JFUE 10023 No.

of Pages 9, Model 5G
23 January 2016

Fuel xxx (2016) xxx–xxx

1

Contents lists available at ScienceDirect

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

5
6

3 Kinetic study on CO2 gasification of brown coal and biomass chars:

4 reaction order
7 Lingmei Zhou a,⇑, Guanjun Zhang b, Denise Reichel c, Krzack Steffen c, Bernd Meyer c
8 a
China University of Mining and Technology, D11, Xueyuan Road, Haidian District, 100083 Beijing, China
9 b
China Datang Corporation Science and Technology Research Institute, Beinong Road 2, Changping District, Beijing, China
10 c
TU Bergakademie Freiberg, Institute of Energy Process Engineering and Chemical Engineering (IEC) and German Center for Energy Resources (DER), Fuchsmühlenweg 9,
11 09599 Freiberg, Germany

12
13

1 5
h i g h l i g h t s
16
17
Higher CO2 partial pressure leads to higher gasification reaction rate.
18
Reaction orders for coal and biomass chars pyrolyzed at high temperature are high.
19
At low gasification temperature, reaction order for biomass is higher than coal.
20
At high gasification temperature, reaction orders for biomass and coal are similar.
21
Reasons for above behaviors are related to catalytic effect and pore distribution.

22
a r t i c l e i n f o a b s t r a c t
2
3 4
7
25 Article history: Thermal co-processing of coal and biomass has been increasingly focused by many researchers. Pyrolysis, 38
26 Received 7 August 2015 as an initial step in thermochemical processes, is crucial for combustion or gasification processes. In the 39
27 Received in revised form 11 January 2016 present work, the effects of blending ratios on co-pyrolysis of wheat straw (WS) and Germany Rhenish 40
28 Accepted 13 January 2016
brown coal (HKN) were investigated using Thermogravimetric analyzer (TGA). Single feeds and blends 41
29 Available online xxxx
with 10, 30, 50, 70, and 90 wt.% addition of wheat straw were pyrolyzed at a heating rate of 10 K/min 42
up to 1100 °C in a constant nitrogen flow. The results showed that the positive synergy effects (interac- 43
30 Keywords:
tions between WS and HKN can promote thermal decomposition of blends leading to more volatiles 44
31 Co-pyrolysis
32 Coal
release than expectation) occurred at temperature higher than around 400 °C, but negative one at lower 45
33 Biomass temperature. And less wheat straw addition promoted decomposition better. Furthermore, the kinetics of 46
34 Blend ratios pyrolysis for WS, HKN and their blends were studied using Coats Redfern method. The results showed 47
35 Kinetics that synergy effects also occurred for kinetic parameters and agreed with the experimental behavior. 48
36 The activation energies E were higher at low temperature (hard for decomposition) and lower at high 49
temperature (easy for decomposition) compared to calculated values. 50
Ó 2016 Elsevier Ltd. All rights reserved. 51
52

53
54
55
56 1. Introduction low-quality coal, especially brown coal, is difficult to use due to 60
its high water content and low fixed carbon content. It is a signif- 61
57 The continuing development of world economy needs more and icant issue to find an effective and clean way to utilize brown coal. 62
58 more energy, which mainly comes from fossil fuels. Coal is world- In addition, extensive use of coal has caused some serious environ- 63
59 wide one of the most important fossil fuels. However, abundant mental problems, such as acid rain, water contamination and 64
greenhouse effect restricting the development of the coal industry. 65
Biomass is a kind of clean and renewable energy source and it is 66
Abbreviations: HKN, German brown coal; WS, wheat straw; B, pyrolysis generally accepted as the energy, which would not accumulate 67
temperature of 800 °C; E, pyrolysis temperature of 1000 °C; TGA, thermogravi-
the greenhouse effect in the atmosphere [1]. Despite biomass is 68
metric analyzer; d, dry; SSA, specific surface area; R, reaction rate; P, partial
pressure; n, reaction order; X, carbon conversion; k, reaction rate constant; the ancestor of coal, it has different chemical and physical proper- 69
t0.5, time required to consumed 50% carbon content in char sample. ties. It contains low fixed carbon content, high moisture content. 70
⇑ Corresponding author. Tel.: +86 18510174819. The low calorific value leads in a comparatively low energy density 71
E-mail address: lingmeizhou@hotmail.com (L. Zhou).

http://dx.doi.org/10.1016/j.fuel.2016.01.042
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.

