氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能

doi:10.16085/j.issn.1000-6613.2016.12.034

化工进展 ›› 2016, Vol. 35 ›› Issue (12): 3976-3984.DOI: 10.16085/j.issn.1000-6613.2016.12.034

氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能

陈少锋, 邢华斌, 杨启炜, 张治国, 苏宝根, 杨亦文, 任其龙, 鲍宗必

浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室, 浙江杭州 310027

收稿日期:2016-04-05 修回日期:2016-05-19 出版日期:2016-12-05 发布日期:2016-12-05
通讯作者: 鲍宗必,副教授,博士生导师,主要从事吸附材料设计制备及应用。E-mail:baozb@zju.edu.cn。
作者简介:陈少锋(1990-),男,硕士研究生。E-mail:chenshaofeng90@126.com。
基金资助:
浙江省自然科学基金（Y13B060002）及国家自然科学基金（21376205、U1407134）项目。

Preparation of amino propanediol functionalized boron-chelating resins and application in adsorption of boric acid

CHEN Shaofeng, XING Huabin, YANG Qiwei, ZHANG Zhiguo, SU Baogen, YANG Yiwen, REN Qilong, BAO Zongbi

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2016-04-05 Revised:2016-05-19 Online:2016-12-05 Published:2016-12-05

摘要/Abstract

摘要： 分别用3-氨基-1，2-丙二醇（3-APD）和2-氨基-1，3-丙二醇（2-APD）对多孔氯甲基聚苯乙烯树脂（CMPS）进行修饰，制备得到含邻、间位二羟基官能团的硼螯合树脂：PS-3-APD和PS-2-APD。用傅里叶红外光谱仪（FTIR）、元素分析仪（EA）、压汞仪（MIP）和激光粒度仪（LPS）对材料进行表征，确认功能单体成功接枝于氯球上。对两种树脂进行了静态提硼性能研究，分别考察了原料液pH、初始硼酸浓度、外来金属离子对硼酸吸附量的影响，当溶液pH为9.15～9.20时，两种树脂对硼酸吸附量最大；溶液中Na⁺、Mg²⁺、Ca²⁺的存在会一定程度削弱树脂对硼酸吸附性能。吸附动力学表明其吸附速率较快，且均满足准二级动力学模型。与Freundlich相比，吸附等温线更符合Langmuir模型，拟合得到的理论最大吸附量分别为0.730mmol/g和0.868mmol/g。本文对未来新型硼螯合树脂的开发及工业化应用提供参考和指导。

关键词: 吸附, 分离, 吸附剂, 硼酸, 3-氨基-1,2-丙二醇, 2-氨基-1,3-丙二醇

Abstract: Two boron-chelating resins containing aliphatic 1,2-diols and 1,3-diols were prepared from porous chloromethyl polystyrene(CMPS)functionalized by 3-amino-1,2-propanediol(3-APD) and 2-amino-1,3-propanediol(2-APD),respectively. The newly synthesized resins were characterized by FTIR,EA,MIP and LPS. The FTIR spectra showed that the functional monomers were successfully grafted onto the polymer matrix. The effect of pH of boron solution,initial boric acid concentration,and foreign ions on the boron adsorption on the synthesized sorbents were studied in batch model. The maximum boron capacities of PS-3-APD and PS-2-APD could be obtained when the pH of boron solution was in the range of 9.15-9.20. Besides,the presence of foreign ions such as Na⁺,Mg²⁺,Ca²⁺ would deteriorate the adsorption performance due to the competitive adsorption. Kinetic studies showed that both resins adsorbed boric acid from aqueous solutions very quickly and their kinetic curves could be fitted well with pseudo second order model. Boron adsorption isotherms on both resins were better correlated with Langmuir model than with Freundlich model. The calculated maximum boron capacities of PS-3-APD and PS-2-APD by Langmuir equation were 0.730mmol/g and 0.868mmol/g,respectively. This study may offer helpful guidance in the development of novel high-performance boron adsorbents.

Key words: adsorption, separation, adsorbents, boric acid, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol

中图分类号:

陈少锋, 邢华斌, 杨启炜, 张治国, 苏宝根, 杨亦文, 任其龙, 鲍宗必. 氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能[J]. 化工进展, 2016, 35(12): 3976-3984.

