CuFe2O4改性脱硫渣氧载体与褐煤的反应特性

doi:10.16085/j.issn.1000-6613.2022-1505

化工进展 ›› 2023, Vol. 42 ›› Issue (6): 2884-2894.DOI: 10.16085/j.issn.1000-6613.2022-1505

CuFe₂O₄改性脱硫渣氧载体与褐煤的反应特性

王保文¹(), 刘同庆¹, 张港¹, 李炜光¹, 林德顺¹, 王梦家¹, 马晶晶²

^1.华北水利水电大学能源与动力工程学院，河南郑州 450045
^2.宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021

收稿日期:2022-08-15 修回日期:2022-10-18 出版日期:2023-06-25 发布日期:2023-06-29
通讯作者: 王保文
作者简介:王保文（1975—），男，教授，从事煤燃烧污染物控制研究。E-mail：david-wn@163.com。
基金资助:
国家自然科学基金(51776073);河南省科技攻关项目(162102210233);省部共建煤炭高效利用与绿色化工国家重点实验室(2021-KF 42)

Reaction characteristics of CuFe₂O₄ modified desulfurization slag oxygen carrier with lignite

WANG Baowen¹(), LIU Tongqing¹, ZHANG Gang¹, LI Weiguang¹, LIN Deshun¹, WANG Mengjia¹, MA Jingjing²

^1.School of Energy and Power Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450045, Henan, China
^2.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China

Received:2022-08-15 Revised:2022-10-18 Online:2023-06-25 Published:2023-06-29
Contact: WANG Baowen

摘要/Abstract

摘要：

基于烟气脱硫渣采用改进的提纯工艺和优化参数获得高纯度和反应活性的CaSO₄，以此作为模板剂结合溶胶凝胶燃烧合成法制备了CuFe₂O₄改性活化并具有“核-壳”结构的CaSO₄-CuFe₂O₄混合氧载体。在固定床反应器上研究了还原反应温度和循环次数作用下自制CaSO₄-CuFe₂O₄混合氧载体与煤化学链燃烧特性，系统研究了CaSO₄副反应与CuFe₂O₄交互作用下不同气相硫的释放和演化。研究表明，改性脱硫渣与煤反应时，CuFe₂O₄还原产物Cu、FeO通过未反应CaSO₄及已还原的CaS形成的熔融界面获得了其中未能利用的晶格氧，实现了本身的原位氧化，不仅明显提高了改性脱硫渣的反应活性，促进了煤的转化，同时也促进了未反应CaSO₄中晶格氧的定向传递和梯级利用。进一步，综合考虑煤的碳转化率以及气相硫的释放特性，确定了改性脱硫渣与煤的最佳反应条件为900℃。而循环实验发现，CaSO₄-CuFe₂O₄氧载体在多次循环中CaSO₄副反应不能完全抑制，少量气相硫的逸出加之还原氧载体的部分烧结导致反应活性衰减。

关键词: 煤, 化学链燃烧, 烟气脱硫渣, CaSO₄-CuFe₂O₄混合氧载体, 碳转化, 硫原位控制

Abstract:

The purified and active CaSO₄ was derived from flue gas desulfurization slag using improved purification technology and relevant parameters, which was further utilized as the template to prepare CuFe₂O₄ modified CaSO₄ mixed oxygen carrier (OC) with special "core-shell" structure via sol-gel combustion synthesis method. Effects of reduction temperature and cycle numbers on the reaction of CaSO₄-CuFe₂O₄ mixed OC with coal were studied on the fixed bed reactor. Meanwhile, gaseous sulfur species emitted from different CaSO₄ side reactions and their interaction with the introduced CuFe₂O₄were further investigated. The results indicated that during reaction of the CaSO₄-CuFe₂O₄ mixed OC with coal, the reduced CuFe₂O₄ products as Cu and FeO regained the unutilized lattice oxygen included in the CaSO₄via the solid eutectics between the unreacted CaSO₄ and reduced CaS to realize their in situ oxidization, which not only enhanced the reactivity of the CaSO₄-CuFe₂O₄ mixed OC and promoted coal conversion, but also benefited the directional transfer of the oxygen involved in the unreacted CaSO₄ to reach cascade utilization of the oxygen involved in the mixed OC. Furthermore, through comprehensive consideration of carbon conversion for coal and gaseous sulfur release from CaSO₄, optimized reaction condition was determined as 900℃. Finally, after reduction and oxidation cyclic experiments, CaSO₄-CuFe₂O₄OC was found to incompletely inhibit the CaSO₄ side reactions coupled with partly sintering of the reduced OC, which caused the cyclic reactivity of the modified OC to decay.

Key words: coal, chemical looping combustion, flue gas desulfurization slag, CaSO₄-CuFe₂O₄ mixed OC, carbon conversion, sulfur in-situ control

中图分类号:

TK16

王保文, 刘同庆, 张港, 李炜光, 林德顺, 王梦家, 马晶晶. CuFe₂O₄改性脱硫渣氧载体与褐煤的反应特性[J]. 化工进展, 2023, 42(6): 2884-2894.

WANG Baowen, LIU Tongqing, ZHANG Gang, LI Weiguang, LIN Deshun, WANG Mengjia, MA Jingjing. Reaction characteristics of CuFe₂O₄ modified desulfurization slag oxygen carrier with lignite[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2884-2894.

图/表 11

表1 褐煤样品的工业分析和元素分析

元素分析（质量分数）/%						工业分析（质量分数）/%
C	H	N	S_t	O^*		M	V	A	FC
71.13	4.64	0.94	0.13	12.47		6.06	49.69	4.63	39.62

图1 固定床实验装置示意图1—供气单元；2—蒸气发生单元；3—温控单元；4—烟气分析仪；5—微量硫分析仪；6—数据收集端

图2 脱硫渣提纯CaSO4 SEM-EDX分析

图3 自制CaSO4-CuFe2O4氧载体SEM-EDX分析

图4 不同改性氧载体的反应特性

图5 反应温度对CaSO4-CuFe2O4反应燃烧特性的影响

图6 反应温度对CaSO4-CuFe2O4硫演化特性的影响

图7 循环次数对CaSO4-CuFe2O4反应燃烧特性的影响

图8 循环次数对CaSO4-CuFe2O4硫演化特性的影响

图9 不同循环次数下氧载体与煤固相产物的XRD分析

图10 第5次循环氧化后CaSO4-CuFe2O4的微观形貌

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CuFe₂O₄改性脱硫渣氧载体与褐煤的反应特性

Reaction characteristics of CuFe₂O₄ modified desulfurization slag oxygen carrier with lignite

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