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2 L. Zhou et al. / Fuel xxx (2016) xxx–xxx

72 and accordingly to a large volume, which is difficult to transport. pyrolyzed at 1000 °C), HKN-B (brown coal char pyrolyzed at 134
73 Therefore an effective way to utilize this kind of renewable energy 800 °C) and HKN-E (brown coal char pyrolyzed at 1000 °C). The 135
74 is necessary. characteristics of the char samples are illustrated in Table 1. 136
75 Gasification is such a useful technology with effective carbon The proximate analysis is showing a decreasing volatile matter 137
76 utilization and also a reasonable way of reduction of atmospheric of brown coal and wheat straw chars with increasing pyrolysis 138
77 pollution. In addition, the kinetic study on char gasification is very temperature. The ash contents is around 24 wt.% (db) for wheat 139
78 important for a better understanding of the process and to design straw chars, which is much higher, than those of brown coal chars 140
79 coal gasifiers. The gasification of char with CO2 is a fundamental (about 9 wt.% db). The ultimate analysis indicates significant drop- 141
80 method to study the char reactivity. The kinetics of gasification ping hydrogen and oxygen contents with increasing temperature, 142
81 reaction for different kinds of chars with CO2 had been widely while other contents stay comparatively constant. The loss of 143
82 investigated [2–17]. However, most authors focused on activation hydrogen could lead to lower reaction rates, because part of the 144
83 energy E and frequency factor A, and assumed the reaction order carbon active sites are associated with bonded hydrogen. Further- 145
84 n as 1. Only a few researchers determined the reaction orders of more, the functional groups, especially those containing oxygen, 146
85 gasification process [2–4,12,13]. Ahn et al. [2] studied gasification would decrease dramatically due to a reducing oxygen percentage. 147
86 kinetics of a sub-bituminous coal-char with CO2 at elevated pres- Therefore chars, produced at high temperature, should show lower 148
87 sure and found: the apparent reaction order was 0.4 with a CO2 reactivity. 149
88 partial pressures of 0.1–0.5 MPa at a temperature of 1300 °C and To study the catalytic effect of mineral matters contained in 150
89 a total system pressure of 1.0 MPa. Kajitani et al. [12] investigated wheat straw and Rhenish brown coal chars, the index of basicity 151
90 the CO2 gasification rate analysis of four different coal chars in [18] is calculated by Eq. (2.1). 152
91 entrained flow coal gasifier and found the reaction orders varied 153
92 from 0.43 to 0.56, showing coal types exhibited a large difference Index of basicity ¼ wðAÞ
93 in the char gasification rate with CO2, but did not give any explana- Fe2 O3 þ CaO þ MgO þ Na2 O þ K2 O
 ð2:1Þ
94 tion. Ollero et al. [13] studied on the CO2 gasification kinetics of SiO2 þ Al2 O3 155
95 olive residue and found the reaction order was about 0.43 when
96 CO2 partial pressures varied from 0.02 to 0.05 MPa. Micco et al. w(A) is the ash content of the sample, others are the content of var- 156

97 [4] made study on kinetics of the gasification of Rio Turbio coal ious ash compositions. Since ashing processing is under oxidizing 157

98 under different pyrolysis temperatures and found a reaction order atmosphere (air), FeO in ash would transform into Fe2O3, which is 158

99 was about 0.5 for char prepared at 850 °C, but no influence was used in Eq. (2.1). The index of basicity for all char samples was cal- 159

100 found for char pyrolyzed at 950 °C. culated as shown in Table 1. It can be seen, that for chars produced 160

101 When reviewing the results of the present literature, it can be at the same pyrolysis temperature, the index of basicity of brown 161

102 found that most researchers [2,13] just calculated the value of coal char was much higher than that of wheat straw char. It can 162

103 reaction order as a normal kinetic parameter, without any inter- be presumed, that the mineral matters in brown coal chars had bet- 163

