多孔粘土材料的合成与研究
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摘要
多孔粘土材料(Porous Clays，PCs)是当今粘土科学研究领域中最活跃的研究方向之一，它是基于粘土矿物的表面活性、层间离子可交换性等性质，通过柱化剂的交联柱化作用形成的一类规整二维孔道结构的多孔性材料，由于具有孔径大、分布规则以及大小可调的特点，可望在石化、环保、精细化工等领域得到广泛的应用。
PCs材料的性能与基质粘土材料、柱化剂、反应温度、干燥方式等制备条件等因素密切相关。本学位论文采用材料化学的研究方法，选择2：1型的蒙脱石和1：1型规则间层累脱石粘土矿物为基质材料，以羟基铝聚合阳离子为柱化剂，合成两个系列的PCs材料，研究不同制备条件下对形成PCs材料以及物化性质的影响，同时采用XRD、IR、TGA、MAS ~(27)Al-NMR、TEM等仪器测试手段对PCs材料进行表征，结果表明：累脱石PCs材料比蒙脱石PCs材料具有更高的热稳定性；柱化剂用量对获得层间开孔大和稳定性高的PCs材料有较大的影响；表面活性剂PVA对PCs材料具有扩孔作用，加入适量的PVA有助于合成大孔径的PCs材料：干燥方式对材料的层间开孔无明显的作用，但对其表面积则有较大的影响；层离现象可以得到大孔道的PCs材料；酸性测试表明，PCs材料的固体表面酸性主要以L酸为主，B酸含量较少，并对温度较为敏感，在高温下容易失效。
Porous clays (PCs) prepared by the reactions of clay minerals with pillared agents base on the surface activity, interlayer ions exchangeable of clay minerals is an area of clays science which has received ever-increasing attention over recent year. Due to PCs possesses the 2D pore gallery or pore channel structure, large cavity, uniform of pore size, and especially its pore size can be controlled by artificial selection, this material is expected to find applications in the area of petroleum catalysis, environmental engineering and fine chemical industry etc.
The properties and characteristics of the PCs is closely related to the prepared conditions such as clay matrix starting materials, pillared agents, reaction temperature and the fashion of.drying etc. In this thesis, the author has carried out a study on the impact factors of preparation on PCs properties by use of materials chemistry. Two series of the PCs prepared by the interlayed crosslinking of a 2:1 layer montmorillonite and a 1:1 interstratified rectorite with the pillared agent of Al polyoxocations are investigated by means of XRD, IR, TGA, MAS 27A1-NMR, and TEM instruments etc. The results show that the thermal stability of rectorite-PCs is higher than that of montmorillite-PCs, implying the clay matrix materials have an obvious influence on the PCs. The consumption of pillared agent is very important for preparing PCs which has large pore structure and high stability. The activatory PVA (polyvinyl alcohol) can expand the pore or cavity of PCs, so presence of suitable PVA consumption is benefit to g
et large pore structure of PCs. Drying fashion cannot be use to expand the PCs pore structure, however, it can be find to influent the PCs surface areas. The PCs with delaminated phenomena possesses very large pore and cavity structure. The acidity measurement indicates that solid acidity composition of PCs are mainly of Lewis acidity type, few of the Bronsted acidity type, sensitive to temperature, and ease to lost in the higher temperature environment.
PCs材料的性能与基质粘土材料、柱化剂、反应温度、干燥方式等制备条件等因素密切相关。本学位论文采用材料化学的研究方法，选择2：1型的蒙脱石和1：1型规则间层累脱石粘土矿物为基质材料，以羟基铝聚合阳离子为柱化剂，合成两个系列的PCs材料，研究不同制备条件下对形成PCs材料以及物化性质的影响，同时采用XRD、IR、TGA、MAS ~(27)Al-NMR、TEM等仪器测试手段对PCs材料进行表征，结果表明：累脱石PCs材料比蒙脱石PCs材料具有更高的热稳定性；柱化剂用量对获得层间开孔大和稳定性高的PCs材料有较大的影响；表面活性剂PVA对PCs材料具有扩孔作用，加入适量的PVA有助于合成大孔径的PCs材料：干燥方式对材料的层间开孔无明显的作用，但对其表面积则有较大的影响；层离现象可以得到大孔道的PCs材料；酸性测试表明，PCs材料的固体表面酸性主要以L酸为主，B酸含量较少，并对温度较为敏感，在高温下容易失效。
Porous clays (PCs) prepared by the reactions of clay minerals with pillared agents base on the surface activity, interlayer ions exchangeable of clay minerals is an area of clays science which has received ever-increasing attention over recent year. Due to PCs possesses the 2D pore gallery or pore channel structure, large cavity, uniform of pore size, and especially its pore size can be controlled by artificial selection, this material is expected to find applications in the area of petroleum catalysis, environmental engineering and fine chemical industry etc.
