化学链气化中准东煤灰对CaSO4载氧体改性及其作用机理

doi:10.16085/j.issn.1000-6613.2022-2010

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4628-4635.DOI: 10.16085/j.issn.1000-6613.2022-2010

化学链气化中准东煤灰对CaSO₄载氧体改性及其作用机理

朱杰¹^,²(), 金晶¹^,²(), 丁正浩¹^,², 杨会盼¹^,², 侯封校³

^1.上海理工大学能源与动力工程学院，上海200093
^2.上海市动力工程多相流与传热重点实验室，上海200093
^3.中北大学能源与动力工程学院，山西太原030051

收稿日期:2022-10-27 修回日期:2022-11-18 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 金晶
作者简介:朱杰（1997—），男，硕士研究生，研究方向为化学链气化。E-mail：2579936484@qq.com。
基金资助:
国家自然科学基金(51976129);山西省基础研究计划(202103021223197);上海市科委项目(23010503500)

Modification of CaSO₄ oxygen carrier by Zhundong coal ash in chemical looping gasification and its mechanism

ZHU Jie¹^,²(), JIN Jing¹^,²(), DING Zhenghao¹^,², YANG Huipan¹^,², HOU Fengxiao³

^1.School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
^2.Shanghai Key Laboratory of Multiphase Flow and Heat Transfer in Power Engineering, Shanghai 200093, China
^3.School of Energy and Power Engineering, North University of China, Taiyuan 030051, Shanxi, China

Received:2022-10-27 Revised:2022-11-18 Online:2023-09-15 Published:2023-09-28
Contact: JIN Jing

摘要/Abstract

摘要：

以CaSO₄为载氧体，采用机械混合法制备了将军庙煤灰修饰的CaSO₄-Ash复合载氧体。借助TG-MS考察复合载氧体CaSO₄-Ash与将军庙煤的化学链气化反应特性，并对将军庙煤灰改性CaSO₄载氧体的作用机理进行了研究。结果表明：将军庙煤灰对CaSO₄载氧体有一定的改性作用。900℃时，与纯CaSO₄载氧体相比，CaSO₄-Ash复合载氧体表现出良好的反应活性和稳定性，CaSO₄-Ash复合载氧体化学链气化产生的CO量明显增多，产率也更加稳定。X射线衍射分析表明，CaSO₄-Ash复合载氧体中存在少量的Ca₂Fe₂O₅和Fe₂O₃，它们附着在CaSO₄表面，作为CaSO₄晶格氧传输的中介，起到促进CaSO₄晶格氧迁移的效果。通过Jade软件计算纯CaSO₄载氧体和改性后的CaSO₄载氧体的晶格常数和晶格体积，并结合拉曼光谱和电子顺磁共振光谱表征，证明了煤灰中Na⁺改性CaSO₄载氧体的机理。通过扫描电子显微镜测试，发现改性后的CaSO₄载氧体表面孔径结构更加清晰。

关键词: 化学链气化, CaSO₄载氧体, 准东煤, 煤灰改性

Abstract:

Using CaSO₄ as the oxygen carrier, the CaSO₄-Ash composite oxygen carrier modified by Jiangjunmiao coal ash was prepared by mechanical mixing method. With the TG-MS device, the chemical looping gasification reaction characteristics of composite oxygen carrier CaSO₄-Ash and Jiangjunmiao coal were investigated, and the action mechanism of Jiangjunmiao coal ash-modified CaSO₄ oxygen carrier was studied. The results showed that Jiangjunmiao coal ash had a certain modification effect on CaSO₄ oxygen carrier. At 900℃, the CaSO₄-Ash composite oxygen carrier showed good reactivity and stability compared with the pure CaSO₄ oxygen carrier. The amount of CO produced by the chemical chain gasification of the CaSO₄-Ash composite oxygen carrier increased significantly, and the yield also more stable. X-ray diffraction (XRD) analysis showed that there were a small amount of Ca₂Fe₂O₅ and Fe₂O₃ in the CaSO₄-Ash composite oxygen carrier, which were attached to the surface of CaSO₄ and promoted the effect of CaSO₄ lattice oxygen migration as an intermediary for the transport of CaSO₄ lattice oxygen. The lattice constant and lattice volume of pure CaSO₄ oxygen carrier and modified CaSO₄ oxygen carrier were calculated by Jade software, and combined with Raman and Electron Paramagnetic Resonance (EPR) characterization, the mechanism for Na⁺ to modify CaSO₄ oxygen carrier in coal ash was proved. Through Scanning Electron Microscope (SEM) test, it was found that the surface pore structure of the modified CaSO₄ oxygen carrier was clearer.

