JFUE 9975 No.

of Pages 7, Model 5G
8 January 2016

Fuel xxx (2016) xxx–xxx

1

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

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6

3 Effect of temperature, solvent/coal ratio and beneficiation on conversion

4 and product distribution from direct coal liquefaction
7 Juan Barraza a, Edwin Coley b, Jorge Piñeres b,⇑
8 a
Escuela de Ingeniería Química, Universidad del Valle, Ciudadela Universitaria Meléndez, Calle 13 # 100-00, Cali, Colombia
9 b
Facultad de Ingeniería, Programa de Ingeniería Química, Universidad del Atlántico Ciudadela Universitaria, km 7 Antigua vía Puerto Colombia, Barranquilla, Colombia

10
11

1 3
h i g h l i g h t s
14
15  Beneficiated coal fractions obtained by column flotation.
16  Direct coal liquefaction of original and beneficiated fractions in a batch reactor.
17  Yield and product distribution depend on temperature, solvent/coal ratio and type of coal.
18  Conversion from beneficiated coal lower than from original coal.

19
a r t i c l e i n f o a b s t r a c t
2
3 1
4
22 Article history: In this paper, the effect of temperature, solvent/coal ratio (S/C) and coal beneficiation (concentrates in 35
23 Received 9 October 2015 organic matter) on the conversion and product distribution from Direct Coal Liquefaction (DCL) is stud- 36
24 Received in revised form 13 December 2015 ied. Coal from Cerrejón, colliery in Colombia, and a non-hydrogenated anthracene oil solvent were used. 37
25 Accepted 29 December 2015
Experiments were carried out in a reactor batch of 500 ml, temperatures at 380, 400 and 420 °C for 38
26 Available online xxxx
30 min and 800 psig (5.5 MPa) hydrogen pressure, using three S/C ratios: 2/1, 3/1 and 4/1. Coal benefici- 39
ation was conducted in a continuous flotation column. Results showed that the S/C ratio has a positive 40
27 Keywords:
effect on the conversion and oil content, whereas temperature has a negative effect for liquefactions of 41
28 Direct coal liquefaction
29 Beneficiated coal
original and beneficiated coal. Moreover, liquefactions showed increasing production of gas when tem- 42
30 Column flotation perature increases while the S/C ratio decreases, independently of the type of coal used. There is a neg- 43
31 Yield ative effect using concentrate’s coal in organic material. A marked reduction on conversion and the 44
32 Product distribution amount of oil is produced due to some minerals which act as catalysts – such as illite, montmorillonite, 45
33 and clay minerals – were removed during the flotation process. 46
Ó 2016 Elsevier Ltd. All rights reserved. 47
48

49
50
51 1. Introduction Production of synthetic fuels from coal is achieved by direct liq- 62
uefaction, which retains many of structures initially present in the 63
52 Colombia has abundant coal reserves represented by 700 billion coal, and by indirect liquefaction, where organic structures are 64
53 of tons. The Cerrejón colliery is located in the North of Colombia destroyed to produce gas mixture of CO and H2. Both processes 65
54 and is one of the most important open mine worldwide. Coal – depend on factors such as type of coal, temperature, pressure, 66
55 in the Cerrejón mine – has low ash and sulphur as well as high amount of hydrogen and steam, as well as types of catalysts [1]. 67
56 calorific value which are exported. This colliery has also some coal However, the range of a coal and chemical composition are the 68
57 beds with high ash contents which cannot be exported. Those coals main factors which influence in coal liquefaction behaviour [2]. 69
58 are susceptible to improves using separation process to reduce its Direct Coal Liquefaction (DCL) is carried out into three stages: 70
59 mineral material content and to concentrate its organic matter. (1) forming slurry of coal in a solvent which serves as a carrier, 71
60 Both, conversion to liquid products and quality products mainly (2) dissolving coal under conditions of high pressure and temper- 72
61 to oil can be achieved using improved coals. ature, and (3) transferring hydrogen to dissolved coal products 73
[3]. During the direct liquefaction, finely ground coal is prepared 74
in suspension with an oil derivative from a liquefaction process, 75
⇑ Corresponding author.
used as a vehicle, and is processed at temperatures between 400 76
E-mail addresses: juan.barraza@correounivalle.edu.co (J. Barraza), edwincoley
@mail.uniatlantico.edu.co (E. Coley), jorgepineres@mail.uniatlantico.edu.co
and 500 °C and pressure between 6.9 and 71 MPa, in the presence 77
(J. Piñeres).