104 pretation for the value and consideration of any influence factor.
105 Micco et al. [4] and Kajitani et al. [12] have already found reaction Table 1
106 orders exhibited different values for different types of coal chars, Analysis of Rhenish brown coal and wheat straw chars (proximate analysis, ultimate
107 but they did not give any explanation for the experimental beha- analysis, BET surface and pore size distribution of HKN and WS).
108 vior. Therefore, system study on the reaction order during gasifica- Sample Wheat straw (WS) Rhenish brown coal
109 tion process should be carried out to fully understand the reaction (HKN)
110 mechanism. In the present work, the gasification behavior of Rhen- WS-B WS-E HKN-B HKN-E
111 ish brown coal and wheat straw chars gasified at 800 and 1000 °C
Ultimate analysis (wt.%). d
112 under ambient pressure with CO2 concentrations ranging from 60
Carbon. C 74.55 75.84 85.80 87.84
113 to 100 vol.% (rest N2) was investigated, with the focus on the deter- Hydrogen. H 0.68 0.24 0.93 0.32
114 mination of the reaction order. The effects of process conditions Nitrogen. N 0.87 0.88 0.97 0.61
115 such as pyrolysis temperature, gasification temperature and the Sulfur. S 0.42 0.43 0.54 0.69
Oxygen. O (diffa) 0.81 0.31 2.72 1.38
116 influence of carbon conversion and char characteristics on reaction
117 order have been studied in detail, which was rarely found in Proximate analysis (wt.%). d
Ash 23.65 24.36 9.04 9.16
118 literature.
Volatile 4.06 3.09 5.16 3.00
Fixed Carbon 72.30 72.55 85.80 87.84
Ash analysisb (wt.%). d
119 2. Materials and methods Na2O 0.05 0.06 0.78 0.72
MgO 0.49 0.48 1.11 1.11
120 2.1. Materials K2O 3.36 3.13 0.05 0.05
CaO 1.77 1.71 4.74 2.74
Fe2O3 0.12 0.19 1.00 0.90
121 Char samples, used in this study, were obtained from pyrolysis
Al2O3 0.14 0.16 0.28 0.27
122 of a Rhenish brown coal (HKN) and wheat straw (WS). The raw SiO2 15.40 15.60 0.28 0.19
123 samples were dried, milled and sieved to get a grain fraction of less Index of basicityc 0.09 0.09 1.24 1.10
124 than 2 mm, which is much bigger than particles usually used in BET surface and pore size distribution
125 TGA (<0.015 mm) [7]. This is more practicable for industrial pro- BET surface area (m2/g) 2 4 170 230
126 duction, since biomass is difficult to be grind into fine particles, Porosity (%) 54 53 46 48
Pore volume (mm3/g)
127 which would come along with much higher energy consumption.
Total pore 573 561 437 429
128 The raw samples were pyrolyzed in a high temperature muffle fur- Macro pore 358 286 250 179
129 nace under ambient pressure in a nitrogen atmosphere with a final Meso pore 0 0 15 15
130 temperature of 800 °C (B) and 1000 °C (E) respectively, at a heating Micro pore 216 274 171 234
131 rate of 10 K/min. The samples were kept at final temperature for a
Calculated by difference.
132 30 min. Hence, there are four samples used in this study, WS-B b
Only oxides in Index of basicity are shown here.
133 (wheat straw char pyrolyzed at 800 °C), WS-E (wheat straw char c
Index of basicity ¼ wðAÞ  Fe2 O3 þCaOþMgOþNa
SiO2 þAl2 O3
2 OþK2 O
.

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206
164 ter catalytic effects than that of wheat straw chars. For wheat straw W0  Wt
X ð%Þ ¼  100 ð2:2Þ
165 chars, the index did not change significantly with the pyrolysis tem- W0  Wa 208
166 perature, while for brown coal chars the index decreased from 1.24
W 0 is the initial char mass, W t is the char mass at time t and W a is 209
167 (HKN-B) to 1.10 (HKN-E).
the ash mass from the proximate analysis of the initial char. The 210
168 The structural properties of fuels have important effects on the
term W 0  W t is equal to the carbon content consumed by gasifica- 211
169 gasification process. Table 1 also illustrates the specific surface
tion reaction. The consumed carbon amount can be calculated by 212
170 area (BET) and pore size distribution of Rhenish brown coal and
product gas CO as Eq. (2.3). The molar mass of consumed carbon 213
171 wheat straw chars. It can be seen that the values of porosity and
is half of molar mass of CO, which can be obtained from the online 214
172 the specific pore volumes were larger for wheat straw chars. How-
GC. 215
173 ever, Rhenish brown coal chars displayed a 60–80 times higher BET 216
174 surface than wheat straw chars. This might be caused by sintering CO2 þ C ¡ 2CO þ 172 kJ=mol ð2:3Þ 218
175 of ash in wheat straw at high temperature covered the surface of
176 WS chars. In addition, the BET surface of both chars increased with
177 pyrolysis temperature. 2.3.2. Reaction rate 219
The reaction rate can be defined by Eq. (2.4) or (2.5): 220
221
178 2.2. Gasification experiments in a fixed bed reactor 1 dw
RX ¼  ð2:4Þ
wC;t dt X
179 A small fixed bed reactor, made of a quartz glass tube (inner 1 dw
180 diameter 15 mm) and a vertical, electrically heated tube furnace, rX ¼  ð2:5Þ
wC;0 dt X 223
181 as used in this study for the CO2 gasification experiments, as shown
182 in Fig. 1. For all gasification experiments, char sample (1 g) was RX and r X are both defined as the reaction rate at carbon conversion 224
183 inserted into the cold reactor, which was afterward purged by X, wC;0 is the initial carbon content of a char, wC;t is the remaining 225
184 the gasifying agent about half an hour to remove the air. When carbon content of the char at the time t, dw is the time dependent 226
185 the oven temperature reached the desired value, the quartz glass carbon consumed and dt X is the time required to consume this car- 227
186 reactor was put into the oven and the experiment was adopted bon content dw . In some literature, RX has been used to represent 228
187 at this temperature isothermally during the whole process. A con- the char reactivity and r X for the reaction rate [7]. 229
188 stant flow of CO2 (4.6 L/h (STP), 60–100 vol.% + N2) was used to
189 supply the gasification reaction and carry the product gases to an 2.3.3. Nth order equation 230
190 on-line GC. The carbon conversion X cannot be obtained directly Many researchers have chosen the nth order equation for their 231
191 but indirectly calculated by on-line CO volume fraction. When gasification experiments. In the nth order equation, it is supposed 232
192 the detected CO content was lower than 0.5 vol.% in the product that the overall char gasification rate is proportional to the nth 233
193 gases, the experiment was considered to be finished. The most power of carbon dioxide partial pressure: 234
194 important feature for the fixed reactor used in this paper is that 235
195 the CO2 flow through the particles, not around or overhead the par- RX ¼ k  PnCO2 ð2:6Þ 237
196 ticles like a TGA did. Hence, the respectively lower CO2 flow rate In Eq. (2.6), RX is the gasification reactivity when carbon conver- 238
197 (4.6 L/h (STP)) (compared with TGA) could better eliminate the sion is X, while k is the temperature dependent effective rate con- 239
198 outer diffusion in chemical controlled zone. In addition, one gram stant, P CO2 is the partial pressure of CO2 and n is the reaction order. 240
199 sample was used instead of several milligrams to make the exper- This can be expressed alternatively as: 241
200 imental conditions more practical. 242
ln RX ¼ ln k þ n  ln PCO2 ð2:7Þ 244