CHEN Shaofeng, XING Huabin, YANG Qiwei, ZHANG Zhiguo, SU Baogen, YANG Yiwen, REN Qilong, BAO Zongbi. Preparation of amino propanediol functionalized boron-chelating resins and application in adsorption of boric acid[J]. Chemical Industry and Engineering Progree, 2016, 35(12): 3976-3984.

参考文献

[1] 郑学家.硼化合物的生产与应用[M].北京:化学工业出版社,2008:1-2.
[2] NASEF M M,NALLAPPAN M,UJANG Z.Polymer-based chelating adsorbents for the selective removal of boron from water and wastewater:a review[J].Reactive and Functional Polymers,2014,85:54-68.
[3] HILAL N,KIM G J,SOMERFIELD C.Boron removal from saline water:a comprehensive review[J].Desalination,2011,273(1):23-35.
[4] EZECHI E H,ISA M H,KUTTY S R,et al.Boron recovery,application and economic significance:a review[C].National Postgraduate Conference,New York:IEEE,2011:1-6.
[5] 唐尧.中国硼矿资源勘查现状及前景分析[J].国土资源情报,2015,2015(3):24-28.
[6] 唐尧,陈春琳,熊先孝,等.世界硼资源分布及开发利用现状分析[J].现代化工,2013,33(10):1-4.
[7] ITAKURA T,SASAI R,ITOH H.Precipitation recovery of boron from wastewater by hydrothermal mineralization[J].Water Research,2005,39(12):2543-2548.
[8] REMY P,MUHR H,PLASARI E,et al.Removal of boron from wastewater by precipitation of a sparingly soluble salt[J].Environmental Progress,2005,24(1):105-110.
[9] GEFFEN N,SEMIAT R,EISEN M S,et al.Boron removal from water by complexation to polyol compounds[J].Journal of Membrane Science,2006,286(1):45-51.
[10] XU Y,JIANG J Q.Technologies for boron removal[J].Industrial&Engineering Chemistry Research,2008,47(1):16-24.
[11] KABAY N,GÜLER E,BRYJAK M.Boron in seawater and methods for its separation-a review[J].Desalination,2010,261(3):212-217.
[12] DE LA FUENTE M M,CAMACHO E M.Boron removal by means of adsorption with magnesium oxide[J].Separation and Purification Technology,2006,48(1):36-44.
[13] FERREIRA O P,DE MORAES S G,DURAN N,et al.Evaluation of boron removal from water by hydrotalcite-like compounds[J].Chemosphere,2006,62(1):80-88.
[14] JACOB C.Seawater desalination:boron removal by ion exchange technology[J].Desalination,2007,205(1):47-52.
[15] LYMAN W R,PREUSS J A F.Boron-adsorbing resin and process for removing boron compounds from fluids:US2813838[P].1957-11-19.
[16] KUNIN R,PREUSS A F.Characterization of a boron-specific ion exchange resin[J].Industrial&Engineering Chemistry Product Research and Development,1964,3(4):304-306.
[17] WANG L,QI T,GAO Z,et al.Synthesis of N-methylglucamine modified macroporous poly (GMA-co-TRIM)and its performance as a boron sorbent[J].Reactive and Functional Polymers,2007,67(3):202-209.
[18] SAMATYA S,KABAY N,TUNCEL A.A hydrophilic matrix for boron isolation:monodisperse porous poly (glycidyl-methacrylate-co-ethylene dimethacrylate) particles carrying diol functionality[J].Reactive and Functional Polymers,2010,70(8):555-562.
[19] SAMATYA S,KABAY N,TUNCEL A.Monodisperse-porous N-methyl-D-glucamine functionalized poly (vinylbenzyl chloride-co-divinylbenzene)beads as boron selective sorbent[J].Journal of Applied Polymer Science,2012,126(4):1475-1483.
[20] IKEDA K,UMENO D,SAITO K,et al.Removal of boron using nylon-based chelating fibers[J].Industrial&Engineering Chemistry Research,2011,50(9):5727-5732.
[21] WANG J,WANG T,LI L,et al.Functionalization of polyacrylonitrile nanofiber using ATRP method for boric acid removal from aqueous solution[J].Journal of Water Process Engineering,2014,3:98-104.
[22] INUKAI Y,TANAKA Y,MATSUDA T,et al.Removal of boron (Ⅲ) by N-methylglucamine-type cellulose derivatives with higher adsorption rate[J].Analytica Chimica Acta,2004,511(2):261-265.
