水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验

doi:10.11949/0438-1157.20220478

化工学报 ›› 2022, Vol. 73 ›› Issue (8): 3720-3730.DOI: 10.11949/0438-1157.20220478

水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验

朱莲峰¹^,²^,³(), 王超¹^,²(), 张梦娟¹^,², 刘方正¹^,², 贾鑫¹^,², 安萍¹^,², 许光文¹^,², 韩振南¹^,²()

^1.特色资源化工与材料教育部重点实验室，辽宁沈阳 110142
^2.沈阳化工大学能源与化工产业技术研究院，辽宁沈阳 110142
^3.沈阳化工大学机械与动力工程学院，辽宁沈阳 110142

收稿日期:2022-04-06 修回日期:2022-05-10 出版日期:2022-08-05 发布日期:2022-09-06
通讯作者: 王超,韩振南
作者简介:朱莲峰（1997—），男，硕士研究生，zhulianfeng0724@163.com
基金资助:
国家自然科学基金新疆联合基金项目(U190310);国家自然科学基金青年科学基金项目(22108175);国家自然科学基金委辽宁联合基金重点项目(U190820065)

Fluidized bed two-stage gasification of coal with steam/O₂ for production of low-tar syngas

Lianfeng ZHU¹^,²^,³(), Chao WANG¹^,²(), Mengjuan ZHANG¹^,², Fangzheng LIU¹^,², Xin JIA¹^,², Ping AN¹^,², Guangwen XU¹^,², Zhennan HAN¹^,²()

^1.Key Laboratory of Resources Chemicals and Materials (Shenyang University of Chemical Technology), Ministry of Education, Shenyang 110142, Liaoning, China
^2.Institute of Energy and Chemical Industry Technology, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^3.School of Mechanical and Power Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2022-04-06 Revised:2022-05-10 Online:2022-08-05 Published:2022-09-06
Contact: Chao WANG, Zhennan HAN

摘要/Abstract

摘要：

由下行床热解和提升管（或输送床）气化组合形成的流化床两段气化将煤气化反应过程解耦为煤热解和半焦气化两个反应阶段，热解产物完全进入气化反应器，利用其中的高温环境和输送的半焦催化作用分别实现焦油的热裂解与催化裂解，完成低焦油气化。利用该流化床两段气化的10 kg/h级实验室工艺实验装置，以榆林烟煤为原料、水蒸气/氧气作为气化剂，变化过量氧气系数ER、蒸汽炭比S/C、热解及气化温度等参数，研究水蒸气/氧流化床两段煤气化制备低焦油合成气的特性。结果表明，流化床两段气化系统可实现稳定运行（实验3 h以上），在ER=0.36和S/C=0.15时，热解和气化的代表温度分别稳定在735℃和877℃，合成气的CO、CO₂、H₂、CH₄、C _n H _m 和N₂含量分别为14.33%、10.07%、18.39%、9.89%、1.82%和45.50%，相应的合成气产量达到1.8 m³/kg，低位热值8.99 MJ/m³，焦油含量0.437 g/m³，展示了制备低焦油合成气的技术特征。对于实际的长时间连续运行，更高的气化温度将使流化床两段气化具有更好的低焦油特性。

关键词: 两段低焦油气化, 循环流化床, 气化, 反应解耦, 煤, 合成气

Abstract:

The fluidized bed two-stage gasification (FBTSG) decouples the reaction process into fuel pyrolysis in a downer and char gasification in a riser or transport bed. By sending all pyrolysis products into the bottom section of the gasifier, the tars containing in the pyrolysis volatile can be thermally and catalytically cracked in the gasifier via its high-temperature circumstance and catalysis of conveyed char, respectively. Thus, low-tar producer gas is possible for the FBTSG. Taking Yulin bituminous coal as raw material and using steam-oxygen as gasification reagent, the FBTSG was tested in a laboratory facility treating about 10 kg/h fuel to produce low-tar syngas under varied excessive oxygen ratio ER, steam to carbon ratio S/C, and temperature of pyrolysis and/or gasification reaction. The results showed that the continuous steady operation of FBTSG is fully feasible, and for a continuous test lasting for more than 3 h at ER = 0.36 and S/C = 0.15, its characteristic temperatures of pyrolysis and gasifier were stable at 735℃ and 877℃, respectively. The produced syngas contained 14.33% CO, 10.07% CO₂, 18.39% H₂, 9.89% CH₄, 1.82% C _n H _m and 45.50% N₂, giving an LHV of 8.99 MJ/m³. The gas yield was 1.8 m³/kg, and tar content in the gas reached its lower value of 0.437 g/m³, showing the technical characteristics of preparing low-tar syngas. For practical long-term continuous operation, higher gasification temperature will result in better low-tar characteristics of two-stage fluidized bed gasification.