201 2.3. Equations For different CO2 partial pressures at the same temperature, a 245
plot can be created to illustrate the relationship between ln RX 246
202 2.3.1. Carbon conversion XC of char and ln PCO2 , while ln k can be obtained by the origin intercept and 247
203 For the determination of kinetic parameters, it is first necessary n by the slope of the curve. 248
204 to calculate the carbon conversion as function of time. The carbon
205 conversion of char is defined by Eq. (2.2):
3. Results and discussion 249

3.1. Effect of the CO2 partial pressure on the gasification behavior 250

The pressure of the gasifying agent plays an important role in 251

the gasification process, by changes in reactant partial pressures 252
and the transport rates [9]. In this section, all experiments were 253
adopted at atmospheric pressure, and the CO2 partial pressure 254
changed from 0.06 to 0.1 MPa to investigate its influence. Chars, 255
pyrolyzed at low temperatures, would firstly transform into high 256
temperature chars, when gasified at higher temperature. Hence, 257
1 g chars pyrolyzed at 1000 °C (WS-E and HKN-E) were used in this 258
section. The gasification behaviors under different CO2 partial pres- 259
sures and temperatures of 800 and 1000 °C are illustrated in Figs. 2 260
and 3. RX was chosen to represent the reaction rate since gasifica- 261
tion reaction was a weight-limited reaction, which can better illus- 262
trate the intrinsic reaction rate. 263
For WS-E gasified at a low temperature, such as 800 °C, it can be 264
seen that at the same experimental duration the carbon conversion 265
Fig. 1. Schematic of quartz glass reactor. was more progressed with higher CO2 partial pressure. As can be 266

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4 L. Zhou et al. / Fuel xxx (2016) xxx–xxx

Fig. 2. Effects of CO2 partial pressure on reactivity at 800 °C, (a) WS-E and (b) HKN-E.

Fig. 3. Effects of CO2 partial pressure on reactivity of WS-E and HKN-E chars at 1000 °C, (a) WS-E and (b) HKN-E.

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L. Zhou et al. / Fuel xxx (2016) xxx–xxx 5

267 seen in Fig. 2(a), the carbon conversion was about 50% when CO2 complexes on the surface of coal particles. Hence, when CO2 con- 292
268 concentration was 60 vol.%, in contrast to almost 70% carbon con- centration was higher, the concentrations of surface complexes 293
269 version when the CO2 concentration was 100 vol.%, with a fixed would also enhance, leading to a high reaction rate. Many 294
270 reaction time at 4 h. This also occurred for HKN-E samples gasified researchers [10,11] found similar results, which the reaction rate 295
271 at same temperature, the gasification reactivity was always higher increased with an increasing CO2 or H2O concentration. 296
272 at equal high CO2 concentrations. In Fig. 2(b), at the same carbon Table 2 shows the dependency of different samples on the CO2 297
273 conversion of 50%, the reaction rate R was 0.46 h1 with 60 vol.% partial pressure, by tabulating the t0.5 (time required to consume 298
274 CO2 and 0.62 h1 with 100 vol.% CO2. 50% carbon content in char sample) values of WS-E and HKN-E at 299
275 At higher gasification temperature, fixed as 1000 °C in this sec- 60 and 100 vol.% CO2. From the value of t0.5(60 vol.%)/t0.5(100 300
276 tion, both WS-E and HKN-E chars reflected similar trend as beha- vol.%), it can be deduced that wheat straw char WS-E was more 301
277 viors at 800 °C. The reaction rate of all char samples showed dependent on the CO2 concentration. In addition, the value at high 302
278 higher values with advanced CO2 partial pressures. As in Fig. 3(a), gasification temperatures was larger, showing the influence of 303
279 the carbon conversion for WS-E was about 45% when CO2 concen- gasifying agent concentration was more obvious. The detailed 304
280 tration was 60 vol.%, compared to almost 77% when CO2 concentra- description and explanation are given in Section 3.2 of reaction 305
281 tion was 100 vol.%, with a fixed reaction time at 0.4 h. For HKN-E order. 306
282 char, the reaction rate R was 3.07 h1 with 60 vol.% CO2 and
283 4.47 h1 with 100 vol.% CO2, at the same carbon conversion of 50%.
3.2. Reaction order 307
284 The explanation for experimental behaviors can be related to
285 effective collisions among reactant particles involved in the reac-
As mentioned above, the partial pressure of the gasifying agent 308
286 tion. From microcosmic view, the reaction was caused by effective
CO2 has significant effects on the gasification reaction rate. There- 309
287 collisions. When CO2 partial pressure was higher, the frequency of
fore, the first step of a kinetic study is to obtain the reaction order. 310
288 effective collision should also increased between gasifying agent
However, just a few authors are paying attention to the reaction 311
289 molecules CO2 and active carbon of char, leading to a higher
order next to focusing on activation energy E and pre- 312
290 reaction rate as seen in experiment behaviors. In addition, it has
exponential factor A. The effects of pyrolysis temperature, gasifica- 313
291 been found that the gasifying agent would firstly form surface
tion temperature and carbon conversion on the reaction order of 314
brown coal and wheat straw chars were investigated in Sections 315
3.2.1–3.2.3 and the possible mechanism was given [8]. 316
Table 2
t0.5 of WS-E and HKN-E gasified at 800 and 1000 °C with 60 vol.% and 100 vol.% CO2.

