有机固废合成气原位净化催化剂设计及反应器分析

doi:10.16085/j.issn.1000-6613.2022-0977

摘要/Abstract

摘要：

焦油脱除是实现有机固废气化制合成气连续运行的关键。常规金属类的焦油裂解催化剂尽管裂解能力强，但在固废气化高焦油、高水的环境下容易失活，催化剂再生和使用成本高。本研究设计并制备了一种比表面积达1384.2m²/g的生物质半焦催化剂，该催化剂用于可原位脱除焦油的有机固废气化反应器中，使用后的生物质半焦无需再生，直接落入气化反应器作为有机固废气化原料，大幅降低了焦油脱除成本。此外，本文通过对生物质半焦表面性质的测定及模型化合物甲苯在生物质半焦上裂解的活性评价，构建了半焦催化剂的失活动力学模型。在此基础上，利用多场耦合软件COMSOL对该催化剂在示范工程工艺条件下的焦油脱除过程进行仿真，考察了催化剂停留时间、装填量以及催化剂反应器形状对裂解过程的影响。结果表明，当脱除焦油的反应器高径比为1.0，全部填充催化剂时，出口焦油浓度可在4~6s内降为0，且合成气中H₂浓度为0.032kg/m³，CO浓度为0.50kg/m³。

关键词: 有机固废, 生物质半焦, 焦油, 动力学, 数值模拟

Abstract:

Tar removal from syngas is key for solid waste gasification. Conventional metal-based catalysts, despite their high cracking capabilities, easily deactivate during gasification in tar- and water vapor-laden environments. In this study, a biochar catalyst with a large specific surface area of 1384.2m²/g was prepared and its kinetics of in-situ tar removal were examined in an organic solid waste gasification reactor. The generated biochar could directly be incorporated into the gasification process without regeneration, enabling efficient tar removal at a considerably lower cost. In addition, the deactivation kinetic model of the char catalyst was constructed by measuring its surface properties and evaluating the activity of toluene cracking reaction. On this basis, the tar removal process under the conditions of the demonstration engineering process was simulated using the multi-field coupling software COMSOL. The effects of residence time, catalyst loading amount, and reactor shape on the cracking process were investigated. The results showed that, in a reactor with a height-to-diameter ratio 1.0 and full catalyst loading, the tar concentration at the outlet was reduced to zero within 4—6s, and the H₂ and CO concentrations in the syngas were 0.032kg/m³ and 0.50kg/m³, respectively.

Key words: organic solid waste, biochar, tar, kinetics, numerical simulation

中图分类号:

TQ524

宋叶, 陈玉卓, 宋云彩, 冯杰. 有机固废合成气原位净化催化剂设计及反应器分析[J]. 化工进展, 2023, 42(3): 1383-1396.

SONG Ye, CHEN Yuzhuo, SONG Yuncai, FENG Jie. Catalyst design and reactor analysis for in-situ purification of organic solid waste syngas[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1383-1396.

图/表 27

表1 生物质原料元素分析[干燥无灰基（daf），质量分数，%]

原料	C	H	O	N	S
核桃壳	51.36	6.16	41.94	0.50	0.05
玉米芯	46.76	4.17	48.45	0.55	0.06
水稻秸秆	39.22	5.27	53.66	1.14	0.71

