“抑制-萃取”法从含铁酸溶液中选择性提钒

doi:10.11944/j.issn.1000-0518.2020.07.190356

摘要/Abstract

摘要： 酸法浸出石煤提钒因具有环保、金属收率高的特点而备受关注,但同时进入母液的铁(高含量的Fe³⁺)严重影响了钒的富集和产品生产。对此,本文提出一种基于“抑制-萃取”效应的钒/铁分离混合萃取体系(P507(2-乙基己基磷酸-单2-乙基己基酯)+ N235(三辛/癸烷基叔胺)+磺化煤油),并详细研究了各因素对钒铁分离和钒富集的影响规律。结果表明,P507是钒铁萃取的主体,N235不具萃Fe³⁺能力,是产生抑制铁萃取的关键因素,其浓度越高铁萃取率越低;对于酸度较高(pH≤0.4)的原料液钒/铁的分离效果仍较好,这表明了该“抑制-萃取”混合萃取体系对高酸度浸出液钒/铁分离的适用性。采用氨水从负载有机相中反萃取钒铁,当氨水浓度为6 mol/L时钒的反萃率99%以上,25 ℃,V(有机相)∶V(水相)=2∶1时的反萃液中钒质量浓度14.73 g/L,铁质量浓度小于0.022 g/L,m(V)/m(Fe)=669.5。该“抑制-萃取”法分离钒/铁操作简单、经济高效,极具工业化前景。

关键词: 溶剂萃取, 抑萃效应, 钒铁分离, 赝反萃, 钒酸铵

Abstract: The extraction of vanadium from stone coal by acid leaching has attracted much attention because of its characteristic of environment friendly and high metal yield. However, the process is seriously affected by concentrated Fe³⁺ in the vanadium mother solution. In this paper, a system (P507(2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester)+N235(Trioctyl/tridecylaklylamines)+sulfonated kerosene) based on the “depressing extraction-extraction” effect was proposed to separate V from Fe. The influence of various factors on the separation and enrichment of V over Fe was studied in details. Results show that P507 is responsible for extraction of Fe and V, while N235 suppresses the extraction of Fe³⁺. The higher the concentration of N235, the less Fe³⁺ is extracted. The separation efficiency of V over Fe is high in the raw solution at pH≤0.4, demonstrating the applicability of the designed “depressing extraction-extraction” mixed extractants toward concentrated acid leaching solution. When 6 mol/L ammonia is used, more than 99% of vanadium can be stripped. Under the condition of 25 ℃, V(organic phase)∶V(aqueous phase)=2∶1 the stripping pregnant solution is obtained, in which the mass concentration of vanadium is 14.73 g/L, the mass concentration of iron is less than 0.022 g/L, and the mass ratio of vanadium to iron is more than 669.5. It is evident that the “depressing extraction-extraction” is a method of easy operation, being economic and efficient, and great industrial prospect.

Key words: solvent extraction, depressing extraction, separation of vanadium over iron, pseudo-stripping, ammonium vanadate

阳征斐, 陈友顺, 张豪杰, 刘志雄, 颜文斌, 李飞. “抑制-萃取”法从含铁酸溶液中选择性提钒[J]. 应用化学, 2020, 37(7): 803-809.

YANG Zhengfei, CHEN Youshun, ZHANG Haojie, LIU Zhixiong, YAN Wenbin, LI Fei. Selective Extraction of Vanadium from the Fe-Bearing Acidic Solution by Method of “Depressing Extraction-Extraction”[J]. Chinese Journal of Applied Chemistry, 2020, 37(7): 803-809.

