蒙脱石活化及其与微结构变化关系研究
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摘要
本文从酸活化处理、热处理、单核及多核柱撑等实验方法入手，对蒙脱石进行多种活化处理，并对未经活化的单矿物(提纯后的蒙脱石)和活化产物的矿物物理化学性质、微结构变化进行了详细的分析研究，阐明了蒙脱石活化以后，其物理化学性质和矿物微结构变化之间的关系。具体表现在以下方面：
蒙脱石酸处理的实质是经过酸化使蒙脱石的表面结构发生变化。活化后的蒙脱石随着八面体片中阳离子的溶出和四面体片中硅结构的重组，增强了蒙脱石的表面酸性，从而增大了它的吸附性能。酸化蒙脱石脱色的根源是由于酸化作用改变了蒙脱石的表面结构，使其表面形成畸变的Q~3硅结构和Q~4硅结构从而具有BrΦnsted酸活性。
HP蒙脱石的热处理研究表明，热处理温度达到600℃时，蒙脱石八面体片中的羟基开始脱失，但层状结构仍然保持。蒙脱石羟基的脱失过程对应着八面体片中Al~Ⅵ向Al~Ⅳ的转变，且其平整的层状结构受到破坏而使其表面粗糙化。当温度达到900℃时，蒙脱石的层状结构完全被破坏，并有新的矿物相X—SiO_2产生。当温度达到1200℃时，出现方英石及莫来石相。当热处理温度达到1350℃时，方英石及莫来石的含量略有减少，并出现较多的堇青石相。
AlCl_3溶液在[OH~-]/[Al~(3+)]=2.4时水解生成的Keggin离子最多，且最稳定。随着Fe/Al比的增加，羟基铁铝柱化液中的四配位Al(Ⅳ)逐渐减少，过量的Fe对Keggin结构具有破坏作用。HP蒙脱石经羟基铝柱撑后其层间距d_(001)由自然状态下的1.57nm增大到2.53nm，经300℃灼烧后其层间距稳定在1.83nm，具有较好的热稳定性。柱撑蒙脱石表面的Lewis酸性明显增强。
用溴化十六烷基吡啶改性后的蒙脱石及柱撑蒙脱石，能大幅度提高其对苯酚的吸附能力。柱撑蒙脱石对苯酚的吸附能力主要取决于改性粘土吸附剂的微孔结构和表面组分；而不仅仅依赖于表面积。经灼烧后的柱撑蒙脱石用少量的Na_2CO_3处理后，再与溴化十六烷基吡啶反应制成有机柱化粘土而可循环使用。
This paper begin with acid activated treatment,thermal activation treatment,single nuclear and multi-nuclear pillared experiment method,and activated montmorillonite in several methods. We study the microstructure change,physics-chemistry characteristic between raw minerals and activated products,interpret the relationship of physics-chemistry characteristic and microstructure change of montmorillonite before and after activation. All of them concrete on following:
The essence of acid activated treatment is that the surface structure of montmorillonite changes after treated by acid. After acid activated treatment,along with the cation in octahedron sheet of montmorillonite dissolved and the Si in tetrahedron sheet of montmorillonite structure recombined,make the surface structure of montmorillonite change greatly. This changes enhance the surface acidity of activated montmorillonite,accrete the adsorption characteristic of activated montmorillonite. There are some Q3 Si structure in montmorillonite transform to distortion QJ Si structure and Q4 Si structure through structure recombination. The distorted Q3 and Q4 Si structure in montmorillonite surface possess Bnjmsted acidity.
It is found that montmorillonite dehydrate adsorbing water and interlayer water when the temperature is between 126C-148C,this process is reversible. When the thermal treatment temperature reach 659C,the hydroxyl in octahedra sheet begin dehydrating,but the layer structure is maintaining. When the temperature reach 900 C,the layer structure of montmorillonite is destroyed,and the new mineral phase SiO2-x is found,when the temperature reach 1200C. It appears cristobalite and mullite,when the temperature reach 1350C. It appears cordierite.
The pillared montmorillonite was prepared by A13+ in Keggin ions which hzs Keggin structure. The results suggest when m=2.4 the quantity of Keggin ions in A1C13 solution is more. In natural state,the d(001) value of pillared montmorillonite is 2.53nm,after incandescing at 300 'C,the basal interlayer spacing is stabilized 1.83nm,with high stability. The pillared montmorillonite containing Fe3+ ion was prepared by substituting Fe3> for A13+ in Keggin ions which has Keggin structure. The results suggest that the structure of hydroxy-Fe-Al oligocation,d(OOI) values and the thermal stability of pillared clay are affected by the Fe/Al ratio in pillared solution. The d(001) values increase and the thermal stability decrease with increasing F;/A1 ratio. Excessive amounts of Fe3+ ions can destroy the Keggin structure. The existence of Keggin structure can improve the thermal stability of the pillared clays.
Both inorganic and organic pillared montmorillonites are used to adsorb the phenol,to study their suitable conditions and adsorption isotherms of adsorbing phenol. It reveals that using modified pillared montmorillonite with surfactant can improve the adsorbing capacity greatly. The adsorbing capacity of phenol by pillared montmorillonites is depended on micropore structure and
surface component of modified clays mainly,not only surface area. After incandescing at 500C,the pillar structure and the basal interlayer spacing (1.83nm) are stable still. So the pillared
montmorillonite can use recycle,it is a potential substance of Adsorption of environmental pollutants.
