SiO2改性Ce-V-W/Ti催化剂载体的抗碱（土）金属中毒性能

doi:10.16085/j.issn.1000-6613.2024-0017

化工进展 ›› 2025, Vol. 44 ›› Issue (1): 266-276.DOI: 10.16085/j.issn.1000-6613.2024-0017

SiO₂改性Ce-V-W/Ti催化剂载体的抗碱（土）金属中毒性能

庄柯¹(), 陈宏², 许芸¹, 仲兆平²(), 周峻伍², 周凯¹, 董月红¹

^1.国家能源集团科学技术研究院有限公司低碳智能燃煤发电与超净排放全国重点实验室，江苏南京 210023
^2.东南大学能源与环境学院能源热转换及其过程测控教育部重点实验室，江苏南京 211189

收稿日期:2024-01-04 修回日期:2024-04-09 出版日期:2025-01-15 发布日期:2025-02-13
通讯作者: 仲兆平
作者简介:庄柯（1983—），博士，高级工程师，研究方向为火电机组超低排放污染物控制技术。E-mail：12083096@ceic.com。
基金资助:
低碳智能燃煤发电与超净排放全国重点实验室开放课题(D2022FK076);江苏省科技成果转化专项资金项目(BA2022073)

Resistance of SiO₂ modified Ce-V-W/Ti catalyst support to alkali (earth) metal poisoning

ZHUANG Ke¹(), CHEN Hong², XU Yun¹, ZHONG Zhaoping²(), ZHOU Junwu², ZHOU Kai¹, DONG Yuehong¹

^1.National Key Laboratory of Low Carbon Intelligent Coal-fired Power Generation and Ultra Clean Emissions, National Energy Group Science and Technology Research Institute Company Limited, Nanjing 210023, Jiangsu, China
^2.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 211189, Jiangsu, China

Received:2024-01-04 Revised:2024-04-09 Online:2025-01-15 Published:2025-02-13
Contact: ZHONG Zhaoping

摘要/Abstract

摘要：

为了提升Ce-V-W/Ti催化剂耐碱（土）金属中毒性能，本文使用溶胶-凝胶法制备了TiO₂载体并进行了SiO₂掺杂改性，通过浸渍法制备了Ce-V-W/Ti-Si催化剂。采用浸渍法模拟了CaCO₃、K₂O等碱物种中毒，探究了SiO₂改性载体对催化剂的脱硝活性和抵御碱（土）金属中毒性能的影响，并使用X射线光电子能谱、N₂吸附-脱附、H₂-程序升温还原、NH₃-程序升温脱附等表征手段对催化剂进行了表征分析。实验结果表明，对Ce-V-W/Ti催化剂载体进行SiO₂改性会降低其中低温段的脱硝活性，但能明显提升催化剂对碱物种的耐受性，总体上，Ce₁V₁W₇/Ti-Si₄对碱物种的耐受性最好，各类碱物种对其脱硝活性的毒害程度为K₂O>Na₂O>CaCO₃>CaO>CaSO₄。表征结果显示，SiO₂改性削弱了催化剂表面Ce氧化物活性，但显著增加了催化剂的比表面积和酸性位点数量，并在催化剂碱中毒时保护了活性金属氧化物的还原性。

关键词: 选择催化还原, 催化剂载体, 活性, SiO₂改性, 碱中毒

Abstract:

In order to improve the resistance of Ce-V-W/Ti catalysts to alkali (earth) metal poisoning, TiO₂ supports were prepared by sol-gel method and then modified by SiO₂ doping, and Ce-V-W/Ti-Si catalysts were prepared by impregnation method. The impregnation method was employed to simulate the poisoning effect on alkali species such as CaCO₃ and K₂O. The influence of SiO₂-modified support on the denitration activity and resistance against alkali metal poisoning of the catalyst was investigated. Characterization techniques including X-ray photoelectron spectroscopy, N₂ adsorption-desorption, H₂-temperature programmed reduction, and NH₃-temperature programmed desorption were employed to analyze the catalysts. Experimental results indicated that the SiO₂ modification of the Ce-V-W/Ti catalyst support reduced its denitration activity at low temperatures but significantly enhanced the catalyst's tolerance against alkali species. Overall, Ce₁V₁W₇/Ti-Si₄ exhibited the best resistance against alkali species, with the poisoning severity of various alkali species ranked as K₂O>Na₂O>CaCO₃>CaO>CaSO₄. The characterization results showed that SiO₂ modification weakened the activity of Ce oxide on the surface of the catalyst, but significantly increased the specific surface area and the number of acidic sites of the catalyst, and protected the reducibility of the active metal oxide during alkalosis.

