微通道制备纳米粒子及沸石膜微反应器的研究
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摘要
微化工系统具有传递性能好、混合时间短、可实现流体间的快速均匀混合等特点而引起了众多学者和生产者的极大关注。针对传统方法不易控制纳米粒子的粒径分布及形貌等缺点,本论文利用微反应器合成纳米分子筛和MOFs粒子。微通道流动法操作简单且连续,安全方便,通过改变反应温度、停留时间等参数,可以精确的调控所合成粒子的性能。同时可以将颗粒的成核及生长过程分开进行,为研究纳米颗粒的形成过程提供了一个良好的途径；沸石分子筛膜具有较好的热稳定性、化学稳定性和催化等性能,将微反应器和沸石分子筛膜结合起来,构建高效微反应器,实现反应器内催化分离一体化,可以用于精细化学品的高效合成。
(1)采用毛细管微通道反应器,研究了清液合成体系流动法条件下纳米NaA和Silicalite-1沸石分子筛的合成。考察了反应温度、陈化时间、停留时间等条件对其粒径大小、分布和形貌的影响。研究结果表明：降低反应温度,增加陈化时间和减少停留时间都能使分子筛的粒径变小。当反应温度为343K、陈化时间为72h、停留时间为5.8h时,可成功获得平均粒径约为60nm的NaA分子筛,且晶粒均匀呈椭球形；反应温度为371K,陈化时间为24h,停留时间为10h时,可获得平均粒径约为50nm的Silicalite-1分子筛。
(2)采用毛细管微通道反应器,以DMF作为溶剂,研究了ZIF-8纳米粒子的合成,考察了不同温度、停留时间对产物的影响。研究发现当停留时间为1min、温度控制在353K时,制备的ZIF-8粒子平均粒径为50nm,且具有典型的六方晶形结构；采用水作为溶剂,在温度为303K时,考察了不同反应物配比、停留时间对产物的影响。优化的合成参数是：停留时间为0.5min,前驱液配方是Zn2+：2-甲基咪唑：H2O=1：70：1240。在同样的合成条件下,分别用微通道和传统反应器制备ZIF-8,研究发现微通道的合成速率优于传统反应器。
(3)采用AP-TMS作为偶联剂,通过连续流动法在不锈钢微通道内表面组装了NaX分子筛晶种,然后通过流动法二次生长NaX沸石膜并进行质子化处理。将膜组装微反应器用于咪唑烷基化反应,并考察了反应条件对主产物N-丁基咪唑收率的影响。结果表明反应温度为333K,咪唑：溴代正丁烷=1：2,在膜组装微反应器中停留30min时,N-丁基咪唑的平均收率为92%,选择性为100%。膜组装微反应器不仅实现连续化制备,同时显示出比传统反应器更好的催化性能。
Micro-chemical system has so many advantages such as excellent transitivity, short mixing time and ability to achieve rapid and uniform mixing between the fluids that it attracts great concern of scholars and producers. Traditional synthesis methods have difficulties in controlling particle size distribution and morphology of nanoparticles. In this paper we investigate the use of microchannel to synthesize zeolite and MOFs nanoparticles. Microchannel continuous flow method is simple, convenient and safe, it can precisely control the properties of synthesized particles by changing reaction temperature, residence time and other parameters. Meanwhile, particle nucleation and particle growth process separately, which provides a good way to study the formation of nanoparticles. Zeolite membranes have good thermal, chemical and catalytic stabilities, which can combine the characteristics of the microreactor and zeolite membrane to construct efficient microreactor to separate catalysis and integration in the reactor and prepare fine chemicals.
(1) Continuous synthesis of NaA and Silicalite-1 Nanoparticles was conducted in a capillary microchannel reactor from clear solutions, and the effects of reaction temperature, aging time and residence time on the particle size distribution and morphology. It was indicated that smaller mean particle size and narrower particle size distribution of the products was obtained with lower reaction temperature, longer aging time and shorter residence time during the synthesis process. At the synthesis temperature of 343K, aging time of 72h and residence time of 5.8h, the NaA zeolite crystal with mean particle size of around 60nm was produced. And at the synthesis temperature of 371K, aging time of 24h and residence time of 1 Oh, the Silicalite-1 zeolite crystal with a mean particle size of around 50nm was obtained.
(2) Using DMF as the solvent, we investigated the influence of temperature and the residence time on the products prepared in a capillary microchannel reactor and found that ZIF-8 particles with an average diameter of 50 nm and a typical hexagonal crystal structure could be obtained at the residence time of 1min and the reaction temperature at 353K. We also explored the effects of different reactants ratios and residence times on the products employing water as solvent at 303K. Optimized synthesis parameters are:reaction temperature (303K), retention time (0.5 min), precursor liquid (Zn2+:2-methylimidazole:H2O=1:70:1240). We compared the microchannel flow method with the traditional synthesis method using the same reaction conditions. It was found that the synthesis speed of micro channel reactor is superior to that of a traditional one.
