Status and research progress on recovery of spent hydrogenation catalysts

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

Abstract

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

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

CLC Number:

X756

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.

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.

Figures/Tables 8

References 63

1	AKCIL A, VEGLIÒ F, FERELLA F, et al. A review of metal recovery from spent petroleum catalysts and ash[J]. Waste Management, 2015, 45: 420-433.
2	MARAFI M, RANA M S. Refinery waste: the spent hydroprocessing catalyst and its recycling options[J]. WIT Transactions on Ecology and the Environment, 2016, 202: 219-230.
3	任春晓, 吴培, 李振昊, 等. 加氢催化剂预硫化技术现状[J]. 化工进展, 2013, 32(5): 1060-1064.
	REN Chunxiao, WU Pei, LI Zhenhao, et al. The status of presulfurization technology for hydrogenation catalyst[J]. Chemical Industry and Engineering Progress, 2013, 32(5): 1060-1064.
4	张利波, 王璐, 曲雯雯, 等. Al₂O₃基石油加氢脱硫催化剂研究现状与进展[J]. 材料导报, 2018, 32(5): 772-779, 795.
	ZHANG Libo, WANG Lu, QU Wenwen, et al. Research and development of petroleum hydrodesulfurization catalysts with Al₂O₃-based supports[J]. Materials Review, 2018, 32(5): 772-779, 795.
5	GRANGE P, VANHAEREN X. Hydrotreating catalysts, an old story with new challenges[J]. Catalysis Today, 1997, 36(4): 375-391.
6	DUFRESNE P. Hydroprocessing catalysts regeneration and recycling[J]. Applied Catalysis A: General, 2007, 322: 67-75.
7	MARAFI M, STANISLAUS A. Spent catalyst waste management: a review: Part Ⅰ—Developments in hydroprocessing catalyst waste reduction and use[J]. Resources, Conservation and Recycling, 2008, 52(6): 859-873.
8	刘勇军, 刘晨光. 炼厂加氢废催化剂的综合利用[J]. 化工进展, 2010, 29(6): 1066-1070.
	LIU Yongjun, LIU Chenguang. Comprehensive utilization of spent hydrotreating catalysts in refinery[J]. Chemical Industry and Engineering Progress, 2010, 29(6): 1066-1070.
9	孙晓雪, 刘仲能, 杨为民. 废弃负载型加氢处理催化剂金属回收技术进展[J]. 化工进展, 2016, 35(6): 1894-1904.
	SUN Xiaoxue, LIU Zhongneng, YANG Weimin. Research progress of metal recovery in spent supported hydroprocessing catalyst[J]. Chemical Industry and Engineering Progress, 2016, 35(6): 1894-1904.
10	PATHAK A, VINOBA M, KOTHARI R. Emerging role of organic acids in leaching of valuable metals from refinery-spent hydroprocessing catalysts, and potential techno-economic challenges: a review[J]. Critical Reviews in Environmental Science and Technology, 2021, 51(1): 1-43.
11	EIJSBOUTS S, BATTISTON A A, LEERDAM G C VAN. Life cycle of hydroprocessing catalysts and total catalyst management[J]. Catalysis Today, 2008, 130(2/3/4): 361-373.
12	BARIK S P, PARK K H, PARHI P K, et al. Direct leaching of molybdenum and cobalt from spent hydrodesulphurization catalyst with sulphuric acid[J]. Hydrometallurgy, 2012, 111/112: 46-51.
13	王曰杰, 李玲玲, 何春宏. 炼油废催化剂生物淋滤脱金属研究进展[J]. 化工学报, 2021, 72(2): 901-912.
	WANG Yuejie, LI Lingling, HE Chunhong. Review on the bioleaching of spent refinery catalysts for metals removal[J]. CIESC Journal, 2021, 72(2): 901-912.
14	LE M N, LEE M S. A review on hydrometallurgical processes for the recovery of valuable metals from spent catalysts and life cycle analysis perspective[J]. Mineral Processing and Extractive Metallurgy Review, 2021, 42(5): 335-354.
