degree of structure ordering and loss modulus with addition of very good

96 coking coals. As blending of two varieties of coals is widely practiced in combustion,

97 gasification and coke making, a fundamental understanding of pyrolysis, which is the primary

98 and paramount step in these processes, is essential. Moreover, in order to advance the efforts

99 of introducing microwave-assisted heating in the above processes, it is imperative to obtain a

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100 fundamental understanding of the effect of microwave heating on thermal behavior of coal

101 blends, and the product characteristics.

102 To the best of authors’ knowledge, this is the first study to report microwave-assisted

103 pyrolysis of coal blends of different ranks, viz., Indonesian coal with high, medium and low

104 ash Indian coals, to evaluate the possible interactions among the coal types and the

105 composition of the products. The objectives of the study are three-fold. Firstly, to assess the

106 yields of tar, gas and char from microwave-assisted pyrolysis of coal blends of different

mixture ratios using coal char as susceptor. Secondly, to evaluate the effect of blending on

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107

the composition of coal tar and pyrolysis gases. Thirdly, to understand the interactions of

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109 different coal blends and their intermediates during co-pyrolysis in terms of the difference in
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110 predicted and experimental yields of products, and various functional groups in pyrolysis tar.
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111 2. Experimental Section

112 2.1. Materials and Characterization

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113 High ash Indian coal (HAC) and Indonesian coal (IC) were obtained from North
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114 Chennai Thermal Power Station, Chennai, India. Medium ash coal (MAC) was obtained from
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115 Rayalaseema Thermal Power Station, India. Coking coal (CC) was obtained from Tata Steel

116 Ltd., India. HAC, MAC and CC were mined at Mahanadi coalfields, Singareni coalfields and

117 Raniganj coalfields, India, respectively. Coals were crushed, ground and sieved to average

118 particle size of 0.5 mm.

119 Thermogravimetric analysis (TGA) was performed in a SDT-Q600 TG analyzer (T.A.

120 Instruments). The coals and coal blends were heated from ambient to 900 0C at 10 0C min-1 in

121 N2 ambience with a flowrate of 100 mL min-1. Proximate analysis was performed according

122 to ASTM E1131-08 in a multiple sample TGA (TGA-2000 A, Navas Instruments) by taking

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123 1.0 g of sample. Ultimate analysis was performed according to ASTM D-3176 in an

124 elemental analyzer (Thermo Flash 2000) by taking 3 mg of sample. Higher heating values

125 (HHVs) of coals, tars and chars were determined using a bomb calorimeter (IKA C2000) by

126 taking 300 mg of sample. Ash analysis was performed according to ASTM D-3682:2011

127 method.

128 Table 1 depicts the proximate analysis, elemental analysis and HHV data of coals.

129 The coals vary significantly in terms of ash, volatile matter and fixed carbon content. CC and

130 IC contain lowest amount of ash among all coals. IC is rich in volatile matter, while MAC

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131 and CC contain similar volatile matter. From elemental analysis, it is evident that CC is rich

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132 in carbon, while IC is rich in oxygen. HHVs of coals follow the trend: CC > MAC > IC >

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HAC. The low HHV of HAC is due to high mineral matter in it. The rank of the coals,
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134 assessed based on volatile matter content in them, follows the trend: CC (high rank) > MAC
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135 > HAC > IC (low rank). Additionally, petrographic analysis of coals from our previous
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136 studies reveals that vitrinite, liptinite and inertinite contents are 89.7%, 0.8% and 9.5%,

137 respectively, in IC, 61%, 10% and 14.6%, respectively, in HAC, 78.4%, 8.4% and 13.2%,
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138 respectively, in MAC and 51%, 0% and 43.7%, respectively, in CC [9,11]. The absence of
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139 liptinite in CC indicates the high maturity of coal. Vitrinite and liptinite are characterized by

140 high O/C and high H/C ratios, respectively. This validates the high amount of oxygen in IC

141 followed by MAC. This is also in agreement with the elemental analysis data.

142 Ash analysis was performed according to ASTM D 3682:2011 and ASTM 1757:2003

143 methods. Table 2 presents the ash composition of different coals. MAC, HAC and CC coal

144 ash contain high amounts of SiO2 and Al2O3 followed by Fe2O3. It is well reported in the

145 literature that Indian coal ash is rich in SiO2 and Al2O3 [9,10]. Interestingly, Indonesian coal

146 ash is rich in CaO, Fe2O3 followed by Na2O, Al2O3. The variation in the ash composition of

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147 various coals can be attributed to differences in the maturity of coal and geographical

148 location.

149 Table 1. Characterization of coals and pyrolysis char.

Medium High ash

Coking Indonesian Pyrolysis
ash coal coal
coal (CC) coal (IC) char
(MAC) (HAC)
Proximate VM 23.6 24.4 31.9 52.3 12.0±2.0
analysis, wt.% FC 67.9 55.1 33.2 38.3 72.0±3.0
(dry basis) Ash 8.5 20.5 34.9 9.4 16.0±2.0

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C 69.7 73.2 72.6 55.7 86.8±2.0

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Elemental
H 5.2 4.9 6.4 4.9 1.5±0.5
analysis, wt.%
(dry ash free
N
S
0.8
0.4
-p1.6
0.1
1.7
0.6
0.8
0.2
3.2±0.5
--
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basis)
O* 23.9 20.2 18.7 38.4 7.1±3.0
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HHV (MJ kg-1) 26.8 23.3 17.9 19.9 27.0±3.0

150 VM – Volatile matter, FC – Fixed carbon, *O=100-C-H-N-S, HHV – Higher heating value
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151 Table 2. Ash composition of coals

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Na2O K2O CaO MgO SiO2 P2O5 Fe2O3 Al2O3 TiO2

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IC 14.1 0.8 21.5 4.0 8.7 0.1 17.1 10.9 0.2

MAC 0.2 0.4 1.5 0.7 46.7 1.2 10.5 35.9 1.1

HAC 0.2 0.7 1.6 0.8 61.7 1.2 11.4 19.8 1.2

CC 0.8 0.3 1.2 0.2 51.0 0.1 2.3 40.6 0.9

152 2.2. Experimental Set-up and Procedure

153 A multimode, domestic on-off microwave oven (Whirlpool-MW 20BS) was modified

154 to conduct pyrolysis experiments. In order to recover the pyrolysis vapors, a 30 mm hole was

155 drilled on top of the microwave oven. A 250 mL quartz flat bottom flask was used as the

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156 reactor, and two stage condensation system was used for the condensation of tar. Chilled

157 water (~5 0C) was used as the condenser coolant. The quartz flask was insulated with quartz

158 wool to prevent the heat losses. Teflon® was used to seal the joints to prevent the leakage of

159 the vapors. A modified K-type thermocouple was used to measure the temperature during off-

160 time of the magnetron. The chromel-alumel wires were separated, and a hot junction was

161 made by electric arcing. Alumina beads were used to separate the wires and keep them apart.

