SCR脱硝催化剂掺废特性及性能影响

doi:10.16085/j.issn.1000-6613.2023-0256

化工进展 ›› 2023, Vol. 42 ›› Issue (S1): 489-497.DOI: 10.16085/j.issn.1000-6613.2023-0256

SCR脱硝催化剂掺废特性及性能影响

王乐乐¹(), 杨万荣², 姚燕¹, 刘涛³, 何川¹, 刘逍², 苏胜³, 孔凡海¹, 朱仓海², 向军³

^1.西安热工研究院有限公司苏州分公司，江苏苏州 215153
^2.中国华能集团有限公司，北京 100031
^3.华中科技大学煤燃烧国家重点实验室，湖北武汉 430074

收稿日期:2023-02-24 修回日期:2023-06-21 出版日期:2023-10-25 发布日期:2023-11-30
通讯作者: 王乐乐
作者简介:王乐乐（1984—），男，博士，研究方向为SCR烟气脱硝技术。E-mail：wanglele003@163.com。
基金资助:
西安热工研究院科研基金项目(GU-22-TYK15);华能集团标准项目(HNBZ21-Q014)

Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst

WANG Lele¹(), YANG Wanrong², YAO Yan¹, LIU Tao³, HE Chuan¹, LIU Xiao², SU Sheng³, KONG Fanhai¹, ZHU Canghai², XIANG Jun³

^1.Xi'an Thermal Power Research Institute Co. , Ltd. , Suzhou Branch, Suzhou 215153, Jiangsu, China
^2.China Huaneng Group Co. , Ltd, Beijing 100031, China
^3.State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2023-02-24 Revised:2023-06-21 Online:2023-10-25 Published:2023-11-30
Contact: WANG Lele

摘要/Abstract

摘要：

以3种品质的废SCR脱硝催化剂粉料M1、M2和M3为原料，与原生钛钨粉M0掺加制备了不同质量掺比的脱硝催化剂，分别对其初始脱硝性能和在实际烟气中运行16000h后的脱硝性能进行跟踪检测评价。实验结果表明，在相同质量掺加比时，掺加废催化剂粉料M1和M2的新催化剂初始性能比未掺加废催化剂粉料M0-0性能降低约30%以上，且运行16000h后的活性劣化速率明显偏快。废催化剂粉料掺加比例越高，负面影响越大。废催化剂的资源化回用应使用高品质粉料，且需严格控制其掺加比。借助激光粒度仪、表面酸量吸附仪（NH₃-TPD）以及X射线荧光光谱仪（XRF）等对废催化剂粉料和所制备的催化剂进行了理化分析，废催化剂粉料微观特性无法完全恢复，杂质含量高，是造成新制备催化剂脱硝性能不佳及使用中活性劣化速率快的主要原因。要实现废催化剂粉料大比例用于新催化剂制备，需进一步提高废催化剂粉料的粒径、微观孔隙、表面酸性及降低杂质含量。

关键词: 选择性催化还原脱硝, 废催化剂粉料, 掺加比例, 活性劣化, 机理分析

Abstract:

Three kinds of waste catalyst powder M1-M3 were used as raw materials to prepare the catalysts. These catalysts had different waste catalyst powder mixing ratios. The denitration performance of these catalysts was tested and evaluated at the initial and after 16000 hours. At the same mass addition ratio, the initial performance of the new catalyst prepared by adding waste catalyst powder M1 and M2 was about 30% lower than that of the catalyst M0-0 without adding waste catalyst powder, and the activity degradation rate was obviously faster. It also indicated that the higher the proportion of waste catalyst powder, the greater the negative impact. It was recommended that the proportion of high-quality powder should be controlled. The physical and chemical analysis of the waste catalyst powder and the prepared catalyst were carried out by means of laser particle size analyzer, surface acid adsorption analyzer (NH₃-TPD) and X-ray fluorescence spectrometer (XRF). The microscopic characteristics of the waste catalyst powder could not be fully restored. The effective active components were low and the impurity content was high. These resulted in poor specific microscopic characteristics and low surface acidity of the catalysts, which were the main reason for the poor denitrification performance of the catalysts. In order to achieve the quality of waste catalyst powder close to the original titanium tungsten powder and effectively used for the preparation of new catalysts, it was necessary to further improve the particle size, micro-pores, impurity content and surface acidity of the waste catalyst powder.

