冰晶模板组装蒙脱石多孔材料及传热传质规律研究
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摘要
为了解决日益严重的工业废气污染问题，对储量丰富的蒙脱石改性研究已成为制备新材料的热点之一。现有技术主要以阳离子交联柱撑和有机模板组装来改性蒙脱石。此技术虽然可以合成微孔丰富、比表面积达200m2/g的纳米蒙脱石粉体，但是，改性后的蒙脱石孔隙结构简单，产品形态单一。大多柱撑剂和有机模板自身含有毒性，对改性蒙脱石和环境造成污染。该类材料也无法同时处理多种废气和固体微粒（PM2.5）。所以，创新合成具有多尺度孔隙结构、环境友好型蒙脱石功能材料的制备方法十分必要。
本研究根据模板组装以及传热传质原理，系统分析了温和反应条件下，胶体悬浮液浓度小于5%时，蒙脱石多孔材料的制备理论。包括蒙脱石微粒与水中羟基、PVA分子中羟基的氢键结合理论,冰晶模板诱导作用下蒙脱石微粒的超分子组装理论；研究确定了“溶胶-凝胶-真空冷冻干燥”制备蒙脱石多孔材料的主要技术条件；试验验证了所制备蒙脱石多孔材料净化汽车尾气的效率。研究揭示的主要规律如下：
对冰晶模板组装蒙脱石形成多孔结构的物理化学本质和孔隙特征研究表明，冰晶模板对蒙脱石微粒的诱导动力主要来源于冰晶特有的片状结构以及二者之间存在的氢键和范德华力。其方向性和加合性强化了氢键和范德华力，促成了蒙脱石微粒在冰晶间隙内定向排列，在多孔蒙脱石微粒组装中起决定作用。由此制备的冻干蒙脱石内部宏观孔隙呈层状结构，而且以贯通孔为主。孔隙率>60%，比表面积>150m2/g，孔体积>0.29cm~3/g；大孔孔径约50μm,中孔孔径35nm～45nm，另外在层状骨架壁面有少量孔径小于5nm的微孔。
研究分析了蒙脱石微粒与聚乙烯醇长链分子间通过氢键结合发生有机化反应的机理，钠基蒙脱石/聚乙烯醇复合多孔材料的孔隙特征。研究表明，聚乙烯醇长链上的羟基与钠基蒙脱石微粒表面的羟基可形成氢键，使两物质之间发生插层反应，氢键在此反应中起着关键作用。在蒙脱石微粒层间域内外，聚乙烯醇浓度梯度所产生的渗透压促使其向层间域内渗透，强化了插层反应，最终生成了钠基蒙脱石/聚乙烯醇复合胶体悬浮液。在此基础上，经冰晶模板组装并冻干的钠基蒙脱石/聚乙烯醇复合材料中，宏观孔隙呈层状结构。其孔隙率>60%，比表面积>213.8m~2/g，孔体积>0.327cm~3/g。内部大孔以贯通孔为主，孔径大于10μm，中孔孔径约7.0nm，在层状骨架壁面也存在着孔径小于5nm的微孔。
通过建立能量传递和质量传递数学模型并求解，揭示了该过程传热传质耦合规律，冻干蒙脱石内瞬时温度场和浓度场分布规律，真空冷冻干燥时间变化规律。研究表明，冻干蒙脱石的导热系数随其内部水蒸汽浓度的提高而增大；水蒸汽扩散通量与系统提供辐射热量也呈现正相关增加趋势，但是，水蒸汽扩散通量的增加会导致系统的热损失加剧；冻干蒙脱石内的二维温度场、浓度场分布类似于抛物曲线；从样品上表面中心至底部中心位置，温度逐渐降低，而水蒸汽浓度则上升；在同一水平面，从样品内部向外温度逐渐升高，水蒸汽浓度则逐渐下降。模拟计算表明，当环境温度为308K时，蒙脱石冻结体所需理论冻干时间约为39.0h。试验测得冻干时间约为40.0h，模拟计算与实验值基本吻合。
研究分析了植物淀粉提高蒙脱石多孔材料结构强度内在规律。研究表明，淀粉长分子链中的羟基与蒙脱石微粒表面的羟基可发生氢键作用，它是二者之间紧密粘结的内在动力。淀粉凝胶化过程中形成三维网络结构，引导蒙脱石微粒形成与淀粉凝胶同样的网状结构。冰晶模板引导蒙脱石/淀粉组成的未定型网络凝胶实现有序排列。增强处理后的冻干蒙脱石及其复合多孔材料，其结构强度达1.0MPa以上，原有的层状孔隙特征完好。
探索了冻干蒙脱石多孔材料作为催化剂的作用机理。研究表明，蒙脱石多孔制品内含有的多尺度孔隙，表面存在的大量不平衡键、断裂键，以及所具有的高离子交换量，形成了层状骨架表面的棱角、突起和缺陷，构成了蒙脱石催化剂的活性中心。冻干蒙脱石层间域内和表面上能够释放出丰富质子，使蒙脱石多孔材料成为一种较强的固体酸催化剂。冻干蒙脱石的催化机理为吸附、离子交换、过滤、分离四种物理化学过程的综合作用。对汽车尾气中CO、HC（碳氢化合物）、NOx、PM2.5、以及CO2的综合净化效率可达25%以上。利用该材料作汽车尾气净化剂，综合作用优于目前先进的铂金电氧化型净化器。
In order to solve the increasingly serious exhaust pollution, modification ofmontomorillonite (MMT) in rich reserves has become a focus in the field of newmaterials. The current techniques for modifying MMT mainly depend on cationiccross-linked pillar holding and organic template assembling to synthesize nano-MMTswith abundant micro-pores and a specific surface area of over200m2/g. However, thiskind of nano-MMT usually just has a single microstructure and size and could becontaminated by toxic pillaring agents or organic templates furthermore polluteenvironment. It also cannot purify various exhausts and adsorb PM2.5particlessimultaneously. Thus, it is necessary to develop a new technique for preparing anenvironment-friendly MMT material with multi-scale pores.