162 Aluminum foil was wrapped to avoid the interaction of microwaves, and the wires were

163 placed in a stainless tube. The schematic of the microwave reactor set-up is shown in Fig. S1

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164 (in Supplementary Data). The details of the experimental set-up are also available in our

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165 earlier publications [9-11].

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As coals possess relatively low dielectric loss tangent (tan δ = 0.02-0.10), coal char
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167 was used as the susceptor. Experiments were carried out by taking 40 g of coal/coal blend
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168 and 20 g of coal char at a fixed microwave power of 560 W. The characteristics of the coal
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169 char used as the susceptor are shown in Table 1. Blends of IC with HAC, IC with MAC, IC

170 with CC were subjected to microwave pyrolysis at different mixture ratios, viz., 100:0, 75:25,
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171 50:50, 25:75 and 0:100 (wt.%/wt.%). A blending device was used for homogeneous mixing.
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172 Pyrolysis was conducted upto a final temperature of 800 0C, and the mixture was maintained

173 isothermal at the final temperature for 10 min in order to achieve complete evolution of

174 volatiles. The evolution of condensable vapors was observed until 600-650 0C, and at higher

175 temperatures, evolution of non-condensable gases was observed. At the end of every

176 experiment, the yields of oil and char were calculated by measuring the mass of tar and solid

177 residue gravimetrically, and the yield of gas was calculated by mass balance. The mass of

178 coal char used as susceptor was subtracted from the solid residue, as char did not decompose

179 significantly (<1 wt.% mass loss) at the reaction conditions [27,28]. The experiments were

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180 repeated non-consecutively three times, and the standard deviation in product yields and

181 composition are reported.

182 2.3. Characterization of Tar, Char and Gases

183 Tar was analyzed semi-quantitatively using gas chromatograph/mass spectrometer

184 (GC/MS) (Shimadzu FC-2010 and QP2020) for its organic composition. An Rxi-5Sil MS

185 column (5% 1,4-bis-(dimethylsiloxy) phenylene dimethyl polysiloxane, 30 m length × 0.25

186 mm i.d. × 0.25 µm film thickness) was used to separate the organic components in the tar

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187 fraction. Ultra-high pure helium (99.9995%) was used as the carrier gas at a flow rate of 1

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188 mL min-1 through the column. The column oven compartment was programmed as follows:

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isothermal at 40 0C for 2 min, heated to 250 0C at a rate of 5 0C min-1, and finally held at 250
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0
190 C for 5 min. The injector, MS ion source and detector temperatures were set at 275 0C, 320
0
C and 150 0C, respectively. Mass range scanned was from 40 to 500 Da, and the electron
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191

192 ionization voltage was 70 eV. The injector split ratio was 25:1. Dichloromethane was used to
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193 dilute the viscous tar. The mass spectra of the unknown organic compounds in tar were
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194 compared with NIST library, and all the identified compounds had a match factor >85%. The
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195 composition of the organic components is presented in terms of relative peak area%. The

196 evolved non-condensable gases, viz. CO2, H2, CO and CH4, were continuously measured

197 using an online gas analyzer (Bhoomi Analyzers, India) whose response time was 1-2 s. Non-

198 dispersive infrared sensors were used to detect CO, CO2 and CH4, while electrochemical

199 sensor was used to detect H2. Chars were characterized for proximate composition, ultimate

200 composition and HHV as per the methods outlined in Section 2.1.

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201 3. Results and Discussion

202 3.1. Conventional Pyrolysis in TGA

203 In order to assess the typical decomposition regimes of individual coals and their

204 blends, TGA was performed. Fig. 1 depicts the mass loss and differential thermogravimetric

205 (DTG) profiles of the individual coals. IC, MAC, HAC and CC exhibit decomposition in the

206 temperature range of 320-750 0C, 380-800 0C, 370-800 0C and 420-900 0C, respectively. The

207 above decomposition patterns are in agreement with the literature [9,29–31]. IC

208 decomposition occurs in a wide temperature range unlike other coals due to its low maturity

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and presence of high volatile matter.

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209

0.25
0
417 C
-p 448 C
0
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IC (b)
0.20
massloss (%/ C)

0
CC
0

481 C MAC
Differential

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HAC
0.10
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0.05

0.00
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100 200 300 400 500 600 700 800 900

100
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Mass remaining (wt.%)

90 (a)
80
70
60
50
40
100 200 300 400 500 600 700 800 900
0
Temperature ( C)
210

211 Fig. 1. (a) TG mass loss and (b) differential thermogravimetric (DTG) data at 10 0C

212 min-1 for individual coal pyrolysis.

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213 Tables 3 and 4 depict the temperatures corresponding to maximum mass loss rate

214 (Tmax), and the temperature required to achieve 50% mass conversion of the total volatile

215 matter (including moisture) (T50%) released during pyrolysis of individual coals and coal

216 mixtures. Coals exhibit different Tmax due to the differences in their maturity and

217 composition. CC exhibits high Tmax (482 0C), whereas IC exhibits low Tmax (410 0C). From

218 Fig. 1, it can be observed that residual mass at the end of 900 0C was high for CC (~72 wt.%)

219 and was low for IC (~45 wt.%). Similarly, T50% for different coals followed the trend: CC

220 (505 0C) > MAC (478 0C) > HAC (469 0C) > IC (441 0C). The trend in T50% of coals is in

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221 agreement with their rank and maturity. Early decomposition of IC can affect the conversion

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222 of blends, especially when IC amount is high in the mixture.