参考文献

[1] ZOU Liqing. The Late Vanadium Ore[J]. Land Resour Her,2011,8(1):38-39(in Chinese).
邹礼卿. 迟来的钒矿[J]. 国土资源导刊,2011,8(1):38-39.
[2] WANG Fei,ZHANG Yimin,LIU Tao,et al. Solvent Extraction Behavior of Vanadium from Direct Acidic Leaching and Roasting Acidic Leaching[J]. Nonferrous Met,2014,(5):30-33(in Chinese).
王非,张一敏,刘涛,等. 直接酸浸与焙烧酸浸钒萃取行为的研究[J]. 有色金属(冶炼部分),2014,(5):30-33.
[3] XUE Nannan. Research on Process Mechanism of the Intensified Leaching of Vanadium from Shale by Particle Cracking with Stress under Oxygen Pressure in Acidic System[D]. Wuhan:Wuhan University of Science and Technology,2017(in Chinese).
薛楠楠. 页岩氧压酸性体系下颗粒应力裂解强化钒溶出过程的机理机制研究[D]. 武汉:武汉科技大学,2017.
[4] LI Dao,LIU Tao,ZHANG Yimin,et al. Leaching Behaviour of V, Fe, Al during Vanadium Extraction from Stone Coal by Sufuric Acid Leaching[J]. Nonferrous Met,2016,(6):50-53(in Chinese).
李道,刘涛,张一敏,等. 石煤酸浸提钒过程中V、Fe、Al的浸出行为研究[J]. 有色金属(冶炼部分),2016,(6):50-53.
[5] Hu P C,Zhang Y M,Liu T,et al. Source Separation of Vanadium over Iron from Roasted Vanadium Bearing Shale During Acid Leaching via Ferric Fluoride Surface Coating[J]. J Clean Prod,2018,181:399-407.
[6] Hong N T,Lee N,Man S. Solvent Extraction of Vanadium(V) from Sulfate Solutions Using LIX63 and PC88A[J]. J Ind Eng Chem,2015,31(25):118-123.
[7] Zhang Y,Zhang T A,Dreisinger D. Chelating Extraction of Vanadium(V) from Low pH Sulfuric Acid Solution by Mextral 973H[J]. Sep Purif Technol,2017,190(8):123-135.
[8] FENG Xueru,LÜ Guozhi,ZHANG Ting′an,et al. Study on Separation Performance of V(IV) and Fe(III) by P204 in Sulfuric Acid Extraction System[J]. Iron Steel Vanadium Titanium,2017,38(2):23-30(in Chinese).
冯雪茹,吕国志,张廷安,等. P204萃取硫酸体系中V(Ⅳ)、Fe(Ⅲ)的分离性能研究[J]. 钢铁钒钛,2017,38(2):23-30.
[9] ZHANG Jian,ZHU Zhaowu,LEI Ze,et al. Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties[J]. Chem J Chinese Univ,2019,40(4):740-746(in Chinese).
张健,朱兆武,雷泽,等. P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能[J]. 高等学校化学学报,2019,40(4):740-746.
[10] XIONG Pu,ZHANG Yimin,HUANG Jing,et al. Separation of Vanadium and Iron in Stone Coal Acidic Leaching Solution with P507-N235 Mixed Extractant[J]. Nonferrous Met,2016,(10):36-39(in Chinese).
熊璞,张一敏,黄晶,等. P507-N235混合萃取剂分离石煤酸浸液中钒与铁[J]. 有色金属(冶炼部分),2016,(10):36-39.
[11] Liu F,Ning P G,Cao H B,et al. Measurement and Modeling for Vanadium Extraction from the (NaVO₃+H₂SO₄+H₂O) System by Primary Amine N1923[J]. J Chem Thermodyn,2015,80:13-21.
[12] Yang X,Zhang Y M,Bao S X,et al. Separation and Recovery of Vanadium from a Sulfuric-Acid Leaching Solution of Stone Coal by Solvent Extraction Using Trialkylamine[J]. Sep Purif Technol,2016,164:49-55.
[13] SHANG Jiguang,SUN Guoxin. Extraction of Fe(Ⅲ) from Aluminum Chloride[J]. Chinese J Appl Chem,2018,35(1):75-81(in Chinese).
尚吉光,孙国新. 氯化铝中萃取铁工艺[J]. 应用化学,2018,35(1):75-81.
[14] YU Shuqiu. Effects of TRPO in the Organic Phase on the Extraction of Fe(Ⅲ) from the Sulfate Solution by HDEHP[J]. Eng Chem Metall,1987,8(4):1-6(in Chinese).
于淑秋. HDEHP-Fe(Ⅲ)-H₂SO₄体系中TRPO作用机理的讨论[J]. 化工冶金,1987,8(4):1-6.
[15] YUAN Chengye. Structure and Properties of Organophosphorus Ligands[J]. Chinese J Org Chem,1979,(1):45-56(in Chinese).
袁承业. 有机磷配位体的结构与性能[J]. 有机化学,1979,(1):45-56.
[16] Ye G H,Hu Y B,Tong X,et al. Extraction of Vanadium from Direct Acid Leaching Solution of Clay Vanadium Ore Using Solvent Extraction with N235[J]. Hydrometallurgy,2018,177:27-33.
[17] Zhang Y,Zhang T A,Lv G Z,et al. Synergistic Extraction of Vanadium(IV) in Sulfuric Acid Media Using a Mixture of D2EHPA and EHEHPA[J]. Hydrometallurgy,2016,166:87-93.
[18] Zhang W G,Zhang T A,Lv G Z,et al. Thermodynamic Study on the V(V)-P(V)-H₂O System in Acidic Leaching Solution of Vanadium-Bearing Converter Slag[J]. Sep Purif Technol,2019,218:164-172.