多核羟基络铝固体柱撑剂和高效絮凝剂的合成及表征
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摘要
本文以合成多核羟基络铝盐酸盐用作“干法”制备柱撑粘土的固体柱撑剂和高效絮凝剂为目标，进行了大量合成方法和条件试验，采用Al+稀HCl法、Al+AlCl_3溶液法、AlCl_3溶液树脂吸附法和补水蒸馏AlCl_3溶液法，在国内首次合成出了一种纯度较高的13核羟基络铝盐酸盐。对比了各种合成方法的优缺点，通过化学分析、XRD、TG-DTA及Al-Ferron逐时络合比色分析，对其化学组成和结构进行了表征。结果表明其化学式为：5AlCl_3·8Al(OH)_3·37.5H_2O，该物质易溶于水和无水甲醇，几乎不溶于无水乙醇。合成条件容易控制，合成效率明显提高。
合成产物的絮凝效果实验表明，除浊效果比AlCl_3、Al_2(SO_4)_3及PAC(聚合氯化铝)更好，可望成为一种新型高效的絮凝剂。
用其作为固体柱撑剂，采用“干法”插入蒙脱石层间的初步试验表明，它是一种好的固体柱撑剂。
合成目标产物的过程中还发现，AlCl_3·6H_2O和CuSO_4·5H_2O随结晶环境的改变，可以结晶出新的变种。
用补水蒸馏法和树脂吸附法调节AlCl_3溶液的pH值，得到了AlCl_3·6H_2O的四种新的结晶变种，采用XRD、TG-DTA对它们进行了表征。其中一种培养了单晶，用四圆衍射仪测定了晶体和分子结构。结果表明，分子对称性下降，所属的空间点群由R3c变为R3c,为AlCl_3·6H_2O结晶形态家族增添了新成员，丰富了AlCl_3·6H_2O结晶化学的内容。
用树脂吸附法改变CuSO_4溶液的pH值，得到了CuSO_4·5H_2O的一种新的结晶变种。XRD、TG-DTA、单晶四圆衍射等结果表明：此种结晶在晶胞参数、晶体密度和单位晶胞中的分子数等方面明显不同于文献报道，拓展了CuSO_4·5H_2O的结晶化学。
Aiming at the synthesis of polynuclear hydroxyl complex Al hydrochlorate-An agent of Solid pillarization for pillared interlayed clays prepared by dried methods and high efficiency flocculation by different means and in different conditions, amounts of experiments have been carried out.A high purification water well dissolved 13-nuclear hydroxyl complex Al hydrochlorate has been synthesized first by means of Al+HCl(aq),Al+AlCl3(solution),resin adsorption and distillation Aids solution accompanied by makeup water in China.Its chemical constituents and structure were identified by methods of chemical analysis,XRD,TG-DTA and Al-Ferron timed complex colorimetric , at the same time,the comparision of different methods has been carried out.The product,with chemical formula of 5AlCl3-8Al (OH) 3-37.5H2O showed by results,can be well dissolved in water and methanol but hardly in ethanol.Featured by well controlled conditions,all the four means show great improvement in efficiency
A new type high efficiency flocculation agent is hopefully to be exploited supported by better removal turbidity than AlCl3,Al2(SO4)3 and PAC.
A efficient solid pillarization can also be exploited supported by the results of experiments done on its insertion into Montmorillonite layers by dried means.
Meanwhile,new types crystal of AlCl3- 6H20 and CuSO4-5H2O have been obtained from the different crystallization conditions.
Four new types of crystal structures of AlCl3-6H2O have been produced through adjusting the solution pH by means of resin adsorption and distillation companied by makeup water,their structures have all been identified by XRD,and TG-DTA,signal crystal have been cultivated for one of the four kinds crystal followed by its structure identification by single-crystal X-ray
diffraction, as the results showed, all the molecular structures have changed from R3c to R3c
which are enriching the crystallogical of AlCU- 6H2O greatly.
A new type of crystal structure of CuSO4-5H2O has been resulted through adjusting the pH of CuSO4-5H2O solution .As the XRD and TG-DTA and single-crystal X-ray diffraction indicated,there are great difference in crystal cell parameters,crystal density and number of molecular in per crystal cell between references showed.