图1 气化反应器h1—催化剂装填高度；h2—空床高度；h3—反应器入口锥体高度；d1—反应器直径

表2 反应过程中涉及的数学模型

方程类别	方程
能量守恒方程^[14]	$ρ c p e f f ∂ T ∂ t ︸ a c c u m u l a t i o n t e r m + ρ c p g, m i x u ⋅ ∇ T ︸ c o n v e c t i v e t e r m + ∇ ⋅ - k e f f ∇ T ︸ c o n d u c t i v e t e r m = Q t o t ︸ s o u r c e t e r m$
热源Q_tot	$Q t o t = - ∑ i = 1 7 r i Δ H i$
有效比热容(ρc_p )_eff	$ρ c p e f f = 1 - η c p, C ρ C + η ρ c p g, m i x$
热导率k_eff	$k e f f = 1 - η k C + η k g, m i x$
反应器内的动量传递守恒方程^[15]	$1 η × ρ × ∂ u ∂ t + 1 η × ρ u ⋅ ∇ u × 1 η =$ $∇ ⋅ - p I + K - μ κ - 1 + β ρ u + Q m η 2 u$
催化剂床层内的动量传递守恒方程	$∂ ε ρ g, m i x ∂ t + ∇ ⋅ ρ g, m i x u = Q m$
黏性应力张量K^[16]	$K = μ × 1 η ∇ u + ∇ u T - 23 μ × 1 η ∇ ⋅ u I$
气体流速u^[17-18]	$u = - κ μ g, m i x$
理想气体状态方程^[18]	$ρ g, m i x = ∑ i = 1 n y i M i T 0 p 22.4 L / m o l × T p 0$ , $p = ρ g, m i x R T M g, m i x$ ， $M g, m i x = ∑ i ρ i ρ g, m i x M i - 1$
多孔基体的渗透率κ^[19]	$κ = κ 0 η η 0 3.55$
质量传递控制方程^[20]	$∂ η ρ g, m i x ω i ∂ t ︸ a c c u m u l a t i o n t e r m + ρ (u ⋅ ∇) ω i ︸ c o n v e c t i v e t e r m + ∇ ⋅ J i ︸ d i f f u s i v e t e r m = R i ︸ s o u r c e t e r m$
扩散通量J_i^[21]	$J i = - ρ g, m i x D i j ∇ ω i$
二元扩散系数D_ij^[22]	$D i j = 0.0101 T 1.75 1 M i + 1 M j 12 p ∑ v i 13 + ∑ v j 13 2$
床层压降∆p^[23]	$Δ p = f L u 02 ρ 1 - η d s η 3$
摩擦系数f	$f = 150 R e + 1.75$
雷诺数Re^[24]	$R e = d ρ g, m i x u μ g, m i x × 1 1 - η$

表2 反应过程中涉及的数学模型

方程类别	方程
能量守恒方程^[14]	$ρ c p e f f ∂ T ∂ t ︸ a c c u m u l a t i o n t e r m + ρ c p g, m i x u ⋅ ∇ T ︸ c o n v e c t i v e t e r m + ∇ ⋅ - k e f f ∇ T ︸ c o n d u c t i v e t e r m = Q t o t ︸ s o u r c e t e r m$
热源Q_tot	$Q t o t = - ∑ i = 1 7 r i Δ H i$
有效比热容(ρc_p )_eff	$ρ c p e f f = 1 - η c p, C ρ C + η ρ c p g, m i x$
热导率k_eff	$k e f f = 1 - η k C + η k g, m i x$
反应器内的动量传递守恒方程^[15]	$1 η × ρ × ∂ u ∂ t + 1 η × ρ u ⋅ ∇ u × 1 η =$ $∇ ⋅ - p I + K - μ κ - 1 + β ρ u + Q m η 2 u$
催化剂床层内的动量传递守恒方程	$∂ ε ρ g, m i x ∂ t + ∇ ⋅ ρ g, m i x u = Q m$
黏性应力张量K^[16]	$K = μ × 1 η ∇ u + ∇ u T - 23 μ × 1 η ∇ ⋅ u I$
气体流速u^[17-18]	$u = - κ μ g, m i x$
理想气体状态方程^[18]	$ρ g, m i x = ∑ i = 1 n y i M i T 0 p 22.4 L / m o l × T p 0$ , $p = ρ g, m i x R T M g, m i x$ ， $M g, m i x = ∑ i ρ i ρ g, m i x M i - 1$
多孔基体的渗透率κ^[19]	$κ = κ 0 η η 0 3.55$
质量传递控制方程^[20]	$∂ η ρ g, m i x ω i ∂ t ︸ a c c u m u l a t i o n t e r m + ρ (u ⋅ ∇) ω i ︸ c o n v e c t i v e t e r m + ∇ ⋅ J i ︸ d i f f u s i v e t e r m = R i ︸ s o u r c e t e r m$
扩散通量J_i^[21]	$J i = - ρ g, m i x D i j ∇ ω i$
二元扩散系数D_ij^[22]	$D i j = 0.0101 T 1.75 1 M i + 1 M j 12 p ∑ v i 13 + ∑ v j 13 2$
床层压降∆p^[23]	$Δ p = f L u 02 ρ 1 - η d s η 3$
摩擦系数f	$f = 150 R e + 1.75$
雷诺数Re^[24]	$R e = d ρ g, m i x u μ g, m i x × 1 1 - η$

图2 原料热解特性曲线分析

表3 不同原料制备的半焦比表面积及孔结构分析

原料	比表面积/m²·g^-1	总孔容/cm³·g^-1
WS-CB-Cat	196.4	0.145
CC-CB-Cat	90.3	0.038
RS-CB-Cat	108.1	0.046