Experiments t0.5 (h) t0.5(60 vol.%)/t0.5(100 vol.%) 3.2.1. Effects of carbon conversion on reaction order 317
This paragraph deals with the effects of carbon conversion on 318
WS-E/800/100 vol.% 3.00 1.50
WS-E/800/60 vol.% 4.50
reaction order. Wheat straw and brown coal chars pyrolyzed at 319
HKN-E/800/100 vol.% 1.80 1.28 800 (WS-B, HKN-B) and 1000 °C (WS-E, HKN-E) were gasified at 320
HKN-E/800/60 vol.% 2.30 the same temperature like pyrolysis and with different CO2 con- 321
WS-E/1000/100 vol.% 0.20 1.80 centrations from 60 to 100 vol.%. The other gas component was 322
WS-E/1000/60 vol.% 0.36
N2 ranging from 40 to 0 vol.%, correspondingly. The reaction order 323
HKN-E/1000/100 vol.% 0.25 1.48
HKN-E/1000/60 vol.% 0.37 n and reaction rate constant k were calculated by Eq. (2.7) at differ- 324
ent carbon conversion X and shown in Table 3 and Fig. 4. 325
Table 3 illustrates the effects of carbon conversion on the reac- 326
tion order n for wheat straw and brown coal chars. It can be found 327
Table 3
that the reaction order at 50% carbon conversion was approxi- 328
Reaction order n at different carbon conversion X of WS and HKN chars.
mately the average value of reaction orders at 10–90%. Most of 329
Carbon conversion X WS-B, HKN-B, WS-E, HKN-E, authors are using the reaction order when carbon conversion is 330
800 800 1000 1000
50–represent the overall reaction [12–14]. The representative 331
0.1 – 0.40 0.25 0.25 average value of the reactivity between two degrees of conversion 332
0.3 0.34 0.40 0.63 0.71
[15,19] is also often used. For both methods, the reaction order at 333
0.5 0.36 0.29 0.64 0.68
0.7 0.28 0.17 0.64 0.71 50% carbon conversion was used in the following discussion. 334
0.9 0.48 0.11 0.65 1.24 Fig. 4(a) illustrates the effects of carbon conversion on the reac- 335
tion rate constant k for wheat straw and brown coal chars. Fig. 4(b) 336

Fig. 4. Effects of carbon conversion X on apparent reaction rate constant k.

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Table 4 tion specific surface area (SSA) at lower carbon conversions and 343
Reaction rate, partial pressure and reaction order for WS-B and WS-E gasified at enhanced catalytic mineral matter at higher carbon conversions. 344
800 °C.

