Ni/Fe/Co助剂对ZnO/MCM-41高温煤气脱硫过程中放硫的抑制作用及改性脱硫剂再生行为

doi:10.16085/j.issn.1000-6613.2023-1714

化工进展 ›› 2024, Vol. 43 ›› Issue (11): 6173-6183.DOI: 10.16085/j.issn.1000-6613.2023-1714

• 工业催化 • 上一篇

Ni/Fe/Co助剂对ZnO/MCM-41高温煤气脱硫过程中放硫的抑制作用及改性脱硫剂再生行为

张然¹^,²(), 杨梦滋¹^,², 武蒙蒙¹^,²(), 米杰¹^,²(), 王建成¹^,²^,³

^1.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
^2.太原理工大学煤科学与技术教育部重点实验室，山西太原 030024
^3.太原理工大学环境科学与工程学院，山西晋中 030600

收稿日期:2023-09-28 修回日期:2024-01-24 出版日期:2024-11-15 发布日期:2024-12-07
通讯作者: 武蒙蒙,米杰
作者简介:张然（1997—），女，硕士研究生，研究方向为气体净化。E-mail：2645575753@qq.com。
基金资助:
国家自然科学基金(22278294);山西省自然科学基金(20210302123191);山西省科技创新人才团队项目(202204051002025);山西省环境催化材料技术创新中心项目(202104010911008)

Inhibition effect of Ni/Fe/Co additives on sulfur-emission behavior during coal gas desulfurization over ZnO/MCM-41 at high temperatures and the regeneration behavior of modified sorbents

ZHANG Ran¹^,²(), YANG Mengzi¹^,², WU Mengmeng¹^,²(), MI Jie¹^,²(), WANG Jiancheng¹^,²^,³

^1.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China

Received:2023-09-28 Revised:2024-01-24 Online:2024-11-15 Published:2024-12-07
Contact: WU Mengmeng, MI Jie

摘要/Abstract

摘要：

高温煤气脱硫是煤炭清洁高效利用的关键步骤之一。前期研究发现，MCM-41负载ZnO高温煤气脱硫剂（ZnO/MCM-41）脱硫性能优良，但其脱硫过程中存在生成COS的放硫现象；尽管提出了引入助剂调变上述放硫行为的策略，但缺乏助剂与脱硫剂匹配特性及改性脱硫剂再生行为的研究。本研究表明，在ZnO/MCM-41中引入质量分数1%~5%助剂（Ni/Fe/Co），均可有效抑制COS释放（释放量分别降低99.4%~99.9%、73.1%~93.4%和69.0%~98.4%），这主要归因于助剂对COS氢解的催化作用；脱硫剂中镍、铁分别以Ni²⁺和Fe³⁺形式存在，而钴以Co²⁺和Co³⁺形式共存；对于性能最优的Ni掺杂（质量分数3%）脱硫剂，其再生温度应不低于600℃（低温再生仍存在部分ZnS）；且脱硫剂经四次循环再生实验后可维持高硫容（初次的91.5%）及低COS释放量（4.8×10^-2g 羰基硫/100g脱硫剂），轻微的性能下降可归因于活性组分及助剂的少部分损失。上述研究可为高性能脱硫剂构筑提供理论指导。

关键词: 热煤气, 氧化锌脱硫剂, 硫化碳, 催化, 再生, 稳定性

Abstract:

High temperature desulfurization of coal gas is one of the key steps for clean and efficient utilization of coal resources. Previous studies had found that MCM-41 supported ZnO sorbents (ZnO/MCM-41) exhibit outstanding hot-coal-gas desulfurization performance. However, there was COS formation (sulfur-release) during desulfurization process. Although the strategy of introducing additives into ZnO/MCM-41 for modifying sulfur-release behavior had been proposed, there was still a lack of research on the matching characteristics between additives and sorbents and the regeneration behavior of modified sorbents. The work showed that the doping of 1%—5% Ni/Fe/Co into ZnO/MCM-41 could effectively inhibit the release of COS by decreasing the corresponding COS-release amount of 99.4%—99.9%, 73.1%—93.4%, and 69.0%—98.4%, respectively. The decrease is mainly attributed to the catalytic effect of additives on the hydrogenolysis of COS. Ni and Fe in modified sorbents exist in the form of Ni²⁺ and Fe³⁺, respectively, while Co coexists in the form of Co²⁺ and Co³⁺. For the optimized Ni-doping sorbent (3%), the regeneration temperature should not be lower than 600℃ because low-temperature regeneration leads to the presence of ZnS in regenerated sorbents. The optimized sorbent could maintain high sulfur capacity (91.5% of that for fresh sorbents) and low COS-release amount (4.8×10^-2g COS/100g sorbents) after four desulfurization-regeneration cycles. The slight decrease in the ability of desulfurization and inhibiting sulfur-release is ascribed to the loss of a small fraction of active components and additives. The research could provide theoretical guidance for the preparation of high-performance sorbents.

