含Ti蒙脱石纳米复合材料基质研制
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摘要
膨润土是当今应用范围较广和经济价值较高的粘土矿物之一，被称为“千种用途土”，广泛地应用于冶金，化工，农业，建筑，环保等多种领域。随着膨润土使用范围日益扩大，加上深层次的应用的需求，对膨润土纯度以及各项物性性能的要求也愈来愈高。
本文选择三种不同产地的钙基膨润土(A样，B样和C样)为研究对象，通过加入合适的分散剂，并控制适宜的工艺条件，成功的制备出了性能优良的蒙脱石基质材料，为下一步含Ti蒙脱石纳米复合材料的研制打下了良好的基础。
试验首先对三种膨润土试样进行了分散提纯处理。重点考察了蒙脱石在分散提纯过程中分散剂的种类和用量、矿浆浓度和搅拌时间对提纯效果的影响。结果表明，三种膨润土矿样的分散提纯过程中的最佳试验条件分别为：A样膨润土以焦磷酸钠为分散剂，用量为4％，矿浆浓度5％，搅拌时间15min；B样膨润土以六偏磷酸钠作为分散剂，用量为4％，矿浆浓度5％，搅拌时间15min；C样膨润土以焦磷酸钠作为分散剂，用量为5％，矿样粒度5～40目，矿浆浓度5％，搅拌时间15min。在最佳条件下，三种精土的膨胀容分别可以达到84ml／g、90ml／g和93ml／g，相应的蒙脱石含量为90％，92％和95％，经过综合测试，确定C样精土更适合作为下一步含Ti蒙脱石纳米复合材料研制的基质材料。
在试验和分析的基础上，本文对蒙脱石的分散提纯机理进行了初步探讨，认为在水介质中添加特定的分散剂，控制合适的工艺条件，可同时完成分散提纯及钠化改型的双重目的。
通过蒙脱石的分散提纯研究从而制备出优良的蒙脱石基质材料是膨润土深层次应用的基础，这对于充分利用我国膨润土资源，提高膨润土矿物的附加值，实现矿物加工与其他学科的交叉发展具有重要的理论和现实意义。
Bentonite, which is called "thousand uses clay", is used as an important mineral raw material hi many fields including metallurgy, chemical industrial, agriculture, construction, environment protection et al. As the use scope is increasing and the need for high technology application, the requirement to a more purify and good quality of bentonite is put forward.
In this paper, three kinds of bentonites from different district (A, B and C) are used as study object. By joining the appropriate dispersant and controlling feasible progress condition, we can get the good quality montmorillonite matrix material. It has a favorable basis for the research and preparation of Ti-montmorillonite nanometer composite.
The three samples are dealt with the purification and dispersion. The effects of various factors including grind fineness, sorts of dispersant, slurry concentration, stirring time on the preparation of refined montmorillonite are emphatically investigated. The results show that sodium pyrophosphate is good regent for A, especially in dispersant dosage of 4%, slurry concentration of 5%, stirring time of 15min; sodium hexametaphospnate is good regent for B, especially in dispersant dosage of 4%, slurry concentration of 5%, stirring time of 15min and sodium pyrophosphate is good regent for C, especially in dispersant dosage of 4%, slurry concentration of 5%, grind fineness of 5~40mesh, stirring time of 15min. In each optimal testing condition, the three samples will have good qualities after separated. The A sample can up to expand volume 85ml/g, montmorillonite content 90%; the B sample can up to expand volume 90ml/g, montmorillonite content 92% and the C sample can up to expand volume 93ml/g, montmorillonite content 95%. After synthetical testing, the C sample is ascertained as the matrix material for the next research and preparation of Ti-montmorillonite nanemeter composite.
On the basis of experiments and analysis, the purification and dispersion mechanism is discussed in an elementary way. In the condition of joining appropriate dispersant and controlling feasible progress, the purpose of purification and modification can get in the same time.
Preparing good quality montmorillonite matrix material via studying of purification and dispersion is the basis of high technology application. It will take good advantage of our bentonite resource, increase mineral value, and enhance interdisciplinary development especially in mineral processing and other science. Thus, the study is of important significance.