表4 不同温度制备的半焦比表面积及孔结构分析

催化剂

比表面积

/m²·g^-1

总孔容

/cm³·g^-1

中孔孔容

/cm³·g^-1

微孔孔容

/cm³·g^-1

图3 半焦催化剂CO2气化反应性分析

表5 半焦催化剂比表面积和孔容分析

样品名称

比表面积

/m²·g^-1

中孔比表面积

/m²·g^-1

微孔孔容

/cm³·g^-1

中孔孔容

/cm³·g^-1

总孔孔容

/cm³·g^-1

WS-H₂O

图4 半焦催化剂N2吸脱附曲线及孔径分布曲线

图5 半焦催化剂表面形貌

图6 半焦催化剂晶相结构及碳结构分析

表6 半焦催化剂微晶参数

样品名称	I_D/I_G	I(_Gr+Vl+Vr)/I_D	L_a	L_c	d₀₀₂
WS-RAW	0.7513	0.3441	3.5361	1.5469	0.3892
WS-KOH	0.9524	0.3375	3.9676	1.1225	0.3731
WS-H₂O	0.8190	0.3883	5.2651	1.6774	0.3749

表7 半焦催化剂元素分析

样品名称	EDS分析（质量分数）/%			元素分析（daf）/%
样品名称	C	O	O/C摩尔比	C	O	O/C
WS-RAW	85.74	13.33	0.16	92.16	6.13	0.07
WS-KOH	88.56	11.10	0.13	87.70	10.52	0.12
WS-H₂O	78.41	14.50	0.18	83.35	14.66	0.18

图7 半焦催化剂XPS谱图分析

表8 半焦催化剂碳原子分数（%）

样品名称	C $̿$ C/C—H _x /C—C	C—O	C $̿$ O	O—C $̿$ O
WS-RAW	59.02	23.49	8.56	8.94
WS-KOH	42.66	29.18	14.92	13.25
WS-H₂O	40.92	37.67	12.24	9.16

表8 半焦催化剂碳原子分数（%）

样品名称	C $̿$ C/C—H _x /C—C	C—O	C $̿$ O	O—C $̿$ O
WS-RAW	59.02	23.49	8.56	8.94
WS-KOH	42.66	29.18	14.92	13.25
WS-H₂O	40.92	37.67	12.24	9.16

表9 半焦催化剂氧原子分数（%）

样品名称	晶格氧	氧缺陷	吸附氧
WS-RAW	96.22	2.56	1.22
WS-KOH	44.64	27.22	28.14
WS-H₂O	77.98	4.49	17.54

图8 不同催化剂对甲苯的转化率

表10 不同催化剂的失活动力学相关参数

催化剂	ξ	a
WS-RAW	13.08	$a (t) W S - R A W = 1.65 - 1.43 × 1 - e x p - t 1.83 - 0.07 × 1 - e x p - t 33.23$
WS-KOH	210.85	$a (t) W S - K O H = 0.19 + 1.21 1 + e x p t - 13.78 17.33$
WS-H₂O	136.57	$a (t) W S - H 2 O = 1.04 - 0.10 × 1 - e x p - t 80.67 - 0.83 × 1 - e x p - t 6.35$

表10 不同催化剂的失活动力学相关参数

催化剂	ξ	a
WS-RAW	13.08	$a (t) W S - R A W = 1.65 - 1.43 × 1 - e x p - t 1.83 - 0.07 × 1 - e x p - t 33.23$
WS-KOH	210.85	$a (t) W S - K O H = 0.19 + 1.21 1 + e x p t - 13.78 17.33$
WS-H₂O	136.57	$a (t) W S - H 2 O = 1.04 - 0.10 × 1 - e x p - t 80.67 - 0.83 × 1 - e x p - t 6.35$

表11 模型中使用的物性参数

物性参数	数值
比热容	(c_p )_g,mix=1390J/(kg·K)；(c_p )_cat=470J/(kg·K)
热导率	k_g,mix=0.08W/(m·K)；k_cat=37.2W/(m·K)
密度	ρ_g,mix=1.05kg/m³；ρ_cat=400kg/m³
黏度	μ_g,mix=1.99×10^-4Pa·s

表12 甲苯裂解反应过程中主要的反应方程式、焓变及反应速率表达式[38-40]