Key words: chemical looping gasification, CaSO₄ oxygen carrier, Zhundong coal, coal ash modification

中图分类号:

TK16

朱杰, 金晶, 丁正浩, 杨会盼, 侯封校. 化学链气化中准东煤灰对CaSO₄载氧体改性及其作用机理[J]. 化工进展, 2023, 42(9): 4628-4635.

ZHU Jie, JIN Jing, DING Zhenghao, YANG Huipan, HOU Fengxiao. Modification of CaSO₄ oxygen carrier by Zhundong coal ash in chemical looping gasification and its mechanism[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4628-4635.

图/表 11

表1 准东煤煤质分析

工业分析/%				元素分析/%					放热量 /kJ·kg^-1
M	A	V	FC	C	H	O	N	S	放热量 /kJ·kg^-1
5.64	5.09	27.24	62.03	63.78	4.42	19.21	1.00	0.87	30517

表2 准东煤灰成分（质量分数，%）分析

煤种	成分质量分数
煤种	Na₂O	K₂O	CaO	Fe₂O₃	MgO	Al₂O₃	SiO₂	SO₃
准东将军庙煤	8.9	0.25	15.8	17.9	5.3	6.1	7.68	30.7

图1 不同煤灰掺混比例下载氧体的气化特性

图2 400~600℃热解阶段CO产量和时间的关系

图3 800~870℃固-固反应阶段CO产量和时间的关系

图4 900℃快速气化阶段CO产量和时间的关系

图5 CaSO4-Ash复合载氧体的XRD图谱

表3 纯CaSO4和改性后CaSO4的晶格常数

样品	a/Å	b/Å	c/Å	V/Å
纯CaSO₄	6.998	6.992	6.238	305.29
改性后CaSO₄	6.984	6.967	6.229	303.13