Key words: selective catalytic reduction, catalyst support, reactivity, SiO₂ modification, alkali poisoning

中图分类号:

TQ426

庄柯, 陈宏, 许芸, 仲兆平, 周峻伍, 周凯, 董月红. SiO₂改性Ce-V-W/Ti催化剂载体的抗碱（土）金属中毒性能[J]. 化工进展, 2025, 44(1): 266-276.

ZHUANG Ke, CHEN Hong, XU Yun, ZHONG Zhaoping, ZHOU Junwu, ZHOU Kai, DONG Yuehong. Resistance of SiO₂ modified Ce-V-W/Ti catalyst support to alkali (earth) metal poisoning[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 266-276.

图/表 16

图1 Ce1V1W7/Ti-Si x 的NO x 脱除率

图2 Ce1V1W7/Ti-Si x 的N2选择性

图3 不同浓度CaCO3中毒对Ce1V1W7/Ti-Si x 的NO x 脱除率影响

图4 CaO中毒对Ce1V1W7/Ti-Si x 的NO x 脱除率影响

图5 CaSO4中毒对Ce1V1W7/Ti-Si x 的NO x 脱除率影响

图6 K2O中毒对Ce1V1W7/Ti-Si x 的NO x 脱除率影响

图7 Na2O中毒对Ce1V1W7/Ti-Si x 的NO x 脱除率影响

图8 进行载体改性前后的催化剂XRD谱图

图9 Ce1V1W7/Ti、Ce1V1W7Ti-Si4的SEM图

图10 Ce1V1W7/Ti-Si4的Ce、V、W、Si元素Mapping图

表1 Ce x V1W7/Ti表面元素分析

催化剂	摩尔分数/%
催化剂	O_ads/(O_ads+O_latt)	V⁴⁺/(V⁴⁺+V⁵⁺)	Ce³⁺/(Ce³⁺+Ce⁴⁺)
Ce₁V₁W₇/Ti	13.86	43.84	54.09
Ce₁V₁W₇/Ti-Si₄	20.07	53.53	23.04

图11 SiO2改性载体前后的催化剂的O 1s、V 2p和Ce 3d的XPS谱图

表2 Ce1V1W7/Ti、Ce1V1W7/Ti-Si4的结构分析

催化剂	比表面积 /m²·g^-1	孔容 /cm³·g^-1	平均孔径 /nm
Ce₁V₁W₇/Ti	74.6	31.8×10^-2	9.9
CaCO₃-Ce₁V₁W₇/Ti	58.3	19.7×10^-2	15.1
K₂O-Ce₁V₁W₇/Ti	70.3	27.1×10^-2	11.6
Ce₁V₁W₇/Ti-Si₄	165.8	33.5×10^-2	5.6
CaCO₃-Ce₁V₁W₇/Ti-Si₄	122.7	21.4×10^-2	8.7
K₂O-Ce₁V₁W₇/Ti-Si₄	152.1	27.8×10^-2	6.3

图12 碱中毒前后的Ce1V1W7/Ti、Ce1V1W7/Ti-Si4碱中毒前后的H2-TPR谱图

图13 Ce1V1W7/Ti、Ce1V1W7/Ti-Si4碱中毒前后的NH3-TPD谱图

表3 Ce1V1W7/Ti、Ce1V1W7/Ti-Si4碱中毒前后的NH3-TPD酸量计算结果

催化剂	中弱酸面积	中强酸面积	强酸面积	总酸面积
Ce₁V₁W₇/Ti	2566	635	789	3990
Ce₁V₁W₇/Ti-Si₄	4577	1082	1231	6890
CaCO₃-Ce₁V₁W₇/Ti	1829	530	468	2827
CaCO₃-Ce₁V₁W₇/Ti-Si₄	2726	681	966	4373
K₂O-Ce₁V₁W₇/Ti	1095	294	254	1643
K₂O-Ce₁V₁W₇/Ti-Si₄	1838	417	415	2670

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SiO₂改性Ce-V-W/Ti催化剂载体的抗碱（土）金属中毒性能

Resistance of SiO₂ modified Ce-V-W/Ti catalyst support to alkali (earth) metal poisoning

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