223
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Table 3. Experimental and calculated maximum decomposition temperatures (Tmax)
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224 during pyrolysis of different coal blends at different mixture ratios.
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(wt.%/ IC:HAC (0C) IC:MAC (0C) IC:CC (0C)

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wt.%) Calculated Experimental Calculated Experimental Calculated Experimental

100:0 -- 417.3 -- 417.3 -- 417.3

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75:25 425.0 443.7 425.0 443.7 443.3 438.2

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50:50 432.7 444.6 432.5 448.8 449.3 467.2

25:75 440.5 446.7 440.0 450.9 465.3 476.9

0:100 -- 448.2 -- 447.6 -- 481.3

225

226

227

228

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229 Table 4. Experimental and calculated temperatures corresponding to 50 wt.%
230 conversion (T50%) during pyrolysis of different coal blends at different mixture ratios.

(wt.%/ IC:HAC (0C) IC:MAC (0C) IC:CC (0C)

wt.%) Calculated Experimental Calculated Experimental Calculated Experimental

100:0 -- 441.4 -- 441.4 -- 441.4

75:25 448.4 449.8 450.4 451.2 457.2 456.2

50:50 455.4 454.0 459.5 462.2 473.0 481.9

25:75 462.3 460.6 468.5 479.8 488.8 496.3

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0:100 -- 469.3 -- 477.5 -- 504.6

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231
232
233
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Fig. 2 depicts the DTG profiles of co-pyrolysis of IC:MAC, IC:HAC, and IC:CC
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234 blends at all mixture ratios. It can be observed that the Tmax values are similar for IC:MAC
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235 and IC:HAC mixtures with <5 oC variation, while the Tmax values for IC:CC mixtures are
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236 completely different from other coal mixtures. In order to understand the possible interactions

237 that might lead to changes in decomposition temperatures, Tmax and T50% values were
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238 calculated for the blends using the experimental values of Tmax and T50% corresponding to the
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239 individual coals, as given by the following expressions.

240 (Tmax)calculated = x×(Tmax)experimental,IC + (1–x)×(Tmax)experimental,HAC or MAC or CC (1)

241 (T50%)calculated = x×( T50%)experimental,IC + (1–x)×( T50%)experimental,HAC or MAC or CC (2)

242 where x denotes the mass fraction of IC in the coal blend.

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 0.12 IC:CC (wt.%/wt.%)
(c)
25:75
0.08 50:50
Differential mass loss (%/ C)

75:25
0.04
0

0.00
0.16
(b) IC:MAC (wt.%/wt.%)
0.12 25:75
50:50
0.08
75:25
0.04

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0.00
0.16 IC:HAC (wt.%/wt.%)
(a)

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0.12 25:75
50:50
0.08

0.04
-p 75:25
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0.00
100 200 300 400 500 600 700 800 900
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0
Temperature ( C)
243
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244 Fig. 2. Differential thermogravimetric (DTG) data for pyrolysis of different coal blends
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245 of different blend ratios at 10 0C min-1.

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246 From Table 3, it is evident that the calculated and experimental Tmax values are

247 significantly different (>10 0C) from each other for all the coal mixtures. The deviation in

248 experimental Tmax compared to calculated Tmax can be attributed, atleast qualitatively, to the

249 possible inhibition of IC pyrolysis by other coal particles that are in contact with them. It is

250 evident from Table 4 that calculated T50% and experimental T50% are similar for all IC:HAC

251 blends, and IC-rich mixtures of IC:MAC blends. Experimental T50% of MAC-rich mixture

252 (IC:MAC 25:75 wt.%/wt.%) and CC-rich mixtures (IC:CC 50:50 and 25:75 wt.%/wt.%) are

253 higher than the corresponding calculated T50%. This deviation is due to the resistance to

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254 devolatilization of low rank IC offered by high rank MAC and CC. Importantly, as the

255 decomposition temperatures of IC and CC are significantly different, the deviations in

256 calculated T50% and experimental T50% are also large.

257 3.2. Product Yields from Pyrolysis of Individual Coals and Blends

258 Initial experiments performed with 40 g of individual coals at 560 W without using

259 coal-char susceptor revealed that, after 20 min of microwave irradiation, the observed

260 temperatures were lower than 200 0C for all coals. This illustrates the poor absorbing

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261 capability of microwaves by coals [9,11,32]. Therefore, coal char was used as microwave

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262 susceptor in all further experiments. Initially, coal char was prepared by conventional

263 -p
pyrolysis of CC at 900 0C in a muffle furnace, and later, char from microwave pyrolysis was
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264 used as susceptor for the microwave pyrolysis experiments. Microwave pyrolysis of only coal

char at 560 W took ~10 min to achieve the final temperature of 800 0C. The properties of
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265

266 coal-char from different batches were characterized. Table 1 depicts the proximate analysis,
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267 elemental analysis and HHV of the char used as susceptor. It is evident from earlier studies
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268 that microwave power and amount of susceptor do not play a significant role in altering the
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269 product yields from coal pyrolysis [9,10]. Therefore, experiments were performed at a fixed

270 microwave power (560 W) and fixed feed-to-susceptor mass ratio (2:1 (wt./wt.)). The

271 specific microwave energy consumption, defined as the ratio of microwave power to the mass

272 of susceptor, is 28 W g-1. The focus of the study is to comprehend the interactions during

273 pyrolysis of different coal blends.