本文选择三种不同产地的钙基膨润土(A样，B样和C样)为研究对象，通过加入合适的分散剂，并控制适宜的工艺条件，成功的制备出了性能优良的蒙脱石基质材料，为下一步含Ti蒙脱石纳米复合材料的研制打下了良好的基础。
试验首先对三种膨润土试样进行了分散提纯处理。重点考察了蒙脱石在分散提纯过程中分散剂的种类和用量、矿浆浓度和搅拌时间对提纯效果的影响。结果表明，三种膨润土矿样的分散提纯过程中的最佳试验条件分别为：A样膨润土以焦磷酸钠为分散剂，用量为4％，矿浆浓度5％，搅拌时间15min；B样膨润土以六偏磷酸钠作为分散剂，用量为4％，矿浆浓度5％，搅拌时间15min；C样膨润土以焦磷酸钠作为分散剂，用量为5％，矿样粒度5～40目，矿浆浓度5％，搅拌时间15min。在最佳条件下，三种精土的膨胀容分别可以达到84ml／g、90ml／g和93ml／g，相应的蒙脱石含量为90％，92％和95％，经过综合测试，确定C样精土更适合作为下一步含Ti蒙脱石纳米复合材料研制的基质材料。
在试验和分析的基础上，本文对蒙脱石的分散提纯机理进行了初步探讨，认为在水介质中添加特定的分散剂，控制合适的工艺条件，可同时完成分散提纯及钠化改型的双重目的。
通过蒙脱石的分散提纯研究从而制备出优良的蒙脱石基质材料是膨润土深层次应用的基础，这对于充分利用我国膨润土资源，提高膨润土矿物的附加值，实现矿物加工与其他学科的交叉发展具有重要的理论和现实意义。
Bentonite, which is called "thousand uses clay", is used as an important mineral raw material hi many fields including metallurgy, chemical industrial, agriculture, construction, environment protection et al. As the use scope is increasing and the need for high technology application, the requirement to a more purify and good quality of bentonite is put forward.
In this paper, three kinds of bentonites from different district (A, B and C) are used as study object. By joining the appropriate dispersant and controlling feasible progress condition, we can get the good quality montmorillonite matrix material. It has a favorable basis for the research and preparation of Ti-montmorillonite nanometer composite.
The three samples are dealt with the purification and dispersion. The effects of various factors including grind fineness, sorts of dispersant, slurry concentration, stirring time on the preparation of refined montmorillonite are emphatically investigated. The results show that sodium pyrophosphate is good regent for A, especially in dispersant dosage of 4%, slurry concentration of 5%, stirring time of 15min; sodium hexametaphospnate is good regent for B, especially in dispersant dosage of 4%, slurry concentration of 5%, stirring time of 15min and sodium pyrophosphate is good regent for C, especially in dispersant dosage of 4%, slurry concentration of 5%, grind fineness of 5~40mesh, stirring time of 15min. In each optimal testing condition, the three samples will have good qualities after separated. The A sample can up to expand volume 85ml/g, montmorillonite content 90%; the B sample can up to expand volume 90ml/g, montmorillonite content 92% and the C sample can up to expand volume 93ml/g, montmorillonite content 95%. After synthetical testing, the C sample is ascertained as the matrix material for the next research and preparation of Ti-montmorillonite nanemeter composite.
On the basis of experiments and analysis, the purification and dispersion mechanism is discussed in an elementary way. In the condition of joining appropriate dispersant and controlling feasible progress, the purpose of purification and modification can get in the same time.
Preparing good quality montmorillonite matrix material via studying of purification and dispersion is the basis of high technology application. It will take good advantage of our bentonite resource, increase mineral value, and enhance interdisciplinary development especially in mineral processing and other science. Thus, the study is of important significance.