Key words: hot coal gas, zinc oxide sorbent, carbonyl sulfide, catalysis, regeneration, stability

中图分类号:

TQ51

张然, 杨梦滋, 武蒙蒙, 米杰, 王建成. Ni/Fe/Co助剂对ZnO/MCM-41高温煤气脱硫过程中放硫的抑制作用及改性脱硫剂再生行为[J]. 化工进展, 2024, 43(11): 6173-6183.

ZHANG Ran, YANG Mengzi, WU Mengmeng, MI Jie, WANG Jiancheng. Inhibition effect of Ni/Fe/Co additives on sulfur-emission behavior during coal gas desulfurization over ZnO/MCM-41 at high temperatures and the regeneration behavior of modified sorbents[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6173-6183.

图/表 11

参考文献 27

1	陈阳, 杨芊. “双碳”背景下现代煤化工高质量发展研究[J]. 煤炭加工与综合利用, 2022(1): 50-54.
	CHEN Yang, YANG Qian. Research on high-quality development of modern coal chemical industry under background of “double carbon”[J]. Coal Processing & Comprehensive Utilization, 2022(1): 50-54.
2	王辉. 高炉煤气干法精脱硫技术研究[J]. 当代化工研究, 2023(18): 119-121.
	WANG Hui. Study on fine desulphurization technology of blast furnace gas[J]. Modern Chemical Research, 2023(18): 119-121.
3	王泽鑫. 改性氧化锌基脱硫剂制备及脱硫性能的研究[D]. 太原: 太原理工大学, 2018.
	WANG Zexin. Study on the preparation of modified zinc oxide based sorbent and its performance of removing sulfide[D]. Taiyuan: Taiyuan University of Technology, 2018.
4	RODRIGUEZ Jose A, MAITI Amitesh. Adsorption and decomposition of H₂S on MgO(100), NiMgO(100), and ZnO(0001) surfaces: A first-principles density functional study[J]. The Journal of Physical Chemistry B, 2000, 104(15): 3630-3638.
5	李俏春, 郭恩惠, 李阳, 等. 类水滑石衍生锌基复合氧化物的硫化再生行为[J]. 化工进展, 2021, 40(11): 6278-6286.
	LI Qiaochun, GUO Enhui, LI Yang, et al. Desulfurization and regeneration behaviors of zinc-based composite oxides derived from hydrotalcite[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6278-6286.
6	IKENAGA Na-oki, OHGAITO Yousuku, MATSUSHIMA Hiroaki, et al. Preparation of zinc ferrite in the presence of carbon material and its application to hot-gas cleaning[J]. Fuel, 2004, 83(6): 661-669.
7	CHEAH Singfoong, CARPENTER Daniel L, MAGRINI-BAIR Kimberly A. Review of mid- to high-temperature sulfur sorbents for desulfurization of biomass- and coal-derived syngas[J]. Energy & Fuels, 2009, 23(11): 5291-5307.
8	LIU Bingsi, WAN Zhengyong, ZHAN Yueping, et al. Desulfurization of hot coal gas over high-surface-area LaMeO _x /MCM-41 sorbents[J]. Fuel, 2012, 98: 95-102.
9	MUREDDU M, FERINO I, ROMBI E, et al. ZnO/SBA-15 composites for mid-temperature removal of H₂S: Synthesis, performance and regeneration studies[J]. Fuel, 2012, 102: 691-700.
10	HUSSAIN Murid, ABBAS Naseem, FINO Debora, et al. Novel mesoporous silica supported ZnO adsorbents for the desulphurization of biogas at low temperatures[J]. Chemical Engineering Journal, 2012, 188: 222-232.
11	贾磊, 李玉红, 张赛赛, 等. 原位制备再生型纳米氧化锌高温煤气脱硫剂[J]. 天然气化工(C1化学与化工), 2017, 42(4): 34-39.
	JIA Lei, LI Yuhong, ZHANG Saisai, et al. In-situ preparation of regenerable nano-zinc oxide sorbent for hot coal gas desulfurization[J]. Natural Gas Chemical Industry, 2017, 42(4): 34-39.
12	史磊. 微波原位制备ZnO/MCM-41中高温煤气脱硫剂及其性能的研究[D]. 太原: 太原理工大学, 2018.
	SHI Lei. The study on desulfurization performance of ZnO/MCM-41 sorbent prepared by microwave assisted in-situ method for hot coal gas[D]. Taiyuan: Taiyuan University of Technology, 2018.
