无机元素对生物质焦炭-CO2气化反应性的催化/抑制作用研究及模型构建

doi:10.11949/0438-1157.20220906

化工学报 ›› 2022, Vol. 73 ›› Issue (11): 5240-5250.DOI: 10.11949/0438-1157.20220906

• 生物质与有机固废热化学转化专栏 • 上一篇下一篇

无机元素对生物质焦炭-CO₂气化反应性的催化/抑制作用研究及模型构建

宋谦石¹(), 王潇伟¹^,³, 张威¹^,⁴, 汪小憨¹(), 李浩文¹, 乔瑜²

^1.中国科学院广州能源研究所，广东广州 510640
^2.华中科技大学煤燃烧国家重点实验室，湖北武汉 430074
^3.广东海洋大学机械与动力工程学院，广东湛江 524088
^4.中国科学技术大学能源科学与技术学院，安徽合肥 230026

收稿日期:2022-06-28 修回日期:2022-09-26 出版日期:2022-11-05 发布日期:2022-12-06
通讯作者: 汪小憨
作者简介:宋谦石（1994—），男，博士，助理研究员，songqs@ms.giec.ac.cn
基金资助:
国家自然科学基金项目(52206285)

Catalytic/inhibitory effects of inorganic elements on biomass char-CO₂ gasification reactivity and model construction

Qianshi SONG¹(), Xiaowei WANG¹^,³, Wei ZHANG¹^,⁴, Xiaohan WANG¹(), Haowen LI¹, Yu QIAO²

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^3.School of Mechanical and Power Engineering, Guangdong Ocean University, Zhanjiang 524088, Guangdong, China
^4.School of Energy Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2022-06-28 Revised:2022-09-26 Online:2022-11-05 Published:2022-12-06
Contact: Xiaohan WANG

摘要/Abstract

摘要：

基于简单碰撞理论，建立了含有无机元素影响的焦炭气化反应动力学模型。建模过程中，考虑了七种无机元素含量、催化/抑制能力以及单一无机元素饱和催化倍率对焦炭反应性的影响。实验部分，选取四种生物质样品置于微型流化床反应器中测试了焦炭反应性，并与模型计算值进行了对比，结果表明模型能够较好预测焦炭反应性，同时表现出对不同样品的适应性。该模型能够通过输入样品特性参数和反应工况条件实现焦炭反应性的定量预测。该模型的建立表明固体燃料通用气化反应的规律是存在的，可以为进一步阐明气化反应规律提供理论参考。

关键词: 生物质, 气化, 动力学模型, 无机元素, 流化床, 二氧化碳

Abstract:

Based on the simple collision theory, a kinetic model of char gasification reaction with the influence of inorganic elements was established. In the modeling process, the effects of the content of seven inorganic elements, the catalytic/inhibitory factor, and the fully catalytic ratio of single inorganic element on the char-CO₂ reactivity were considered. In the experimental part, four biomass samples were selected and placed in a micro-fluidized bed reactor to test the char-CO₂ reactivity, and compared with the model calculated values. The results show that the model can accurately predict the char-CO₂ reactivity, and also shows adaptability to different samples. The model can achieve quantitative prediction of char-CO₂ reactivity by inputting sample characteristic parameters and reaction conditions. The establishment of this model shows that the general law of biomass thermal conversion process exists, which can provide a theoretical reference for further clarifying the gasification reaction law.

Key words: biomass, gasification, kinetic modeling, inorganic matter, fluidized-bed, carbon dioxide

中图分类号:

TK 6

宋谦石, 王潇伟, 张威, 汪小憨, 李浩文, 乔瑜. 无机元素对生物质焦炭-CO₂气化反应性的催化/抑制作用研究及模型构建[J]. 化工学报, 2022, 73(11): 5240-5250.

Qianshi SONG, Xiaowei WANG, Wei ZHANG, Xiaohan WANG, Haowen LI, Yu QIAO. Catalytic/inhibitory effects of inorganic elements on biomass char-CO₂ gasification reactivity and model construction[J]. CIESC Journal, 2022, 73(11): 5240-5250.

图/表 10

表1 生物质样品的工业分析和元素分析

Table 1 Proximate analysis and ultimate analysis of samples

样品名称	工业分析 /% (质量，干燥基）			元素分析 /% (质量，干燥基）					M_v/ (g/mol）
样品名称	V	FC	A	C	H	N	S	O^①	M_v/ (g/mol）
烟杆	79.65	13.19	7.16	44.90	5.98	1.70	0.01	40.25	72.43
玉米芯	85.77	12.72	1.51	44.18	6.11	0.10	0.03	48.07	80.93
杉木	88.43	11.49	0.08	49.40	6.17	0.01	0.01	44.33	92.35
核桃皮	82.17	16.38	1.45	48.01	6.14	0.37	0.02	44.01	60.21

图1 微型流化床反应器装置示意图

Fig.1 Schematic diagram of micro-fluidized bed reactor

图2 生物质样品中不同赋存形态的无机元素所占比例

Fig.2 Proportion of inorganic elements in different existing forms in biomass samples

表2 生物质样品中Si元素和Al元素以及离子态K、Na、Ca、Mg、Fe元素的含量

Table 2 Contents of Si and Al elements and ion-exchanged K， Na， Ca， Mg， Fe elements in biomass samples

生物质样品	N_ion,K/(mg/kg)	N_ion,Na/(mg/kg)	N_ion,Ca/(mg/kg)	N_ion,Mg/(mg/kg)	N_ion,Fe/(mg/kg)	Si/(mg/kg)	Al/(mg/kg)
烟杆	309	53	9717	822	891	7046	3254
玉米芯	434	110	94	159	18	6136	2965
杉木	103	104	151	121	132	5465	2979
核桃皮	400	5	120	53	323	6539	2945

图3 无机元素负载比例对焦炭气化反应速率的影响

Fig.3 Influence of loading ratio of inorganic elements on char gasification reaction rate

表3 无机元素催化/抑制指数计算结果

Table 3 Calculation results of catalysis/inhibition factor of inorganic elements

无机元素	拟合线斜率	催化指数α_i,*	抑制指数α_j,*
K	0.611	1.000	—
Na	0.519	0.849	—
Ca	0.752	1.231	—
Mg	0.125	0.205	—
Fe	0.373	0.610	—
Si	-0.451	—	0.738
Al	-0.379	—	0.620

图4 不同负载比例的K2CO3对焦炭气化过程的影响

Fig.4 Effect of loading different proportion of K2CO3 on char gasification process

图5 CO2气流量对焦炭气化过程的影响

Fig.5 Effect of CO2 flow rate on char gasification process

表4 生物质焦炭的初始反应速率

Table 4 Initial gasification rate of char from four biomass samples

生物质样品	R_c0×10³/min^-1
生物质样品	873 K	923 K	973 K	1023 K
烟杆焦炭	9.33	26.77	68.67	113.00
玉米芯焦炭	4.05	15.17	35.52	48.32
杉木焦炭	0.28	0.73	1.80	5.44
核桃皮焦炭	1.45	7.60	18.11	35.90

图6 实验结果与模型计算值的对比

Fig.6 The comparison of experimental and simulation results

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无机元素对生物质焦炭-CO₂气化反应性的催化/抑制作用研究及模型构建

Catalytic/inhibitory effects of inorganic elements on biomass char-CO₂ gasification reactivity and model construction

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