摘要
高硫铝土矿硫酸焙烧的浸出液中含有高浓度的铝,同时存在一定浓度的铁和钛。以生物质海藻为原料,用萃取剂二(2-乙基己基)磷酸(D2EHPA)经过简单浸渍,制备海藻酸钙微球吸附剂(CA-P204)用于去除高硫铝土矿浸出液中的钛。红外光谱和X射线光电子能谱表征证明,吸附机理为阳离子交换和螯合作用。柱实验结果表明:CA-P204可从含有Ti(Ⅳ)-Al(Ⅲ)-Fe(Ⅲ)的高硫铝土矿浸出液中去除钛,当pH=1.0时去除率可达95%,对Ti(Ⅳ)的最大吸附量为66.79 mg/g。3次连续的吸附-脱附实验证明,吸附剂CA-P204具有较好的可再生性。该方法具有操作简单、价格低廉、没有其他废物排放等优点,同时CA-P204是一个可用于从高硫铝土矿的浸出液中除钛,具有良好应用前景、高效和经济性的吸附剂。
In the leaching solution of high-sulfur bauxite roasted by sulfuric acid, a high concentration of aluminum presented along with titanium and iron. The present work was to remove Ti(IV) from the leach liquor by calcium alginate microsphere sorbent material(CA-P204) based on natural alginate impregnated with di-(2-ethylhexyl) phosphoric acid(D2EHPA) to purify leaching solution. Cation exchange and chelation make major contributions to the adsorption mechanism according to Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis. The results showed that Ti(Ⅳ) was successfully removed by the CA-P204 adsorbent from the Ti(Ⅳ)-Al(Ⅲ)-Fe(Ⅲ) ternary system with a dynamic column experiment. The removal rate of titanium was nearly 95% under optimal conditions and the maximum adsorption capacity was 66.79 mg/g at pH 1.0. Reusability of CA-P204 was evaluated over three consecutive adsorption/desorption cycles. The adsorption process was simple, low-cost, and had no waste discharge, suggesting that the CA-P204 was promising, efficient, and economical for removing Ti(Ⅳ) from high-sulfur bauxite leaching solution.
引文
[1]ZHU Zhao-wu,ZHANG Wen-sheng,CHENG Chu-yong.A literature review of titanium solvent extraction in chloride media[J].Hydrometallurgy,2011,105:304-313.
[2]MENG Fan-cheng,XUE Tian-yan,LIU Ya-hui,ZHANG Guo-zhi,QI Tao.Recovery of titanium from undissolved residue(tionite)in titanium oxide industry via NaOH hydrothermal conversion and H2SO4 leaching[J].Transactions of Nonferrous Metals Society of China,2016,26:1696-1705.
[3]GERASIMOVA L,MASLOVA M.Precipitation of titanium(IV)and iron(III)phosphates from sulfuric acid solutions[J].Russian Journal of Applied Chemistry,2003,76:1855-1857.
[4]KIRIYAMA T,HARAGUCHI M,KURODA R.Combined anion-exchange separation and spectrophotometric determination of traces of titanium in sea water[J].Fresenius Zeitschrift Für Analytische Chemie,1981,307:352-355.
[5]HAO Xiao-li,LU Li,LIANG Bin,LI Chun,WU Pan.Solvent extraction of titanium from the simulated ilmenite sulfuric acid leachate by trialkylphosphine oxide[J].Hydrometallurgy,2012,s113-114:185-191.
[6]BISWAS R K,KARMAKAR A K.Solvent extraction of Ti(IV)in the Ti(IV)-24SO-(H+,Na+)-Cyanex302-kerosene-5%(v/v)hexan-1-ol system[J].Hydrometallurgy,2013,1-10:134-135.
[7]ALLAL K M,HAUCHARD D,STAMBOULI M,PAREAU D,DURAND G.Solvent extraction of titanium by tributylphosphate,trioctylphosphine oxide and decanol from chloride media[J].Hydrometallurgy,1997,45:113-128.
[8]KATHRYN C S.Recovery of titanum from the leach liquors of titaniferous magnetites by solvent extraction:Part 1.Review of the literature and aqueous thermodynamics[J].Hydrometallurgy,1999,51:239-253.
[9]ISLAM M F,BISWAS R K.Solvent Extraction of Ti(IV),Fe(III)and Fe(II)from acidic sulphate medium with di-o-tolyl phosphori c-benzene-hexan-1-ol system:A separation and mechanism study[J].Hydrometallurgy,1985,13:365-376.
[10]SEYFI S,ABDI M.Extraction of titanium(IV)from acidic media by tri-n-butyl phosphate in kerosene[J].Minerals Engineering,2009,22:116-118.
[11]WANG Qi,JIANG Lin,NI Fan,WANG Tao.The separation and concentration of titanium(IV)from sulfuric acid solution with trioctylamine[J].Industrial&Engineering Chemistry Research,2012,51:3430-3435.
[12]TAICHI S,TAKATO N.The extraction of titanium(IV)and aluminium(III)from sulphuric acid solutions by di-(2-ethylhexyl)-phosphoric acid[J].Analytica Chimica Acta,1975,76:401-408.