引文
[1] 崔学奇，吕宪俊，周国华．膨润土的性能及其应用[J]．中国非金属矿工业导刊，2000，2：6—9
[2] 李建平．膨润土的工艺特性及其应用[J]．地质找矿论丛，1998，1(13)：67—73
[3] 郭瓦力，张德金，于桂香．多功能原料—膨润土[J]．辽宁化工，1999，7：191—194
[4] 汪多仁．膨润土的开发应用[J]．现代涂料与涂装，2002，4：44—46
[5] 单承湘，于少明，杨保俊．膨润土提纯方法的研究[J]．合肥工业大学学报(自然科学版)，1997，4：29—33
[6] 刘四海．膨润土的提纯和钠化改性方法[J]．石油钻探技术，1993，6：24，41
[7] 杨能谓，洪朝煌，伏专红等．钙基膨润土湿法提纯工艺的研究[J]．浙江化工，1990，3(21)：30—32
[8] 杨有学．膨润土在水介质中的分选提纯[J]．化工矿山技术，1991，20(1)：35—36
[9] 梁成钢，苏海全，刘树堂．膨润土的提纯，改型及脱水方法研究[J]．内蒙古大学学报(自然科学版)，1996，5：361—364
[10] 黄明华．二次分级法在膨润土矿提纯上的应用[J]．非金属矿，1994，2：27—29
[11] 张颖心，钟大勇，张天胜．低品位钙基膨润土矿粉的直接钠化研究[J]．化工矿物与加工，2002，10：10—13
[12] 曹明礼，于阳辉，袁继祖．膨润土的钠化改型研究[J]．矿冶工程，2001，6：24—26
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[20] Yamada H., Nakazawa., Hashizume H etal. Formation of smectite crystals at high pressres and temperatures[J], Clays and Clay Minerals, 1994, 42(6): 674
[21] 章永化，龚克成．可聚合性季铵盐—蒙脱石嵌入复合物的制备[J]．硅酸盐通报，1998(1)：24—28
[22] 王旭．膨润土的有机及其产品应用[J]．辽宁化工，2000，9(5)：295—297
[23] 刘优．柱撑粘土矿物的研究新进展[J]．矿物岩石，1999，3(1)：101—104
[24] 吴平宵．柱撑蒙脱石制备与表征[J]．矿物学报，1997，6(2)：200—207
[25] T.KANEKO, H.SHIMOTSUMA; Synthesis and Photocatalytic Activity of Titania Pillared Clays; Journal of Porous Materials 2001,8:295-301
[26] H.L. Del Castillo, A. Gil; Influce of the nature of titanium alkoxide and of the acid of hydrolysis in the preparation of titanium-pillared montmorillonites; J. Phys. Chem Solids Vol 58,No.7, pp. 1053-1062
[27] Ho Jeong Chae, In-Sik Nam; Physicochemical characteristics of pillasred interlayered clays; Catalysis Todsay, 2001,68:31-40
[28] Ahmad Saeed. Bentonite in animal feed Minerals [J]. Industrial Minerals, July, 1996: 48—50
[29] 易发成．利用四川三台膨润土制备5A沸石分子筛[J]．中国矿业，1999，8(1)：19—21
[30] Akane Okada, Masaya kawasumi, Toshi Kurauchi, etal. Synthesis and Characterization of Nylon 6—ClayHybrid[J]. Polym. Prepr., 1987,28(2):447—450
[31] R.A. Vaia, E. P. Giannelis. Lattice Model of Polymer melt Intercalation in Organically—Modified layered silicates [J]. Macromolecules, 1997, 30: 7990—7999
[32] R.A. Vaia, B. B. Sauer, O. K. Tse, E. P. Giannelis. J. Relaxations of Confined chains in Polymer Nanoconposites Glass Transiction properties of Poly Intercalated in Montmorillonite [J]. Polym. Sci: PartB: Polym. Phys., 1997, 35:59—67
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[51] 李凯琦，曾玉风，王万祥等．一种新型分散剂的性能及分散机理[J]．非金属矿，2000，11：16—17
[52] 任俊，卢寿兹．亲水性及疏水性颗粒在水中的分散行为研究[J]．中国粉体技术，1999，4：6—9
[53] 李运康，陈德芳，王重．膨润土胶溶过程的研究[J]．西安交通大学学报，2000，8：108—110