[23] SABARUDIN A,OSHITA K,OSHIMA M,et al.Synthesis of cross-linked chitosan possessing N-methyl-d-glucamine moiety(CCTS-NMDG)for adsorption/concentration of boron in water samples and its accurate measurement by ICP-MS and ICP-AES[J].Talanta,2005,66(1):136-144.
[24] WEI Y T,ZHENG Y M,CHEN J P.Design and fabrication of an innovative and environmental friendly adsorbent for boron removal[J].Water Research,2011,45(6):2297-2305.
[25] TURAL B.Separation and preconcentration of boron with a glucamine modified novel magnetic sorbent[J].Clean-Soil,Air,Water,2010,38(4):321-327.
[26] XU L,LIU Y,HU H,et al.Synthesis,characterization and application of a novel silica based adsorbent for boron removal[J].Desalination,2012,294:1-7.
[27] AMOR T B,LEBEAU B,TLILI M,et al.Synthesis,characterization and application of glucamine-modified mesoporous silica type SBA-15 for the removal of boron from natural water[J].Desalination,2014,351:82-87.
[28] SENKAL B F,BICAK N.Polymer supported iminodipropylene glycol functions for removal of boron[J].Reactive and Functional Polymers,2003,55(1):27-33.
[29] INCE A,KARAGOZ B,Bicak N.Solid tethered imino-bis-propanediol and quaternary amine functional copolymer brushes for rapid extraction of trace boron[J].Desalination,2013,310:60-66.
[30] YAVUZ E,GURSEL Y,SENKAL B F.Modification of poly (glycidyl methacrylate) grafted onto crosslinked PVC with iminopropylene glycol group and use for removing boron from water[J].Desalination,2013,310:145-150.
[31] MISHRA H,YU C,CHEN D P,et al.Branched polymeric media:boron-chelating resins from hyperbranched polyethylenimine[J].Environmental Science&Technology,2012,46(16):8998-9004.
[32] GAZI M,BICAK N.Selective boron extraction by polymer supported 2-hydroxylethylamino propylene glycol functions[J].Reactive and Functional Polymers,2007,67(10):936-942.
[33] GAZI M,GALLI G,BICAK N.The rapid boron uptake by multi-hydroxyl functional hairy polymers[J].Separation and Purification Technology,2008,62(2):484-488.
[34] MISHRA H,YU C,CHEN D P,et al.Branched polymeric media:boron-chelating resins from hyperbranched polyethylenimine[J].Environmental Science&Technology,2012,46(16):8998-9004.
[35] 钱国强,林雪.缩聚型邻苯二酚树脂的合成及对硼酸的吸附性能[J].离子交换与吸附,1995,11(5):389-394.
[36] WANG B,LIN H,GUO X,et al.Boron removal using chelating resins with pyrocatechol functional groups[J].Desalination,2014,347:138-143.
[37] YU S,XUE H,FAN Y,et al.Synthesis,characterization of salicylic-HCHO polymeric resin and its evaluation as a boron adsorbent[J].Chemical Engineering Journal,2013,219:327-334.
[38] MORISADA S,RIN T,OGATA T,et al.Adsorption removal of boron in aqueous solutions by amine-modified tannin gel[J].Water Research,2011,45(13):4028-4034.
[39] ERDEM P,BURSALI E A,YURDAKOC M.Preparation and characterization of tannic acid resin:study of boron adsorption[J].Environmental Progress&Sustainable Energy,2013,32(4):1036-1044.
[40] 李朝华,苏庆平,唐志坚,等.我国盐湖卤水提硼的研究进展[J].盐业与化工,2009,38(2):44-47.
[41] BICAK N,ÖZBELGE HÖ,YILMAZ L,et al.Crosslinked polymer gels for boron extraction derived from N-glucidol-N-methyl-2-hydroxypropyl methacrylate[J].Macromo lecularChemistry and Physics,2000,201(5):577-584.
[42] SIMONNOT M O,CASTEL C,NICOLAI M,et al.Boron removal from drinking water with a boron selective resin:is the treatment really selective?[J].Water Research,2000,34(1):109-116.

氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能

Preparation of amino propanediol functionalized boron-chelating resins and application in adsorption of boric acid

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