应用杯芳烃衍生物回收废水中重金属及稀贵金属离子的研究
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摘要
实验主要研究了对叔丁基杯[4]芳烃及其衍生物的合成，并利用合成的对叔丁基杯[4]芳烃醚类衍生物和氯磺化衍生物对汞、银、铬离子进行萃取能力、萃取选择性及反萃取能力的研究，探讨了实验中离子测定之间的相互干扰和三废的回收处理并循环利用。通过分析核磁共振谱图及红外光谱图，发现合成的对叔丁基杯[4]芳烃结构与文献报道基本符合。杯芳烃吡啶衍生物(衍生物1)、苄氯衍生物(衍生物2)、氯磺酸衍生物(衍生物3)都达到合成的预定结构。汞离子萃取实验中，考察了不同pH值、不同汞离子浓度和不同相比对萃取效果的影响；银离子萃取实验中，主要考察了pH值对萃取的影响以及不同温度对纯溶剂萃取银离子的影响；铬离子萃取实验中，主要考察了pH值、不同铬离子浓度对萃取效果的影响。结果表明，衍生物2对汞离子的萃取效果最好，衍生物1对银离子的萃取效果最好，衍生物1和衍生物2对铬离子基本没有萃取效果，只有衍生物3对铬离子有一定的萃取效果，同时还探讨使用各种试剂从有机相中反萃取回收汞、铬离子的可行性。并且研究了三种离子相互间对测定的影响以及萃取剂对三种离子的萃取选择性。对合成杯芳烃及衍生物1、2和3进行成本核算，对每回收1mg汞、银、铬离子所需药剂费也进行成本核算。
Calixarene is a kind of respecting host macrocyclic compound, followed cyclodextrin and crown ether, and has strong ability of selective extraction of metal ions. P-tert-butylcalix[4]arene and its derivatives are synthesized in the experiment. Selective extraction for silver, mercury and chromium ions is also studied in this paper. Waste liquid produced in the experiment are recovered. According to the analysis of NMR and FTIR, the structure of p-tert-butylcalix[4]arene synthesized in the experiment is mainly coincide to the literature. The structures of derivative 1,2 and 3 are also determined by FTIR. In the mercury ion extraction experiment, the different conditions of pH, mercury ion concentration and phase ratio, which affect on the extraction efficiency are examined. In the silver ion extraction experiment, the effect of solution's pH is mainly examined. In the chromium ion extraction experiment, the different conditions of pH and chromium ion concentration, which affect on the extraction efficiency ar
e examined. The results indicate: the derivative 2 has extraction abilities for mercury ion; the derivative 1 has extraction abilities for silver ion; the derivative 3 has extraction abilities for chromium. These results show that the derivative 1, 2 and 3 have selective extraction abilities for mercury, silver and chromium ions. At the end of this paper, the anti extraction abilities of some reagents for mercury and chromium ion are discussed. And calculate the cost of synthesis derivative 1 ,2,3 and the recovering silver, mercury and chromium ions .
Calixarene is a kind of respecting host macrocyclic compound, followed cyclodextrin and crown ether, and has strong ability of selective extraction of metal ions. P-tert-butylcalix[4]arene and its derivatives are synthesized in the experiment. Selective extraction for silver, mercury and chromium ions is also studied in this paper. Waste liquid produced in the experiment are recovered. According to the analysis of NMR and FTIR, the structure of p-tert-butylcalix[4]arene synthesized in the experiment is mainly coincide to the literature. The structures of derivative 1,2 and 3 are also determined by FTIR. In the mercury ion extraction experiment, the different conditions of pH, mercury ion concentration and phase ratio, which affect on the extraction efficiency are examined. In the silver ion extraction experiment, the effect of solution's pH is mainly examined. In the chromium ion extraction experiment, the different conditions of pH and chromium ion concentration, which affect on the extraction efficiency ar
e examined. The results indicate: the derivative 2 has extraction abilities for mercury ion; the derivative 1 has extraction abilities for silver ion; the derivative 3 has extraction abilities for chromium. These results show that the derivative 1, 2 and 3 have selective extraction abilities for mercury, silver and chromium ions. At the end of this paper, the anti extraction abilities of some reagents for mercury and chromium ion are discussed. And calculate the cost of synthesis derivative 1 ,2,3 and the recovering silver, mercury and chromium ions .