The properties and characteristics of the PCs is closely related to the prepared conditions such as clay matrix starting materials, pillared agents, reaction temperature and the fashion of.drying etc. In this thesis, the author has carried out a study on the impact factors of preparation on PCs properties by use of materials chemistry. Two series of the PCs prepared by the interlayed crosslinking of a 2:1 layer montmorillonite and a 1:1 interstratified rectorite with the pillared agent of Al polyoxocations are investigated by means of XRD, IR, TGA, MAS 27A1-NMR, and TEM instruments etc. The results show that the thermal stability of rectorite-PCs is higher than that of montmorillite-PCs, implying the clay matrix materials have an obvious influence on the PCs. The consumption of pillared agent is very important for preparing PCs which has large pore structure and high stability. The activatory PVA (polyvinyl alcohol) can expand the pore or cavity of PCs, so presence of suitable PVA consumption is benefit to g
et large pore structure of PCs. Drying fashion cannot be use to expand the PCs pore structure, however, it can be find to influent the PCs surface areas. The PCs with delaminated phenomena possesses very large pore and cavity structure. The acidity measurement indicates that solid acidity composition of PCs are mainly of Lewis acidity type, few of the Bronsted acidity type, sensitive to temperature, and ease to lost in the higher temperature environment.
引文
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[3] . R. M. Barrer and D. M. Macleod, Trans. Faraday Soc., 1995, 51:1290．
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[7] . K. Carrado-Gregar, R. E. Winaus, R. E Botto, Organic or organometallic template mediated clay synthesis, 1994, US Pat. 5308808．
[8] . R. H. Loeppert, Jr., M. M. Moriland, T. J. Pinnavaia, Clays and clay minerals, 1979,27,201．
[9] . G. W. Brindley and R. E. Semples Preparation and properties of some hydroxyl-aluminum beidellites, Clay Minerals, 1977,12: 229-237．
[10] . N. Lahav, U. Shani and J. Shabtai, Cross-linked smectites, (I). Synthesis and properties of hydroxyl-aluminum montmorillonite, Clays and clay minerals, 1978,26:107-115．
[11] . D. E. W. Vaughan, R. J. Lussier and J. S. Magee, Pillared interlayed clay materials useful as catalysts and sorbents, 1979, US Pat. 4176090．
[12] . D. E. W. Vaughan, R. J. Lussier and J. S. Magee, Stabilized pillared interlayed clays, 1981, US Pat. 4284739．
[13] . D. E. W. Vaughan, R. J. Lussier and J. S. Magee, Pillared interlayed clay products, 1981, US Pat. 4271043．
[14] . J. Shabtai, N. Lahav, Cross-linked montmorillonite molecular sieves, 1980, US Pat. 4216188．
[15] . D. E. W. Vaughan, R. J. Lussier, Preparation of molecular sieves based on pillared interlayed clays, 1980, in: Proc. 5th int. conf. zeolites, Naples, 1980, L. V. C. Recs ed., Heyden, London, p94-101．
[16] . G. W. Brindley, C.-C. Kao, Formation, composition and properties of hydroxyl-A1-and hydroxyl-Mg-montmorillonite, Clays and clay minerals, 1980,28:435-442．
[17] . S. Yamanaka and G. W. Brindley, High surface area solids obtained by reaction of montmorillonite with zirconyl chloride, Clays and clay minerals, 1979,27:119-124．
[18] . J. Shabtai, R. Lazar, A. G. Oblad, Acidic forms of cross-linked smectites-a novel type of cracking catalysts, in: Proc. 7th int. congr. catal., Tokyo, 1980, T. Seiyamat, K. Tanabe eds., Kodansha-Elsevier, Tokyo, p828-837．
[19] . S. Yamanaka et al. High surface area solids obtained by intercalation of iron oxide pillars in montmorillonite. Mat.Res.Bull., 1984,19:161-168．
[20] . R. Burch, C. I. Warburton, Pillared clays as demetallisation catalysts, Appl. Catal., 1987, 33:395-404．
[21] . R. Burch, C. I. Warburton, Sulphide pillared interlayer clays, J. Chem. Soc., Chem. Commun., 1987,2:117-118．
[22] . C. I. Warburton, Preparation and catalytic properties of iron oxide and iron sulphide pillared clays, Catal. Today, 1988, 2:271-280．
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