(3) NaX zeolites were assembled onto the internal surface of stainless steel multichannel microreactors using AP-TMS covalent linker. NaX Membrane was regrown in the channel on assembled reactor by continuous flow method. The hydrogen ion exchange was taken by the similar flow method, too. The performance of the synthesized membrane was tested by the alkylation of 1-bromobutane with imidazole, we studied the influences of reaction factors on N-alkylimidazoles yield (%). N-alkylimidazoles were obtained in high yields (average yield=92%) as main product (100% selectivity) under the following conditions:reaction temperature (333 K), molar ratio of imidazole to 1-bromobutane (1:2) and at the residence time of 30min. Assembled membrane microreactors not only make the production process continuous but also exhibit better catalytic property than that of conventional reactor.
(1)采用毛细管微通道反应器,研究了清液合成体系流动法条件下纳米NaA和Silicalite-1沸石分子筛的合成。考察了反应温度、陈化时间、停留时间等条件对其粒径大小、分布和形貌的影响。研究结果表明：降低反应温度,增加陈化时间和减少停留时间都能使分子筛的粒径变小。当反应温度为343K、陈化时间为72h、停留时间为5.8h时,可成功获得平均粒径约为60nm的NaA分子筛,且晶粒均匀呈椭球形；反应温度为371K,陈化时间为24h,停留时间为10h时,可获得平均粒径约为50nm的Silicalite-1分子筛。
(2)采用毛细管微通道反应器,以DMF作为溶剂,研究了ZIF-8纳米粒子的合成,考察了不同温度、停留时间对产物的影响。研究发现当停留时间为1min、温度控制在353K时,制备的ZIF-8粒子平均粒径为50nm,且具有典型的六方晶形结构；采用水作为溶剂,在温度为303K时,考察了不同反应物配比、停留时间对产物的影响。优化的合成参数是：停留时间为0.5min,前驱液配方是Zn2+：2-甲基咪唑：H2O=1：70：1240。在同样的合成条件下,分别用微通道和传统反应器制备ZIF-8,研究发现微通道的合成速率优于传统反应器。
(3)采用AP-TMS作为偶联剂,通过连续流动法在不锈钢微通道内表面组装了NaX分子筛晶种,然后通过流动法二次生长NaX沸石膜并进行质子化处理。将膜组装微反应器用于咪唑烷基化反应,并考察了反应条件对主产物N-丁基咪唑收率的影响。结果表明反应温度为333K,咪唑：溴代正丁烷=1：2,在膜组装微反应器中停留30min时,N-丁基咪唑的平均收率为92%,选择性为100%。膜组装微反应器不仅实现连续化制备,同时显示出比传统反应器更好的催化性能。
Micro-chemical system has so many advantages such as excellent transitivity, short mixing time and ability to achieve rapid and uniform mixing between the fluids that it attracts great concern of scholars and producers. Traditional synthesis methods have difficulties in controlling particle size distribution and morphology of nanoparticles. In this paper we investigate the use of microchannel to synthesize zeolite and MOFs nanoparticles. Microchannel continuous flow method is simple, convenient and safe, it can precisely control the properties of synthesized particles by changing reaction temperature, residence time and other parameters. Meanwhile, particle nucleation and particle growth process separately, which provides a good way to study the formation of nanoparticles. Zeolite membranes have good thermal, chemical and catalytic stabilities, which can combine the characteristics of the microreactor and zeolite membrane to construct efficient microreactor to separate catalysis and integration in the reactor and prepare fine chemicals.
(1) Continuous synthesis of NaA and Silicalite-1 Nanoparticles was conducted in a capillary microchannel reactor from clear solutions, and the effects of reaction temperature, aging time and residence time on the particle size distribution and morphology. It was indicated that smaller mean particle size and narrower particle size distribution of the products was obtained with lower reaction temperature, longer aging time and shorter residence time during the synthesis process. At the synthesis temperature of 343K, aging time of 72h and residence time of 5.8h, the NaA zeolite crystal with mean particle size of around 60nm was produced. And at the synthesis temperature of 371K, aging time of 24h and residence time of 1 Oh, the Silicalite-1 zeolite crystal with a mean particle size of around 50nm was obtained.
(2) Using DMF as the solvent, we investigated the influence of temperature and the residence time on the products prepared in a capillary microchannel reactor and found that ZIF-8 particles with an average diameter of 50 nm and a typical hexagonal crystal structure could be obtained at the residence time of 1min and the reaction temperature at 353K. We also explored the effects of different reactants ratios and residence times on the products employing water as solvent at 303K. Optimized synthesis parameters are:reaction temperature (303K), retention time (0.5 min), precursor liquid (Zn2+:2-methylimidazole:H2O=1:70:1240). We compared the microchannel flow method with the traditional synthesis method using the same reaction conditions. It was found that the synthesis speed of micro channel reactor is superior to that of a traditional one.
(3) NaX zeolites were assembled onto the internal surface of stainless steel multichannel microreactors using AP-TMS covalent linker. NaX Membrane was regrown in the channel on assembled reactor by continuous flow method. The hydrogen ion exchange was taken by the similar flow method, too. The performance of the synthesized membrane was tested by the alkylation of 1-bromobutane with imidazole, we studied the influences of reaction factors on N-alkylimidazoles yield (%). N-alkylimidazoles were obtained in high yields (average yield=92%) as main product (100% selectivity) under the following conditions:reaction temperature (333 K), molar ratio of imidazole to 1-bromobutane (1:2) and at the residence time of 30min. Assembled membrane microreactors not only make the production process continuous but also exhibit better catalytic property than that of conventional reactor.
引文
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