不同反应器中氧化反应与水蒸气气化反应协同作用差异性

doi:10.16085/j.issn.1000-6613.2018-1882

化工进展 ›› 2019, Vol. 38 ›› Issue (05): 2179-2188.DOI: 10.16085/j.issn.1000-6613.2018-1882

不同反应器中氧化反应与水蒸气气化反应协同作用差异性

程相龙^1,²(),郭晋菊^1,²,王永刚³(),申恬³,孙加亮³,张海永³

1. 河南城建学院材料与化工学院，河南平顶山 467036
2. 河南城建学院煤盐资源高效利用河南省工程实验室，河南平顶山 467036
3. 中国矿业大学(北京)化学与环境工程学院，北京 100083

收稿日期:2018-09-19 修回日期:2018-12-20 出版日期:2019-05-05 发布日期:2019-05-05
通讯作者: 王永刚
作者简介:<named-content content-type="corresp-name">程相龙</named-content>（1983—），男，博士，研究方向为煤炭热解和气化。E-mail：<email>chengxianglong420@163.com</email>。
基金资助:
国家自然科学基金(21506251);“十二五”国家科技支撑计划重点项目(2012BAA04B02);河南城建学院高级人才科研启动基金(2017015Q);煤盐资源高效利用河南省工程实验室(河南城建学院)

Synergistic effect of oxidation reaction and steam gasification reaction in different reactors

Xianglong CHENG^1,²(),Jinju GUO^1,²,Yonggang WANG³(),Tian SHEN³,Jialiang SUN³,Haiyong ZHANG³

1. School of Materials and Chemical Engineering, Henan University of Urban Construction, Pingdingshan 467036, Henan, China
2. Henan Province Engineering Laboratory of Coal-Salt Resources Efficient Utilization, Henan University of Urban Construction, Pingdingshan 467036, Henan, China
3. School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

Received:2018-09-19 Revised:2018-12-20 Online:2019-05-05 Published:2019-05-05
Contact: Yonggang WANG

摘要/Abstract

摘要：

在?80mm×3000mm气流床和?40mm×200mm流化床中进行了O₂、H₂O、H₂O+O₂气氛下800℃胜利褐煤气化实验，同时在流化床中进行了O₂、H₂O、H₂O+O₂气氛下半焦原位气化实验和H₂O气氛下半焦完全气化实验。比较了2种反应器中氧化反应与水蒸气气化反应协同作用的大小（强弱）；结合实验条件利用缩核模型分别推导了2种反应器中协同作用影响下水蒸气气化反应速率方程；同时，从传质（扩散）速率、动力学、半焦-挥发分相互作用3方面探讨了2种反应器中协同作用存在显著差异的原因。结果发现，气流床中H₂O+O₂气氛下褐煤转化率明显大于H₂O和O₂单独气氛下褐煤转化率之和，其差值稳定在2.11%～4.01%，而在流化床中差值仅为0～0.75%，相对流化床，气流床中协同作用更明显。这是由于，在流化床中水蒸气向炭粒表面扩散的传质速率约为气流床的11%～25%，水蒸气气化过程受气膜扩散控制，炭粒表面水蒸气全部参与气化反应，炭粒表面无“多余”水分子，氧气开孔/扩孔作用提供的活性位“闲置”，而气流床中气化反应为速控步，炭粒表面有“富裕”水分子，可充分利用氧气开孔/扩孔作用提供的活性位，促进作用显著；挥发分-半焦相互作用不是流化床反应器中协同作用不显著的原因。

关键词: 水蒸气气化, 气流床, 流化床, 协同作用, 气化速率, 挥发分-半焦相互作用

Abstract:

Shengli brown coal was gasified at 800℃ under O₂, H₂O, H₂O+O₂ atmospheres comparatively by using a entrained-flow reactor with ?80× 3000 mm and a fluidized-bed reactor with ?40mm×200mm. Besides, in the fluidized-bed reactor, situ char gasification experiments under O₂, H₂O, H₂O+O₂ atmospheres and complete gasification experiments (coal conversion is close to 100%) under H₂O atmospheres were carried out to investigate the promoting effect of oxidation reaction on steam gasification reaction in different reactors. The rate equations of steam gasification reaction in two reactors were deduced based on unreacted shrinking core model. The results showed that the lignite conversion under H₂O+O₂ atmospheres was greater than the sum of those under H₂O atmosphere and O₂ atmosphere with a difference of 2.11%—4.01% in the entrained-flow reactor. In contrast, only 0—0.75% difference was observed in fluidized-bed reactor. The obtained difference can be explained that in the fluidized-bed reactor the mass transfer rate of steam to the carbon particles surface was 11%—25% of that in entrained-flow reactor and the steam gasification reaction occurred in the membrane diffusion controlled regime. This poor mass transfer led to a low steam concentration on carbon particles surface and some idle micro-/mesopores created by O₂. However, in entrained-flow reactor the steam gasification reaction happened in chemical kinetic controlled regime, and the rich steam can be absorbed by pores (created by O₂) on carbon particles surface to promote steam gasification. Moreover, it was verified that the volatile-char interaction was not main reason of the weak promotion of oxidation reaction to steam gasification reaction in the fluidized-bed reactor.

Key words: steam gasification, entrained-flow reactor, fluidized-bed, the promotion effect, gasification rate, volatile-char interaction

中图分类号:

TQ 53
TQ 54

程相龙, 郭晋菊, 王永刚, 申恬, 孙加亮, 张海永. 不同反应器中氧化反应与水蒸气气化反应协同作用差异性[J]. 化工进展, 2019, 38(05): 2179-2188.

Xianglong CHENG, Jinju GUO, Yonggang WANG, Tian SHEN, Jialiang SUN, Haiyong ZHANG. Synergistic effect of oxidation reaction and steam gasification reaction in different reactors[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2179-2188.

图/表 10

表1 胜利褐煤的工业分析及元素分析

工业分析w/% 元素分析w/%
M _ad	A	V	FC		C	H	S	O^① N
5.89	9.87	36.23	53.90		62.26	6.12	0.66	29.85 1.11

图1 气化实验装置

图2 气流床中800℃时向蒸汽气氛中添加1%氧气前后褐煤转化率的变化曲线

图3 在800℃流化床反应器中向水蒸气中添加氧气前后褐煤转化率的变化

图4 气流床中H2O、1% O2、H2O+1% O2气氛下气化半焦孔容和比表面积变化

图5 32.5% H2O气氛下流化床气化过程半焦转化率随时间的变化曲线

图6 流化床水蒸气气化过程褐煤转化率与水蒸气浓度线性拟合情况（膜扩散为速控步）

图7 流化床水蒸气气化过程褐煤转化率与水蒸气

表3 气化反应控制时速率方程参数理论值与实验值比较

常数项

图8 向32.5% H2O中添加O2前后流化床气化过程半焦转化率随时间的变化曲线

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不同反应器中氧化反应与水蒸气气化反应协同作用差异性

Synergistic effect of oxidation reaction and steam gasification reaction in different reactors

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