Reaction rate R0.5 and partial pressure PCO2 for WS-B and WS-E gasified at 3.2.2. Effects of pyrolysis temperature on gasification reaction order 345
800 °C In this section the effects of pyrolysis temperature on reaction 346
Samples R0.5 (1/h) ln(R0.5) PCO2 (MPa) ln(PCO2) order at a fixed gasification temperature of 800 °C for Rhenish 347
WS-B/800/100 vol.% 0.44 0.82 0.09 2.36 brown coal and wheat straw chars were studied. The chars were 348
WS-B/800/80 vol.% 0.40 0.91 0.07 2.67 pyrolyzed at temperatures of 800 and 1000 °C. The CO2 concentra- 349
WS-B/800/70 vol.% 0.39 0.94 0.06 2.75 tions varied from 60 to 100 vol.% and N2 was ranging from 40 to 0 350
WS-B/800/60 vol.% 0.36 1.01 0.06 2.90
vol.%, correspondingly. 351
WS-E/800/100 vol.% 0.36 1.03 0.09 2.41
WS-E/800/80 vol.% 0.31 1.18 0.07 2.63 The reaction rate at 50% carbon conversion R0.5, and CO2 partial 352
WS-E/800/70 vol.% 0.27 1.29 0.06 2.81 pressure, PCO2, for wheat straw char and Rhenish brown coal are 353
WS-E/800/60 vol.% 0.26 1.36 0.05 2.94 illustrated in Table 4. The logarithmic values of reaction rate R0.5 354
HKN-B/800/100 vol.% 0.89 0.12 0.09 2.47
and partial pressure were calculated to fit the Eq. (2.7). 355
HKN-B/800/80 vol.% 0.80 0.22 0.07 2.69
HKN-B/800/70 vol.% 0.77 0.26 0.06 2.83
Based on Table 4, the reaction rate constant k can be attained 356
HKN-B/800/60 vol.% 0.71 0.34 0.04 3.15 from the intercept of ln k as well as reaction order n is obtained 357
HKN-E/800/100 vol.% 0.61 0.50 0.08 2.51 from the slope of the plot by fitting Eq. (2.7) and shown in Fig. 5. 358
HKN-E/800/80 vol.% 0.57 0.57 0.06 2.75 Table 4 also shows the reaction orders, n, and reaction rate con- 359
HKN-E/800/70 vol.% 0.53 0.63 0.06 2.90
stants, k, for wheat straw chars (WS-B, WS-E) and Rhenish brown 360
HKN-E/800/60 vol.% 0.49 0.71 0.05 3.06
coal chars (HKN-B, HKN-E) gasified at 800 °C. For wheat straw 361
Reaction order n and reaction rate constant k for chars gasified at 800 °C
chars, the reaction order was 0.35 for WS-B and 0.62 for WS-E. 362
Samples ln k (intercept) k (1/h) n (slope) R2 The effects of CO2 partial pressure on wheat straw chars were more 363
WS-B, 800 0.01 1.01 0.35 0.98 significant when it was pyrolyzed at higher temperatures. For 364
WS-E, 800 0.47 1.60 0.62 1.00 brown coal char the reaction order was 0.32 for HKN-B and 0.38 365
HKN-B, 800 0.65 1.91 0.32 0.96
for HKN-E. The reaction order was also higher for brown coal char 366
HKN-E, 800 0.47 1.60 0.38 0.97
pyrolyzed at higher temperatures, but the effect was less than that 367
for wheat straw chars. 368
Possible reasons for the larger reaction order of char pyrolyzed 369
337 is focusing on the lower part of reaction rate constant (0–5 1/h) for at high temperatures: 370
338 more comprehensible effects on chars gasified at 800 °C. For most
339 experiments, it can be found that k values increased with increas- (1) As shown in Table 1, the index of basicity of high tempera- 371
340 ing the carbon conversion X. This agreed with experimental beha- ture char was lower than that of low temperature char, 372
341 vior in Figs. 2 and 3, where the reaction rate R also increased with showing the decrease of catalytic compound. Bläsing et al. 373
342 carbon conversion. This may be attributed to the increased reac- [20]
reported that many alkali metals would release under 374

Fig. 5. Reaction order by linear fitting (a) WS-B, (b) WS-E, (c) HKN-B and (d) HKN-E gasified at 800 °C.

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Fig. 6. Kinetics of WS-E and HKN-E by linear fitting Arrhenius model with parameters from RPM.