引文
[1] Chen Langxing, Zeng xianshun, Ju Hongfang. Calixarene derivatives as the sensory molecules for silver ion-selective electrode. Microchemcal journal, 2000, 65(2): 129-136
[2] Chen L, He X, Zhao B. Calixarene derivative as the neutral carrier in silver ion-selective electrode and liquid membrane transport. Analytica chimca acta, 2000, 417(1):51-56
[3] Keisuke Ohto, Emi Murakami, Takaaki Shinohara. Selective extraction of silver(Ⅰ) over palladium(Ⅱ) with ketonic derivative of calixarene from highly concentrated nitric acid. Analytica Acta, 1997, 314:275-283
[4] Pappalardo S, Giunta L, Foti M. unctionlization of calix[4] arenes by alkylation with 2-(chloromethyl)pyridine hydrochloride. J. Org. Chem. 1992, 57(9): 2611-2617
[5] 梅素容，何季平，李建森，陈震华，卢雪然．杯[8] 芳烃的红外光谱和拉曼光谱研究．武汉大学学报(自然科学版)，1998，44(2)：159—162
[6] C. D. Gutsche. Calixarenes, mongraphs in supermolcular Chemistry. The Royal Society of Chemistry: Cambridge, 1989(2): 387—392
[7] Gutsche C D, Lqbal M, Stewart D. Synthesis procedures for p-tertbutylcalix [4] arene. Org. chem., 1986, 51:742—745
[8] Balram D, Chen S I, Gutsche C O. Studies of the formation of calixarenes via condensation of p-alkylphenols and formaldehyde. Makromol Chem, 1987(188):921—928
[9] A. Zinke, R. Kretz, E. Leggewie, K. Hossinger, Monatsh. Chemistry, 83,1213(1952)
[10] 林琳，吴采樱．杯芳烃衍生物在分析化学中的应用．分析化学，1997，15(7)：850—856
[11] 胡昌明，钟振林，卢雪然．杯芳冠醚研究进展．化学通报，1997(4)：18—25
[12] 陆国元，依布拉音·买买提，玉素甫江·尼亚孜．对位取代酚亚甲基桥三聚物的合成．有机化学，1995，15(6)：638-641
[13] 郑炎松．杯芳烃的超分子催化性质．化学世界．1997(5)：234—237
[14] 胡昌明，申存唏．杯芳烃．化学通报，1993(2)：17-24
[15] 郑晓宇，孙梵．表面化学中的杯芳烃．精细化工，2001(11)：22—25
[16] 丁时超，施宪法，朱志良，陆国弟，徐迪民，陈与德．杯芳烃的配位化学(Ⅱ)——对叔丁基杯芳烃对过渡金属的萃取．铀矿治，1994，13(3)：180-183
[17] 朱志良，吕宏林，陆国弟，施宪法，陈与德．杯芳烃的配位化学(Ⅷ)——几种杯芳烃的固体配合物的合成和表征．同济大学学报，1997．25(6)：718—722
[18] 陆国弟，曹锡康，朱志良，乔俊莲．杯芳烃的配位化学(Ⅸ)——杯芳烃萃取金属的机理．同济大学学报，1997，25(6)：723—725
[19] 陆国弟，曹锡康，刘艳生，施宪法．杯芳烃的配位化学(Ⅺ)——4种杯[4] 芳烃萃取铁(Ⅲ)的研究．同济大学学报，1999，27(3)：375—377
[20] 施宪法，丁时超，杨宇翔，徐迪民，陈与德．杯芳烃的配位化学研究(Ⅰ)——对叔丁基杯芳烃对铜的萃取．无机化学学报，1993，9(4)：423—425
[21] 1 Wainwright K P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216
[22] Wainwright K P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216—218
[23] Ohoto K, Murakami E, Shinohara T, Shiratsche K. The Synthesis, Characterization, and Properties of the Calixarenes from p—tert-butylpHenol. Chem. Lett., 1996(2): 173—175