13	PARK No-Kuk, LEE Jong Dae, LEE Tae Jin, et al. The preparation of a high surface area metal oxide prepared by a matrix-assisted method for hot gas desulphurization[J]. Fuel, 2005, 84(17): 2165-2171.
14	SASAOKA Eiji, TANIGUCHI Kazuo, UDDIN Md Azhar, et al. Characterization of reaction between ZnO and COS[J]. Industrial & Engineering Chemistry Research, 1996, 35(7): 2389-2394.
15	WU Mengmeng, ZHANG Minxuan, WANG Xiaowen, et al. Functionalized Zn-based desulfurizer with ordered mesoporous structure based on insights into sulfur-release mechanism during hot coal gas desulfurization[J]. Chemical Engineering Journal, 2023, 477: 146909.
16	谢巍, 常丽萍, 余江龙, 等. 煤气净化中H₂S干法脱除的研究进展[J]. 化工学报, 2006, 57(9): 2012-2020.
	XIE Wei, CHANG Liping, YU Jianglong, et al. Research progress of removal of H₂S from coal gas by dry method[J]. Journal of Chemical Industry and Engineering, 2006, 57(9): 2012-2020.
17	杨梦滋, 段新伟, 冯宇, 等. ZnO/MCM-41煤气脱硫剂脱硫过程COS生成行为及Co助剂的影响[J]. 低碳化学与化工, 2023, 48(4): 55-62.
	YANG Mengzi, DUAN Xinwei, FENG Yu, et al. COS formation behavior and influence of Co additive of ZnO/MCM-41 coal gas desulfurizer in desulfurization process[J]. Low-Carbon Chemistry and Chemical Engineering, 2023, 48(4): 55-62.
18	YU Xiang, GAO Yang, SUN Shicheng, et al. Magnetic and electric properties of Co doped ZnO films via in situ growth[J]. Physica B: Condensed Matter, 2023, 649: 414493.
19	LI Qiaochun, WANG Xiaowen, ZHANG Ran, et al. Insights into the effects of metal-ion doping on the structure and hot-coal-gas desulfurization properties of Zn-based sorbents supported on SBA-15[J]. Fuel, 2022, 315: 123198.
20	YANG Chao, WANG Jian, FAN Huiling, et al. Contributions of tailored oxygen vacancies in ZnO/Al₂O₃ composites to the enhanced ability for H₂S removal at room temperature[J]. Fuel, 2018, 215: 695-703.
21	ZHAO Xin, HUANG Lei, LI Hongrui, et al. Promotional effects of zirconium doped CeVO₄ for the low-temperature selective catalytic reduction of NO _x with NH₃ [J]. Applied Catalysis B: Environmental, 2016, 183: 269-281.
22	FUKUDA Kenzo, DOKIYA Masayuki, KAMEYAMA Tetsuya, et al. Catalytic activity of metal sulfides for the reaction, H₂S+CO=H₂+COS[J]. Journal of Catalysis, 1977, 49(3): 379-382.
23	Hee Kwon JUN, LEE Tae Jin, Si Ok RYU, et al. A study of Zn-Ti-based H₂S removal sorbents promoted with cobalt oxides[J]. Industrial & Engineering Chemistry Research, 2001, 40(16): 3547-3556.
24	李俏春. SBA-15负载锌基氧化物的煤气脱硫与再生行为研究[D]. 太原: 太原理工大学, 2021.
	LI Qiaochun. Study on desulfurization and regeneration behavior of coal gas with SBA-15 loaded zinc-based oxides[D]. Taiyuan: Taiyuan University of Technology, 2021.
25	ZHANG Xingyan, WEI Lu, GUO Xin. Ultrathin mesoporous NiMoO₄-modified MoO₃ core/shell nanostructures: Enhanced capacitive storage and cycling performance for supercapacitors[J]. Chemical Engineering Journal, 2018, 353: 615-625.
26	LIN Yi-Hsing, CHEN Yen-Chiao, CHU Hsin. The mechanism of coal gas desulfurization by iron oxide sorbents[J]. Chemosphere, 2015, 121: 62-67.
27	WU Mengmeng, LI Teng, LI Hongyu, et al. Desulfurization of hot coal gas over regenerable low-cost Fe₂O₃/mesoporous Al₂O₃ prepared by the sol-gel method[J]. Energy & Fuels, 2017, 31(12): 13921-13932.