274 Fig. 3 depicts the tar, gas and char yields obtained from pyrolysis of individual coals.

275 Highest tar yield (≈ 26 wt.%) was obtained from IC and lowest tar yield (≈ 12 wt.%) was

276 obtained from MAC and CC. High tar yield from IC is due to the high volatile matter content

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277 and low maturity, while CC and MAC contain low volatile matter. The char yields follow the

278 trend: 42.7 wt.% (IC) < 67.0 wt.% (HAC) < 70.0 wt.% (MAC) < 75.8 wt.% (CC). The char

279 yields are in accordance with the sum of ash and fixed carbon in the respective coals, with

280 lesser than 5% deviation. This illustrates nearly complete devolatilization. Fig. S2 (in

281 Supplementary Data) presents the reaction temperature profiles. The average heating rates (in
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282 C min-1) calculated in the entire temperature range for individual coals is given by: 57

283 (MAC) < 64 (IC) < 66 (HAC) ≈ 66 (CC). Typically, the final temperature was reached within

284 12-14 min. Generally, the heating rate of a material in the microwave field is influenced by

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285 carbonaceous materials and inorganic oxides that are typically present in the ash of coals. The

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286 high heating rates achieved in HAC and CC pyrolysis can be attributed to the high amount of

287 ash in HAC and carbon in CC.

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288 Fig. 3 also depicts the product yields obtained from different mass ratios of IC:HAC,
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289 IC:MAC and IC:CC blends. The mixture composition significantly influences the distribution
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290 of products. It is evident that the tar yields vary systematically with coal composition. With
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291 decrease in mass of IC in the mixture, the tar yield also decreased due to lowering of effective
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292 volatile matter in the mixture. In order to evaluate the interactions during co-pyrolysis of coal

293 blends, the experimental product yields (Yexperimental-blend) were compared with the calculated

294 yields (Ycalculated-blend). The calculated yields were determined using a linear algebraic

295 equation, which is given below.

296 Ycalculated-blend = x×Yexperimental,IC + (1–x)×Yexperimental,HAC or MAC or CC (3)

297 The calculated or experimental yield given in the above expression can correspond to tar, gas

298 or char, and the term x corresponds to the mass fraction of IC in the blend. The increase or

299 decrease in the experimental values with respect to the calculated values is termed as

16
300 synergetic or inhibition effect. These effects due to the possible interactions are represented

301 using the parameter, deviation in yield (Yd), defined as follows.

302 Yd = Yexperimental-blend – Ycalculated-blend (4)

303 Non-zero value of Yd (Yd ≠ 0) signifies the possible interactions. Positive and negative values

304 of Yd represent the synergy and inhibition in the formation of a particular product,

305 respectively.

Tar Gas Char

of
100

ro
90 66 70
43 45 54 62 67 58 61 50 62 70 76
80

70
-p
re
Yield (wt.%)

60
lP

50

40
na

30
ur

20

10
Jo

27 23 23 17 14 21 19 14 12 18 16 14 12
0
0
0

0
0

5
0

5
0
0
5
5

:5
0:

10
10

:2
:5

:7
10
:5
:7
:2

:2

:7

50
10

75
50

25
50
25
75

75

25
0:

0:
0:

IC:HAC IC:MAC IC:CC

(wt.%/wt.%) (wt.%/wt.%) (wt.%/wt.%)
306
307 Fig. 3. Yields of tar, gas and char obtained from microwave pyrolysis of individual

308 coals and different coal blends.

309 Fig. S2 (in Supplementary Data) depicts the reaction temperature profiles for co-

310 pyrolysis of coal blends. The average heating rates were high (90-105 0C min-1) for the IC-

311 rich mixtures (75:25 wt.%/wt.% IC:MAC and IC:CC). Compared to microwave pyrolysis of
17
312 individual coals, the final temperature of 800 oC was attained at a shorter time of 8-11 min

313 when the coals were blended. This is due to the variation in feed composition of the mixture

314 that results in the early char formation from IC during the pyrolysis process. This enhances

315 the dielectric loss tangent of the entire mixture, thus improving the reaction heating rate.

316 Importantly, this could alter the evolution of volatile matter and the product yields.

317 Fig. 4 depicts the deviation in product yields for various coal blends. Major deviation

318 is observed in gas and char yields for all the coal blends. The deviation is, in fact, pronounced

in IC-rich mixtures. The highest deviations in gas yield (-7%) and in char yield (+8%) were

of
319

observed for IC:MAC 75:25 (wt.%/wt.%). Similarly, large deviations were observed for

ro
320

321 75:25 (wt.%/wt.%) IC:HAC in gas (+4%) and char (+4%) yields. For all other mixture
-p
322 combinations, the deviations were within the range of ±2%. The deviations in gas and char
re
323 yields could be due to variation in heating rates for these blends. However, the yields of tar
lP

324 were not influenced by the mixture ratio for all blends, which shows that the tar production
na

325 follows an additive rule based on tar yields from individual coal pyrolysis. It is worthwhile to

note that during microwave pyrolysis complete evolution of liquid tar occurs within 650 oC,
ur

326

while the liberation of gases continues even until 800 oC. The late evolution of gases,
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327

328 especially at high temperatures, can be attributed to the secondary char decomposition

329 reactions. This results in the liberation of gases like CO, CO2, CH4 and H2 due to pyrolysis-

330 gasification reactions. Early formation of carbonaceous residue from IC pyrolysis results in

331 an increased dielectric loss tangent of the medium, which accelerates the heating rate in IC-

332 rich mixtures. Thus, the gas forming reactions are accelerated by the high density of local

333 microplasma hotspots generated in the solid residue. These processes lead to the alteration of

334 gas and char yields in co-pyrolysis of coal blends. The typical reactions are given below

335 [33,34]:
18
336 Coal–OH(s) + Coal’–OH(s) → Coal–O–Coal’(s) + H2O(g)

337 Coal–COOH(s) + Coal’–OH(s) → Coal–C(=O)─O–Coal’(s) + H2O(g)

338 Coal–COOH(s) + Coal’–COOH(s) → Coal–C(=O)─O–C(=O)─Coal’(s) + H2O(g)

339 Coal–O–Coal’(s) → Coal”(s) + CO(g)

340 Coal–C(=O)─O–Coal’(s) → Coal’”(s) + CO2(g)

341 Coal–C(=O)─O–C(=O)─Coal’(s) → Coal’”(s) + CO2(g) / CO(g)

342 C(s) + H2O(g) → CO(g) + H2(g)

343 C(s) + 2H2O(g) → CO2(g) + 2H2(g)

of
344 C(s) + CO2(g) → 2CO(g)

ro
345 Coal–CH3(s) + Aromatic–H(v) → Char(g) + CH4(g)

346
-p
Aromatic–H(s) + Aromatic–H(s) → Polyaromatic(s) + H2(g)
re
347 In the above sequence of reactions Coal, Coal’, Coal” refer to different coal
lP

348 fragments. The formation of moisture initially occurs at temperatures more than 300 oC via
na

349 bimolecular condensation of hydroxyl and carboxyl moieties, after which the decomposition

350 of ether, ester and anhydrides lead to the formation of CO and CO2. These gases can then
ur

351 react with the solid carbonaceous matrix during microwave pyrolysis to form CO and H2. The
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352 formation of CH4 and H2 can be independently traced to the decomposition of methyl groups

353 and H radicals at high temperatures followed by their recombination [11].