[24] Kondo Y, Yamamoto Z. Recovery of Silver from Thiourea Seperation Science and Technology, 1998(3): 141—149
[25] Perrin K, Harris S. Calixarenes, A versatile class of macrocylic compounds. Vicens J. and Bohmer V. Dordrencht: Kluwer Academic Publishers, 1991(3): 235—238
[26] 王腾凤，杨世柱．杯芳烃催化剂在有相反应中的应用．化学试剂，2000，22(5)：274—278
[27] Komiyama M. Water—soluble calixarene as the first man—made catalysts for regioselective cleavage of ribonulleoside 2,3—cylic phosephate. Chem. Lett., 1991(5): 937—942
[28] 余晓冬，吴采樱．杯芳烃的超分子化学．化学通报，1998(11)：13—16
[29] 施宪法，汪宇平，刘艳生，蒋忠良，陶凌，孙红保．高等学校化学学报，1999，20：193—195
[30] Wieser Jeunesse C, Matt D, Harrowfield J M. A new type inopHore made from a rigid Calixarene analog. C. R. Acad. Sci, 1998(2): 479—482
[31] Komiyama M. Host-guest-type acid catalysts derivearened from calixarene. Chem. Lett., 1985(7): 1033—1038
[32] Yordanov A T, Falana O. M. Calixarene—Based molecular capsule. Inorg. Chem., 1995 34: 5084—5090
[33] Wainwright K. P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216—218
[34] 洪学传，冯严青，李熙凤，郭兵，周立出．杯芳烃——新型有机材料抗氧剂．合成材料老化与应用．1999(2)：19—22
[35] Pappalardo S, Giunta L, Foti M. Functionlization of calix[4] arenes by alkylation with
2-(chloromethyl) pyridine hydrochloride. Org. Chem., 1992, 57(9): 2611—2617
[36] Agrawal Y K, Sanyal Mallika. Seperation and determination of uranium()with calixarene hydrxamic acid. Journal of radioanalytical and nuclear chemistry, 1995, 198(2):349-358
[37] 林慧芳，林默颖，张安有等．对叔丁皋杯[4] 芳烃乙陵对铀(Ⅵ)的萃取研究．核技术，1999，22(1)：1/5-5/5
[38] Sebastiano Pappalardo, Luigi Giunta, Mario Foti, George Ferguson, John F. Gallagher, Branko Kaitner. Functionalization of Calix[4] arenas by Alkylation with 2-(Chlormethyl)pyridine Hydrochloride. J. Org. Chem, 1992, 57(9):2611-2624
[39] 余应新．汤又文．杨世柱．杯[4] 芳烃醚衍生物的合成研究(Ⅰ)．华南师范大学学报，2002．3：59-62
[40] Chen L, He X, Zhao B. Calixarene derivative as the neutral carrier in silver ion-selective electrode and liquid membrane transport. Analytica chimca acta, 2000, 417(1):51-56
[41] 中国化工学会石油化工学会组织编写，魏义德主编．有机化工原料大全(第一卷)．化学工业出版社，1989．
[42] B．H．库兹涅佐夫等编著．化学试剂与制剂手册．化学工业出版社，1959．
[43] 国标GB7469-87．中华人民共和国国家标准．水质总贡的测定 钾-过硫酸钾消解法双硫腙分光光度法，国家环境保护局 1987-03-14批准
[44] 国标GB7469-87．中华人民共和国国家标准．水质银的测定火焰原子吸收分光光度法，国家环境保护局1989-12-25批准
[45] 国标GB7467-87．中华人民共和国国家标准．水质六价铬的测定二苯碳酰二肼分光光度法国家环境保护局1987-03-14批准