http://dx.doi.org/10.1016/j.fuel.2015.12.072
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Barraza J et al. Effect of temperature, solvent/coal ratio and beneficiation on conversion and product distribution from
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78 of hydrogen gas with or without catalyst, with residence time usu- the mineral matter plays a secondary role in donor extraction, and 144
79 ally between 30 and 150 min. can cause undesirable catalytic dehydrogenation of the solvent. 145
80 A thermal breakdown occurs in the coal molecular links under In this paper, the effect of the temperature, the S/C ratio and the 146
81 those conditions and depending on heating rate and maximum beneficiation coal on conversion and product distribution is 147
82 temperature. It has been observed, from a thermodynamic point reported with coal from the Cerrejón – a colliery in Colombia – liq- 148
83 of view, the reaction between coal and hydrogen increases produc- uefied with anthracene oil and hydrogen using a stirred batch 149
84 tion of aliphatic and alicyclic compounds at low temperature; pro- reactor. 150
85 duces gases and aromatics at medium temperature; while
86 undesirable compounds – such as: coke and gas – are produced
2. Experimental section 151
87 at the highest temperature.
88 Different temperature ranges related to coal decomposition
2.1. Equipment 152
89 have been reported. A work [4] using a Kentucky No. 9 coal, found
90 that no apparent disintegration of the coal particles occur until a
Coal samples were crushed in a ball mill and sieved down to a 153
91 temperature of 340 °C is reached, at which time fragmentation
particle size <75 lm to liberate organic matter. A flotation process 154
92 begins, whilst at 360 °C disintegration appears complete. However,
was carried out in a flotation column – which is 0.05 m in diameter 155
93 Berkowitz [5] showed that the first stage of decomposition com-
and 5.0 m high – to produce beneficiated coal. Further details of 156
94 mences below 200 °C, whilst Van Krevelen [6] revealed that in
the flotation column rig are presented by Barraza & Piñeres 157
95 the presence of a solvent, the ‘‘extractive disintegration” period is
[29,30]. Direct liquefactions were carried out in a 500 ml Parr batch 158
96 >200 °C and ‘‘extractive chemical disintegration” is >300 °C.
stirred reactor. 159
97 The mechanism of hydrogen transfer in DCL is not clear. A great
A PANalytical equipment X’Pert Pro series with Cu–K radiation 160
98 effort has been done to investigate a mechanism of hydrogen
(h = 0.1548 nm), in a 2h range of 10–80° with a scan speed of 5°/ 161
99 transfer [7–9]. In DCL, there is a competence between liquid hydro-
min, at an acceleration voltage of 45 kV and 40 mA, was used for 162
100 genation and destructive distillation to produce solids. The first
X-ray diffraction (XRD) mineral analysis. Data processing was car- 163
101 reaction represents the goal of the process [2]. Other studies [10–
ried out using X’Pert HighScore Plus, version 2.2e (2.2.5), and the 164
102 13] have suggested that hydrogen transfer occurs leading directly
data base from ICST (Inorganic Crystal Structure Database) version 165
103 from hydrogen molecular to carbon, rather than via the donor sol-
2008-2. 166
104 vent, especially in presence of active catalysts and pressurised
105 hydrogen.
106 The employed solvent for coal liquefaction plays a fundamental 2.2. Materials 167

107 role in the process performance. According to the conventional

108 theory of coal liquefaction, hydrogen donor solvents promote coal A bituminous coal supplied by the Cerrejón was used. The flota- 168

109 liquefaction through stabilisation of free radicals generated by tion separation used a kerosene collector and Aerofroth 65 com- 169

110 thermal breakdown. The catalyst promotes the transfer of hydro- mercial frother. Anthracene oil was used as solvent in the 170

111 gen from molecular hydrogen to solvent, and solvent to coal. liquefaction. Pressurised hydrogen at 800 psig was employed in 171

112 Therefore, the solvent acts as a vehicle for transferring hydrogen all the runs. Characterization of original and beneficiated coal is 172