合成产物的絮凝效果实验表明，除浊效果比AlCl_3、Al_2(SO_4)_3及PAC(聚合氯化铝)更好，可望成为一种新型高效的絮凝剂。
用其作为固体柱撑剂，采用“干法”插入蒙脱石层间的初步试验表明，它是一种好的固体柱撑剂。
合成目标产物的过程中还发现，AlCl_3·6H_2O和CuSO_4·5H_2O随结晶环境的改变，可以结晶出新的变种。
用补水蒸馏法和树脂吸附法调节AlCl_3溶液的pH值，得到了AlCl_3·6H_2O的四种新的结晶变种，采用XRD、TG-DTA对它们进行了表征。其中一种培养了单晶，用四圆衍射仪测定了晶体和分子结构。结果表明，分子对称性下降，所属的空间点群由R3c变为R3c,为AlCl_3·6H_2O结晶形态家族增添了新成员，丰富了AlCl_3·6H_2O结晶化学的内容。
用树脂吸附法改变CuSO_4溶液的pH值，得到了CuSO_4·5H_2O的一种新的结晶变种。XRD、TG-DTA、单晶四圆衍射等结果表明：此种结晶在晶胞参数、晶体密度和单位晶胞中的分子数等方面明显不同于文献报道，拓展了CuSO_4·5H_2O的结晶化学。
Aiming at the synthesis of polynuclear hydroxyl complex Al hydrochlorate-An agent of Solid pillarization for pillared interlayed clays prepared by dried methods and high efficiency flocculation by different means and in different conditions, amounts of experiments have been carried out.A high purification water well dissolved 13-nuclear hydroxyl complex Al hydrochlorate has been synthesized first by means of Al+HCl(aq),Al+AlCl3(solution),resin adsorption and distillation Aids solution accompanied by makeup water in China.Its chemical constituents and structure were identified by methods of chemical analysis,XRD,TG-DTA and Al-Ferron timed complex colorimetric , at the same time,the comparision of different methods has been carried out.The product,with chemical formula of 5AlCl3-8Al (OH) 3-37.5H2O showed by results,can be well dissolved in water and methanol but hardly in ethanol.Featured by well controlled conditions,all the four means show great improvement in efficiency
A new type high efficiency flocculation agent is hopefully to be exploited supported by better removal turbidity than AlCl3,Al2(SO4)3 and PAC.
A efficient solid pillarization can also be exploited supported by the results of experiments done on its insertion into Montmorillonite layers by dried means.
Meanwhile,new types crystal of AlCl3- 6H20 and CuSO4-5H2O have been obtained from the different crystallization conditions.
Four new types of crystal structures of AlCl3-6H2O have been produced through adjusting the solution pH by means of resin adsorption and distillation companied by makeup water,their structures have all been identified by XRD,and TG-DTA,signal crystal have been cultivated for one of the four kinds crystal followed by its structure identification by single-crystal X-ray
diffraction, as the results showed, all the molecular structures have changed from R3c to R3c
which are enriching the crystallogical of AlCU- 6H2O greatly.
A new type of crystal structure of CuSO4-5H2O has been resulted through adjusting the pH of CuSO4-5H2O solution .As the XRD and TG-DTA and single-crystal X-ray diffraction indicated,there are great difference in crystal cell parameters,crystal density and number of molecular in per crystal cell between references showed.
引文
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[6] A. Benito, DelRiego et al., Toluence methylation on All3-and GAA112-pillared clay catalysts, Applied Catalysis: A, 1999: 180
[7] Matthes Winnie, Madsen Fritz and Kahr Guenther, Sorption of heavy-metal cations by A1 and Zr-hydroxyintercalated and pillared bentonite, Clays and Clay Minerals, 1999,47(5)
[8] Robert Mokaye, Willam Jones et al., Preparation of alumina-pillared acid- activated clays and their use as chlorophyll absorbents, J. Mater. Chem., 1993, 3(4)
[9] D.T. Koramanis, X.A. Aslanoglou, An aluminum pillared montmorillonite with fast uptake of strontium and cesium and cesium from aqueous solutions, Clays and Clay Minerals, 1997, (45)
[10] L. Storarda, M. Lenarda, et al. Microporous and Mesoporous Materials 1998, 20:317-331
[11] Lahav N. et al., Clays and Clay Miner., 1978, 26(2):107
[12] T.J. Pinnavaia, M. Tzou, S.D. Landau, J. Am. Chem. Soc. 1985, 107:4783-4785
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[14] 吴平霄，张惠芬，郭九皋等，羟基铝柱撑蒙脱石Keggin结构的稳定性，矿物学报，1999，19(2)，132-138
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[16] 赵东源，杨亚书，郭燮贤等，铁铝复合柱撑粘士的制备、柱结构和稳定性(Ⅰ)物理化学学报，1993，9(2)，193-199
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[18] S. Yamanaka, G. W. Brindley, Am. Miner., 1979, 64: 830
[19] E.M. Farfan-Torres, E. Sham and P. Grange, Catalysis Today. 1992, 15:515-526
[20] G. J. J. Bradley, Catalysis today, 1988, 2: 233-241
[21] S. Yamanaka, G. W. Brindley, High Surface Area Solids Obtained by Reaction of Montmorillonite with Zirconyl Chloride, Clays Clay Miner, 1979, 27: 119-124
[22] D. E.W. Vaughan, Pillared clays—a historical perspective, Catal. Today, 1998, 2:187-198
[23] M. R. Sunkou, S. Mendioroz, M.I. Guijarro, A thermal study of Zr-pillared montmorillonite, Thermochimica Acta, 1988, 323: 145-157
[24] Shaobin Wang, H.Y. Zhu, G.Q. (Max) Lu, Preparation, Characterization, and Catalytic Properties of Clay-Based Nickel Catalysts for Methane Reforming, J. of Colloid and Interface Sci., 1998, 201: 128-134
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