CN106824268A - 一种提高负载型催化剂催化选择性的方法及其应用 - Google Patents
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Abstract
本发明涉及一种提高负载型催化剂催化选择性的方法及其应用，当催化剂载体为有孔载体时，使用动力学直径大于载体孔尺寸的毒化剂与预先制备的负载型催化剂进行充分搅拌反应；当催化剂载体为无孔载体时，使用动力学直径大于目标选择性反应物的毒化剂与预先制备的负载型催化剂进行充分搅拌反应，得到毒化的负载型催化剂。该方法通过降低载体外表面金属纳米粒子的催化活性，保留内部金属纳米粒子的催化活性，亦或利用毒化剂对目标反应物的筛分，达到提高负载型催化剂催化选择性的效果。这种方法可有效提高烯烃的催化加氢反应中分子尺寸选择或化学反应位点选择性。
Description
技术领域
本发明涉及选择性催化剂技术领域，具体涉及一种提高负载型催化剂催化选择性的方法及其应用。
背景技术
择形催化自1960年由Weisz和Frilette提出以来已有近60年的历史，随着ZSM-5等系列分子筛材料在精细化工，石油化工中的广泛使用，择形催化被越来越多的人所熟知，也引起了研究者们广泛的兴趣。择形催化的选择性机理主要是利用纳米孔道的受限效应，通过扩散限制和空间位阻效应，对反应物、生成物或中间产物进行选择，从而达到选择性加氢、选择性氧化等选择性催化效果。近年来，随着纳米催化剂制备技术的突飞猛进，催化机理的研究深入，新型高效择形催化剂的设计与制备引起了研究者们广泛的关注。研究者们为了进一步提高择形催化剂的催化效率、拓展择形催化的适用范围，往往将纳米金属活性组分与其复合，利用纳米金属的高催化活性进一步提高选择性催化的转化率、开发新型择形催化反应体系，但由于择形催化剂(分子筛、金属有机骨架材料)纳米孔道的受限效应，纳米金属组分往往难以全部进入择形催化剂孔道内，造成催化剂选择性的大幅下降。研究者针对该问题，不断完善负载和复合技术手段，开发了双溶剂法、气相沉积法、等离子溅射法等复合方法，一定程度上解决了转化率和选择性不能兼得的问题，但还是很难保证活性组分全部进孔，从而降低活性组分对选择性的影响，同时这些方法往往较为复杂，很难用于高效择形催化剂的大规模制备。
发明内容
本发明的目的是提供一种提高负载型催化剂催化选择性的方法。该方法利用多孔载体的孔道选择性，选择分子动力学直径大于多孔载体孔径并且可以钝化或毒化金属纳米粒子催化活性的试剂，使负载于多孔载体外表面的金属纳米粒子降低或者失去催化活性，同时保留位于多孔载体孔道内部的金属纳米粒子的催化活性，或者利用动力学直径大于目标选择性反应物的毒化剂与无孔载体表面的金属纳米粒子相互作用，利用纳米粒子周围配位的毒化剂对目标反应物进行筛分，从而达到提高负载型催化剂催化选择性的效果。
本发明的目的通过以下技术方案实现：
一种提高负载型催化剂催化选择性的方法，当催化剂载体为有孔载体时，使用动力学直径大于载体孔尺寸的毒化剂与预先制备的负载型催化剂进行充分搅拌反应；当催化剂载体为无孔载体时，使用动力学直径大于目标选择性反应物的毒化剂与预先制备的负载型催化剂进行充分搅拌反应，得到毒化的负载型催化剂。
上述的提高负载型催化剂催化选择性的方法，进行催化反应之前预先向负载型催化剂的分散溶液中加入毒化剂进行处理。
上述的提高负载型催化剂催化选择性的方法，所述负载型催化剂是指活性组分负载在载体上的催化剂。
上述的提高负载型催化剂催化选择性的方法，所述的活性组分是指具有催化反应活性的组分；优选Pt、Pd、Au、Ag、Cu、Co、Fe、Zn、Ni、Mo纳米粒子中的至少一种。
上述的提高负载型催化剂催化选择性的方法，所述的有孔载体包括所有的有孔材料，优选A、X、Y型分子筛、活性炭、碳纳米管、氧化钛纳米管、多孔氧化铝、多孔氧化硅、多孔氧化钛中的至少一种；所述无孔载体包括所有的无孔材料，优选无孔氧化钛、无孔氧化铝、无孔氧化硅、无孔氧化铜中的至少一种。
上述的提高负载型催化剂催化选择性的方法，所述的毒化剂包括所有能与活性组分发生强相互作用的氮化物和硫化物，优选喹啉、1,8-二氮杂萘、8-羟基氮杂萘、2,3-二氮杂萘、苯硫酚、环己硫醇、三苯甲硫醇中的至少一种。
上述的提高负载型催化剂催化选择性的方法，所述搅反应的时间为1～48h，优选为2～24h。
采用上述的方法制备的高催化选择性负载型催化剂。
上述的方法在提高负载型催化剂分子尺寸选择性或化学反应位点选择性中的应用。
针对背景技术提出的技术问题问题，本发明的技术方案另辟蹊径，通过毒化剂毒化外表面的金属活性组分，使其丧失催化活性，从而在保证择形催化剂选择性的同时，进一步利用孔道内金属活性组分的催化活性提高催化剂的催化效率。同时，利用反应物、毒化剂与活性组分的竞争配位作用，使常见多孔甚至是无孔载体具有了择形催化效果，大大拓展了择形催化的适用范围。