113 to coal [11]. Some studies [8,10] have used different solvents to showed in Section 3.1, whilst characterization of anthracene oil 173

114 evaluate the composition effect. is presented in Section 3.2. 174

115 Different types of coals exhibit considerable variations in reac-

116 tivity, and therefore differences in the products yield. Furthermore, 2.3. Procedures 175
117 organic matter of coal is formed by different macerals groups,
118 which may also have different reactivity. Thus, a knowledge of Flotation process was carried out using a Cerrejón coal sample 176
119 the behaviour of macerals groups may help in pursuing a better sized to <75 lm in a column flotation. The coal–water slurry was 177
120 understanding of coals, and giving a chance to optimise yields homogenised by recirculation of the feed in the sump tank. Collec- 178
121 through using rich materials in maceral groups [14–19]. Feng tor and frother were added at the desired concentration (330 g/ton 179
122 et al. [20] investigated the effect of chemical structure and physical of coal). The feeding valve was opened up until the desired flow was 180
123 properties of coal macerals on the liquefaction by quantum chem- obtained in the column flotation. When the slurry reached approx- 181
124 istry calculation, and thought that the average pore size of macer- imately 0.23 m above the feeder position, the air rotameter valve 182
125 als has a positive correlation with liquefaction yield, that is, larger was opened until the desired air flow (air velocity of 1.6 cm/s). 183
126 average pore size facilitates rapid migration of the solvent mole- Thus, wash water flow was adjusted to maintain the desired 184
127 cules. Jin et al. [21] concluded that the effects of catalyst and sol- height above the feeder position. A pH natural was used. The oper- 185
128 vent on the liquefaction performances are related with the ation time was 20 min from the first quantity of coal arrived to the 186
129 liquefaction atmospheres and the properties of coal macerals. collection zone. Beneficiated coal and tails were collected, filtered, 187
130 On the other hand, mineral matter of coal plays an important dried and stored in an inert atmosphere and a sample was taken 188
131 role in catalysis of coal liquefaction reactions. The observed cat- for proximate analysis. All runs were carried out using a single sep- 189
132 alytic activity has usually been attributed to pyrite (FeS2) or pyr- aration stage and a pulp concentration of 5% w/w. The tails flow 190
133 rhotite (Fe11S12) [22–25]. Other studies [26–27] have considered was adjusted according to air flow, in order to guarantee a constant 191
134 the H2S and iron sulphides as catalysts in coal liquefaction, sug- interface level at 0.23 m above the feeder position. 192
135 gesting that H2S, produced in the decomposition of pyrite, is Liquefaction digestions were conducted in a 500 ml Parr batch 193
136 responsible for catalytic effects and that the presence of pyrite in stirred reactor at average temperatures of 380, 400 and 420 °C 194
137 the coal tends to increase the production of low viscosity liquids. using anthracene oil in the S/C ratio 2/1 and 4/1, solvent to ‘‘as 195
138 However, some disadvantages have been reported by the presence received” coal. The conversion rates and product distribution were 196
139 of mineral matter. For instance, metals can deactivate rapidly cat- evaluated as a function of temperature, S/C ratio and type of coal. 197
140 alyst, solid deposits can form in the reactor which can lead to Original and beneficiated coals were liquefied during 30 min at 198
141 reduce the conversion and poor heat transfer and blockage prob- the desired temperature. At the end of the digestion period, the 199
142 lems can occur. Curran [28] reported that in coal liquefaction by mixture in the reactor was cooled to room temperature by quench- 200
143 means of donor extraction, in the absence of pressurised hydrogen, ing with water. 201