19
 75:25 50:50 25:75 (wt.%/wt.%)
5
IC:CC

5 IC:HAC
Sd (%)

-5

of
10
IC:MAC

ro
5
0
-p
re
-5
lP

Tar Gas Char

354
na

355 Fig. 4. Deviation in product yields (Yd) for different coal blends.
ur

356 3.3. Tar composition

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357 The organic compounds in tar were classified into six major categories, viz.,

358 monoaromatics, naphthalene derivatives, polyaromatics, simple phenols, aliphatic

359 hydrocarbons, and other compounds that were observed in minor quantities or those that were

360 identified with low match factor in GC/MS. Tables S1-S13 (in Supplementary Data) depict

361 the classified list of organics present in the tar fraction from various experiments. The

362 category of monoaromatics included a wide variety of compounds like (a) alkyl substituted

363 benzenes like toluene, xylenes, trimethyl benzenes, ethyl methyl benzene and styrene, (b)

364 methyl-substituted indene, (c) oxygenated non-phenols like methyl and dimethyl

365 benzofurans, and methoxy benzenes. Alkyl substituted naphthalenes like methyl-, dimethyl-
20
366 and trimethyl naphthalenes, naphthols and naphthalenols were the major naphthalene

367 derivatives. Polyaromatics include anthracene (C14H10), acenaphthylene (C12H8),

368 phenanthrene (C14H10), fluorene (C13H10), dibenzofuran (C12H8O), pyrene (C16H10), biphenyl

369 (C12H10) and their alkyl-substituted derivatives. Aromatic compounds result from the

370 cleavage of polycyclic rings of the coal molecule. Phenolic compounds mainly include

371 phenol, methyl phenols (cresols), dimethyl phenols (xylenols), ethyl phenols and ethyl methyl

372 phenols. Phenolic compounds mainly arise from the decomposition of lignified matter present

373 in coal [11,35]. Aliphatic hydrocarbons are produced from the pyrolysis of long chain

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374 aliphatic, saturated and unsaturated esters via decarboxylation reactions to form alkanes,

ro
375 alkenes and alkynes [36]. Most of the aliphatic hydrocarbons were C10-C30 alkanes and

376
-p
alkenes. As mentioned in Section 2.1, vitrinite-rich IC is expected to result in more
re
377 oxygenated compounds, while liptinite-rich HAC and MAC are expected to result in high
lP

378 amount of linear chain hydrocarbons.

na

379 3.3.1. Tar Composition from Pyrolysis of Individual Coals

ur

380 Fig. 5 depicts the composition of tar obtained from individual pyrolysis of coals. It is
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381 evident that phenols are the major compounds in pyrolysis tar from IC. The trend in the total

382 phenolic selectivity in the coal tars from individual pyrolysis of coals is given by: 65.5% (IC)

383 > 25.5% (HAC) ≈ 26.0% (MAC) > 20.7% (CC). The selectivity to total aromatic non-

384 phenols, i.e., sum of monoaromatics, naphthalene derivatives and polyaromatics, followed the

385 trend: 25% (IC) < 40% (HAC) < 49% (MAC) < 65% (CC). The selectivity to polyaromatics

386 also followed the same trend: 2.1% (IC) < 14.5% (HAC) < 19.5% (MAC) < 26.1% (CC). The

387 selectivity of aliphatic hydrocarbons was high in HAC tar, and the trend is given by: 31.0%

388 (HAC) > 22.2% (MAC) > 10.64% (CC) > 5.2% (IC). It is well known that coking

389 coals/bituminous coals are highly aromatized and matured as compared to other coals, and
21
390 the pyrolysis of these coals essentially result in high yield of polyaromatics [37]. MAC is a

391 low volatile sub-bituminous rank coal, and yields low aromatics than that from CC, and

392 relatively high yield of aliphatic hydrocarbons. HAC is a high volatile sub-bituminous coal,

393 and results in low aromatic yield, while high selectivity to aliphatic hydrocarbons and simple

394 phenols. Indonesian coal is basically a lignite coal, and its pyrolysis is known to yield high

395 phenolics [38].

Monoaromatics Naphthalene derivatives Polyaromatics

Simple phenols Aliphatic hydrocarbons Others

of
100

ro
90 14 22 11 14 15 11
12 25
21 29 33 31
80

70
-p 29 27 30 21
re
Selectivity (%)

60 33 53 28 26
lP

50 26
65 40 26 31 25 15 12
11 16
40
na

16 19
30 15
ur

20 36 25
36 26
13 19 21 15 16 30 20 20 17
10
Jo

0
0
0
5

5
0

5
0

5
0

:5

10
:5
:2

:7
10

:2
:5

:7

:7
0:

:2

10

50
75

50

25
75
50

25

25

0:
10

75

0:
0:

IC:HAC IC:MAC IC:CC

(wt.%/wt.%) (wt.%/wt.%) (wt.%/wt.%)
396

397 Fig. 5. Composition of tar obtained from microwave pyrolysis of individual coals and

398 different coal blends.

399 Lin et al. [39] characterized Indonesian brown coal, and came up with a molecular

400 formula given by C190H170O5N2. They concluded that the oxygen present in Indonesian coal

401 mainly occurs in the form of phenolic hydroxyl oxygen, and the pyrolysis of IC resulted in

22
402 high selectivity to phenolic compounds. As mentioned in Section 2.1, high amount of vitrinite

403 maceral in IC is indicative of the high oxygen content in it, which is responsible for the

404 phenolic-rich tar.