本发明的有益效果：
相比于未经中毒剂处理的负载型催化剂，本发明提出的方法明显地提高负载型催化剂在不饱和烃尤其是烯烃的催化加氢反应中的分子尺寸选择性以及化学反应位点选择性。
具体实施方式
以下实施例是对本发明的进一步说明，不是对本发明的限制。
实施例1：分子筛催化剂烯烃的选择性催化加氢反应
选取孔径为的A型分子筛，通过传统的浸渍法制得Pt/分子筛负载型催化剂。反应前，将所制得的催化剂置于真空干燥箱中于120℃干燥处理10h。称取20mg处理后的分子筛催化剂置于12ml的玻璃瓶中，加入3ml的乙酸乙酯、62.5μL的正己烯和65μL的顺式-环辛烯，用硅胶塞密封。再用真空泵抽出瓶内气体，同时注入纯氢气，重复操作5次。将混合物进行超声分散10min后，室温搅拌反应24h。
实施例2：毒化Pt/分子催化剂烯烃的选择性催化加氢反应
称取20mg实施例1中处理后的分子筛催化剂置于12ml的玻璃瓶中，加入2ml乙酸乙酯和100μL毒化剂喹啉，用硅胶塞密封，将混合物进行超声分散10min后，室温搅拌反应2h。离心分离，用乙酸乙酯洗涤3次，烘干，再置于12ml的玻璃瓶中。加入3ml的乙酸乙酯、62.5μL的正己烯和65μL的顺式-环辛烯，用硅胶塞密封。再用真空泵抽出瓶内气体，同时注入纯氢气，重复操作5次。将混合物进行超声分散10min后，室温搅拌反应24h。对比实施例1、2的反应产物产率和选择性如表1所示。
表1分子筛催化剂用于正己烯和顺式-环辛烯的催化加氢反应的结果
实施例3：Pt/C催化剂毒化前后烯烃的选择性催化加氢反应
按照实施例1、2的过程将催化剂载体换成活性炭进行Pt/C催化剂催化加氢反应，结果如表2所示。
表2Pt/C催化剂用于正己烯和顺式-环辛烯的催化加氢反应的结果
实施例4：Pt/TiO2催化剂毒化前后烯烃的选择性催化加氢反应
按照实施例1、2的过程将催化剂载体换成无孔TiO2进行Pt/TiO2催化剂催化加氢反应，结果如表3所示。
表3 Pt/C催化剂用于正己烯和顺式-环辛烯的催化加氢反应的结果
实施例5：Pd/CNT催化剂毒化前后烯烃的选择性催化加氢反应
按照实施例1、2的过程将催化剂载体换成多壁碳纳米管(CNT)，活性组分换成Pd进行Pd/CNT催化剂催化加氢反应，结果如表4所示。
表4 Pd/CNT催化剂用于正己烯和顺式-环辛烯的催化加氢反应的结果
实施例6：催化剂毒化前后在烯烃的催化加氢反应中的应用
按照实施例1、2的过程将催化剂活性组分换成Pd，烯烃换成1,3-己二烯进行催化剂反应位点催化选择性加氢，结果如表5所示。
表5催化剂用于1,3-己二烯的催化加氢反应的结果
Claims (9)
1.一种提高负载型催化剂催化选择性的方法，其特征在于：当催化剂载体为有孔载体时，使用动力学直径大于载体孔尺寸的毒化剂与预先制备的负载型催化剂进行充分搅拌反应；当催化剂载体为无孔载体时，使用动力学直径大于目标选择性反应物的毒化剂与预先制备的负载型催化剂进行充分搅拌反应，得到毒化的负载型催化剂。
2.根据权利要求1所述的提高负载型催化剂催化选择性的方法，其特征在于：进行催化反应之前预先向负载型催化剂的分散溶液中加入毒化剂进行处理。
3.根据权利要求1所述的提高负载型催化剂催化选择性的方法，其特征在于：所述负载型催化剂是指活性组分负载在载体上的催化剂。
4.根据权利要求3所述的提高负载型催化剂催化选择性的方法，其特征在于：所述的活性组分是指具有催化反应活性的组分；优选Pt、Pd、Au、Ag、Cu、Co、Fe、Zn、Ni、Mo纳米粒子中的至少一种。
5.根据权利要求1所述的提高负载型催化剂催化选择性的方法，其特征在于：所述的有孔载体包括所有的有孔材料，优选A、X、Y型分子筛、活性炭、碳纳米管、氧化钛纳米管、多孔氧化铝、多孔氧化硅、多孔氧化钛中的至少一种；所述无孔载体包括所有的无孔材料，优选无孔氧化钛、无孔氧化铝、无孔氧化硅、无孔氧化铜中的至少一种。
6.根据权利要求1所述的提高负载型催化剂催化选择性的方法，其特征在于：所述的毒化剂包括所有能与活性组分发生强相互作用的氮化物和硫化物，优选喹啉、1,8-二氮杂萘、8-羟基氮杂萘、2,3-二氮杂萘、苯硫酚、环己硫醇、三苯甲硫醇中的至少一种。
7.根据权利要求1所述的提高负载型催化剂催化选择性的方法，其特征在于：所述搅拌反应的时间为1～48h，优选为2～24h。
8.采用权利要求1所述的方法制备的高催化选择性负载型催化剂。
9.权利要求1所述的方法在提高负载型催化剂分子尺寸选择性或化学反应位点选择性中的应用。
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