Key words: two-stage low-tar gasification, circulating fluidized bed, gasification, reaction decoupling, coal, syngas

中图分类号:

TQ 546.2

朱莲峰, 王超, 张梦娟, 刘方正, 贾鑫, 安萍, 许光文, 韩振南. 水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验[J]. 化工学报, 2022, 73(8): 3720-3730.

Lianfeng ZHU, Chao WANG, Mengjuan ZHANG, Fangzheng LIU, Xin JIA, Ping AN, Guangwen XU, Zhennan HAN. Fluidized bed two-stage gasification of coal with steam/O₂ for production of low-tar syngas[J]. CIESC Journal, 2022, 73(8): 3720-3730.

图/表 11

图1 耦合下行床热解和提升管气化的两段流化床气化工艺原理示意图HCPs—heating carrier particles

Fig.1 A conceptual diagram of two-stage fluidized bed gasification coupling downer pyrolysis and riser gasification

图2 流化床两段气化炉实验装置流程示意图

Fig.2 Schematic diagram of the experimental two-stage fluidized bed gasification system

表1 实验原料烟煤工业分析和元素分析结果

Table 1 Industrial and elemental analyses of tested bituminous coal

Industrial analysis/ %(mass,ad)				Elemental analysis/%(mass,ad)
M	A	V	FC	C	H	O^①	N	S
4.80	9.23	30.20	55.77	70.85	3.96	23.74	1.01	0.44

图3 实验原料烟煤粉碎后的颗粒及其粒径分布

Fig.3 Crashed particles and particle size distribution of tested bituminous coal

图4 原煤及其半焦在空气氛围中的失重特性（煤半焦样品对应气化条件为ER=0.36和S/C=0.15，下同）

Fig.4 Thermogravimetric analysis of tested coal and produced char in air atmosphere (char samples generated from coal gasification under ER=0.36 and S/C=0.15)

图5 原煤及其半焦的形貌表征结果

Fig.5 Morphological characterization of coal and its gasification char samples

图6 流化床两段气化实验系统典型操作的温度与压力变化曲线

Fig.6 Typical temperature and pressure variations for the tested two-stage fluidized bed gasification system

图7 流化床两段气化稳定运行气体组成与热值变化

Fig.7 Variation of composition and heating value of produced gas for the tested fluidized bed two-stage gasification

图8 不同过量氧气系数及蒸汽炭/比条件下的燃气气体组成

Fig.8 Composition of produced gas of gasification at different ER and S/C values

图9 稳定运行条件下：(a)气体收率、焦油含量和焦油模拟蒸馏结果；(b)随着水煤比增加气化反应器温度分布曲线；(c)冷态气化效率与碳转化率变化曲线

Fig.9 Gas yield, tar content and simulated distillation results of tar (a), the temperature variation with S/C ratio increasing (b), and the variations of cold gas efficiency and carbon conversion efficiency (c) at realized steady gasification test

表2 文献中不同气化技术之间的对比

Table 2 Comparison of different gasification technologies in references

Typical applied gasifier name	Feedstock	Institute	Caloric value/ (MJ/m³)	Tar content/ (g/m³)	Ref.
downdraft gasiﬁer	high ash biomass and high ash coal	Institute of Technology, Nirma University, Ahmedabad, India	4.98—5.62	0.11—0.52	[34]
top-lit updraft gasifier (TLUD)	palm kernel shell, high-volatile bituminous coal	Department of Mechanical Engineering, Universidad del Norte, Colombia	3.7—5.1	8.55—132.4	[35]
staged fixed-bed gasifier	wood, bark, and sunflower husk pellets	VTT Technical Research Centre of Finland Ltd., Finland	2.4—12.1	0.01—0.254	[36]
bubbling fluidized bed	pinewood, maple-oak wood, seed corn	Department of Mechanical Engineering, Iowa State University, USA	4.28—8.26	6.62—19.55	[25]
circulating fluidized bed	cypress, hemlock, cedar, spruce, pine, and mixed sawdust	The University of British Columbia, Canada	2.43—6.13	0.4—15.2	[37]
dual fluidized bed	wood chips, coal, sewage sludge, and plastics	Vienna University of Technology, Austria	12—14	0.5—20	[11, 38]
two-stage fluidized bed	low-rank coal	IPE, China	4.6	0.365—1.13	[14]
this work	bituminous coal	Shenyang University of Chemical Technology, China	8.99	0.437	—

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水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验

Fluidized bed two-stage gasification of coal with steam/O₂ for production of low-tar syngas

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水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验

Fluidized bed two-stage gasification of coal with steam/O2 for production of low-tar syngas

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Fluidized bed two-stage gasification of coal with steam/O₂ for production of low-tar syngas