[13]SILVA G C D,DWECK J,AFONSO J C.Liquid-liquid extraction(LLE)of iron and titanium by bis-(2-ethyl-hexyl)phosphoric acid(D2EHPA)[J].Minerals Engineering,2008,21:416-419.
[14]BISWAS R K,BEGUM D A.Solvent extraction of tetravalent titanium from chloride solution by di-2-ethylhexyl phosphoric acid in kerosene[J].Hydrometallurgy,1998,49:263-274.
[15]BISWAS R K,ZAMAN M R,ISLAM M N.Extraction of Ti O2+from 1M(Na+,H+)SO42-by D2EHPA[J].Hydrometallurgy,2002,63:159-169.
[16]PHALKE P N,SHERIKAR A V,DHADKE P M.Extraction of titanium(IV)from sulphate media with bis-2-ethyl hexyl phosphoric acid[J].Indian Journal of Chemistry Section A,1997,36:446-448.
[17]SINGH R K,DHADKE P M.Extraction and separation of titanium(IV)with D2EHPA and PC-88A from aqueous perchloric acid solutions[J].Journal of the Serbian Chemical Society,2002,67:507-521.
[18]SAJI J,REDDY M L P.Selective extraction and separation of titanium(IV)from multivalent metal chloride solutions using2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester[J].Separation Science&Technology,2003,38:427-441.
[19]YAN Ping,HE Man,CHEN Bei-bei,HU Bin.Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection[J].Spectrochimica Acta,Part B:Atomic Spectroscopy,2017,136:73-80.
[20]MENDOZA-REYES L G,GYVESS J D.Novel D2EHPA-polysiloxane-based sorbent for titanium(IV)extraction and separation[J].Journal of the Mexican Chemical Society,2011,55:72-78.
[21]BARMAN M K,SRIVASTAVA B,CHATTERJEE M,MANDAL B.Solid-phase extraction,separation and preconcentration of titanium(IV)with SSG-V10 from some other toxic cations:Amolecular interpretation supported by DFT[J].RSC Advances,2014,4:33923-33934.
[22]WU Dong-bei,SUN Yan-hong,WANG Qi-gang.Adsorption of lanthanum(III)from aqueous solution using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester-grafted magnetic silica nanocomposites[J].Journal of Hazardous Materials,2013,260:409-419.
[23]HUANG Yan-jun,WU Hai-ling,SHAO Tai-kang,ZHAO Xia,PENGHong,GONG Yue-fa,WAN Hui-hai.Enhanced copper adsorption by DTPA-chitosan/alginate composite beads:Mechanism and application in simulated electroplating wastewater[J].Chemical Engineering Journal,2018,339:322-333.
[24]VIJAYALAKSHMI K,MAHALAKSHMI B D,SRINIVASAN L,THANDAPANI G,SUDHA P N,VENKATESAN J,SUKUMARANA.Batch adsorption and desorption studies on the removal of lead(II)from aqueous solution using nanochitosan/sodium alginate/microcrystalline cellulose beads[J].International Journal of Biological Macromolecules,2017,104:1483-1494.
[25]GOKILA S,GOMATHI T,SUDHA P N,SUKUMARAN A.Removal of the heavy metal ion chromium(VI)using Chitosan and Alginate nanocomposites[J].International Journal of Biological Macromolecules,2017,104:1459-1468.
[26]MOHAMAD A F,ZOHREH M,ANI I.Mass transfer kinetics of Cd(II)ions adsorption by titania polyvinylalcohol-alginate beads from aqueous solution[J].Chemical Engineering Journal,2017,308:700-709.
[27]WANG Fu-chun,ZHAO Jun-mei,LI Wen-song,ZHOU Hua-cong,YANG Xing-fu,SUI Na,LIU Hui-zhou.Preparation of several alginate matrix gel beads and their adsorption properties towards rare earths(III)[J].Waste Biomass Valor,2013,4:665-674.
[28]XIONG Ying,XU Jia,SHAN Wei-jun,LOU Zhen-ning,FANGDa-wei,ZANG Shu-liang,HAN Guang-xi.A new approach for rhenium(VII)recovery by using modified brown algae Laminaria japonica adsorbent[J].Bioresource Technology,2013,127:464-472.
[29]LOU Zhen-ning,WANG Jing,JIN Xu-dong,WAN Li,WANG Yue,CHEN Hui,SHAN Wei-jun,XIONG Ying.Brown algae based new sorption material for fractional recovery of molybdenum and rhenium from wastewater[J].Chemical Engineering Journal,2015,273:231-239.
[30]BEUKENKAMP J,HERRINGTON K D.Ion-exchange investigation of the nature of titanium(IV)in sulfuric acid and perchloric acid[J].Journal of the American Chemical Society,1960,82:3025-3031.
[31]BAILLON F,PROVOST E,FURST W.Study of titanium(IV)speciation in sulphuric acid solutions by FT-Raman spectrometry[J].Journal of Molecular Liquids,2008,143:8-12.
[32]SHAN Wei-jun,FANG Da-wei,ZHAO Zhi-yi,YUE Shuang,LOUZhen-ning,XING Zhi-qiang,XIONG Ying.Application of orange peel for adsorption separation of molybdenum(VI)from Re-containing industrial effluent[J].Biomass Bioenergy,2012,37:289-297.