15	AL-SALEM S M, CONSTANTINOU A, LEEKE G A, et al. A review of the valorization and management of industrial spent catalyst waste in the context of sustainable practice: the case of the State of Kuwait in parallel to European industry[J]. Waste Management & Research, 2019, 37(11): 1127-1141.
16	WANG Hongjun, FENG Yali, LI Hailong, et al. Recovery of vanadium from acid leaching solutions of spent oil hydrotreating catalyst using solvent extraction with D2EHPA (P204)[J]. Hydrometallurgy, 2020, 195: 105404.
17	LE M N, LEE M S. Separation of Al(Ⅲ), Mo(Ⅵ), Ni(Ⅱ), and V(Ⅴ) from model hydrochloric acid leach solutions of spent petroleum catalyst by solvent extraction[J]. Journal of Chemical Technology & Biotechnology, 2020, 95(11): 2886-2897.
18	WANG Hongjun, FENG Yali, LI Haoran, et al. The kinetics of vanadium extraction from spent hydroprocessing catalyst by leaching with sulfuric acid at atmospheric pressure[J]. Metallurgical Research & Technology, 2019, 116(2): 214.
19	SHEIK A R, GHOSH M K, SANJAY K, et al. Dissolution kinetics of nickel from spent catalyst in nitric acid medium[J]. Journal of the Taiwan Institute of Chemical Engineers, 2013, 44(1): 34-39.
20	VUYYURU K R, PANT K K, KRISHNAN V V, et al. Recovery of nickel from spent industrial catalysts using chelating agents[J]. Industrial & Engineering Chemistry Research, 2010, 49(5): 2014-2024.
21	CHAUHAN G, PANT K K, NIGAM K D P. Metal recovery from hydroprocessing spent catalyst: a green chemical engineering approach[J]. Industrial & Engineering Chemistry Research, 2013, 52(47): 16724-16736.
22	IMAM D M, EL-NADI Y A. Recovery of molybdenum from alkaline leach solution of spent hydrotreating catalyst by solvent extraction using methyl tricaprylammonium hydroxide[J]. Hydrometallurgy, 2018, 180: 172-179.
23	AL-SHEEHA H, MARAFI M, RAGHAVAN V, et al. Recycling and recovery routes for spent hydroprocessing catalyst waste[J]. Industrial & Engineering Chemistry Research, 2013, 52(36): 12794-12801.
24	SZYMCZYCHA-MADEJA A. Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide[J]. Journal of Hazardous Materials, 2011, 186(2/3): 2157-2161.
25	MA Zhiyuan, LIU Yong, ZHOU Jikui, et al. Recovery of vanadium and molybdenum from spent petrochemical catalyst by microwave-assisted leaching[J]. International Journal of Minerals, Metallurgy, and Materials, 2019, 26(1): 33-40.
26	BANDA R, NGUYEN T H, SOHN S H, et al. Recovery of valuable metals and regeneration of acid from the leaching solution of spent HDS catalysts by solvent extraction[J]. Hydrometallurgy, 2013, 133: 161-167.
27	VALVERDE I M, PAULINO J F, AFONSO J C. Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium[J]. Journal of Hazardous Materials, 2008, 160(2/3): 310-317.
28	KIM H I, PARK K H, MISHRA D. Sulfuric acid baking and leaching of spent Co-Mo/Al₂O₃ catalyst[J]. Journal of Hazardous Materials, 2009, 166(2/3): 1540-1544.
29	LAI Y C, LEE W J, HUANG Kuolin, et al. Metal recovery from spent hydrodesulfurization catalysts using a combined acid-leaching and electrolysis process[J]. Journal of Hazardous Materials, 2008, 154(1/2/3): 588-594.
30	ARSLANOĞLU H, YARAŞ A. Recovery of precious metals from spent Mo-Co-Ni/Al₂O₃ catalyst in organic acid medium: process optimization and kinetic studies[J]. Petroleum Science and Technology, 2019, 37(19): 2081-2093.
31	ILHAN S. Extraction of molybdenum, nickel and aluminium from spent Ni-Mo hydrodesulphurization (HDS) catalyst in oxalic acid solutions[J]. Canadian Metallurgical Quarterly, 2020, 59(1): 26-35.
