改性聚丙烯酸钠的合成及其对水中重金属离子Pb～（2+）、Zn～（2+）、Ni～（2+）的去除研究
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摘要
综述了聚丙烯酸钠的性质、用途及合成。将它用顺丁烯二酸酐加以改性，得到了改性的聚丙烯酸钠。用于无磷洗涤助剂，对水中Ca~(2+)、Mg~(2+)有良好的螯合(吸附)作用。同时，研究了它对废水中Pb~(2+)、Zn~(2+)、Ni~(2+)的螫合(吸附)性能。
经过试验，优化了合成改性聚丙烯酸钠的工艺条件：丙烯酸与顺丁烯二酸酐的摩尔比为4：1，引发剂占单体量的4％-6％，还原剂占单体量的5％-7％，反应温度80-85℃，反应时间为3小时，固含量设计为35％-40％，在此工艺条件下，得到浅黄色的透明液体，经过IR谱图分析，工艺条件设计合理。
将改性的聚丙烯酸钠用于对水中Ca~(2+)、Mg~(2+)的螯合，其最大吸附容量分别为425mgCaCO_3／g，360mgMgCO_3／g，其吸附性能优于未改性的聚丙烯酸钠367mgCaCO_3／g，302mgMgCO_3／g。
将改性聚丙烯酸钠用于对废水中Pb~(2+)、Zn~(2+)、Ni~(2+)的吸附，经过正交试验，确定了其对各种离子的最佳吸附条件。通过做每种配比聚合物对Pb~(2+)、Zn~(2+)、Ni~(2+)的等温吸附线，得到各种离子的最大吸附容量，分别为Pb~(2+)：922mg／g，Zn~(2+)：246 mg／g，Ni~(2+)：201.3 mg／g，据此可以得到最佳配比的改性聚丙烯酸钠。
由于改性聚丙烯酸钠良好的生物降解性，较高的软化点及较好的热稳定性，将它与废水中重金属离子去除的其它方法相结合，预计可以取得满意的效果。
The paper summarizes properties, uses, and synthesis of acrylic-acid sodium salt(AA-Na). By putting up maleic anhydride(MA) into
acrylic-acid--acrylic-acid copolymer(MA-CO-AA) is synthesized. This synthetic
material could be applied in such respects as Phosphate-free,which owns excellent chelate ability and dispersibility to Ca2+, Mg2+. In addition, the chelate ability to Pb2+, Zn2+, Ni2+ in waste water is also studied in this paper.
Through experience, the technological conditions of synthesising MA-CO-AA are optimized. The ratio of AA and MA is 4 to 1, initiation agent takes up 4-6%, reducer does 5-7%, reaction temperature 80-90C, reaction time 3 h.,and designed solid content of 35-40%. Under such technological conditions, the light yellow transparent liquid can be obtained. The analysis with infrared spectroscopy(IR) proves the rational conditions provided.
When MA-CO-AA is applied to chelate Ca2+ Mg2+ in water, its biggest chelate ability is 425mgCaCO3 /g 360mgMgCO3/g. Which appears much better than that of AA, 367 mgCaCO3/g, 302 mgMgCO3/g.
When MA-CO-AA is applied to chelate Pb2+, Zn2+, Ni2+ in waste water, the best chelate conditions of various ions can be defined through orthogonal experiments . By means of isothermal adsorption chelate of each proportional MA-CO-AA to Pb2+, Zn2+, Ni2+ , the biggest chelate ability of each ions can be obtained, Pb2+: 922mg/g, Zn2+: 264mg/g, Ni2+: 201.3mg/g. Hence the best proportional of MA-CO-AA can be obtained.
With good biological degradation,higher softening nature and better heating stability. It is estimated that much more satisfactory results can be caused if the MA-CO-AA can be used in other methods to remove heavy metals- Pb2+, Zn2+, Ni2+ in waste water.