405 3.3.2. Tar Composition from Pyrolysis of Blends

406 Fig. 5 also depicts the composition of pyrolysis tars from blends of IC:HAC, IC:MAC

407 and IC:CC at different mixture ratios of 75:25, 50:50 and 25:75 wt.%/wt.%. The selectivity to

408 aliphatic hydrocarbons was more in IC:HAC blend as compared to all other blends. The

of
409 selectivity to phenols gradually decreased with decrease in IC in the mixture. The trends in

ro
410 the selectivity to simple phenols for IC:HAC (wt.%/wt.%) is given by: 65.5% (100:0) >

411 -p
39.6% (75:25) > 31.0% (25:75) > 26.4% (50:50) > 25.0% (0:100), for IC:MAC: 65.5%
re
412 (100:0) > 52.6% (50:50) > 32.7% (75:25) > 27.5% (25:75) ≈ 26.5% (0:100), and for IC:CC:
lP

413 65.5% (100:0) > 28.7% (75:25) ≈ 27.0% (50:50) ≈ 29.9% (25:75) > 20.7% (0:100). In order

414 to obtain a better understanding of the interactions, the deviation plots were drawn according
na

415 to following equation.

ur

416 Sd = Sexperimental – Scalculated (5)

Jo

417 where Sexperimental is the actual selectivity to a particular organic functional group in co-

418 pyrolysis tar, Scalculated is the calculated selectivity to a particular organic functional group in

419 co-pyrolysis tar, and Sd is the deviation in selectivity. Scalculated was calculated using an

420 expression similar to equation (3). As mentioned earlier, the interactions are understood by

421 the non-zero values of Sd (Sd ≠ 0). Positive and negative values of Sd represent the synergy

422 and inhibition effects in the formation of a particular product, respectively.

423 Fig. 6 depicts the deviations for all the functional groups in tar from different coal

424 blends. It is important to note that the selectivities to various organic functional groups do not

23
425 follow the additive rule, which indicates the occurrence of possible vapor phase interactions.

426 Deviations are especially significant for mixture ratios of 75:25 and 50:50 wt.%/wt.% for

427 IC:HAC, IC:MAC, IC:CC blends, while there are no significant deviations observed for

428 25:75 mixtures of these blends. This is primarily attributed to the heating rate and differences

429 in feed composition. Importantly, in IC-rich mixtures of 75:25 and 50:50 early decomposition

430 and char formation of IC are expected to significantly alter the tar composition. In addition,

431 the heating rate determines the pyrolysis severity and the extent of secondary decomposition,

432 which in turn determine the interactions of the primary volatile species as they pass through

of
433 the feedstock bed to the surface. As mentioned earlier, the average heating rates of IC-rich

ro
434 mixtures are high, which aids in vapor phase interactions.

435
-p
The absence of interactions in 25:75 mixtures can be attributed to low IC content in
re
436 the mixture, and different decomposition temperatures of coals as compared to other mixture
lP

437 ratios. Importantly, the selectivity to monoaromatics is not influenced by mixture ratio for all
na

438 blends. The selectivity to simple phenols is low as compared to calculated values in all the
ur

439 blends. The interactions among the pyrolysis intermediates from coal blends are evidenced in
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440 the form of enhanced selectivity to naphthalene derivatives and polyaromatic hydrocarbons

441 with a concomitant reduction in selectivity to simple phenols.

442 The catalytic role played by the ash constituents in coal on tar composition cannot be

443 completely ignored. Earlier works have shown that elements like Fe, Ca and K can affect the

444 yield of products, especially in improving the yield of gases (like CO, H2) and light aromatics

445 in the tar due to excessive cracking and better heating rates [13,35]. From the ash

446 composition in Table 2, it is evident that HAC and MAC contain significant amounts of SiO2

447 and Al2O3, accounting for >80% of the ash, followed by Fe. CC contains high amount of

448 SiO2 and Al2O3 accounting for >90% of the ash. Therefore, it can be understood that CC ash
24
449 may only exhibit low catalytic activity. As IC contains higher proportion of Ca, Fe, Na, and

450 Mg in ash, equal composition and IC-rich mixtures of IC:HAC, IC:MAC and IC:CC are

451 expected to exhibit similar effect. Moreover, as the char from CC pyrolysis was used as a

452 susceptor in all the experiments, the role of ash in the susceptor in altering the product

453 distribution is expected to be minimal. Therefore, the combined effect of early decomposition

454 of IC and ash constituents (Ca, Fe, Na, Mg) in IC-rich mixtures could have resulted in the

455 aforesaid variations in the tar composition. More detailed studies are required to unravel the

456 effect of specific inorganic constituents on the tar composition.

of
Fig. 7 depicts the possible transformations leading to the formation of major pyrolysis

ro
457

458 products, and conversion of phenols to naphthalene and polyaromatic hydrocarbons during
-p
459 microwave pyrolysis. A model coal macro-molecular structure is shown, and the salient steps
re
460 involved in the formation of gas, tar and char are depicted by considering 5-hydroxytetralin
lP

461 as the primary pyrolysate. The plausible pathway for the enhanced formation of naphthalene
na

462 and polyaromatics are proposed using phenol as a precursor compound. This is justified by
ur

463 the decrease in production of phenol in the tar fraction when IC-rich coal blends. One
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464 pathway by which phenol degrades is through the formation of cyclopentadiene via

465 decarbonylation [40,41]. The reaction of cyclopentadienyl radical with cyclopentadiene

466 yields a resonance stabilized dimer radical, which can either take the C–H and C–C bond β-

467 scission pathways to form naphthalene, or form indene via intramolecular addition pathways

468 [41]. This reaction pathway justifies the reduction in simple phenols in tar from IC-rich

469 mixtures along with concomitant increase in production of naphthalene derivatives. Such a

470 reaction sequence for the formation of polyaromatic hydrocarbons is also shown to occur in

471 pyrolysis of algae [42].