[2] Chen L, He X, Zhao B. Calixarene derivative as the neutral carrier in silver ion-selective electrode and liquid membrane transport. Analytica chimca acta, 2000, 417(1):51-56
[3] Keisuke Ohto, Emi Murakami, Takaaki Shinohara. Selective extraction of silver(Ⅰ) over palladium(Ⅱ) with ketonic derivative of calixarene from highly concentrated nitric acid. Analytica Acta, 1997, 314:275-283
[4] Pappalardo S, Giunta L, Foti M. unctionlization of calix[4] arenes by alkylation with 2-(chloromethyl)pyridine hydrochloride. J. Org. Chem. 1992, 57(9): 2611-2617
[5] 梅素容，何季平，李建森，陈震华，卢雪然．杯[8] 芳烃的红外光谱和拉曼光谱研究．武汉大学学报(自然科学版)，1998，44(2)：159—162
[6] C. D. Gutsche. Calixarenes, mongraphs in supermolcular Chemistry. The Royal Society of Chemistry: Cambridge, 1989(2): 387—392
[7] Gutsche C D, Lqbal M, Stewart D. Synthesis procedures for p-tertbutylcalix [4] arene. Org. chem., 1986, 51:742—745
[8] Balram D, Chen S I, Gutsche C O. Studies of the formation of calixarenes via condensation of p-alkylphenols and formaldehyde. Makromol Chem, 1987(188):921—928
[9] A. Zinke, R. Kretz, E. Leggewie, K. Hossinger, Monatsh. Chemistry, 83,1213(1952)
[10] 林琳，吴采樱．杯芳烃衍生物在分析化学中的应用．分析化学，1997，15(7)：850—856
[11] 胡昌明，钟振林，卢雪然．杯芳冠醚研究进展．化学通报，1997(4)：18—25
[12] 陆国元，依布拉音·买买提，玉素甫江·尼亚孜．对位取代酚亚甲基桥三聚物的合成．有机化学，1995，15(6)：638-641
[13] 郑炎松．杯芳烃的超分子催化性质．化学世界．1997(5)：234—237
[14] 胡昌明，申存唏．杯芳烃．化学通报，1993(2)：17-24
[15] 郑晓宇，孙梵．表面化学中的杯芳烃．精细化工，2001(11)：22—25
[16] 丁时超，施宪法，朱志良，陆国弟，徐迪民，陈与德．杯芳烃的配位化学(Ⅱ)——对叔丁基杯芳烃对过渡金属的萃取．铀矿治，1994，13(3)：180-183
[17] 朱志良，吕宏林，陆国弟，施宪法，陈与德．杯芳烃的配位化学(Ⅷ)——几种杯芳烃的固体配合物的合成和表征．同济大学学报，1997．25(6)：718—722
[18] 陆国弟，曹锡康，朱志良，乔俊莲．杯芳烃的配位化学(Ⅸ)——杯芳烃萃取金属的机理．同济大学学报，1997，25(6)：723—725
[19] 陆国弟，曹锡康，刘艳生，施宪法．杯芳烃的配位化学(Ⅺ)——4种杯[4] 芳烃萃取铁(Ⅲ)的研究．同济大学学报，1999，27(3)：375—377
[20] 施宪法，丁时超，杨宇翔，徐迪民，陈与德．杯芳烃的配位化学研究(Ⅰ)——对叔丁基杯芳烃对铜的萃取．无机化学学报，1993，9(4)：423—425
[21] 1 Wainwright K P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216
[22] Wainwright K P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216—218
[23] Ohoto K, Murakami E, Shinohara T, Shiratsche K. The Synthesis, Characterization, and Properties of the Calixarenes from p—tert-butylpHenol. Chem. Lett., 1996(2): 173—175
[24] Kondo Y, Yamamoto Z. Recovery of Silver from Thiourea Seperation Science and Technology, 1998(3): 141—149