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202 2.4. Analysis netite (M), Fe3O4, (peaks 35.0, 29.7, and 42.5), and calcium silicate 243
(CS), CaSiO3 (peaks 36.6, 37.9 and 54.7). The X-ray diffractogram 244
203 Proximate analysis was obtained using a thermal balance, with did not show any presence of pyrite nor pyrrhotite. However, there 245
204 the same temperatures as those specified in ASTM D3173, ASTM was presence of iron sulphide (F) (FeS), as indicated by the peak 246
205 D3175 and ASTM D3174, respectively. The quantity of undissolved located at 2h positions of 42.5, 40.4 and 68.4, which can have cat- 247
206 coal was determined by analysing filter cake from the hexane alytic effect, as it has been reported [22–25]. The X-ray diffrac- 248
207 insolubles for ash and Tetrahydrofuran-insolubles (THFIs) in order togram of the beneficiated coal, as it was expected, exhibited 249
208 to calculate the conversion (X, %, dry ash free, daf) of coal during considerable amorphous nature since mineral matter is removed 250
209 batch digestions. THFI analysis was obtained using a Soxhlet sys- during the flotation process. 251
210 tem with hot THF to 80 °C. It was assumed that mineral matter
211 and undissolved coal are insoluble in THF. The filtered coal extract 3.2. Characterization of anthracene oil 252
212 solution was analysed into product fractions by first determining
213 the hexane-insolubles. Oils (O, %) were determined as hexane- Table 3 shows the ultimate analysis and calorific value of 253
214 soluble material and asphaltenes and preasphaltenes (A + PA, %) anthracene oil used in the liquefactions. 254
215 as hexane-insolubles. Data of oils, asphaltenes and presaphaltenes, As seen in Table 3, the ratio H/C of anthracene oil is low com- 255
216 and gas were obtained on the coal feed basis. pared with other oils used in coal liquefaction, which are previ- 256
ously hydrogenated and used as hydrogen donors. In this paper, 257
the used oil has the function of serving as solvent in the coal sus- 258
217 3. Results and discussion pension, which can have influence on conversion and product dis- 259
tribution when using different S/C ratios. 260
218 3.1. Characterization of original and beneficiated coals
3.3. Effect of temperature, S/C ratio and beneficiation on conversion 261
219 Table 1 shows the proximate, the ultimate and the petrographic
220 analysis of original and beneficiated coals used in the liquefaction The conversion as a function of temperature, S/C ratio and coal 262
221 runs. Ash yield decreased from 25.44% to 3.98%, whereas vitrinite beneficiation is presented in Fig. 2. For the original coal, it was 263
222 and liptinite were enriched in the beneficiated sample from observed that keeping constant the S/C ratio, the conversion 264
223 92.94% v/v to 94.03% v/v and from 1.67% to 3.61% v/v respectively. decreased with increasing temperature. The above behaviour 265
224 Inertinite concentration decreased during the flotation separation. may be due to increase rupture of carbon structure into radicals 266
225 Total sulphur decreased from 0.8% in the original coal to 0.6% in the of smaller molecular weight. Those radicals are stabilised with 267
226 beneficiated coal, whereas calorific value increased from other from the same coal (repolymerization and condensation 268
227 10,160 Btu/lb in the original coal to 12,168 Btu/lb in the benefici- reactions), producing compounds of higher molecular weight. It 269
228 ated coal, due to ash reduction of the beneficiated coal. is also added, the fact that anthracene oil, although representing 270
229 Given the high ash content (25.44%) of the original coal, it was a good solvent for solubilising organic carbon compounds, is not 271
230 carried out an elemental analysis, which is showed in Table 2. Iron considered a hydrogen donor solvent. Also, the molecular hydro- 272
231 and aluminum had the highest concentration, with 0.27% and gen injected into the reactor is not efficient compared to the hydro- 273
232 0.21% w/w, respectively. It was also found that titanium presented gen from any donor solvent, which is not counted in this case. 274
233 low content (less than 80.65 ppb). The low sulphur content of this These findings were consistent with those of by Guin et al. [4], 275
234 coal is positive, since obtained products with low presence of sul- who carried out a series of experiments in order to analyse the 276
235 phur compounds reduce the negative impact in the environment. temperature effects on coal dissolution at a DCL process. They 277
236 Fig. 1(a) and (b) shows the X-ray diffractograms of original and found that at higher temperatures decrease the conversion, due 278
237 beneficiated coal respectively. The X-ray diffractogram of the orig- to the production of gases and aromatics is favoured, while a 279
238 inal coal exhibited identifiable peaks corresponding to materials higher increase of temperature, produces undesirable compounds 280
239 with some crystalline degree [31,32]. such as coke and gas. 281
240 Some minerals were identified on the X-ray diffractogram of the Fig. 2 shows also the conversion obtained as a function of tem- 282
241 original coal, for example, quartz (Q), SiO2, (peaks 26.6, 20.8, and perature, S/C ratio and coal beneficiation using the beneficiated 283
242 50.1), kaolinite (C), Al2(Si2O5)(OH)4, (peaks 12.3 and 24.8); mag- coal. At a constant S/C ratio, the conversion has a similar behaviour 284
compared to the original coal. An increasing of temperature 285
decreased the conversion. It can be seen mainly at a S/C ratio 286
Table 1
Properties of original and beneficiated coals. 2:1, where the conversion decreased from 47.2% at 380 °C to 287
21.5% at 420 °C. 288
Original Beneficiated
On the other hand, it was found that at a constant temperature, 289
Proximate analysis (w/w %, dry coal basis, db) the conversion increased with S/C ratio, which was appreciable at 290
Volatile 32.3 34.7
420 °C. At this temperature, the conversion increased around 132%, 291
Ash 25.4 4.1
Fixed carbon 42.3 61.2 from 21.5% (S/C = 2:1) to 49.9% (S/C = 4:1). Those results may be 292
HHV, Btu/lb 10,160 12,168 due to the beneficiated coal concentrated in organic matter 293