经过试验，优化了合成改性聚丙烯酸钠的工艺条件：丙烯酸与顺丁烯二酸酐的摩尔比为4：1，引发剂占单体量的4％-6％，还原剂占单体量的5％-7％，反应温度80-85℃，反应时间为3小时，固含量设计为35％-40％，在此工艺条件下，得到浅黄色的透明液体，经过IR谱图分析，工艺条件设计合理。
将改性的聚丙烯酸钠用于对水中Ca~(2+)、Mg~(2+)的螯合，其最大吸附容量分别为425mgCaCO_3／g，360mgMgCO_3／g，其吸附性能优于未改性的聚丙烯酸钠367mgCaCO_3／g，302mgMgCO_3／g。
将改性聚丙烯酸钠用于对废水中Pb~(2+)、Zn~(2+)、Ni~(2+)的吸附，经过正交试验，确定了其对各种离子的最佳吸附条件。通过做每种配比聚合物对Pb~(2+)、Zn~(2+)、Ni~(2+)的等温吸附线，得到各种离子的最大吸附容量，分别为Pb~(2+)：922mg／g，Zn~(2+)：246 mg／g，Ni~(2+)：201.3 mg／g，据此可以得到最佳配比的改性聚丙烯酸钠。
由于改性聚丙烯酸钠良好的生物降解性，较高的软化点及较好的热稳定性，将它与废水中重金属离子去除的其它方法相结合，预计可以取得满意的效果。
The paper summarizes properties, uses, and synthesis of acrylic-acid sodium salt(AA-Na). By putting up maleic anhydride(MA) into
acrylic-acid--acrylic-acid copolymer(MA-CO-AA) is synthesized. This synthetic
material could be applied in such respects as Phosphate-free,which owns excellent chelate ability and dispersibility to Ca2+, Mg2+. In addition, the chelate ability to Pb2+, Zn2+, Ni2+ in waste water is also studied in this paper.
Through experience, the technological conditions of synthesising MA-CO-AA are optimized. The ratio of AA and MA is 4 to 1, initiation agent takes up 4-6%, reducer does 5-7%, reaction temperature 80-90C, reaction time 3 h.,and designed solid content of 35-40%. Under such technological conditions, the light yellow transparent liquid can be obtained. The analysis with infrared spectroscopy(IR) proves the rational conditions provided.
When MA-CO-AA is applied to chelate Ca2+ Mg2+ in water, its biggest chelate ability is 425mgCaCO3 /g 360mgMgCO3/g. Which appears much better than that of AA, 367 mgCaCO3/g, 302 mgMgCO3/g.
When MA-CO-AA is applied to chelate Pb2+, Zn2+, Ni2+ in waste water, the best chelate conditions of various ions can be defined through orthogonal experiments . By means of isothermal adsorption chelate of each proportional MA-CO-AA to Pb2+, Zn2+, Ni2+ , the biggest chelate ability of each ions can be obtained, Pb2+: 922mg/g, Zn2+: 264mg/g, Ni2+: 201.3mg/g. Hence the best proportional of MA-CO-AA can be obtained.
With good biological degradation,higher softening nature and better heating stability. It is estimated that much more satisfactory results can be caused if the MA-CO-AA can be used in other methods to remove heavy metals- Pb2+, Zn2+, Ni2+ in waste water.
引文
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[3] 周爱林．国内外超吸水性树脂现状与展望[J]．化学时刊，1998．12(10)：7-10
[4] 公开特许．昭-50 15581．
[5] 公开特许．昭50 14388．
[6] 公开特许．昭-53 87309．
[7] 公开特许．昭-53 51287
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[10] 公开特许．昭-54，21336．
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[38] Shukla S R, Jawed M. Column studies on metal ion removal by dyed
celluloic materials[J]. J. Appl. Polymer Sci. , 1992, 44(5): 903-910.
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[42] Kandori K, Schechter R S. Selection of surfactant for micellar-enhanced ultrafiltration[J]. Sep. Sci. and Tech. , 1990, 25(1-2): 83-108.