[2] 李建平．膨润土的工艺特性及其应用[J]．地质找矿论丛，1998，1(13)：67—73
[3] 郭瓦力，张德金，于桂香．多功能原料—膨润土[J]．辽宁化工，1999，7：191—194
[4] 汪多仁．膨润土的开发应用[J]．现代涂料与涂装，2002，4：44—46
[5] 单承湘，于少明，杨保俊．膨润土提纯方法的研究[J]．合肥工业大学学报(自然科学版)，1997，4：29—33
[6] 刘四海．膨润土的提纯和钠化改性方法[J]．石油钻探技术，1993，6：24，41
[7] 杨能谓，洪朝煌，伏专红等．钙基膨润土湿法提纯工艺的研究[J]．浙江化工，1990，3(21)：30—32
[8] 杨有学．膨润土在水介质中的分选提纯[J]．化工矿山技术，1991，20(1)：35—36
[9] 梁成钢，苏海全，刘树堂．膨润土的提纯，改型及脱水方法研究[J]．内蒙古大学学报(自然科学版)，1996，5：361—364
[10] 黄明华．二次分级法在膨润土矿提纯上的应用[J]．非金属矿，1994，2：27—29
[11] 张颖心，钟大勇，张天胜．低品位钙基膨润土矿粉的直接钠化研究[J]．化工矿物与加工，2002，10：10—13
[12] 曹明礼，于阳辉，袁继祖．膨润土的钠化改型研究[J]．矿冶工程，2001，6：24—26
[13] 陈淑祥，袁健，刘海彬等．钙基膨润土钠化改型新方法研究[J]．非金属矿，1999，1：8—9，31
[14] 殷锡鹏．对辊挤压在生产人工钠膨润土中的应用[J]．非金属矿，1992，4：13—15
[15] 马宝国，李文华．膨润上资源综合利用浅析[J]．资源节约和综合利用，1997，9(3)：50—52
[16] 汪镜亮．膨润土的某些加工和应用[J]．江西建材，1995，4：18—23
[17] 苑金生．膨润土在建材工业中的应用[J]．矿产保护与利用，1998，8：11—13
[18] B. Fenelonov; The characterization of the structure and texture of pillared interlayer materials; Microporous and Mesoporous Materials, 2001, (47) 359-368
[19] 张术根，谢志勇，申少华等．膨润土高层次开发利用研究新进展[J]．中国非金属矿工业导刊，2002，1：17—20
[20] Yamada H., Nakazawa., Hashizume H etal. Formation of smectite crystals at high pressres and temperatures[J], Clays and Clay Minerals, 1994, 42(6): 674
[21] 章永化，龚克成．可聚合性季铵盐—蒙脱石嵌入复合物的制备[J]．硅酸盐通报，1998(1)：24—28
[22] 王旭．膨润土的有机及其产品应用[J]．辽宁化工，2000，9(5)：295—297
[23] 刘优．柱撑粘土矿物的研究新进展[J]．矿物岩石，1999，3(1)：101—104
[24] 吴平宵．柱撑蒙脱石制备与表征[J]．矿物学报，1997，6(2)：200—207
[25] T.KANEKO, H.SHIMOTSUMA; Synthesis and Photocatalytic Activity of Titania Pillared Clays; Journal of Porous Materials 2001,8:295-301
[26] H.L. Del Castillo, A. Gil; Influce of the nature of titanium alkoxide and of the acid of hydrolysis in the preparation of titanium-pillared montmorillonites; J. Phys. Chem Solids Vol 58,No.7, pp. 1053-1062
[27] Ho Jeong Chae, In-Sik Nam; Physicochemical characteristics of pillasred interlayered clays; Catalysis Todsay, 2001,68:31-40
[28] Ahmad Saeed. Bentonite in animal feed Minerals [J]. Industrial Minerals, July, 1996: 48—50
[29] 易发成．利用四川三台膨润土制备5A沸石分子筛[J]．中国矿业，1999，8(1)：19—21
[30] Akane Okada, Masaya kawasumi, Toshi Kurauchi, etal. Synthesis and Characterization of Nylon 6—ClayHybrid[J]. Polym. Prepr., 1987,28(2):447—450
[31] R.A. Vaia, E. P. Giannelis. Lattice Model of Polymer melt Intercalation in Organically—Modified layered silicates [J]. Macromolecules, 1997, 30: 7990—7999
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