In the present study, according to the principle of template assembling and heat andmass transfer, the synthesis of porous MMT materials by the MMT colloidal suspensionof below5%concentration was investigated systematically. Hydrogen bonding betweenthe MMT particles and hydroxyl group of H2O molecules or PVA long-chain molecules,supramolecule-assembling induced by ice template are included. A new preparationmethod of porous MMT materials called “sol-gel-vacuum freeze drying” was developed.It was proved that automobile exhaust could be efficiently purified using porous MMTmaterials prepared by this method. The findings are described below.
The physical-chemical process and characteristics of the porous MMT materialassembled by ice template were investigated. The results displayed that the mainadditive force comed from hydrogen bonding and Van der Waals force between uniquesheet-like structure in ice and surface of MMT micro-particles. The directivity andadditivity strengthened hydrogen bonding and Van der Waals force and resulted in theorientation of the MMT particles in ice crystal gaps. The force added was decisive in theassembling of porous MMT material. The macro-pores were layered, with a porosity ofover60%, a specific surface area of over150m2/g and a pore volume of over0.29cm~3/g.The sizes of the internal macro-pores and meso-pores are50μm and35~45nm,respectively. In addition, a small amount of micro-pores with sizes of less than5nmcould be found.
The mechanism of the organic reaction between MMT particles and polyvinylalcohol (PVA) long-chain molecules by hydrogen bonding was revealed and pore characteristics of freeze-dried MMT/PVA composite was also disclosed. It has beenreported that the hydroxyl groups of PVA long chains and the hydroxyl groups ofsodium MMT particle surfaces can form hydrogen bonds. The hydrogen bonds played avital role in the intercalative reaction between the two substances. Osmotic pressurecaused by concentration gradients of PVA within and outside the MMT layer helped thePVA long-chain molecules to infiltrate the inter-layer domain of MMT, and reinforcedthe intercalative reaction. In the end, the two reactants generated sodium MMT/PVAcomposite colloidal suspension. By means of ice template assembly, macro-pores of thelyophilized MMT/PVA composite showed a lamellar structure, with its porosity of over60%, specific surface area of over213.8m2/g and pore volume of over0.327cm3/g. Thesizes of the internal macro-pores and meso-pores were10μm and7.0nm respectively.Some micro-pores (aperture below5nm) were also found in the mesh skeleton of thelyophilized MMT/PVA composites.