[43] 崔正刚，朱立强．表面活性剂在废水处理中的应用[A]．97日用化工学术研讨会论文集[C]．无锡，1997．497-507．
[44] Huang Yi-chu, Batchelor B. Crossflow surfactant-based ultrafiltration of heavy metals from waste streams[J]. Separation Science and Technology, 1994, 29(15): 1979-1998.
[45] Ahmadi S, seng L K, actchelor B. icellar-enhanced ultrafiltration of heavy metal using lecithin[J]. Sep. Sci. and Tech. , 1994, 29(18): 2435-2450.
[46] Kato T, Takeuchi H, Seimiya T. Change in size and composition of mixed micellars with concentration of anionic/cationic surfactant solutions[J]. J. Colloid and Interface Sci. , 1990, 140(1): 253-257.
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[2] 路建美，朱秀林，万悠纯．反向聚合分散剂的合成及性能[J]．应用化学，1999，16(1)：87-91．
[3] 周爱林．国内外超吸水性树脂现状与展望[J]．化学时刊，1998．12(10)：7-10
[4] 公开特许．昭-50 15581．
[5] 公开特许．昭50 14388．
[6] 公开特许．昭-53 87309．
[7] 公开特许．昭-53 51287
[8] 大森英三．聚丙烯酸及其共聚物(日)．1昭晃堂，1973．
[9] EP. 97063, EP. 129329.
[10] 公开特许．昭-54，21336．
[11] 钟以诚，吴冯波，彭小平．涂料工业．1990，(1)：1-7．
[12] 清华同方化工公司精细化学品部．SP-Ⅱ日用化工高分子助洗剂技术资料．
[13] 沈阳新奇日化公司．PAA高分子有机助洗剂产品资料．
[14] Woff Winth．刘有才译．洗涤剂配方用的有机聚合物．日用化学工业，1988，6：11．
[15] Crutch-field M. M. Organic. builder: an revien of world-wale efforts to find oganic replanements for detergent phosphates. J Am OL chem. Sci, 1978, 55(1)58.
[16] 黄瑞光．21世纪电渡废水治理的发展趋势[J]．电镀与精饰，2000，(3)：1-2．
[17] 国家环境保护总局．环境保护[R]．1999年中国环境状况公报，2000，(7)．
[18] 化科技健康收藏网Q．谈谈铅的危害．
[19] 境保护辞典．化学工业部化工设计公司编．
[20] 树桂主编．环境化学[M]．北京：高等教育出版社．
[21] Perales-Perez, Oscar Tohji, Kazuyuki Vmetsu, etal. Theory and practice of the removal of heavy-metal ions by their precipitation as ferrite-type compounds from aqueous solution at ambit temperature[J]. Metallurgical Review of MMIJ, 2001, 17(2): 137-139.
[22] Bolto B A, Pawlowski. waster water Treatment by Ion Exchange[M]. London: E and F. N. Spon Ltd, 1987: 263-279.
[23] EI EI-Shafet, Cox M, Pichugin A, et al. Application of a Carbon sorbet for the removal of cadmium and other heavy metal ions from aqueous solution[J]. Journal of chemical Technology and Biotechnology, 2002, 77(4): 429-436.
[24] 谈辉明，杨启文．重金属废水处理技术的现状与展望[J]．环境科学与技术，1997，2(11)：35-36．
[25] 废弃物研究财团编．特别管理废弃物Ⅲ特别管理一般废弃物处理．东京：化学工业日报社，1993：103．
[26] Butter T J, Evison L M, Hancock I C, etal. The removal and recovery of cadmiumform dilute aqueons solutions by biosorption and electrolysist at laboratory scale[J] Water Reseach, 1998, 32(2): 400.
[27] Masri M S, Reuter F W, Friedman M. Binding of metal cations by natural substance[J]. J. Appl. Polymer Sci, 1974, 18(3): 400.
