P204/4PC协萃体系在酸性硫酸盐溶液中选择性萃取镍的机理研究
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摘要
采用斜率法、恒摩尔法、饱和容量法研究从酸性硫酸盐溶液中用P204和4PC协同萃取镍的机理,并测定协萃反应的热力学平衡常数,得到协萃反应的焓变和熵变。结果表明,P204/4PC协同萃取镍的反应呈正协同效应,镍萃合物的结构为NiA_2L_2,且协萃过程为吸热反应,焓变和熵变分别为29.52J/mol和-6.53kJ/(mol·K)。采用P204与4PC协萃体系可显著提高酸性硫酸盐溶液介质中镍的选择性萃取效果。
The mechanism of synergistic solvent extraction of nickel by P204 and 4 PC from acidic sulfate solution was studied with slope method,constant molecale method and saturation extraction method,respectively.The thermodynamic equilibrium constant of the synergistic reaction was determined,and its enthalpy and entropy changes were also obtained.The results show that the combination of P204 with 4 PC has a positive synergistic effect for nickel extraction,and the extracted complex is identified as NiA_2 L_2.The synergistic solvent extraction is an endothermic reaction with enthalpy change of 29.52 J/mol and entropy change of-6.53 kJ/(mol·K).The synergistic solvent extraction system of P204 and 4 PC can obviously promote the selective extraction of nickel from acidic sulfate solution.
The mechanism of synergistic solvent extraction of nickel by P204 and 4 PC from acidic sulfate solution was studied with slope method,constant molecale method and saturation extraction method,respectively.The thermodynamic equilibrium constant of the synergistic reaction was determined,and its enthalpy and entropy changes were also obtained.The results show that the combination of P204 with 4 PC has a positive synergistic effect for nickel extraction,and the extracted complex is identified as NiA_2 L_2.The synergistic solvent extraction is an endothermic reaction with enthalpy change of 29.52 J/mol and entropy change of-6.53 kJ/(mol·K).The synergistic solvent extraction system of P204 and 4 PC can obviously promote the selective extraction of nickel from acidic sulfate solution.
引文
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[20]VAN DE VOORDE I,PINOY L,COURTIJN E,et al.Equilibrium studies of nickel(Ⅱ),copper(Ⅱ),and cobalt(Ⅱ)extraction with Aloxime 800,D2EHPA and Cyanex reagents[J].Solvent Extraction and Ion Exchange,2006,24(6):893-914.
[2]刘大星.从红土矿中回收镍、钴技术的进展[J].有色金属(冶炼部分),2002(3):6-12.
[3]SHEN Y F,XUE W Y,NIU W Y.Recovery of Co(Ⅱ)and Ni(Ⅱ)from hydrochloric acid solution of alloy scrap[J].Transactions of Nonferrous Metals Society of China,2008,18(5):1262-1268.
[4]肖超,肖连生.钴、镍萃取分离原理与方法[J].湿法冶金,2010,29(4):225-228.
[5]PRESTON J S.α-Substituted oxime extractants—Ⅱ:Extraction of Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ)and Fe(Ⅱ)by aliphaticα-hydroxyiminoketones andα-dioximes[J].Journal of Inorganic and Nuclear Chemistry,1975,37(5):1 235-1 242.
[6]FLETT D S,WEST D W.Extraction of metal ions by LIX 63/carboxylic acid mixtures[C]∥International Solvent Extraction Conference.Hague:Society of Chemical Industry,1971:214-223.
[7]PRESTON J S.Solvent extraction of base metals by mixtures of organophosphorus acids and non-chelating oximes[J].Hydrometallurgy,1983,10(2):187-204.
[8]REDDEN L D,GROVES R D.The extraction of nickel with aliphatic oximes[J].Separation Science and Technology,1993,28(1/3):201-225.
[9]PRESTON J S,PREEZA C D.Synergistic effects in the solvent extraction of some divalent metals by mixtures of Versatic 10acid and pyridinecarboxylate esters[J].Journal of Chemical Technology and Biotechnology,1994,61(2):159-165.
[10]PRESTON J S,PREEZ A C D.Solvent extraction of nickel from acidic solutions using synergistic mixtures containing pyridinecarboxylate esters.Part 1.Systems based on organophosphorus acids[J].Journal of Chemical Technology and Biotechnology,1996,66(1):86-94.
[11]PRESTON J S,PREEZ A C D.Separation on nickel and calcium by solvent extraction using mixtures of carboxylic acids and alkylpyridines[J].Hydrometallurgy,2000,58(3):239-250.
[12]PREEZ A C D,PRESTON J S.Separation of nickel and cobalt from calcium,magnesium and manganese by solvent extraction with synergistic mixtures of carboxylic acids[J].Journal of the South African Institute of Mining and Metallurgy,2004,104(6):333-338.
[13]CHENG C Y.Solvent extraction of nickel and cobalt with synergistic systems consisting of carboxylic acid and aliphatic hydroxyoxime[J].Hydrometallurgy,2006,84(1/2):109-117.
[14]HUTTON-ASHKENNY M,IBANA D,BARNARD K R.Reagent selection for recovery of nickel and cobalt from nitric acid nickellaterite leach solutions by solvent extraction[J].Minerals Engineering,2015,77:42-57.
[15]CHENG C Y,MARK D U,MICHAEL G D,et al.Recovery of nickel and cobalt from leach solutions of nickel lateritesusing a synergistic system consisting of Versatic 10and Acorga CLX 50[J].Minerals Engineering,2015,77:17-24.
[16]CHENG C Y,KEITH R B,ZHANG W S,et al.Recovery of nickel,cobalt,copper and zinc in sulphate and chloride solutions usingsynergistic solvent extraction[J].Chinese Journal of Chemical Engineering,2016,24(2):237-248.
[17]XU G X,WANG W Q,WU J,et al.Extraction chemistry of the nuclear fuel(1):Synergistic extraction with chelating andcomplexing extractants[J].Atomic Energy Science and Technology,1963,7:487-508.
[18]黄小卫,李建宁,张永奇,等.P204-P507在酸性硫酸盐溶液中对Nd3+和Sm3+的协同萃取[J].中国有色金属学报,2008,18(2):366-371.
[19]TAILI Z,BATRIC P.A pyridine-base chelating solvent extraction system for selective extraction of nickel and cobalt[J].Journal of Chemical Technology and Biotechnology,1994,61(2):159-165.
[20]VAN DE VOORDE I,PINOY L,COURTIJN E,et al.Equilibrium studies of nickel(Ⅱ),copper(Ⅱ),and cobalt(Ⅱ)extraction with Aloxime 800,D2EHPA and Cyanex reagents[J].Solvent Extraction and Ion Exchange,2006,24(6):893-914.