25
472 HHVs of pyrolysis tars obtained from individual coals and their mixtures under different

473 conditions were estimated using the empirical correlation given by following equation [11].

474 HHV (MJ/kg) = 0.3406 %C + 1.4324 %H − 0.1532 %O + 0.1047 %S (5)

475 The %C, %H, %N, %S and %O were calculated using GC/MS composition data of

476 coal-tars. The calculated HHVs of pyrolysis tars from individual coals followed the trend:

477 31.3 MJ kg-1 (IC) < 35.6 MJ kg-1 (MAC) ≈ 35.5 MJ kg-1 (HAC) < 37.8 MJ kg-1 (CC). The

478 low HHV of IC tar is due to the presence of high amount of phenolics, which contain high

of
479 oxygen, while high HHVs of tars from MAC, HAC and CC are due to high carbon and

ro
480 hydrogen content in the form of monoaromatics, polyaromatics and long chain aliphatic

481 -p
hydrocarbons. The elemental analysis of tars revealed that the oxygen content of IC tar was
re
482 high (18.5 wt.%) and CC tar was lowest (11 wt.%), The HHVs of tars from coal blends

followed an additive trend, and were in the range of 33-36 MJ kg-1. This shows that
lP

483

484 significant value addition of coal tars from low rank coals can be achieved by blending.
na
ur
Jo

26
 75:25 50:50 25:75 (wt.%/wt.%)

15 IC:CC

-15

-30
IC:MAC
10
Sd (%)

-10

of
-20

IC:HAC

ro
10

-10
0 -p
re
-20
lP

Mono- Naphthelene Poly- Simple Aliphatic

aromatics derivatives aromatics phenols hydrocarbons
485
na

486 Fig. 6. Deviation in selectivity (Sd) to different functional groups in coal tars from
ur

487 microwave pyrolysis of different coal blends.

Jo

27
 of
ro
-p
re
lP

488
na

489 Fig. 7. Plausible pyrolysis reactions and transformations during microwave pyrolysis.
ur

490 3.4. Analysis of Gases and Pyrolysis Char

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491 The time evolution of non-condensable pyrolysis gases (CO, CO2, H2 and CH4) from

492 individual coals and blends was monitored using an online gas analyzer. Fig. 8 depicts the

493 gas composition from individual coal pyrolysis. The evolution of non-condensable gases was

494 observed at low bulk reaction temperature of 150-200 0C, which is in agreement with the

495 literature [11,43]. In a typical experiment involving conventional pyrolysis of coal, the

496 evolution of CO2 and CO begins at 400 0C, CH4 starts at 550 0C, and H2 starts at above 650 0C

497 [44]. CH4 and H2 formation require high temperatures as the bond dissociation energy of R-H

498 (c.a. 435 kJ mol-1) and R-CH3 (c.a. 428 kJ mol-1) are high [45]. However, the instantaneous

28
499 and localized heating caused by micro plasma in microwave pyrolysis can lead to very high

500 localized temperature zones, which facilitates the cleavage of these bonds to form free

501 radicals. The hydrogen and methyl free radicals undergo recombination reactions to form

502 these gases. From Fig. 8, it is evident that H2 was the major gas produced from MAC (≈45

503 vol.%) and HAC (≈40 vol.%) pyrolysis, while CO2 (≈ 30 vol.%) was the major gas produced

504 from IC pyrolysis, and CH4 (≈40 vol.%) and H2 (≈45 vol.%) were the major gases from CC.

505 Compared to other coals, the yields of CO2 and CO released from IC were higher due to the

506 high oxygen content and its low maturity. The sum of the concentrations of CH4 and H2 was

of
507 high (≈75 vol.%), and the concentrations of CO (≈7 vol.%) and CO2 (≈5 vol.%) were low

ro
508 from CC owing to its maturity, low O/C ratio and low volatile matter content. However, the

509
-p
concentration of CO (≈17 vol.%) was high in MAC and HAC than that from CC. Similar
re
510 yields of H2 and CH4 were reported in microwave pyrolysis of Indian coals and coking coals,
lP

511 while the similar amounts of CO2 and H2 were reported in microwave pyrolysis of low rank
na

512 Indonesian and American lignite coals [11,23,46,47].

ur

513 In order to understand the evolution of pyrolysis gases from coal blends, the gases
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514 from co-pyrolysis of equal composition blends (50:50 wt.%/wt.%) were quantified. Fig. S3

515 (in Supplementary Data) depicts the time evolution of concentration of non-condensable

516 gases from different coal blends. H2 was the major gas produced from IC:MAC and IC:CC

517 blends, while the concentrations of CO2 and CO were significant from IC:HAC as IC and

518 HAC are of low rank, and rich in oxygen. Moreover, from the tar composition, it is evident

519 that vapor phase conversion of phenolics to naphthalene derivatives results in the release of

520 CO and CO2. CO production was typically 14-16 vol.% from the co-pyrolysis of blends,

521 while CO2 content in the gases followed the trend: IC:HAC (14.7 vol.%) > IC:CC (11.5

522 vol.%) > IC:MAC (5.3 vol.%). The concentration of H2 was 40-45 vol.% from IC:MAC and
29
523 IC:CC blends, while it was low from IC:HAC blend (≈30 vol.% ). Methane yield was more

524 than 40 vol.% from IC:HAC and IC:MAC blends, while it was low from IC:CC blend (22

525 vol.%).

CO CO2 CH4 H2
35 Indonesian coal Medium ash coal
30 40
25
30
20
15 20
Composition (vol.%)

of
10
10
5

ro
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14

40
High ash coal
-p 40
Coking coal
re
30 30
lP

20 20
na

10 10
ur

0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 16
Jo

Pyrolysis time (min)

526
527

528 Fig. 8. Time evolution of non-condensable gases during microwave pyrolysis of

529 individual coals. Methane evolution was more than 39 vol.% for coking coal, and this

530 saturated the detector response.