样品	比表面积/m²·g^-1	总孔体积/cm³·g^-1	平均孔径/nm	最可几孔径/nm	D₍₁₀₁₎^②/nm	D₍₁₁₁₎^②/nm
ZnO/MCM-41	553/(493)^①	0.46/(0.41)^①	3.34/(3.30)^①	2.65/(2.64)^①	19.3	21.7
1Ni-ZnO/MCM-41	503/(434)^①	0.49/(0.38)^①	3.90/(3.46)^①	2.59/(2.49)^①	28.7	19.3
3Ni-ZnO/MCM-41	521/(442)^①	0.47/(0.39)^①	3.64/(3.56)^①	2.60/(2.59)^①	27.9	20.2
5Ni-ZnO/MCM-41	424/(391)^①	0.39/(0.36)^①	3.72/(3.64)^①	2.53/(2.56)^①	37.1	23.5
1Fe-ZnO/MCM-41	479/(476)^①	0.41/(0.40)^①	3.45/(3.34)^①	2.53/(2.52)^①	17.7	19.2
3Fe-ZnO/MCM-41	480/(449)^①	0.44/(0.39)^①	3.68/(3.45)^①	2.64/(2.57)^①	18.5	20.0
5Fe-ZnO/MCM-41	468/(428)^①	0.43/(0.37)^①	3.66/(3.42)^①	2.55/(2.60)^①	22.1	22.6
1Co-ZnO/MCM-41	492/(461)^①	0.46/(0.40)^①	3.74/(3.50)^①	2.58/(2.52)^①	23.9	19.7
3Co-ZnO/MCM-41	422/(404)^①	0.44/(0.39)^①	4.21/(3.83)^①	2.58/(2.57)^①	27.2	19.6
5Co-ZnO/MCM-41	435/(397)^①	0.41/(0.33)^①	3.77/(3.35)^①	2.56/(2.59)^①	28.4	18.4
1re-3Ni-ZnO/MCM-41	297	0.28	3.81	2.45	19.1	—
5re-3Ni-ZnO/MCM-41	291	0.28	3.86	2.41	23.5	—

样品	比表面积/m²·g^-1	总孔体积/cm³·g^-1	平均孔径/nm	最可几孔径/nm	D₍₁₀₁₎^②/nm	D₍₁₁₁₎^②/nm
ZnO/MCM-41	553/(493)^①	0.46/(0.41)^①	3.34/(3.30)^①	2.65/(2.64)^①	19.3	21.7
1Ni-ZnO/MCM-41	503/(434)^①	0.49/(0.38)^①	3.90/(3.46)^①	2.59/(2.49)^①	28.7	19.3
3Ni-ZnO/MCM-41	521/(442)^①	0.47/(0.39)^①	3.64/(3.56)^①	2.60/(2.59)^①	27.9	20.2
5Ni-ZnO/MCM-41	424/(391)^①	0.39/(0.36)^①	3.72/(3.64)^①	2.53/(2.56)^①	37.1	23.5
1Fe-ZnO/MCM-41	479/(476)^①	0.41/(0.40)^①	3.45/(3.34)^①	2.53/(2.52)^①	17.7	19.2
3Fe-ZnO/MCM-41	480/(449)^①	0.44/(0.39)^①	3.68/(3.45)^①	2.64/(2.57)^①	18.5	20.0
5Fe-ZnO/MCM-41	468/(428)^①	0.43/(0.37)^①	3.66/(3.42)^①	2.55/(2.60)^①	22.1	22.6
1Co-ZnO/MCM-41	492/(461)^①	0.46/(0.40)^①	3.74/(3.50)^①	2.58/(2.52)^①	23.9	19.7
3Co-ZnO/MCM-41	422/(404)^①	0.44/(0.39)^①	4.21/(3.83)^①	2.58/(2.57)^①	27.2	19.6
5Co-ZnO/MCM-41	435/(397)^①	0.41/(0.33)^①	3.77/(3.35)^①	2.56/(2.59)^①	28.4	18.4
1re-3Ni-ZnO/MCM-41	297	0.28	3.81	2.45	19.1	—
5re-3Ni-ZnO/MCM-41	291	0.28	3.86	2.41	23.5	—

再生条件	比表面积/m²·g^-1	总孔体积/cm³·g^-1	平均孔径/nm
4% O₂
550℃	286	0.26	3.60
600℃	301	0.27	3.54
650℃	297	0.28	3.81
700℃	288	0.28	3.90
650℃
2% O₂	328	0.28	3.44
6% O₂	277	0.30	4.38
8% O₂	279	0.25	3.63

