溶剂萃取法分离回收废催化剂碱浸渣中铝、镍的研究

doi:10.12422/j.issn.1006-396X.2023.02.003

摘要/Abstract

摘要：

通过溶剂萃取法分离回收废加氢催化剂碱浸渣的硫酸浸出液中铝和镍，分析并比较了萃取剂P204（二（2?乙基己基）磷酸酯）和P507（2?乙基己基磷酸单2?乙基己基酯）的萃取分离效果，同时考察了P204萃取体系中原料液初始pH、P204体积分数、P204皂化率、V(有机相)/V(水相)等因素对铝、镍萃取率的影响。结果表明，与P507相比，P204可更好地分离铝和镍；在萃取剂P204体积分数为35%、P204皂化率为30%、原料液初始pH为2.75、V(有机相)/V(水相)＝3∶1的条件下，铝的萃取率达到96.45%，而镍的萃取率仅为2.77%；经过二级逆流萃取流程，铝的萃取率可达到99.50%以上，而镍的萃取率低于3.60%。采用盐酸溶液对负载有机相进行反萃，在盐酸浓度为6 mol/L、反萃温度为60 ℃、V(有机相)/V(水相)=2∶1的条件下反萃20 min，有机相中铝的反萃率为98.04%，可有效地实现废加氢催化剂中铝、镍的分离。

关键词: 溶剂萃取法, 废加氢催化剂, 铝, 镍, 反萃

Abstract:

This study uses the solvent extraction method to separate and recover aluminum and nickel from the alkali leaching residue of spent hydrogeneration catalysts. It compared and analyzed the extraction efficiency of P204 (Di (2?ethylhexyl) phosphate) and P507 (2?ethylhexylphosphonic acid mono?2?ethylhexyl ester) and investigated the effects of initial pH, the volume fraction of P204, the saponification rate of P204, and the ratio of V(org)/V(aq) on the extraction of aluminum and nickel in the P204 extraction system. The experimental results show that P204 demonstrates better extraction performance than P507 in the separation of aluminum and nickel. Under a concentration of 35% and saponification ratio of 30% of P204, initial pH of 2.75, and V(org)/V(aq) of 3∶1, the extraction rate of aluminum and nickel is 96.45% and 2.77%, respectively. In the two?stage countercurrent extraction process, the extraction rate of aluminum can reach more than 99.50% while that of nickel is below 3.60%. The loaded organic solvent was stripped at 60 ℃ and V(org)/V(aq) =2∶1 for 20 minutes by 6 mol/L HCl solution, and the stripping efficiency of aluminum in the organic phase is 98.04%. Thus, the separation of aluminum and nickel in spent catalysts can be effectively realized.

Key words: Solvent extraction, Spent hydrogenation catalyst, Aluminium, Nickel, Stripping

中图分类号:

TQ09

于博, 凌江华, 贾富智, 刘美. 溶剂萃取法分离回收废催化剂碱浸渣中铝、镍的研究[J]. 石油化工高等学校学报, 2023, 36(2): 20-26.

Bo Yu, Jianghua Ling, Fuzhi Jia, Mei Liu. Separation and Recovery of Aluminum and Nickel from Alkali Leaching Residue of Spent Catalysts[J]. Journal of Petrochemical Universities, 2023, 36(2): 20-26.

图/表 7

图1 原料液初始pH对铝、镍萃取率的影响

Fig.1 Effect of initial pH of feed solution on extraction efficiency of aluminum and nickel

图2 萃取剂体积分数对铝、镍萃取率的影响

Fig.2 Effect of extractant volume fraction on extraction efficiency of aluminum and nickel

图3 P204皂化率对铝、镍萃取率的影响

Fig.3 Effect of saponification rate of P204 on extraction efficiency of aluminum and nickel

图4 V（org）/V（aq）对铝、镍萃取率的影响

Fig.4 Effect of V（org）/V（aq） on extraction efficiency of aluminum and nickel

图5 铝的McCabe?Thiele萃取级数图

Fig.5 McCabe?Thiele extraction stage diagram of aluminum

表1 两级逆流萃取实验结果

Table 1 Experimental results of two?stage counter current extraction

循环次数	萃取率/%
循环次数	铝	镍
1	99.52	3.03
2	99.76	3.58
3	99.68	2.48
4	99.84	1.93
5	99.84	2.21