531 The solid residue produced from microwave pyrolysis was characterized for

532 proximate composition, elemental composition, and HHV. Table 5 presents the char

533 characterization data. It is evident that devolatilization is significant, and the chars are

30
534 enriched in fixed carbon and ash content as compared to the respective coals. Among all the

535 blends, chars from IC:CC blend contain high fixed carbon (~70 wt.%) and low ash (~16

536 wt.%) as compared to fixed carbon and ash in chars from IC:MAC and IC:HAC. This is also

537 reflected in the enhanced carbon and depleted hydrogen content in chars from IC:CC blends.

538 Table 5. Proximate, elemental and calorific value analyses of microwave pyrolysis chars
539 from different coal blends.

Proximate analysis Elemental analysis HHV

(wt.%, dry basis) (wt.%, dry basis) (MJ kg-1)

of
VM FC Ash C H N O*

ro
MAC 12.7 57.6 29.7 93.3 2.7 2.3 1.7 21.7

HAC 13.7 42.9

-p
43.4 84.5 2.8 4.9 7.8 20.5
re
CC 11.2 71.2 17.6 86.7 1.6 3.2 8.5 27.1
lP

IC 14.5 60.2 25.3 89.2 2.3 3.6 4.9 23.0

na

IC:MAC 75:25 14.4 60.7 24.9 89.6 1.6 1.9 6.9 22.5

(wt.%/wt.%) 50:50 15.4 60.2 24.4 85.8 2.4 6.0 5.8 22.1
ur

25:75 11.9 60.3 27.8 90.3 3.3 1.5 4.9 21.7

Jo

IC:HAC 75:25 13.5 58.7 27.8 88.2 2.1 4 5.7 22.6

(wt.%/wt.%) 50:50 11.4 55.3 33.3 90.6 1.5 2.2 5.7 21.5

25:75 12.3 48.8 38.9 89.5 1.8 2.5 6.2 20.8

IC:CC 75:25 11.2 70.0 18.8 86.5 3.2 2.3 8.0 24.5

(wt.%/wt.%) 50:50 12.5 71.5 16.0 84.9 1.7 3 10.4 25.2

25:75 13.5 70.6 15.9 86.3 3.9 7.5 2.3 26.2

540 VM- Volatile matter, FC- Fixed carbon, HHV- Higher heating value *O=100-C-H-N-S

31
541 The reduction in hydrogen content was from ~4 wt.% (in coals) to ~1.5 wt.% (in all

542 coal chars). The H/C ratio decreased from 0.088 (for coal) to 0.025 (for coal char) in the case

543 of IC, 0.087 to 0.033 in the case of HAC, 0.067 to 0.029 in the case of MAC, and 0.075 to

544 0.019 in the case of CC. A significant reduction in the O/C ratio in coal chars with respect to

545 the coals was achieved, especially in the case of IC and IC-rich coal blends. Typically, the

546 O/C in chars from coal blends ranged between 0.06 and 0.07. Chars from CC and its blends

547 possess high HHV (24-26 MJ kg-1), and the HHVs of the remaining chars lie in the range of

548 21-23 MJ kg-1. Lowest HHV (~20.5 MJ kg-1) was observed for chars from HAC and IC:HAC

of
549 25:75 wt.%/wt.%, which is clearly due to high ash content in them. The chars from co-

ro
550 pyrolysis of coal blends can be further utilized as good susceptors for microwave heating

551
-p
application, or as a feedstock for gasification owing to the relatively low ash content in them
re
552 as compared to the parent coal chars.
lP

553 4. Conclusions
na

554 The results from this study clearly demonstrate that high-quality tar that is rich in
ur

555 aromatic and aliphatic hydrocarbons can be produced by blending coals of different ranks and
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556 qualities. The co-pyrolysis tars possess good calorific value (35±1 MJ kg-1) with high

557 proportion of hydrocarbons like monoaromatics, naphthalene derivatives, polyaromatics and

558 aliphatics, and low amount of oxygenated compounds like phenols. The co-pyrolysis gases

559 are rich in H2, CH4 and CO, and thus can be used as a fuel gas or for the production of liquid

560 fuels by reforming. Co-pyrolysis char is also a valorized product as it contains lower ash,

561 better fixed carbon and lower O/C ratio as compared to raw coals and chars from individual

562 coal pyrolysis.

32
563 Besides proving the valorization potential of coal blends, this study has also unraveled

564 the possible interactions during microwave-assisted co-pyrolysis. A deviation parameter was

565 used to quantify the interactions, and based on this, it is shown that the coal tar yields follow

566 additive behavior. However, the yields of gas and char are not strictly additive owing to the

567 effect of coal blend composition on heating rate, which affects the secondary transformation

568 of char to light gases. The thermogravimetric analysis of coal blends did indicate qualitatively

569 the presence of interactions during co-pyrolysis in terms of deviations in temperatures

570 corresponding to maximum mass loss rate (Tmax) and 50% conversion (T50%). A quantitative

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571 understanding of the interactions was obtained by analyzing the tar composition. In coal

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572 blends containing a high fraction of Indonesian coal, the production of phenolic compounds

573
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was suppressed and the selectivity to naphthalene derivatives increased in the tar fraction.
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574 The formation of naphthalene derivatives from degradation of phenol via cyclopentadiene
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575 intermediate is proposed as a plausible pathway.

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576 Acknowledgments
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577 The National Center for Combustion Research and Development is funded by
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578 Department of Science and Technology (DST), India.

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Highlights

• Indonesian coal was co-pyrolyzed with medium ash, high ash and coking coals
• Tar, gas and char yields from co-pyrolysis exhibited additive behavior and followed
mixture rule
• Formation of naphthalene derivatives increased in the tar fraction due to interactions
• The deviation in selectivity of naphthalene derivatives varied in the range of 5-15%
• HHVs of co-pyrolysis tars were high (33-36 MJ/kg)

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Manuscript title: Evidence of Interactions in Microwave-Assisted Co-pyrolysis of Different
Varieties of Coals

Authors: B. Rajasekhar Reddy and R. Vinu

Conflicts of Interest
It is declared that the authors have no conflicts of interest or personal relationships that could
have appeared to influence the work reported in this paper.

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Dr. R. Vinu
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Associate Professor & Corresponding Author
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