The mathematical models of heat and mass transfer in the vacuum freeze-dryingprocess of MMT were built up to reveal the coupling of heat and mass transfer, thedistribution of instantaneous temperature field and concentration field of freeze-driedMMT and time variation of vacuum freeze-drying. The results showed that the thermalconductivity of the lyophilized MMT increased with the increase of its internal vaporconcentration; the water vapor diffusion flux increases with the increase of radiant heatof the system absorbed from the external environment, but the increased water vapordiffusion flux could increase heat loss of the system; the two-dimensional distribution ofthe temperature field and concentration field within the freeze-dried MMT is similar tothe parabolic curve; The sample temperature dropped gradually from its top center tothe bottom center, while the water vapor concentration was on the rise; In the samehorizontal plane, the sample temperature rise gradually from the inside to outward, andthe water vapor concentration was on the decline. The calculation results showed thatthe simulation freeze-drying time required for about39.0h when the ambienttemperature was308K, while time measured was40.0h. The calculated time wasbasically consistent with the experimental time.
The inherent reason of starch to improve the structural strength of lyophilizedporous MMT material was researched. Previous studies report that the hydroxyl groupson the long-chains of starch molecules and on the surface of freeze-dried MMT particlescan generate hydrogen bonding reaction. In turn, the reaction can promote closerbonding between starch molecules and MMT particles. The process in which starch sol changes into gel helps form a three-dimensional network and makes MMT particlesform a mesh structure similar to gel matrix above. The ice templates were found toguide the MMT/starch amorphous gels to form the porous MMT materials, whichstrength was over1.0MPa and the lamellar pore structure was retained.
The mechanism of the lyophilized porous MMT products used as a catalyst wasexplored. The results showed that some multi-scale pores, large number of unbalancebonds, broken bonds, and high ion-exchange capacity existed in the freeze-dried MMT.These may result in the edges, protrusions and defects on the lamellar surface of theMMT skeleton, which may become active centers for the MMT catalyst. Thelyophilized porous MMT material which we developed could be used as a strong solidcatalyst for acid because its crystal surface was capable of releasing large amount ofprotons. The catalytic mechanism of MMT is combined by adsorption, ion exchange,filtration and separation. It was found that the purifying efficiency of such porouscomposite was more than25%for CO, HC (hydrocarbons), NOx, PM2.5and CO2inautomobile exhaust, even better than the current state-of-the-art exhaust purifier ofplatinum electro-oxidation.