蒙脱石酸处理的实质是经过酸化使蒙脱石的表面结构发生变化。活化后的蒙脱石随着八面体片中阳离子的溶出和四面体片中硅结构的重组，增强了蒙脱石的表面酸性，从而增大了它的吸附性能。酸化蒙脱石脱色的根源是由于酸化作用改变了蒙脱石的表面结构，使其表面形成畸变的Q~3硅结构和Q~4硅结构从而具有BrΦnsted酸活性。
HP蒙脱石的热处理研究表明，热处理温度达到600℃时，蒙脱石八面体片中的羟基开始脱失，但层状结构仍然保持。蒙脱石羟基的脱失过程对应着八面体片中Al~Ⅵ向Al~Ⅳ的转变，且其平整的层状结构受到破坏而使其表面粗糙化。当温度达到900℃时，蒙脱石的层状结构完全被破坏，并有新的矿物相X—SiO_2产生。当温度达到1200℃时，出现方英石及莫来石相。当热处理温度达到1350℃时，方英石及莫来石的含量略有减少，并出现较多的堇青石相。
AlCl_3溶液在[OH~-]/[Al~(3+)]=2.4时水解生成的Keggin离子最多，且最稳定。随着Fe/Al比的增加，羟基铁铝柱化液中的四配位Al(Ⅳ)逐渐减少，过量的Fe对Keggin结构具有破坏作用。HP蒙脱石经羟基铝柱撑后其层间距d_(001)由自然状态下的1.57nm增大到2.53nm，经300℃灼烧后其层间距稳定在1.83nm，具有较好的热稳定性。柱撑蒙脱石表面的Lewis酸性明显增强。
用溴化十六烷基吡啶改性后的蒙脱石及柱撑蒙脱石，能大幅度提高其对苯酚的吸附能力。柱撑蒙脱石对苯酚的吸附能力主要取决于改性粘土吸附剂的微孔结构和表面组分；而不仅仅依赖于表面积。经灼烧后的柱撑蒙脱石用少量的Na_2CO_3处理后，再与溴化十六烷基吡啶反应制成有机柱化粘土而可循环使用。
This paper begin with acid activated treatment,thermal activation treatment,single nuclear and multi-nuclear pillared experiment method,and activated montmorillonite in several methods. We study the microstructure change,physics-chemistry characteristic between raw minerals and activated products,interpret the relationship of physics-chemistry characteristic and microstructure change of montmorillonite before and after activation. All of them concrete on following:
The essence of acid activated treatment is that the surface structure of montmorillonite changes after treated by acid. After acid activated treatment,along with the cation in octahedron sheet of montmorillonite dissolved and the Si in tetrahedron sheet of montmorillonite structure recombined,make the surface structure of montmorillonite change greatly. This changes enhance the surface acidity of activated montmorillonite,accrete the adsorption characteristic of activated montmorillonite. There are some Q3 Si structure in montmorillonite transform to distortion QJ Si structure and Q4 Si structure through structure recombination. The distorted Q3 and Q4 Si structure in montmorillonite surface possess Bnjmsted acidity.
It is found that montmorillonite dehydrate adsorbing water and interlayer water when the temperature is between 126C-148C,this process is reversible. When the thermal treatment temperature reach 659C,the hydroxyl in octahedra sheet begin dehydrating,but the layer structure is maintaining. When the temperature reach 900 C,the layer structure of montmorillonite is destroyed,and the new mineral phase SiO2-x is found,when the temperature reach 1200C. It appears cristobalite and mullite,when the temperature reach 1350C. It appears cordierite.
The pillared montmorillonite was prepared by A13+ in Keggin ions which hzs Keggin structure. The results suggest when m=2.4 the quantity of Keggin ions in A1C13 solution is more. In natural state,the d(001) value of pillared montmorillonite is 2.53nm,after incandescing at 300 'C,the basal interlayer spacing is stabilized 1.83nm,with high stability. The pillared montmorillonite containing Fe3+ ion was prepared by substituting Fe3> for A13+ in Keggin ions which has Keggin structure. The results suggest that the structure of hydroxy-Fe-Al oligocation,d(OOI) values and the thermal stability of pillared clay are affected by the Fe/Al ratio in pillared solution. The d(001) values increase and the thermal stability decrease with increasing F;/A1 ratio. Excessive amounts of Fe3+ ions can destroy the Keggin structure. The existence of Keggin structure can improve the thermal stability of the pillared clays.
Both inorganic and organic pillared montmorillonites are used to adsorb the phenol,to study their suitable conditions and adsorption isotherms of adsorbing phenol. It reveals that using modified pillared montmorillonite with surfactant can improve the adsorbing capacity greatly. The adsorbing capacity of phenol by pillared montmorillonites is depended on micropore structure and
surface component of modified clays mainly,not only surface area. After incandescing at 500C,the pillar structure and the basal interlayer spacing (1.83nm) are stable still. So the pillared
montmorillonite can use recycle,it is a potential substance of Adsorption of environmental pollutants.
引文
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