图6 纯CaSO4载氧体和CaSO4-Ash复合载氧体拉曼光谱

图7 纯CaSO4载氧体和CaSO4-Ash复合载氧体ERP光谱（1GS=10-4T）

图8 纯CaSO4载氧体和CaSO4-Ash复合载氧体SEM图

参考文献 22

1	NGUYEN Nhut Minh, ALOBAID Falah, DIERINGER Paul, et al. Biomass-based chemical looping gasification: Overview and recent developments[J]. Applied Sciences, 2021, 11(15): 7069.
2	DING Ning, ZHENG Ying, LUO Cong, et al. Development and performance of binder-supported CaSO₄ oxygen carriers for chemical looping combustion[J]. Chemical Engineering Journal, 2011, 171(3): 1018-1026.
3	LIU Yongzhuo, GUO Qingjie. Investigation into syngas generation from solid fuel using CaSO₄-based chemical looping gasification process[J]. Chinese Journal of Chemical Engineering, 2013, 21(2): 127-134.
4	胡修德, 贾伟华, 刘永卓, 等.K₂CO₃修饰钙基载氧体的煤化学链气化反应特性[J]. 高校化学工程学报, 2015, 29(1): 108-115.
	HU Xiude, JIA Weihua, LIU Yongzhuo, et al. Coal chemical-looping gasification of Ca-based oxygen carriers decorated by K₂CO₃ [J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(1): 108-115.
5	SUNPHORKA Sasithorn, POONSRITANAKUL Oranee, KUCHONTHARA Prapan. Chemical-looping combustion of methane using CaSO₄ as an oxygen carrier: Effects of MgO addition[J]. Arabian Journal for Science and Engineering, 2019, 44(6): 5359-5370.
6	GUO Qingjie, LIU Yongzhuo, JIA Weihua, et al. Performance of Ca-based oxygen carriers decorated by K₂CO₃ or Fe₂O₃ for coal chemical looping combustion[J]. Energy & Fuels, 2014, 28(11): 7053-7060.
7	曾宪鹏. 准东煤燃烧过程中灰的生成、沉积及控制机理研究[D]. 武汉：华中科技大学, 2019.
	ZENG Xianpeng. Ash formation, deposition and prevention during Zhundong coal combustion[D]. Wuhan: Huazhong University of Science and Technology, 2019.
8	DAI Jinze, WHITTY Kevin J. Predicting and alleviating coal ash-induced deactivation of CuO as an oxygen carrier for chemical looping with oxygen uncoupling[J]. Fuel, 2019, 241: 1214-1222.
9	ADANEZ Juan, ABAD Alberto, Francisco GARCIA-LABIANO, et al. Progress in chemical-looping combustion and reforming technologies[J]. Progress in Energy and Combustion Science, 2012, 38(2): 215-282.
10	汪沪军. 准东煤混煤热解特性实验研究[D]. 马鞍山: 安徽工业大学, 2019.
	WANG Hujun. Experimental study on the pyrolysis characteristics of Zhundong coals blended with other coals[D]. Maanshan: Anhui Universit of Technology, 2019.
11	JIA Xin, WANG Qinhui, CEN Kefa, et al. An experimental study of CaSO₄ decomposition during coal pyrolysis[J]. Fuel, 2016, 163: 157-165.
12	杜昌帅. 准东煤低温气化中离子交换型Na和Ca的催化特性研究[D]. 哈尔滨: 哈尔滨工业大学, 2018.
	DU Changshuai. Research on catalytic characteristics of ion-exchangeable Na and Ca in Zhundong coal gasification at mild temperature[D]. Harbin: Harbin Institute of Technology,2018.
13	CHEN Dingkai, HE Dedong, LU Jichang, et al. Investigation of the role of surface lattice oxygen and bulk lattice oxygen migration of cerium-based oxygen carriers: XPS and designed H₂-TPR characterization[J]. Applied Catalysis B: Environmental, 2017, 218: 249-259.
14	LIU Yongzhuo, ZHANG Xintao, GAO Minggang, et al. Effect of coal ash on Fe-based oxygen carrier in coal char chemical looping gasification[J]. International Journal of Chemical Reactor Engineering, 2019, 17(8):1-13.
15	WANG Yanan, NIU Pengjie, ZHAO Haibo. Chemical looping gasification of coal using calcium ferrites as oxygen carrier[J]. Fuel Processing Technology, 2019, 192: 75-86.
16	粟自然, 沈来宏, 闫景春,等.基于铁酸钙载氧体的稻壳化学链气化反应特性[J]. 石油学报(石油加工), 2020, 36(6): 1219-1228.
	SU Ziran, SHEN Laihong, YAN Jingchun, et al. Characteristics of rice-hull chemical looping gasification with calcium-ferrite as oxygen carrier[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2020, 36(6): 1219-1228.
17	DING Ning, ZHANG Chengwu, LUO Cong, et al. Effect of hematite addition to CaSO₄ oxygen carrier in chemical looping combustion of coal char[J]. RSC Advances, 2015, 5(69): 56362-56376.
18	刘喆, 邢志国, 王海斗,等.PZT掺杂改性研究进展及其机理探究[J]. 功能材料, 2015, 46(4): 4009-4015.
	LIU Zhe, XING Zhiguo, WANG Haidou, et al. Current investigation of doping modification of PZT[J]. Journal of Functional Materials, 2015, 46(4): 4009-4015.
19	LIU Xiangwen, ZHOU Kebin, WANG Lei, et al. Oxygen vacancy clusters promoting reducibility and activity of ceria nanorods[J]. Journal of the American Chemical Society, 2009, 131(9): 3140-3141.
20	郑烨, 李建波, 关彦军, 等. 碱性氧化物对煤灰熔融特征行为的影响[J]. 化工进展, 2020, 39(2): 496-505.
	ZHENG Ye, LI Jianbo, GUAN Yanjun, et al. Effects of basic oxides on ash fusion characteristic of coal ash[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 496-505.
21	YANG Sai, ZHAO Haijun, DONG Fang, et al. Highly efficient catalytic combustion of O-dichlorobenzene over lattice-distorted Ru/OMS-2: The rapidly replenishing effect of surface adsorbed oxygen on lattice oxygen[J]. Molecular Catalysis, 2019, 470: 127-137.
22	YE Kaihang, LI Kunshan, LU Yirui, et al. An overview of advanced methods for the characterization of oxygen vacancies in materials[J]. Trends in Analytical Chemistry, 2019, 116: 102-108.

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化学链气化中准东煤灰对CaSO₄载氧体改性及其作用机理

Modification of CaSO₄ oxygen carrier by Zhundong coal ash in chemical looping gasification and its mechanism

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