[28] Srivastava S K, Singh A k, Sharma A. Studies on the uptake of Lead and Zinc by ligin obtained from black liquor-a paper industry waster materica[J]. Environ. Technol, 1994, 15(4): 353-
361.
[29] Peniche-Covas C, Alvarez LW, Arguelles-Monal W. The adsorption of mercuric ions by chitosan[J]. J. Appl. Polymer Sci, 1992, 46(7): 1147-1150.
[30] Rorrer G L, Hsien T Y, Way J D. Synthesis of porous-magnetic chitosan beads for removal of cadmium from wastewater[J]. Ind. End. Chem. Res, 1993, 32(9): 2170-2178.
[31] Roy D, Geenlaw P N, Shanc B S. Adsorption of heavy metals by green algac and ground rice hulls[J]. J. Environ. Sci. Health. A, 1993, 28(1): 37-50.
[32] Niu H, Xu X S, Wang J H. Removal of lead from aqueous solutions by penicillium biomass[J]. Biotechnol. Bioeng. , 1993, 42: 785-787.
[33] Leppert D. Heavy metal sorption with clinoptilolite zeolite: alternatives for treating contaminated soil and water[J]. Mining Eng. , 1990, 42 (6) : 604-608.
[34] Khan S A, Riaz-ui-Rehman A, Khan M A. Adsorption of chromium(Ⅲ), chromium(Ⅳ)and silver(Ⅰ)on bentonite[J]. Waste Manage. , 1995, 15(4) : 271-282.
[35] Yadava K P, Tyagi B S, Singh Y N. Effect of temperature on the removal of lead(Ⅱ)by adsorption on China clay and wollastonic[J]. J. Chen. Tech. Biotechnol. , 1991, 51(1): 41-60.
[36] Sharma D C, Forster C F. Removal of hexavalent chromium using sphagnum moss peat[J]. Water Research, 1993, 27(7): 1201-1208.
[37] Sharma D C, Forster C F. Continuous adsorption and desorption of chromium ions by sphagnum moss peat[J]. Process Biochemistry, 1995, 30(4): 293-298.
[38] Shukla S R, Jawed M. Column studies on metal ion removal by dyed
celluloic materials[J]. J. Appl. Polymer Sci. , 1992, 44(5): 903-910.
[39] Freeland GN, Hoskiason R M, Mayfield R J. Adsorption of heavy metal aqueous solutions by polyethylenimine-modified wool fibers[J]. Envir. Sci. Technol. , 1974, 8(10): 943-944.
[40] Markels John H, Lynn Scott, Radke Clayton J. Cross-flow ultrafiltration of micellar surfactant solutions[J]. Separations, 1995, 41(9): 2058-2066.
[41] Wasan D T, Ginn M E, Shah D O. Surfactant science series: Vol. 28 surfactants in chemical/process engineering[M]. New York: Marcel Dekker, 1998, 152-362.
[42] Kandori K, Schechter R S. Selection of surfactant for micellar-enhanced ultrafiltration[J]. Sep. Sci. and Tech. , 1990, 25(1-2): 83-108.
[43] 崔正刚，朱立强．表面活性剂在废水处理中的应用[A]．97日用化工学术研讨会论文集[C]．无锡，1997．497-507．
[44] Huang Yi-chu, Batchelor B. Crossflow surfactant-based ultrafiltration of heavy metals from waste streams[J]. Separation Science and Technology, 1994, 29(15): 1979-1998.
[45] Ahmadi S, seng L K, actchelor B. icellar-enhanced ultrafiltration of heavy metal using lecithin[J]. Sep. Sci. and Tech. , 1994, 29(18): 2435-2450.
[46] Kato T, Takeuchi H, Seimiya T. Change in size and composition of mixed micellars with concentration of anionic/cationic surfactant solutions[J]. J. Colloid and Interface Sci. , 1990, 140(1): 253-257.
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