375 high temperatures and lose the catalytic effects by thermal temperature. The results here are consistent with the previous dis- 423
376 processing. For carbon connected with catalytic metals cussion in experimental behavior (Section 3.1), stating that brown 424
377 (M), CO2 is chemisorbed on catalytic metal (M) oxides and coal chars would display higher reactivity than wheat straw chars 425
378 forms reactive oxygen-containing complex (M–O–C), which due to more catalytic compounds. 426
379 acts as an oxygen transfer media and thus enhances the
380 CO2 gasification reaction [21–23]. When all metal ions are
381 occupied by CO2 (this reaction is much quicker than normal 3.2.3. Effects of gasification temperature on reaction order 427
382 absorption without catalytic compound), the reaction order In this section, to study the effects of gasification temperature 428
383 would be zero for these active carbons. For zero-order reac- on reaction order, the char pyrolysis temperature was fixed at 429
384 tions [24], the reaction rate is independent of the concentra- 1000 °C. The chars were gasified at 800 and 1000 °C. The CO2 con- 430
385 tion of the reactant. This occurs for many catalytic reactions. centrations varied from 60 to 100 vol.%, and N2 was ranging from 431
386 When concentration of the reactant is much higher than that 40 to 0 vol.%, correspondingly. The experiments with WS-E and 432
387 of catalytic material, like the situation within the quartz HKN-E gasified at 800 °C from the section above are also illustrated 433
388 glass reactor, the change of reactant concentration has no here for comparison. 434
389 effect on the reaction rate. Chars containing more catalytic The reaction rate, R0.5, and CO2 partial pressure, PCO2, are illus- 435
390 compounds (low temperature chars) would be affected trated in Table 5 for WS-E and HKN-E chars gasified at 1000 °C. 436
391 stronger by this mechanism and have lower values of reac- The logarithmic values of reaction rate R0.5 and partial pressure 437
392 tion order [8]. are calculated to fit the Eq. (2.7) and shown in Fig. 7. By fitting 438
393 (2) As shown in Table 1, the porosity of char is not changing sig- the Eq. (2.7), reaction rate constant k and reaction order n, shown 439
394 nificantly with increasing pyrolysis temperature. However, in Table 5, are obtained for WS-E and HKN-E chars, when gasifica- 440
395 the macro-pores, which were in charge of transporting the tion temperature was 800 and 1000 °C. 441
396 gasifying agent to micro pores, decreased appreciably at For brown coal char HKN-E, the reaction order was 0.38 at 442
397 1000 °C. For example, the macro-pore volume was 800 °C and 0.72 at 1000 °C respectively. This shows that the effect 443
398 358 mm3/g for WS-B, compared to 286 mm3/g for WS-E. of CO2 partial pressure on gasification of brown coal char was more 444
399 For chemical controlled reaction, diffusion from the char significant at higher temperatures. Ahn et al. [2] studied the gasifi- 445
400 surface to the inlets of the micro-pores is quick and the con- cation kinetics of a sub-bituminous coal at elevated temperatures 446
401 centration of gas reactants within the particle is similar to with CO2, and mentioned that the diffusion resistance of reactant 447
402 that on the char surface. However, the particle size of chars gas into the pore structure would increase with an increasing reac- 448
403 in the present study was 2 mm, which was definitely limited
404 by the diffusion. This was already proved by kinetics study
Table 5
405 shown in Fig. 6 [8]. It showed the gasification kinetics of Reaction rate, partial pressure and reaction order for WS-B and WS-E gasified at 800
406 WS-E and HKN-E by linear fitting Arrhenius model, at tem- and 1000 °C.
407 perature from 750 to 1000 °C. It can be found that the gasi-
Reaction rate R0.5 and partial pressure PCO2 for chars gasified at 1000 °C
408 fication reaction was affected by diffusion when
409 temperature was higher than and around 850 °C, approxi- Samples R0.5 (1/h) ln(R0.5) PCO2 (bar) ln(PCO2)

410 mately. With less macro-pores, the gas diffusion would be WS-E/1000/100 vol.% 4.37 1.48 0.06 2.80
411 not as fast as that in char with enough macro pores. Hence, WS-E/1000/80 vol.% 3.81 1.34 0.05 3.06
WS-E/1000/70 vol.% 3.36 1.21 0.04 3.19
412 the reaction order was high, showing more significant
WS-E/1000/60 vol.% 3.07 1.12 0.04 3.35
413 dependence on the gas concentration. HKN-E/1000/100 vol.% 4.70 1.55 0.05 2.94
414 HKN-E/1000/80 vol.% 4.13 1.42 0.04 3.19
415 In addition, when Rhenish brown coal and wheat straw chars HKN-E/1000/70 vol.% 3.54 1.26 0.04 3.30
HKN-E/1000/60 vol.% 3.27 1.18 0.03 3.47
416 were pyrolyzed at same temperatures, the reaction orders were
417 0.35 and 0.32 for WS-B and HKN-B, 0.62 and 0.38 for WS-E and Reaction order n and reaction rate constant k for chars gasified at 1000 °C
418 HKN-E. It can be found that the reaction order of wheat straw char Samples ln k (intercept) k (1/h) n (slope) R2
419 was a little higher than that of brown coal char. This might be caused WS-E, 800 0.47 1.60 0.62 1.00
420 by much more catalytic compounds for brown coal char. For WS-E, 1000 3.34 28.26 0.66 0.98
421 apparent reaction rate constant, k value of wheat straw char was HKN-E, 800 0.47 1.60 0.38 0.97
422 lower than that of brown coal char, especially at lower pyrolysis HKN-E, 1000 3.67 39.40 0.72 0.93

Please cite this article in press as: Zhou L et al. Kinetic study on CO2 gasification of brown coal and biomass chars: reaction order. Fuel (2016), http://dx.doi.
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8 L. Zhou et al. / Fuel xxx (2016) xxx–xxx

Fig. 7. Reaction order by linear fitting (a) WS-E and (b) HKN-E gasified in 1000 °C.