本研究根据模板组装以及传热传质原理，系统分析了温和反应条件下，胶体悬浮液浓度小于5%时，蒙脱石多孔材料的制备理论。包括蒙脱石微粒与水中羟基、PVA分子中羟基的氢键结合理论,冰晶模板诱导作用下蒙脱石微粒的超分子组装理论；研究确定了“溶胶-凝胶-真空冷冻干燥”制备蒙脱石多孔材料的主要技术条件；试验验证了所制备蒙脱石多孔材料净化汽车尾气的效率。研究揭示的主要规律如下：
对冰晶模板组装蒙脱石形成多孔结构的物理化学本质和孔隙特征研究表明，冰晶模板对蒙脱石微粒的诱导动力主要来源于冰晶特有的片状结构以及二者之间存在的氢键和范德华力。其方向性和加合性强化了氢键和范德华力，促成了蒙脱石微粒在冰晶间隙内定向排列，在多孔蒙脱石微粒组装中起决定作用。由此制备的冻干蒙脱石内部宏观孔隙呈层状结构，而且以贯通孔为主。孔隙率>60%，比表面积>150m2/g，孔体积>0.29cm~3/g；大孔孔径约50μm,中孔孔径35nm～45nm，另外在层状骨架壁面有少量孔径小于5nm的微孔。
研究分析了蒙脱石微粒与聚乙烯醇长链分子间通过氢键结合发生有机化反应的机理，钠基蒙脱石/聚乙烯醇复合多孔材料的孔隙特征。研究表明，聚乙烯醇长链上的羟基与钠基蒙脱石微粒表面的羟基可形成氢键，使两物质之间发生插层反应，氢键在此反应中起着关键作用。在蒙脱石微粒层间域内外，聚乙烯醇浓度梯度所产生的渗透压促使其向层间域内渗透，强化了插层反应，最终生成了钠基蒙脱石/聚乙烯醇复合胶体悬浮液。在此基础上，经冰晶模板组装并冻干的钠基蒙脱石/聚乙烯醇复合材料中，宏观孔隙呈层状结构。其孔隙率>60%，比表面积>213.8m~2/g，孔体积>0.327cm~3/g。内部大孔以贯通孔为主，孔径大于10μm，中孔孔径约7.0nm，在层状骨架壁面也存在着孔径小于5nm的微孔。
通过建立能量传递和质量传递数学模型并求解，揭示了该过程传热传质耦合规律，冻干蒙脱石内瞬时温度场和浓度场分布规律，真空冷冻干燥时间变化规律。研究表明，冻干蒙脱石的导热系数随其内部水蒸汽浓度的提高而增大；水蒸汽扩散通量与系统提供辐射热量也呈现正相关增加趋势，但是，水蒸汽扩散通量的增加会导致系统的热损失加剧；冻干蒙脱石内的二维温度场、浓度场分布类似于抛物曲线；从样品上表面中心至底部中心位置，温度逐渐降低，而水蒸汽浓度则上升；在同一水平面，从样品内部向外温度逐渐升高，水蒸汽浓度则逐渐下降。模拟计算表明，当环境温度为308K时，蒙脱石冻结体所需理论冻干时间约为39.0h。试验测得冻干时间约为40.0h，模拟计算与实验值基本吻合。
研究分析了植物淀粉提高蒙脱石多孔材料结构强度内在规律。研究表明，淀粉长分子链中的羟基与蒙脱石微粒表面的羟基可发生氢键作用，它是二者之间紧密粘结的内在动力。淀粉凝胶化过程中形成三维网络结构，引导蒙脱石微粒形成与淀粉凝胶同样的网状结构。冰晶模板引导蒙脱石/淀粉组成的未定型网络凝胶实现有序排列。增强处理后的冻干蒙脱石及其复合多孔材料，其结构强度达1.0MPa以上，原有的层状孔隙特征完好。
探索了冻干蒙脱石多孔材料作为催化剂的作用机理。研究表明，蒙脱石多孔制品内含有的多尺度孔隙，表面存在的大量不平衡键、断裂键，以及所具有的高离子交换量，形成了层状骨架表面的棱角、突起和缺陷，构成了蒙脱石催化剂的活性中心。冻干蒙脱石层间域内和表面上能够释放出丰富质子，使蒙脱石多孔材料成为一种较强的固体酸催化剂。冻干蒙脱石的催化机理为吸附、离子交换、过滤、分离四种物理化学过程的综合作用。对汽车尾气中CO、HC（碳氢化合物）、NOx、PM2.5、以及CO2的综合净化效率可达25%以上。利用该材料作汽车尾气净化剂，综合作用优于目前先进的铂金电氧化型净化器。
In order to solve the increasingly serious exhaust pollution, modification ofmontomorillonite (MMT) in rich reserves has become a focus in the field of newmaterials. The current techniques for modifying MMT mainly depend on cationiccross-linked pillar holding and organic template assembling to synthesize nano-MMTswith abundant micro-pores and a specific surface area of over200m2/g. However, thiskind of nano-MMT usually just has a single microstructure and size and could becontaminated by toxic pillaring agents or organic templates furthermore polluteenvironment. It also cannot purify various exhausts and adsorb PM2.5particlessimultaneously. Thus, it is necessary to develop a new technique for preparing anenvironment-friendly MMT material with multi-scale pores.
In the present study, according to the principle of template assembling and heat andmass transfer, the synthesis of porous MMT materials by the MMT colloidal suspensionof below5%concentration was investigated systematically. Hydrogen bonding betweenthe MMT particles and hydroxyl group of H2O molecules or PVA long-chain molecules,supramolecule-assembling induced by ice template are included. A new preparationmethod of porous MMT materials called “sol-gel-vacuum freeze drying” was developed.It was proved that automobile exhaust could be efficiently purified using porous MMTmaterials prepared by this method. The findings are described below.
