Research on disposal methods of spent vanadium-titanium-based catalysts

doi:10.16085/j.issn.1000-6613.2021-0568

Abstract

Abstract:

At present, coal-fired power generation still accounts for a large proportion of the total power generation in China. Coal-fired power plants will produce a large amount of NO_x which can cause harm to the human body and the environment. Therefore, it is essential to properly handle the NO_x produced by coal-fired power plants. It is very important to control NO_x emissions through using the selective catalytic reduction (SCR) technology. As the core of SCR system, a large number of vanadium-titanium-based SCR catalysts has been applied to remove NO_x in coal-fired power plants. It has been an urgent problem to dispose the spent SCR catalysts. In order to motivate further research in the regeneration process of catalyst and the recovery of valuable metals, this paper systematically collated the literature in the corresponding background. The latest research on the catalyst regeneration process and the valuable metals recovery technology were introduced. The challenges related to the regeneration processes and the technologies of valuable metals recovery were analyzed. In addition, the guidelines on how to develop effective regeneration processes and recovery techniques for spent vanadium-titanium-based catalyst were proposed.

Key words: vanadium-titanium-based catalysts, SCR, hazardous wastes, regeneration, valuable metal recovery, resource recycling

摘要：

当前中国燃煤发电量仍占总发电量很大比重，燃煤电厂会产生大量的氮氧化物，其会对人体和环境造成危害。因此，处理好燃煤电厂产生的氮氧化物十分重要。选择性催化还原（SCR）技术是控制氮氧化物排放的重要手段。而作为该技术的核心，大量的钒钛基SCR催化剂被应用到燃煤电厂氮氧化物的处理工艺中，对废弃的SCR催化剂进行妥善处理也成为了急需解决的问题。本文对相应背景下的文献进行了系统整理，介绍了催化剂再生处理工艺以及有价金属回收技术的最新研究，分析了与再生处理工艺以及有价金属回收技术优化相关的挑战，提出了有关如何开发高效催化剂再生处理工艺以及有价金属回收技术的建议，以推动该方向的进一步研究。

关键词: 钒钛基催化剂, 选择催化还原, 危险废弃物, 再生, 有价金属回收, 资源循环

CLC Number:

X705

HOU Xuejun, ZHANG Xiaoming, CHENG Wenbo, WANG Xin, WANG Chunxia, XU Shengming, HUANG Guoyong. Research on disposal methods of spent vanadium-titanium-based catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5313-5324.

侯学军, 章小明, 程文博, 王馨, 王春霞, 徐盛明, 黄国勇. 废钒钛基SCR催化剂的处置方法研究进展[J]. 化工进展, 2021, 40(10): 5313-5324.

Figures/Tables 12

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催化剂类型	构造	工况条件	特点
蜂窝式催化剂	挤压成型/蜂窝载体负载成型	适合各种工况条件	比表面积大，活性高，耐磨性好，再生性好
平板式催化剂	金属板/网为骨架，表面负载活性涂层	适用于烟气状况较为干净的状况	拆卸方便，催化剂用量少，耐磨性较差
波纹板式催化剂	以波纹状玻纤为载体，负载活性涂层	条件苛刻，烟气必须较为清洁	比表面积中等，质量轻，但易沉积阻塞

催化剂类型	构造	工况条件	特点
蜂窝式催化剂	挤压成型/蜂窝载体负载成型	适合各种工况条件	比表面积大，活性高，耐磨性好，再生性好
平板式催化剂	金属板/网为骨架，表面负载活性涂层	适用于烟气状况较为干净的状况	拆卸方便，催化剂用量少，耐磨性较差
波纹板式催化剂	以波纹状玻纤为载体，负载活性涂层	条件苛刻，烟气必须较为清洁	比表面积中等，质量轻，但易沉积阻塞

类型	再生介质	再生条件	再生后脱硝效率	杂质脱除情况	参考文献
酸洗再生工艺	H₂SO₄	去离子水中超声清洗30min；0.5mol·L^-1稀硫酸清洗1h；110℃干燥10h；450℃煅烧3h	42.62%→78.30% 350℃	Na、K、Fe、As得到有效去除	［77］
	HNO₃	去离子水中超声清洗，0.01mol·L^-1 HNO₃清洗30min	44.60%→82.70% 380℃	Na、K、Ca、P去除率>80%	［75］
	EDTA-2Na+H₂SO₄	去离子水中超声清洗，0.04mol·L^-1 EDTA-2Na清洗15min，0.04mol·L^-1 H₂SO₄清洗15min	44.60%→93.70% 380℃	Na、K、Pb、Ca去除率>90%，P去除率>80%	［75］
酸洗再生工艺	NaOH	0.2mol·L^-1 NaOH中洗涤4min	85.12%左右 300~450℃	S 54.30%、K 64.80%、 Mg 58.50%	［81］
酸洗再生工艺	Ca（NO₃）₂/Ca（OH）₂	Ca（NO₃）₂/Ca（OH）₂溶液中超声0.5h，静置4h，用pH为2的稀HNO₃洗涤，110℃干燥，500℃焙烧3h	>80.00%	As 63.30%	［78］
聚醚洗再生工艺	烷基酚聚氧乙烯（10）醚（OP-10）	1%的OP-10洗涤，然后用去离子水洗涤，450℃煅烧4h	95.00% 350℃	Ca 78.00%	［80］
水蒸气洗再生	水蒸气	300~350℃下用水蒸气原位处理336h	91.40% 350℃	As有效去除	［81］

类型	再生介质	再生条件	再生后脱硝效率	杂质脱除情况	参考文献
酸洗再生工艺	H₂SO₄	去离子水中超声清洗30min；0.5mol·L^-1稀硫酸清洗1h；110℃干燥10h；450℃煅烧3h	42.62%→78.30% 350℃	Na、K、Fe、As得到有效去除	［77］
	HNO₃	去离子水中超声清洗，0.01mol·L^-1 HNO₃清洗30min	44.60%→82.70% 380℃	Na、K、Ca、P去除率>80%	［75］
	EDTA-2Na+H₂SO₄	去离子水中超声清洗，0.04mol·L^-1 EDTA-2Na清洗15min，0.04mol·L^-1 H₂SO₄清洗15min	44.60%→93.70% 380℃	Na、K、Pb、Ca去除率>90%，P去除率>80%	［75］
酸洗再生工艺	NaOH	0.2mol·L^-1 NaOH中洗涤4min	85.12%左右 300~450℃	S 54.30%、K 64.80%、 Mg 58.50%	［81］
酸洗再生工艺	Ca（NO₃）₂/Ca（OH）₂	Ca（NO₃）₂/Ca（OH）₂溶液中超声0.5h，静置4h，用pH为2的稀HNO₃洗涤，110℃干燥，500℃焙烧3h	>80.00%	As 63.30%	［78］
聚醚洗再生工艺	烷基酚聚氧乙烯（10）醚（OP-10）	1%的OP-10洗涤，然后用去离子水洗涤，450℃煅烧4h	95.00% 350℃	Ca 78.00%	［80］
水蒸气洗再生	水蒸气	300~350℃下用水蒸气原位处理336h	91.40% 350℃	As有效去除	［81］

序号	浸出试剂	浸出条件	浸出效率	参考文献
1	H₂SO₄	5mol·L^-1 H₂SO₄，60℃，600r·min^-1，20mL·g^-1，1h	V，56.0%	［83］
2	HCl	38% HCl，80℃，25mL·L^-1，12h	V，72.9%	［84］
3	H₂SO₄	98% H₂SO₄，80℃，25mL·L^-1，12h	V，64.4%	［84］
4	HNO₃	38% HNO₃，80℃，25mL·L^-1，12h	V，34.9%	［84］
5	H₂C₂O₄	1mol·L^-1 H₂C₂O₄，80℃，10mL·g^-1、3h	V，63.5%；W，13.1%	［85］
6	酒石酸（C₄H₆O₆）	0.5mol·L^-1 C₄H₆O₆，100℃，10mL·g^-1，3h	V，44.0%；W，9.0%	［85］
7	H₂C₂O₄	1mol·L^-1 H₂C₂O₄，90℃，20mL·L^-1，3h	V，86.3%；Fe，96.0%	［64］
8	H₂SO₄+Na₂SO₃	5% H₂SO₄，95℃，10mL·g^-1，2h，1g/0.5h Na₂SO₃	V，接近100%	［88］