反应方程式	∆H/kJ·mol^-1	反应速率表达式
C₇H₈ $→$ 7C+4H₂	-50.0	$r 1 = 1.03 × 1013 e x p - 324500 R T C C 7 H 8$
C+2H₂ $→$ CH₄	-74.6	$r 2 = 3.18 × 102 e x p - 237400 R T C H 2$
C₇H₈+10.5H₂O $→$ 3.5CO+3.5CO₂+14.5H₂	725.0	$r 3 = 1.0 × 108 e x p - 100000 R T C C 7 H 8$
CO+H₂O CO₂+H₂	-41.2	$r 4 = k f C C O C H 2 O - k b C C O 2 C H 2$ , $k f = 2.79 × 102 e x p - 12560 R T$ , $k b = 1.26 × 104 e x p - 47290 R T$
CO₂+C $→$ 2CO	-172.4	$r 5 = 1.18 × 107 e x p - 245000 R T C C O 2$
CH₄+H₂O $→$ CO+3H₂	205.9	$r 6 = 3.10 × 103 e x p - 124700 R T C C H 4 C H 2 O$
C+H₂O $→$ CO+H₂	131.3	$r 7 = 3.6 × 1012 e x p - 310000 R T C C C H 2 O$

表12 甲苯裂解反应过程中主要的反应方程式、焓变及反应速率表达式[38-40]

反应方程式	∆H/kJ·mol^-1	反应速率表达式
C₇H₈ $→$ 7C+4H₂	-50.0	$r 1 = 1.03 × 1013 e x p - 324500 R T C C 7 H 8$
C+2H₂ $→$ CH₄	-74.6	$r 2 = 3.18 × 102 e x p - 237400 R T C H 2$
C₇H₈+10.5H₂O $→$ 3.5CO+3.5CO₂+14.5H₂	725.0	$r 3 = 1.0 × 108 e x p - 100000 R T C C 7 H 8$
CO+H₂O CO₂+H₂	-41.2	$r 4 = k f C C O C H 2 O - k b C C O 2 C H 2$ , $k f = 2.79 × 102 e x p - 12560 R T$ , $k b = 1.26 × 104 e x p - 47290 R T$
CO₂+C $→$ 2CO	-172.4	$r 5 = 1.18 × 107 e x p - 245000 R T C C O 2$
CH₄+H₂O $→$ CO+3H₂	205.9	$r 6 = 3.10 × 103 e x p - 124700 R T C C H 4 C H 2 O$
C+H₂O $→$ CO+H₂	131.3	$r 7 = 3.6 × 1012 e x p - 310000 R T C C C H 2 O$

表13 网格无关性检验

网格类型	单元数	相同条件下出口焦油浓度为0的时间/s
较细化	723359	11
常规	80855	11
较粗化	16238	11

图9 不同高径比对出口焦油浓度的影响

表14 不同高径比设置

项目	d₁/m	h₁/m	h₂/m	h₃/m	高径比	停留时间/s
Case1	0.06	0.12	0.18	0.02	5.00	0.67
Case2	0.08	0.03	0.14	0.02	2.10	1
Case3	0.10	0.02	0.09	0.01	1.08	4

图10 不同高径比对出口合成气浓度的影响

图11 不同装填量对出口焦油浓度的影响

表15 不同装填量催化反应器相关参数

项目	d₁/m	h₁/m	催化剂床层压降/Pa	停留时间/s
Case4	0.10	0.02	2301.18	0.67
Case5	0.10	0.08	9204.73	2.67
Case6	0.10	0.11	12656.50	3.60

图12 催化剂装填量对出口合成气浓度的影响

参考文献 40

1	蔡峰, 徐海. 我国固体废物处置的现状及进展[J]. 现代盐化工, 2022, 49(1): 84-85.
	CAI Feng, XU Hai. Current status and progress of solid waste disposal in China[J]. Modern Salt and Chemical Industry, 2022, 49(1): 84-85.
2	BUENTELLO-MONTOYA D, ZHANG Xiaolei, LI Jun, et al. Performance of biochar as a catalyst for tar steam reforming: effect of the porous structure[J]. Applied Energy, 2020, 259: 114176-114188.
3	HERVY M, WEISS-HORTALA E, PHAM MINH D, et al. Reactivity and deactivation mechanisms of pyrolysis chars from bio-waste during catalytic cracking of tar[J]. Applied Energy, 2019, 237: 487-499.
4	SHEN Yafei, ZHAO Peitao, SHAO Qinfu, et al. In-situ catalytic conversion of tar using rice husk char-supported nickel-iron catalysts for biomass pyrolysis/gasification[J]. Applied Catalysis B: Environmental, 2014, 152/153: 140-151.
5	PAN Dengfeng, QU Xuan, BI Jicheng. Effect of gasified semi-coke on coal pyrolysis in the poly-generation of CFB gasification combined with coal pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2017, 127: 461-467.
6	ZENG Xi, WANG Yin, YU Jian, et al. Gas upgrading in a downdraft fixed-bed reactor downstream of a fluidized-bed coal pyrolyzer[J]. Energy & Fuels, 2011, 25(11): 5242-5249.
7	付大庆. 生物质半焦催化提质煤低温热解焦油研究[D]. 太原: 太原理工大学, 2018.
	FU Daqing. Study on catalytic upgrading of coal low temperature pyrolysis tar over bio-char[D]. Taiyuan: Taiyuan University of Technology, 2018.
8	王兴栋. 半焦基催化剂裂解煤热解产物调控油气品质[D]. 乌鲁木齐: 新疆大学, 2012.
	WANG Xingdong. Catalytic cracking of coal pyrolysis product for oil and gas upgrading over char-based catalysts[D]. Urumqi: Xinjiang University, 2012.
9	SHEN Yafei. Chars as carbonaceous adsorbents/catalysts for tar elimination during biomass pyrolysis or gasification[J]. Renewable and Sustainable Energy Reviews, 2015, 43: 281-295.
10	DONG L, ASADULLAH M, ZHANG S, et al. An advanced biomass gasification technology with integrated catalytic hot gas cleaning (I): Technology and initial experimental results in a lab-scale facility[J]. Fuel, 2013, 108: 409-416.
11	ARRHENIUS S. Über Die reaktionsgeschwindigkeit Bei der inversion von rohrzucker durch säuren[J]. Zeitschrift Für Physikalische Chemie, 1889, 4U(1): 226-248.
12	OSTROVSKII N M. Catalyst deactivation kinetics: an apparent delay in decreasing of catalyst activity, “inflection point” and data interpretation[J]. Russian Journal of Physical Chemistry A, 2011, 85(13): 2336-2343.
13	ZHANG Shuping, SU Yinhai, XIONG Yuanquan, et al. Physicochemical structure and reactivity of char from torrefied rice husk: effects of inorganic species and torrefaction temperature[J]. Fuel, 2020, 262: 116667.
14	DI BLASI C. Heat, momentum and mass transport through a shrinking biomass particle exposed to thermal radiation[J]. Chemical Engineering Science, 1996, 51(7): 1121-1132.
15	刘永忠, 王乐. 多孔介质中超临界流体可调特性的模拟与分析——温度梯度的作用[J]. 高校化学工程学报, 2008, 22(6): 915-920.
	LIU Yongzhong, WANG Le. Simulation and analysis of tunable performances of supercritical fluid flow in porous medium — effect of temperature gradients[J]. Journal of Chemical Engineering of Chinese Universities, 2008, 22(6): 915-920.
16	席肖玉. 某些与黏性流体力学方程耦合的方程解的相关性质的研究[D]. 北京: 中国工程物理研究院, 2017.
	XI Xiaoyu. The study of the related properties of some of the solutions of equations coupled to viscous hydrodynamic equations[D]. Beijing: China Academy of Engineering Physics, 2017.
17	ATANGANA A. Fractional variable order derivatives[M]// Fractional operators with constant and variable order with application to geo-hydrology. Pittsburgh: Academic Press, 2018: 221-243.
18	GRØNLI M G, MELAAEN M C. Mathematical model for wood pyrolysiscomparison of experimental measurements with model predictions[J]. Energy & Fuels, 2000, 14(4): 791-800.
19	SALLÈS J, THOVERT J F, ADLER P M. Deposition in porous media and clogging[J]. Chemical Engineering Science, 1993, 48(16): 2839-2858.
20	曾子粤, 杨建森, 魏永起. 脱硫石膏灌芯墙脱水过程的仿真模拟与分析[J]. 材料导报, 2022, 36(5): 89-94.