[25] Perrin K, Harris S. Calixarenes, A versatile class of macrocylic compounds. Vicens J. and Bohmer V. Dordrencht: Kluwer Academic Publishers, 1991(3): 235—238
[26] 王腾凤，杨世柱．杯芳烃催化剂在有相反应中的应用．化学试剂，2000，22(5)：274—278
[27] Komiyama M. Water—soluble calixarene as the first man—made catalysts for regioselective cleavage of ribonulleoside 2,3—cylic phosephate. Chem. Lett., 1991(5): 937—942
[28] 余晓冬，吴采樱．杯芳烃的超分子化学．化学通报，1998(11)：13—16
[29] 施宪法，汪宇平，刘艳生，蒋忠良，陶凌，孙红保．高等学校化学学报，1999，20：193—195
[30] Wieser Jeunesse C, Matt D, Harrowfield J M. A new type inopHore made from a rigid Calixarene analog. C. R. Acad. Sci, 1998(2): 479—482
[31] Komiyama M. Host-guest-type acid catalysts derivearened from calixarene. Chem. Lett., 1985(7): 1033—1038
[32] Yordanov A T, Falana O. M. Calixarene—Based molecular capsule. Inorg. Chem., 1995 34: 5084—5090
[33] Wainwright K. P. Studies on the coulometric determination and recovery of rhodium and silver. Bulletin of electrochemistry, 1997(5): 216—218
[34] 洪学传，冯严青，李熙凤，郭兵，周立出．杯芳烃——新型有机材料抗氧剂．合成材料老化与应用．1999(2)：19—22
[35] Pappalardo S, Giunta L, Foti M. Functionlization of calix[4] arenes by alkylation with
2-(chloromethyl) pyridine hydrochloride. Org. Chem., 1992, 57(9): 2611—2617
[36] Agrawal Y K, Sanyal Mallika. Seperation and determination of uranium()with calixarene hydrxamic acid. Journal of radioanalytical and nuclear chemistry, 1995, 198(2):349-358
[37] 林慧芳，林默颖，张安有等．对叔丁皋杯[4] 芳烃乙陵对铀(Ⅵ)的萃取研究．核技术，1999，22(1)：1/5-5/5
[38] Sebastiano Pappalardo, Luigi Giunta, Mario Foti, George Ferguson, John F. Gallagher, Branko Kaitner. Functionalization of Calix[4] arenas by Alkylation with 2-(Chlormethyl)pyridine Hydrochloride. J. Org. Chem, 1992, 57(9):2611-2624
[39] 余应新．汤又文．杨世柱．杯[4] 芳烃醚衍生物的合成研究(Ⅰ)．华南师范大学学报，2002．3：59-62
[40] Chen L, He X, Zhao B. Calixarene derivative as the neutral carrier in silver ion-selective electrode and liquid membrane transport. Analytica chimca acta, 2000, 417(1):51-56
[41] 中国化工学会石油化工学会组织编写，魏义德主编．有机化工原料大全(第一卷)．化学工业出版社，1989．
[42] B．H．库兹涅佐夫等编著．化学试剂与制剂手册．化学工业出版社，1959．
[43] 国标GB7469-87．中华人民共和国国家标准．水质总贡的测定 钾-过硫酸钾消解法双硫腙分光光度法，国家环境保护局 1987-03-14批准
[44] 国标GB7469-87．中华人民共和国国家标准．水质银的测定火焰原子吸收分光光度法，国家环境保护局1989-12-25批准
[45] 国标GB7467-87．中华人民共和国国家标准．水质六价铬的测定二苯碳酰二肼分光光度法国家环境保护局1987-03-14批准
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