The physical-chemical process and characteristics of the porous MMT materialassembled by ice template were investigated. The results displayed that the mainadditive force comed from hydrogen bonding and Van der Waals force between uniquesheet-like structure in ice and surface of MMT micro-particles. The directivity andadditivity strengthened hydrogen bonding and Van der Waals force and resulted in theorientation of the MMT particles in ice crystal gaps. The force added was decisive in theassembling of porous MMT material. The macro-pores were layered, with a porosity ofover60%, a specific surface area of over150m2/g and a pore volume of over0.29cm~3/g.The sizes of the internal macro-pores and meso-pores are50μm and35~45nm,respectively. In addition, a small amount of micro-pores with sizes of less than5nmcould be found.
The mechanism of the organic reaction between MMT particles and polyvinylalcohol (PVA) long-chain molecules by hydrogen bonding was revealed and pore characteristics of freeze-dried MMT/PVA composite was also disclosed. It has beenreported that the hydroxyl groups of PVA long chains and the hydroxyl groups ofsodium MMT particle surfaces can form hydrogen bonds. The hydrogen bonds played avital role in the intercalative reaction between the two substances. Osmotic pressurecaused by concentration gradients of PVA within and outside the MMT layer helped thePVA long-chain molecules to infiltrate the inter-layer domain of MMT, and reinforcedthe intercalative reaction. In the end, the two reactants generated sodium MMT/PVAcomposite colloidal suspension. By means of ice template assembly, macro-pores of thelyophilized MMT/PVA composite showed a lamellar structure, with its porosity of over60%, specific surface area of over213.8m2/g and pore volume of over0.327cm3/g. Thesizes of the internal macro-pores and meso-pores were10μm and7.0nm respectively.Some micro-pores (aperture below5nm) were also found in the mesh skeleton of thelyophilized MMT/PVA composites.
The mathematical models of heat and mass transfer in the vacuum freeze-dryingprocess of MMT were built up to reveal the coupling of heat and mass transfer, thedistribution of instantaneous temperature field and concentration field of freeze-driedMMT and time variation of vacuum freeze-drying. The results showed that the thermalconductivity of the lyophilized MMT increased with the increase of its internal vaporconcentration; the water vapor diffusion flux increases with the increase of radiant heatof the system absorbed from the external environment, but the increased water vapordiffusion flux could increase heat loss of the system; the two-dimensional distribution ofthe temperature field and concentration field within the freeze-dried MMT is similar tothe parabolic curve; The sample temperature dropped gradually from its top center tothe bottom center, while the water vapor concentration was on the rise; In the samehorizontal plane, the sample temperature rise gradually from the inside to outward, andthe water vapor concentration was on the decline. The calculation results showed thatthe simulation freeze-drying time required for about39.0h when the ambienttemperature was308K, while time measured was40.0h. The calculated time wasbasically consistent with the experimental time.
The inherent reason of starch to improve the structural strength of lyophilizedporous MMT material was researched. Previous studies report that the hydroxyl groupson the long-chains of starch molecules and on the surface of freeze-dried MMT particlescan generate hydrogen bonding reaction. In turn, the reaction can promote closerbonding between starch molecules and MMT particles. The process in which starch sol changes into gel helps form a three-dimensional network and makes MMT particlesform a mesh structure similar to gel matrix above. The ice templates were found toguide the MMT/starch amorphous gels to form the porous MMT materials, whichstrength was over1.0MPa and the lamellar pore structure was retained.
The mechanism of the lyophilized porous MMT products used as a catalyst wasexplored. The results showed that some multi-scale pores, large number of unbalancebonds, broken bonds, and high ion-exchange capacity existed in the freeze-dried MMT.These may result in the edges, protrusions and defects on the lamellar surface of theMMT skeleton, which may become active centers for the MMT catalyst. Thelyophilized porous MMT material which we developed could be used as a strong solidcatalyst for acid because its crystal surface was capable of releasing large amount ofprotons. The catalytic mechanism of MMT is combined by adsorption, ion exchange,filtration and separation. It was found that the purifying efficiency of such porouscomposite was more than25%for CO, HC (hydrocarbons), NOx, PM2.5and CO2inautomobile exhaust, even better than the current state-of-the-art exhaust purifier ofplatinum electro-oxidation.
引文
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