图6 反萃条件对铝反萃率的影响

Fig.6 Effect of stripping conditions on the stripping efficiency of aluminum

参考文献 24

1	Furimsky E.Spent refinery catalysts： Environment， safety and utilization［J］.Catalysis Today，1996，30（4）：223⁃286.
2	Liang X，Tang J J，Li L S，et al.A review of metallurgical processes and purification techniques for recovering Mo，V，Ni， Co，Al from spent catalysts［J］.Journal of Cleaner Production，2022，376：134108.
3	Cai Y Y，Ma L W，Xi X L，et al.Comprehensive recovery of metals in spent Ni⁃Mo/γ⁃Al₂O₃ hydrofining catalyst［J］. Hydrometallurgy，2022，208：105800.
4	谭佳文，王嘉华，宋盈盈，等.化学沉淀法分离回收碱性溶液中V、Mo、Al的研究［J］.石油化工高等学校学报，2020， 33（6）：13⁃18.
	Tan J W，Wang J H，Song Y Y，et al.Research on separation and recovery of vanadium，molybdenum，aluminium in alkaline solution by chemical precipitation［J］.Journal of Petrochemical Universitits，2020，33（6）：13⁃18.
5	Pathak A，Kothari R，Vinoba M，et al.Fungal bioleaching of metals from refinery spent catalysts：A critical review of current research， challenges， and future directions［J］.Journal of Environmental Management，2021，280：111789.
6	Singh R，Mahandra H，Gupta B.Optimization of a solvent extraction route for the recovery of Mo from petroleum refinery spent catalyst using cyphos IL 102［J］.Solvent Extraction & Ion Exchange，2018，36（4）：401⁃419.
7	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.
8	李雨恩，于博，凌江华，等.空气焙烧—碱浸法回收废加氢催化剂中的钼和钒［J/OL］.过程工程学报：1⁃9（2022⁃08⁃22）［2023⁃03⁃14］.http：//kns.cnki.net/kcms/detail/11.4541.TQ.20220822.1004.002.html.
	Li Y E，Yu B，Ling J H，et al.Recovering molybdenum and vanadium from spent hydroprocessing catalyst by air roasting⁃alkaline leaching process［J/OL］.The Chinese Journal of Process Engineerin：1⁃9（2022⁃08⁃22）［2023⁃03⁃14］.http：//kns.cnki.net/kcms/detail/11.4541.TQ.20220822.1004.002.html.
9	Parhi P K，Misra P K.Environmental friendly approach for selective extraction and recovery of molybdenum （Mo） from a sulphate mediated spent Ni⁃Mo/Al₂O₃ catalyst baked leach liquor［J］.Journal of Environmental Management，2022，306： 114474.
10	Rao M J，Zhang T，Li G H，et al.Solvent extraction of Ni and Co from the phosphoric acid leaching solution of laterite ore by P204 and P507［J］.Metals，2020，10（4）：545.
11	董存武，叶剑鸣，张霞，等.利用P507和P204从多金属离子溶液中萃取分离镍钴离子的研究［J］.辽宁石油化工大学学报，2014，34（3）：26⁃28.
	Dong C W，Ye J M，Zhang X，et al.The extraction of nickel and cobalt from multi⁃metal ionic solution by P507 and P204［J］. Journal of Liaoning Shihua University，2014，34（3）：26⁃28.
12	Padh B，Rout P C，Mishra G K，et al.Recovery of nickel and molybdate from ammoniacal leach liquors of spent HDS catalysts using chelating ion exchange resin［J］.Hydrometallurgy，2019，184：88⁃94.
13	Batti N R，Mandre N R.Nickel and aluminium recovery from spent reforming catalyst through selective leaching， crystallization and precipitation［J］.Transactions of Nonferrous Metals Society of China，2022，32（1）：345⁃353.
14	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.
15	Rao S V，Yang D H，Sohn J S，et al.Purification sulphate leach liquor of spent Raneynickel catalyst containing Al and Ni by solvent extraction with organophosphorus⁃based extractants［J］.Scientific World Journal，2012（7）：1⁃5.
16	Park K H，Kim H I，Parhi P K，et al.Extraction of metals from Mo⁃Ni/Al₂O₃ spent catalyst using H₂SO₄ baking⁃leaching⁃solvent extraction technique［J］.Journal of Industrial and Engineering Chemistry，2012，18（6）：2036⁃2045.
17	Gao B Y，Jiang H H，Zeng M，et al.High⁃efficiency recycling method for Mo and Ni from spent catalyst via soda roasting and solvent extraction［J］.Journal of Cleaner Production，2022，367：132976.
18	Mohapatra D，Kim H I，Nam C W，et al.Liquid⁃liquid extraction of aluminium （III） from mixed sulphate solutions using sodium salts of Cyanex 272 and D2EHPA［J］.Separation and Purification Technology，2007，56（3）：311⁃318.
19	于凯，艾峥嵘，谢宏伟，等.用P507从高浓度氯化钴溶液中萃取分离钴镍试验研究［J］.湿法冶金，2020，39（6）：502⁃506.
	Yu K，Ai Z R，Xie H W，et al.Solvent extraction of cobalt and nickel from high concentration cobalt chloride solution using P507［J］.Hydrometallurgy of China，2020，39（6）：502⁃506.
20	Shi Q H，Zhang Y M，Huang J，et al.Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A［J］.Separation and Purification Technology，2017，181：1⁃7.
21	Nathsarma K C，Devi N.Separation of Zn（II） and Mn（II） from sulphate solutions using sodium salts of D2EHPA，PC 88A and Cyanex 272［J］.Hydrometallurgy，2006，84（3）：149⁃154.
22	Wu W Y，Li D，Zhao Z H，et al.Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507⁃HCl system［J］.Journal of Rare Earths，2010，28（1）：174⁃178.
23	Zhang W J，Xie X，Tong X，et al.Study on the effect and mechanism of impurity aluminum on the solvent extraction of rare earth elements （Nd， Pr， La） by P204⁃P350 in chloride solution［J］.Minerals，2021，11（1）：1⁃13.
24	Zhou J，Ma S Y，Chen Y D，et al.Recovery of scandium from red mud by leaching with titanium white waste acid and solvent extraction with P204［J］.Hydrometallurgy，2021，204（1）：105724.

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