再生条件	比表面积/m²·g^-1	总孔体积/cm³·g^-1	平均孔径/nm
4% O₂
550℃	286	0.26	3.60
600℃	301	0.27	3.54
650℃	297	0.28	3.81
700℃	288	0.28	3.90
650℃
2% O₂	328	0.28	3.44
6% O₂	277	0.30	4.38
8% O₂	279	0.25	3.63

[1]	高聪志, 张雅萱, 林璐, 邓晓婷, 殷霞, 丁一刚, 肖艳华, 杜治平. 新戊二醇的合成工艺[J]. 化工进展, 2024, 43(S1): 469-478.
[2]	万震, 王绍庆, 李志合, 赵天生. HZSM-5分子筛催化木质素热解制芳烃研究进展[J]. 化工进展, 2024, 43(S1): 517-532.
[3]	李磊, 赵宴民, 田海洋, 李江伟, 周强, 何佳妮, 武琬越. 燃气烟气中低浓度CO₂的低能耗高效捕集工艺模拟优化[J]. 化工进展, 2024, 43(S1): 581-589.
[4]	李琳, 黄国勇, 徐盛明, 郁丰善, 翁雅青, 曹才放, 温嘉玮, 王春霞, 王俊莲, 顾斌涛, 张袁华, 刘斌, 王才平, 潘剑明, 徐泽良, 王翀, 王珂. 铝基废催化剂载体的回收与再生制备[J]. 化工进展, 2024, 43(S1): 640-649.
[5]	李新月, 李振京, 韩沂杭, 郭永强, 闫瑜, 哈力米热·卡热木拉提, 赵会吉, 柴永明, 刘东, 殷长龙. 油脂加氢脱氧生产绿色柴油催化剂的研究进展[J]. 化工进展, 2024, 43(S1): 351-364.
[6]	王月, 张学瑞, 宋玺文, 陈渤燕, 李庆勋, 钟海军, 胡孝伟, 何帅. 电解制氢合成氨技术综述与展望[J]. 化工进展, 2024, 43(S1): 180-188.
[7]	林梅洁, 米烁东, 包成. 金属-掺杂氧化铈体系H₂/CO电化学反应机理研究进展[J]. 化工进展, 2024, 43(S1): 209-224.
[8]	李帅哲, 聂懿宸, PHIDSAVARD Keomeesay, 顾雯, 张伟, 刘娜, 徐高翔, 刘莹, 李兴勇, 陈玉保. 非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展[J]. 化工进展, 2024, 43(S1): 225-242.
[9]	熊磊, 丁飞燕, 李聪, 王群乐, 吕起, 翟晓娜, 刘峰. 金属Pt负载型非均相催化剂研究进展[J]. 化工进展, 2024, 43(S1): 295-304.
[10]	宋财城, 陈晓贞, 刘丽, 杨成敏, 郑步梅, 尹晓莹, 孙进, 姚运海, 段为宇. 碳基载体负载加氢脱硫催化剂的研究进展[J]. 化工进展, 2024, 43(S1): 305-314.
[11]	韩洪晶, 车宇, 田宇轩, 王海英, 张亚男, 陈彦广. 木质素催化氢解催化剂及溶剂的研究进展[J]. 化工进展, 2024, 43(S1): 315-324.
[12]	胡兴, 刘易, 杜泽学. 3-氯丙烯直接合成环氧氯丙烷催化剂研究进展[J]. 化工进展, 2024, 43(S1): 325-334.
[13]	于梦洁, 吴语童, 罗发祥, 豆义波. 低浓度二氧化碳还原光催化剂结构设计的研究进展[J]. 化工进展, 2024, 43(S1): 335-350.
[14]	张浩, 刘世钰, 沈卫华, 方云进. Ca-ZSM-5催化尿素脱水制备单氰胺[J]. 化工进展, 2024, 43(S1): 365-373.
[15]	何世坤, 张荣花, 李昊阳, 潘晖, 冯君锋. 脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛[J]. 化工进展, 2024, 43(S1): 374-381.

Ni/Fe/Co助剂对ZnO/MCM-41高温煤气脱硫过程中放硫的抑制作用及改性脱硫剂再生行为

Inhibition effect of Ni/Fe/Co additives on sulfur-emission behavior during coal gas desulfurization over ZnO/MCM-41 at high temperatures and the regeneration behavior of modified sorbents

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价