32	ALPASLAN O, YARAS A, ARSLANOĞLU H. A kinetic model for chelating extraction of metals from spent hydrodesulphurization catalyst by complexing agent[J]. Transactions of the Indian Institute of Metals, 2020, 73(7): 1925-1937.
33	RUIZ V, MEUX E, SCHNEIDER M, et al. Hydrometallurgical treatment for valuable metals recovery from spent CoMo/Al₂O₃Catalyst. 2. Oxidative leaching of an unroasted catalyst using H₂O₂[J]. Industrial & Engineering Chemistry Research, 2011, 50(9): 5307-5315.
34	MULAK W, SZYMCZYCHA A, LESNIEWICZ A, et al. Preliminary results of metals leaching from a spent hydrodesulphurization (HDS) catalyst[J]. Physicochemical Problems of Mineral Processing, 2006, 40: 69-76.
35	KIM J W, LEE W G, HWANG I S, et al. Recovery of tungsten from spent selective catalytic reduction catalysts by pressure leaching[J]. Journal of Industrial and Engineering Chemistry, 2015, 28: 73-77.
36	ZHAO Zhipeng, GUO Min, ZHANG Mei. Extraction of molybdenum and vanadium from the spent diesel exhaust catalyst by ammonia leaching method[J]. Journal of Hazardous Materials, 2015, 286: 402-409.
37	PARK K H, MOHAPATRA D, REDDY B R. Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method[J]. Journal of Hazardous Materials, 2006, 138(2): 311-316.
38	PARK K H, MOHAPATRA D, NAM C W. Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272[J]. Journal of Hazardous Materials, 2007, 148(1/2): 287-295.
39	MARAFI M, STANISLAUS A. Spent hydroprocessing catalyst management: a review: Part Ⅱ. Advances in metal recovery and safe disposal methods[J]. Resources, Conservation and Recycling, 2008, 53(1/2): 1-26.
40	SÁMANO V, RANA M S, ANCHEYTA J. An easy approach based on textural properties to evaluate catalyst deactivation during heavy oil hydrotreating[J]. Catalysis Communications, 2020, 133: 105823.
41	LE M N, LEE M S. Selective dissolution of vanadium(Ⅴ) from spent petroleum catalysts by oxalic acid solution[J]. Journal of Mining and Metallurgy, Section B: Metallurgy, 2020, 56(1): 127-133.
42	YANG Yue, XU Shengming, LI Zhen, et al. Oil removal of spent hydrotreating catalyst CoMo/Al₂O₃via a facile method with enhanced metal recovery[J]. Journal of Hazardous Materials, 2016, 318: 723-731.
43	FU Pengbo, WANG Hualin, LI Jianping, et al. Cyclonic gas stripping deoiling and gas flow acceleration classification for the resource utilization of spent catalysts in residue hydrotreating process[J]. Journal of Cleaner Production, 2018, 190: 689-702.
44	DE SOUZA PEREIRA A L, SILVA C N D, AFONSO J C, et al. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery[J]. Química Nova, 2011, 34(1): 145-150.
45	MENOUFY M F, AHMED H S. Treatment and reuse of spent hydrotreating catalyst[J]. Energy Sources A: Recovery, Utilization, and Environmental Effects, 2008, 30(13): 1213-1222.
46	ZHANG Di, LIU Yunqing, HU Qizhao, et al. Sustainable recovery of nickel, molybdenum, and vanadium from spent hydroprocessing catalysts by an integrated selective route[J]. Journal of Cleaner Production, 2020, 252: 119763.
47	FERELLA F, OGNYANOVA A, DE MICHELIS I, et al. Extraction of metals from spent hydrotreating catalysts: physico-mechanical pre-treatments and leaching stage[J]. Journal of Hazardous Materials, 2011, 192(1): 176-185.
48	HUANG Shaobo, ZHAO Zhongwei, CHEN Xingyu, et al. Alkali extraction of valuable metals from spent Mo-Ni/Al₂O₃ catalyst[J]. International Journal of Refractory Metals and Hard Materials, 2014, 46: 109-116.