Ultimate analysis (w/w %, dry ash free, daf) (93% w/w). Therefore, high amount of solvent facilitates the dis- 294
C 76.6 80.3 solution of macromolecular compounds structures which are 295
H 5.4 5.1 breakdown and hydrogenated, being beneficial to increase of con- 296
N 1.6 1.6 version. Industrial efforts tend to minimize the solvent to coal ratio 297
S 1.9 0.6
O 14.5 13.0
due to it affects the cost of production. A work [33] looked for an 298
H/C 0.85 0.76 alternative solvent having low cost, but the direct liquefaction pro- 299
O/C 0.14 0.12 cess required high pressure and special reactor metallurgy. 300
Petrographic analysis (v/v %, mineral matter free, mmf) Conversions using the original coal were higher than those 301
Vitrinite 92.9 95.1 obtained with the beneficiated coal. This may be due to a high con- 302
Liptinite 1.7 3.6 centration of mineral matter presents in the original coal having 303
Inertinite 5.4 1.3
catalytic effect. This has been reported in other studies [34,35] 304

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Table 2
Elemental analysis of the original coal.

Element Al (%p/p) Ca (%p/p) Fe (%p/p) Mn (ppm) Mg (ppm) K (ppm) Si (ppm) Na (ppm) Ti (ppb)
Value 0.21 0.01 0.27 31.27 322.04 571.09 420.72 248.22 N.D. <80.65

N.D. No detected.

and is attributed mainly to the presence of pyrite and some acid 305
clays – such as: illite, montmorillonite, and halloysite. Some of 306
those compounds were identified at the original coal using the 307
XRD. By the contrary, the XRD analysis of beneficiated coal did 308
not show presence of minerals, such as illite, montmorillonite, 309
and clay minerals. This mineral composition can explain both the 310
low conversion and low quantities of oil compared to those 311
obtained with the original coal. 312

3.4. Effect of temperature, S/C ratio and beneficiation on oils 313

production 314

As it is seen in Fig. 3, a similar behaviour to the conversion, 315

using original coal, occurred for oil production: oil decreased with 316
the increasing of temperature from 62.8% at 380 °C to 41.4% at 317
420 °C at a S/C ratio of 2:/1, indicating that this can be associated 318
by gas formation and production of A + PA. 319
It can be also seen that the percentage of oil increased with the 320
increasing of S/C ratio at constant temperature. The S/C ratio effect 321
was most appreciable at 420 °C than 380 °C. Regarding the 322
obtained oils from both coals, produced oils from the original coal 323
was higher than the beneficiated one. Those results may be due to 324
the catalysis effect of mineral matter occurs in the original coal. 325
Although some processes claimed running without catalyst, most 326
coals themselves contain a significant amount of minerals such 327
as pyrite and iron oxides that could play a role in the DCL process 328
as a catalyst. Iron-based catalysts, such as pyrite (FeS2), troilite 329
(FeS), pyrrhotite (Fe1 xS), iron oxide, iron sulfate, iron hydroxide 330
and other iron resources, have been studied extensively due to 331
their low costs and environmental tolerance [36]. It is widely 332
accepted that pyrrhotite is the most active form for iron sulphide 333
catalysts. These findings were consistent with those reported in 334
other studies [22–25]. 335