449 tion temperature. This could explain the enhanced reaction order on characteristics of char sample and the gasification conditions. 497
450 at 1000 °C. For the apparent reaction rate constant k, the k value The present paper was trying to reveal how these aspects affected 498
451 for HKN-E gasified at 800 °C was 1.60 and 39.4 at 1000 °C. This the reaction order. 499
452 illustrates that the reactivity of brown coal char was enhanced sig-
453 nificantly at higher temperatures.
4. Summary 500
454 For wheat straw char WS-E, the reaction order was 0.62 at
455 800 °C and 0.66 at 1000 °C. This shows that the gasification tem-
In the present study, the gasification behaviors of German 501
456 perature had less effect on the reaction order. The reason should
Rhenish brown coal and wheat straw chars under different CO2 502
457 be caused by a much higher pore volume value for wheat straw
partial pressures were studied and the reaction orders were deter- 503
458 chars, as shown in Table 1. Therefore, the diffusion resistance of
mined. In addition, the effects of different feeds (biomass and coal), 504
459 reactant gas into the pore structure of wheat straw char should
pyrolysis temperature of char and gasification temperature on 505
460 be also much lower than that of brown coal char, thus showing
reaction order were also investigated. 506
461 similar reaction orders. For the apparent reaction rate constant k,
For experimental behavior, higher CO2 partial pressure leaded 507
462 the k value for WS-E gasified at 800 °C was 1.60 and 28.26 at
to higher reaction rate by increasing the frequency of effective col- 508
463 1000 °C, showing much higher reactivity at 1000 °C.
lisions between gasifying agent molecules and active carbon. In 509
464 When Rhenish brown coal and wheat straw chars were gasified
addition, increasing the pressure of CO2 could increase higher con- 510
465 at 800 °C, the reaction order of WS-E was much higher than that of
centrations of surface complexes on the char surface and a higher 511
466 HKN-E (0.62 compared to 0.38). However, at 1000 °C, the reaction
reaction rate would be observed. 512
467 order was 0.66 for WS-E compared to 0.72 for HKN-E, showing that
For kinetic study, the reaction orders n in this study ranged 513
468 the dependence on CO2 concentration was similar during the
from 0.32 to 0.72 for different chars at various gasification temper- 514
469 gasification process. Possible reasons are that the gasification pro-
atures. The main results could be summarized as follows: 515
470 cess was under chemical control at low temperature. Hence, differ-
471 ent fuels, such as coal and biomass, demonstrated different
(1) For effects of pyrolysis temperature: The reaction orders for 516
472 reaction orders. However, at high temperatures, the gasification
wheat straw and brown coal chars increased at higher pyrol- 517
473 process was appreciably limited by diffusion (inner and outer)
ysis temperature. The catalytic effect by mineral matter in 518
474 effects. The reaction order was not strongly dependent on the fuel
chars took more charge. 519
475 property and thus showing little difference.
(2) For effects of gasification temperature: For wheat straw char 520
476 The reaction orders n in this study ranged from 0.32 to 0.72 for
WS-E, the gasification temperature just had a little effect on 521
477 different chars at various gasification temperatures. Ahn et al. [2]
reaction order. For brown coal char HKN-E, the reaction 522
478 obtained a reaction order of 0.4 for the CO2 partial pressure and
order at 1000 °C was almost double that at 800 °C. 523
479 0.65 for the total pressure. Kasaoka et al. [16] assumed a reaction
(3) For effects of different feeds: At low temperature, the reac- 524
480 order of 0.5 with the modified volume reaction model, irrespective
tion order for wheat straw char was obviously higher than 525
481 of coal type and different gasification temperatures. Ollero et al.
that for HKN char. However, at high temperature, the reac- 526
482 [13] reported the reaction order of the nth order model for olive
tion orders were approximate for both chars, showing simi- 527
483 residue was 0.43. Fermoso et al. [17] found that the reaction order
lar dependence on CO2 partial pressure, which was caused 528
484 with respect to CO2 partial pressure was 0.33 at 0.1 MPa and 0.35 at
by diffusion effects. 529
485 1 MPa for gasification reaction. It can be seen that the reaction order
530
486 differs from one researcher to another and that the orders obtained
487 in this study, were still within the literature range. In addition, as
488 mentioned above, if the value of reaction order is larger, the Acknowledgements 531
489 reaction is more dependent on the concentration of the reactant.
490 Compared to 1, which was assumed by many researches, the values Special thanks are given to: 532
491 here showed that the gasification reactions of coal and biomass 533
492 were more independent on the CO2 concentration. However, for a
493 given value, it cannot be explained by one simple sentence. Since (1) German Center for Energy Resources, TU Bergakademie Frei- 534
494 there were several influence conditions, such as catalytic berg, provides the experimental facility. 535
495 compounds, porosity of char, pyrolysis conditions, and gasification (2) China Scholarship Council (CSC) provides the financially 536
496 temperature. To conclude, the reaction order value was depended support. 537

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540 L. Zhou et al. / Fuel xxx (2016) xxx–xxx 9

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Please cite this article in press as: Zhou L et al. Kinetic study on CO2 gasification of brown coal and biomass chars: reaction order. Fuel (2016), http://dx.doi.
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