	ZENG Ziyue, YANG Jiansen, WEI Yongqi. The simulation and analysis of dehydration process of FGD gypsum grouted wall[J]. Materials Reports, 2022, 36(5): 89-94.
21	VAN DE VEN-LUCASSEN I M J J, OTTEN A M V J, VLUGT T J H, et al. Molecular dynamics simulation of the maxwell-stefan diffusion coefficients in Lennard-Jones liquid mixtures[J]. Molecular Simulation, 1999, 23(1): 43-54.
22	FULLER E N, SCHETTLER P D, GIDDINGS J C. New method for prediction of binary gas-phase diffusion coefficients[J]. Industrial & Engineering Chemistry, 1966, 58(5): 18-27.
23	ERGUN S. Fluid flow through packed column[J]. Journal of Materials Science and Chemical Engineering, 1952, 48(2): 89-94.
24	陈耀壮, 姚松柏, 马磊, 等. 工业反应器中催化剂床层压力降的模拟计算[J]. 天然气化工(C1化学与化工), 2008, 33(5): 72-75.
	CHEN Yaozhuang, YAO Songbai, MA Lei, et al. Simulation of the pressure drop of the catalyst bed in industrial reactor[J]. Natural Gas Chemical Industry, 2008, 33(5): 72-75.
25	WANG J C, KASKEL S. KOH activation of carbon-based materials for energy storage[J]. Journal of Materials Chemistry, 2012, 22(45): 23710-23725.
26	YUAN M J, KIM Y, JIA C Q. Feasibility of recycling KOH in chemical activation of oil-sands petroleum coke[J]. The Canadian Journal of Chemical Engineering, 2012, 90(6): 1472-1478.
27	ROMANOS J, BECKNER M, RASH T, et al. Nanospace engineering of KOH activated carbon[J]. Nanotechnology, 2012, 23(1): 015401.
28	FEBRIANA S, RIYANTO E S, DIMYATI A, et al. Characterization studies of cyclotron CS-30 carbon puller material using powder X-ray diffraction and SEM, EDX cross section method[J]. IOP Conference Series: Materials Science and Engineering, 2018, 299: 012054.
29	SIDDIQUI M N, ALI M F, SHIROKOFF J. Use of X-ray diffraction in assessing the aging pattern of asphalt fractions[J]. Fuel, 2002, 81(1): 51-58.
30	吴娟霞, 徐华, 张锦. 拉曼光谱在石墨烯结构表征中的应用[J]. 化学学报, 2014, 72(3): 301-318.
	WU Juanxia, XU Hua, ZHANG Jin. Raman spectroscopy of graphene[J]. Acta Chimica Sinica, 2014, 72(3): 301-318.
31	SONIBARE O O, HAEGER T, FOLEY S F. Structural characterization of Nigerian coals by X-ray diffraction, Raman and FTIR spectroscopy[J]. Energy, 2010, 35(12): 5347-5353.
32	LU L, SAHAJWALLA V, KONG C, et al. Quantitative X-ray diffraction analysis and its application to various coals[J]. Carbon, 2001, 39(12): 1821-1833.
33	BALACHANDRAN M, AG K. Study of stacking structure of amorphous carbon by X-ray diffraction technique[J]. International Journal of Electrochemical Science, 2012, 7(4): 3127-3134.
34	LI Bin, LIU Dongjing, LIN Dan, et al. Changes in biochar functional groups and its reactivity after volatile-char interactions during biomass pyrolysis[J]. Energy & Fuels, 2020, 34(11): 14291-14299.
35	SONG Yao, WANG Yi, HU Xun, et al. Effects of volatile-char interactions on in situ destruction of nascent tar during the pyrolysis and gasification of biomass (I): Roles of nascent char[J]. Fuel, 2014, 122: 60-66.
36	CHEN Xiangnan, WANG Xiaohui, FANG De. A review on C1s XPS-spectra for some kinds of carbon materials[J]. Fullerenes, Nanotubes and Carbon Nanostructures, 2020, 28(12): 1048-1058.
37	Gang OU, XU Yushuai, WEN Bo, et al. Tuning defects in oxides at room temperature by lithium reduction[J]. Nature Communications, 2018, 9: 1302-1311.
38	FOURCAULT A, MARIAS F, MICHON U. Modelling of thermal removal of tars in a high temperature stage fed by a plasma torch[J]. Biomass and Bioenergy, 2010, 34(9): 1363-1374.
39	DU Yupeng, LIU Haitao, REN Wanzhong. Numerical investigations of a fluidized bed biomass gasifier coupling detailed tar generation and conversion kinetics with particle-scale hydrodynamics[J]. Energy & Fuels, 2020, 34(7): 8440-8451.
40	李政, 王天骄, 韩志明, 等. Texaco煤气化炉数学模型的研究——建模部分[J]. 动力工程, 2001, 21(2): 1161-1165.
	LI Zheng, WANG Tianjiao, HAN Zhiming, et al. Study on mathematical model of texaco gasifier-modeling[J]. Power Engineering, 2001, 21(2): 1161-1165.

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