3.5. Effect of temperature, S/C ratio and beneficiation on A + PA 336

production 337
Fig. 1. X-ray diffractograms of (a) original and (b) beneficiated coals. Quartz, Q;
kaolinite, C; magnetite, M; calcium silicate, CS; iron sulphide, F. As it is shown in Fig. 4, for the original coal, the A + PA fraction 338

Table 3
increased with the increasing of temperature at a constant S/C 339
Proximate analysis of anthracene oil. ratio. As it was established above, at high temperature occurred 340
reduction on the oil percentages, which may be due to oil break- 341
C H N O H/C O/C HHV (Btu/lb)
down. This generated heavy free radicals that being repoly- 342
64.4 3.3 0.6 31.7 0.61 0.37 16,428 merisated, producing high concentration of A + PA. 343

Fig. 2. Conversion as a function of temperature, S/C ratio and coal beneficiation.

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Fig. 3. Oil percentages as a function of temperature, S/C ratio and coal beneficiation.

Fig. 4. A + PA percentages as function of temperature, S/C ratio and coal beneficiation.

Fig. 5. Gas percentages as function of temperature, S/C ratio and beneficiation.

344 Such as it occurred in the oils, the catalytic effect of the mineral which may be due to the ruptured of light compounds, such as oils. 355
345 matter in the original coal also produced significant difference in Those findings are in agreement with those reported in [37], who 356
346 the A + PA content. As it is seen in Fig. 4, those products obtained proposed gas production mechanisms from oils and A + PA. 357
347 from the original coal were higher than the beneficiated coal. As it is seen in Fig. 5, both original and beneficiated coals do not 358
show significant differences. This indicates that the control vari- 359
ables that affect the production of gases were mainly the temper- 360
348 3.6. Effect of temperature, S/C ratio and beneficiation on gas
ature and the S/C ratio. 361
349 production

350 As it is shown in Fig. 5, both high temperature and low S/C ratio 3.7. Material balance 362
351 produced high proportion of gases. The temperature had a good
352 influence, especially at the lower S/C ratio, where there was an Tables 4 and 5 show the material balance for original and ben- 363
353 increase in the percentage of gases from 8.9% at 380 °C to 16.7% eficiated coals respectively, according to the percentage of ITHF 364
354 at 420 °C. The higher temperatures produced high gas content, (which determined the unconverted coal), oils, A + AP and gas. As 365

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Table 4
Material balance for original coal.

S/C ratio Feed, (g)

H2 Solvent, daf Coal, daf Total
02:01 2.30 26.70 9.92 38.92
03:01 2.30 30.00 7.46 39.76
04:01 2.30 32.00 5.97 40.27
Temperature, °C S/C ratio Products, (g)
Unconverted coal Oils A + AP Gas Total
380 02:01 2.22 24.44 8.80 3.46 38.92
380 04:01 0.94 27.18 9.83 2.32 40.27
420 02:01 2.86 16.11 13.43 6.52 38.92
420 04:01 1.18 23.64 10.63 4.82 40.27
400 03:01 1.57 24.13 9.26 4.79 39.76

Table 5
Material balance for beneficiated coal.

S/C ratio Feed, (g)

H2 Solvent, daf Coal, daf Total
02:01 2.30 26.70 12.77 41.77
03:01 2.30 30.00 9.60 41.90
04:01 2.30 32.00 7.68 41.98
Temperature, °C S/C ratio Products, (g)
Unconverted coal Oils A + AP Gas Total
380 02:01 6.74 24.14 5.10 5.79 41.77
380 04:01 3.47 28.17 6.26 4.09 41.98
420 02:01 10.02 14.03 8.73 8.98 41.77
420 04:01 3.85 24.98 8.23 4.93 41.98
400 03:01 5.06 23.46 7.08 6.30 41.90

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Please cite this article in press as: Barraza J et al. Effect of temperature, solvent/coal ratio and beneficiation on conversion and product distribution from
direct coal liquefaction. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2015.12.072