Key words: selective catalytic reduction denitrification, waste catalyst powder, mixing proportion, activity deterioration, mechanism analysis

中图分类号:

X511

王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.

WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.

图/表 15

参考文献 27

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参数	设计值	备注
烟气体积流量/m³·h^-1	10.5	湿基，实际 O₂
空塔流速/m·s^-1	1.2
孔道内流速/m·s^-1	3.8
空速/h^-1	8400
烟气温度/℃	380
H₂O体积分数/%	10.0
O₂体积分数/%	4.0	湿基
NO _x 浓度/mg·m^-3	450	干基，6% O₂
SO₂浓度/mg·m^-3	800	干基，6% O₂
氨氮摩尔比	1.01

参数	设计值	备注
烟气体积流量/m³·h^-1	10.5	湿基，实际 O₂
空塔流速/m·s^-1	1.2
孔道内流速/m·s^-1	3.8
空速/h^-1	8400
烟气温度/℃	380
H₂O体积分数/%	10.0
O₂体积分数/%	4.0	湿基
NO _x 浓度/mg·m^-3	450	干基，6% O₂
SO₂浓度/mg·m^-3	800	干基，6% O₂
氨氮摩尔比	1.01

样品	微观比表面积/m²·g^-1	粒径/nm
M0	100.4	1.0
M1	45.2	8.9
M2	48.1	8.8
M3	92.4	1.3

样品	微观比表面积/m²·g^-1	粒径/nm
M0	100.4	1.0
M1	45.2	8.9
M2	48.1	8.8
M3	92.4	1.3

样品	TiO₂	WO₃	V₂O₅	SO₃	SiO₂	Al₂O₃	Fe₂O₃	K₂O	Na₂O	As₂O₃
M0	88.46	4.76	0	0.085	NA	NA	0.005	NA	NA	NA
M1	80.89	4.41	0.76	1.17	5.32	2.68	0.28	0.034	0.062	0.093
M2	82.39	4.32	1.15	0.96	3.13	1.02	0.17	0.022	0.027	0.052
M3	86.66	4.07	0.32	0.89	2.67	0.78	0.11	0.009	0.016	0.057

SCR脱硝催化剂掺废特性及性能影响

Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst

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样品	处理过程
M0	原生钛钨粉
M1	物理除杂+研磨
M2	物理化学除杂+热处理+研磨
M3	物理化学除杂+热处理+酸碱活化+研磨

催化剂	运行时间/h	微观比表面积/m²·g^-1	孔容/cm³·g^-1
M0-0	0	55.3	0.308
M0-0	16000	48.5	0.282
M1-30%	0	45.6	0.252
M1-30%	16000	41.4	0.253
M1-50%	0	41.2	0.232
M1-50%	16000	38.7	0.240
M2-30%	0	47.8	0.265
M2-30%	16000	42.9	0.247
M2-50%	0	42.6	0.258
M2-50%	16000	39.5	0.223
M3-30%	0	53.7	0.287
M3-30%	16000	47.6	0.263
M3-50%	0	52.0	0.276
M3-50%	16000	46.9	0.257
M3-100%	0	48.2	0.261
M3-100%	16000	42.7	0.240

脱附峰次序	脱附量/cm³·g^-1
脱附峰次序	M3-30%	M3-50%	M3-100%
第1个	44.4	50.0	36.0
第2个	196.8	92.6	99.2
总脱附量	241.2	242.6	235.2

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[4]	冯刚. 换热器管束流体诱导振动机理与防振研究进展[J]. 化工进展, 2012, 31(03): 508-512.

SCR脱硝催化剂掺废特性及性能影响

Influence of spent SCR catalyst blending on the characteristics and deNO x performance for new SCR catalyst

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Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst