废加氢催化剂的回收现状与研究进展

doi:10.16085/j.issn.1000-6613.2021-0654

摘要/Abstract

摘要：

废加氢催化剂因含难降解有机物和Mo、W、Ni、Co、V等战略金属，是危险废弃物和重要的二次资源，资源化利用具有显著的经济、社会和环境效益。本文介绍了加氢催化剂概况，综述了废加氢催化剂的回收现状，包括酸浸出、碱浸出、焙烧-浸出、火法富集。文章指出，回收前需采用溶剂洗涤法、机械法或焙烧法进行有机物脱除。酸法浸出酸浓度较高，对设备腐蚀性大；碱法浸出对Ni和Co的回收率低，采用碱法、酸法两步浸出可实现多金属高效回收；但湿法回收存在废水量大、污染严重等问题。焙烧-浸出是目前主流回收方法，已产业化应用，但存在回收流程长、后续浸出废水量大等问题。针对现有技术废水量大、污染严重等问题，本文提出了碳热还原富集回收有价金属、尾渣用于绿色建材的方法。

关键词: 加氢, 催化剂, 废物处理, 回收, 浸取

Abstract:

Spent hydrogenation catalysts are hazardous wastes and important secondary resources because they contain refractory organics and strategic metals such as Mo, W, Ni, Co and V. Resource utilization of spent catalysts has significant economic, social and environmental benefits. In this paper, the general situation of hydrogenation catalysts is introduced, and the recovery status of spent hydrogenation catalysts, including acid leaching, alkali leaching, roasting-leaching progress and pyrometallurgical progress is reviewed. Organic matter should be removed by solvent washing, mechanical method or roasting before recovery. The acid concentration of acid leaching is high, which is corrosive to equipment. The recovery rate of Ni and Co by alkali leaching is low, and the high-efficiency recovery of polymetallic can be realized by alkali leaching and acid leaching. However, hydrometallurgical progress has serious problems, such as the generation of wastewater and serious pollution. Roasting-leaching is the main recovery method at present, which has been industrially applied, but there are some problems such as long recovery process and a large amount of subsequent leaching wastewater. In order to solve the problems of water pollution, the method of enriching and recovering valuable metals by carbothermic reduction and using tailings for green building materials is put forward, and the prospect of metal recovery of waste catalyst is discussed.

Key words: hydrogenation, catalyst, waste treatment, recovery, leaching

中图分类号:

X756

史志胜, 丁云集, 张深根. 废加氢催化剂的回收现状与研究进展[J]. 化工进展, 2021, 40(10): 5302-5312.

SHI Zhisheng, DING Yunji, ZHANG Shengen. Status and research progress on recovery of spent hydrogenation catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5302-5312.

图/表 8

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加氢过程	催化活性对比
加氢脱硫	Mo-Co>Mo-Ni>W-Ni
加氢脱氮	Mo-Ni=W-Ni>Mo-Co
加氢脱氧	Mo-Ni>Mo-Co>W-Ni
加氢饱和	W-Ni>Mo-Ni>Mo-Co

加氢过程	催化活性对比
加氢脱硫	Mo-Co>Mo-Ni>W-Ni
加氢脱氮	Mo-Ni=W-Ni>Mo-Co
加氢脱氧	Mo-Ni>Mo-Co>W-Ni
加氢饱和	W-Ni>Mo-Ni>Mo-Co

废催化剂组成	浸出方法	主要工艺参数	浸出率	参考文献
Mo，Co	HCl	3mol/L，固体添加量5%（质量分数），90℃，60min	Mo 97%；Co 94%	［26］
Mo，Ni	H₂SO₄	9mol/L，固液比1/2.54（g/mL），90℃，90min	Mo 99%；Ni 99%	［27］
Mo，Co	H₂SO₄	20%（体积分数），固体添加量5%（质量分数），90℃，2h	Mo 91%；Co 78%	［28］
Ni	HNO₃	5mol/L，固液比1/10（g/mL），90℃，120min	Ni 99%	［19］
Mo，Ni，V	HNO₃∶H₂SO₄∶HCl=2∶1∶1（体积比）	固液比为70g/L，70℃，60min	Mo 90%；Ni 99%；V 99%	［29］
Mo，Ni，Co	HCOOH	0.6mol/L，固液比1/10（g/mL），80℃，90min	Mo 76%、Ni 93%、Co 97%	［30］
Mo，Ni	H₂C₂O₄	1mol/L，固液比1/10（g/mL），40℃，3h	Mo 92%；Ni 19%	［31］
Mo，Ni，Co	EDTA	0.2mol/L，固液比1/15（g/mL），60℃，60min	Mo 90%；Ni 95%；Co 97%	［32］
Mo，Co	H₂SO₄+H₂O₂（pH=1.3）	H₂O₂浓度3.75mol/L，固液比1/7.5（g/mL），60℃，1h	Mo 90%；Co 83%	［33］
Mo，Ni，V	H₂C₂O₄+H₂O₂	H₂C₂O₄浓度0.5mol/L，H₂O₂浓度3mol/L，60℃，1h	Mo 90%；Ni 65%；V 94%	［34］
Mo，V	NaOH加压	NaOH 30%（g/mL），250℃	Mo 98%；V 95%	［22］
W，V	NaOH+Na₂CO₃加压	NaOH浓度2mol/L，Na₂CO₃浓度0.2mol/L，固液比1/20（g/mL），300℃，2h	W>90%；V>90%	［35］
Mo，V	NH₃·H₂O+H₂O₂	NH₃·H₂O浓度4.5mol/L，H₂O₂浓度为1.0mol/L，固液比1/20（g/mL），140℃，2h	Mo 95%；V 46%	［36］
Mo	Na₂CO₃+H₂O₂	Na₂CO₃浓度85g/L，H₂O₂ 10%（体积分数），废催化剂添加量20%（质量分数），25℃，1h	Mo 84%	［37］
Mo，Ni，Co	Na₂CO₃+H₂SO₄两步浸出	Na₂CO₃浓度为30g/L，固液比1/10（g/mL），90℃，60min；H₂SO₄浓度为6mol/L，固液比1/10（g/mL），90℃，60min	Mo 98%；Ni 90%；Co 93%	［38］
Mo，V	NaOH微波辅助	微波功率600W，NaOH浓度2mol/L，固液比1/5（g/mL），90℃，10min	Mo 96%；V 94%	［25］

废催化剂组成	浸出方法	主要工艺参数	浸出率	参考文献
Mo，Co	HCl	3mol/L，固体添加量5%（质量分数），90℃，60min	Mo 97%；Co 94%	［26］
Mo，Ni	H₂SO₄	9mol/L，固液比1/2.54（g/mL），90℃，90min	Mo 99%；Ni 99%	［27］
Mo，Co	H₂SO₄	20%（体积分数），固体添加量5%（质量分数），90℃，2h	Mo 91%；Co 78%	［28］
Ni	HNO₃	5mol/L，固液比1/10（g/mL），90℃，120min	Ni 99%	［19］
Mo，Ni，V	HNO₃∶H₂SO₄∶HCl=2∶1∶1（体积比）	固液比为70g/L，70℃，60min	Mo 90%；Ni 99%；V 99%	［29］
Mo，Ni，Co	HCOOH	0.6mol/L，固液比1/10（g/mL），80℃，90min	Mo 76%、Ni 93%、Co 97%	［30］
Mo，Ni	H₂C₂O₄	1mol/L，固液比1/10（g/mL），40℃，3h	Mo 92%；Ni 19%	［31］
Mo，Ni，Co	EDTA	0.2mol/L，固液比1/15（g/mL），60℃，60min	Mo 90%；Ni 95%；Co 97%	［32］
Mo，Co	H₂SO₄+H₂O₂（pH=1.3）	H₂O₂浓度3.75mol/L，固液比1/7.5（g/mL），60℃，1h	Mo 90%；Co 83%	［33］
Mo，Ni，V	H₂C₂O₄+H₂O₂	H₂C₂O₄浓度0.5mol/L，H₂O₂浓度3mol/L，60℃，1h	Mo 90%；Ni 65%；V 94%	［34］
Mo，V	NaOH加压	NaOH 30%（g/mL），250℃	Mo 98%；V 95%	［22］
W，V	NaOH+Na₂CO₃加压	NaOH浓度2mol/L，Na₂CO₃浓度0.2mol/L，固液比1/20（g/mL），300℃，2h	W>90%；V>90%	［35］
Mo，V	NH₃·H₂O+H₂O₂	NH₃·H₂O浓度4.5mol/L，H₂O₂浓度为1.0mol/L，固液比1/20（g/mL），140℃，2h	Mo 95%；V 46%	［36］
Mo	Na₂CO₃+H₂O₂	Na₂CO₃浓度85g/L，H₂O₂ 10%（体积分数），废催化剂添加量20%（质量分数），25℃，1h	Mo 84%	［37］
Mo，Ni，Co	Na₂CO₃+H₂SO₄两步浸出	Na₂CO₃浓度为30g/L，固液比1/10（g/mL），90℃，60min；H₂SO₄浓度为6mol/L，固液比1/10（g/mL），90℃，60min	Mo 98%；Ni 90%；Co 93%	［38］
Mo，V	NaOH微波辅助	微波功率600W，NaOH浓度2mol/L，固液比1/5（g/mL），90℃，10min	Mo 96%；V 94%	［25］

废催化剂组成	回收方法	主要工艺参数	回收率	参考文献
Mo，Co	H₂SO₄焙烧+H₂SO₄浸出	焙烧条件：300℃，2h；浸出条件：H₂SO₄体积分数2%，95℃，60min	Mo>90%；Co>90%	［28］
Mo，Ni，Co	KHSO₄焙烧-水浸	焙烧条件：500℃，4h；90℃水浸4h	Mo>90%；Ni>90%；Co>90%	［55］
Mo，V	Na₂CO₃焙烧-水浸	焙烧条件：750℃，45min；90℃水浸15min	Mo 90%；V 90%	［56］
Mo	Na₂CO₃焙烧-水浸	焙烧条件：600℃，45min；60℃水浸	Mo 99%	［57］