49	DELIA ROJAS-RODRÍGUEZ A, FLORES-FAJARDO O, SELENE ALCÁNTAR GONZÁLEZ F, et al. Chemical treatment to recover molybdenum and vanadium from spent heavy gasoil hydrodesulfurization catalyst[J]. Advances in Chemical Engineering and Science, 2012, 2(3): 408-412.
50	PARK K H, REDDY B R, MOHAPATRA D, et al. Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst[J]. International Journal of Mineral Processing, 2006, 80(2/3/4): 261-265.
51	PINTO I S S, SOARES H M V M. Selective leaching of molybdenum from spent hydrodesulphurisation catalysts using ultrasound and microwave methods[J]. Hydrometallurgy, 2012, 129/130: 19-25.
52	WANG Wenqiang, ZHANG Lei, HAN Yu, et al. Cleaner recycling of spent Ni-Mo/γ-Al₂O₃ catalyst based on mineral phase reconstruction[J]. Journal of Cleaner Production, 2019, 232: 266-273.
53	ZHANG Jialiang, YANG Cheng, CHEN Yongqiang, et al. Efficient phase transformation of γ-Al₂O₃ to α-Al₂O₃ in spent hydrodesulphurization catalyst by microwave roasting method[J]. Industrial & Engineering Chemistry Research, 2019, 58(4): 1495-1501.
54	LIU Qi, WANG Wenqiang, YANG Yue, et al. Recovery and regeneration of Al₂O₃ with a high specific surface area from spent hydrodesulfurization catalyst CoMo/Al₂O₃[J]. Rare Metals, 2019, 38(1): 1-13.
55	BUSNARDO R G, BUSNARDO N G, SALVATO G N, et al. Processing of spent NiMo and CoMo/Al₂O₃ catalysts via fusion with KHSO₄[J]. Journal of Hazardous Materials, 2007, 139(2): 391-398.
56	CHEN Yun, FENG Qiming, SHAO Yanhai, et al. Investigations on the extraction of molybdenum and vanadium from ammonia leaching residue of spent catalyst[J]. International Journal of Mineral Processing, 2006, 79(1): 42-48.
57	YE Xiaolei, GUO Shenghui, QU Wenwen, et al. Microwave sodium roasting (MWSR) spent HDS catalysts for recovery Mo and in situ sulfur fixation[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 97: 146-157.
58	KIM H I, PARK K H, MISHRA D. Influence of sulfuric acid baking on leaching of spent Ni-Mo/Al₂O₃ hydro-processing catalyst[J]. Hydrometallurgy, 2009, 98(1/2): 192-195.
59	YE Xiaolei, GUO Shenghui, QU Wenwen, et al. Microwave field: high temperature dielectric properties and heating characteristics of waste hydrodesulfurization catalysts[J]. Journal of Hazardous Materials, 2019, 366: 432-438.
60	张邦胜, 刘贵清, 王芳, 等. 一种从废镍钼催化剂中回收镍、钼的方法: CN108467939A[P]. 2018-08-31.
	ZHANG Bangsheng, LIU Guiqing, WANG Fang, et al. Method for recovering nickel and molybdenum from waste nickel-molybdenum catalyst: CN108467939A[P]. 2018-08-31.
61	朱兆鹏, 杨夫清, 梁宗跃, 等. 用等离子炉处理含钼废催化剂回收有价金属的研究[J]. 中国钼业, 2003, 27(3): 14-16.
	ZHU Zhaopeng, YANG Fuqing, LIANG Zongyue, et al. Study on recovering valuable metals by treating molybdenum-containing waste catalysts using plasma furnace[J]. China Molybdenum Industry, 2003, 27(3): 14-16.
62	王成彦, 杨成, 张家靓, 等. 废加氢催化剂还原熔炼回收有价金属试验[J]. 有色金属(冶炼部分), 2019(9): 12-17.
	WANG Chengyan, YANG Cheng, ZHANG Jialiang, et al. Study on recovery of valuable metals from spent hydrodesulphurization catalysts by reduction smelting[J]. Nonferrous Metals (Extractive Metallurgy), 2019(9): 12-17.
63	YAO Zan, MA Xiaodong, Sha LYU. Phase equilibria of the Al₂O₃-CaO-SiO₂-(0%, 5%, 10%)MgO slag system for non-metallic inclusions control[J]. Calphad, 2021, 72: 102227.

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］