CN105797765A - 一种纳米级环己烯水合制备环己醇催化剂的合成方法 - Google Patents
一种纳米级环己烯水合制备环己醇催化剂的合成方法 Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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Abstract
本发明涉及一种纳米级环己烯水合制备环己醇催化剂的合成方法，通过微波法合成载体ZSM‑5，通过浸渍法将活性组分锆负载于ZSM‑5，将合成的负载型催化剂应用于环己烯水合反应中，具有与工业成熟应用催化剂相当的催化效果，反应后易分离，具有更好的市场前景。
Description
技术领域
本发明的技术方案属于环己醇的合成，涉及一种以环己烯为原料水合制备环己醇的工艺，具体涉及一种纳米级分子筛催化剂的合成及应用方法。
背景技术
环己醇是一种优良的中高沸点有机化工产品，被广泛应用于有机化工、纺织和涂料等行业，也可应用于消毒剂、香料、杀虫剂、皮革柔软剂和木材防腐剂等领域。环己醇可以作为制备尼龙6和尼龙66原料—己内酰胺和己二酸的中间体，工业需求量大。环己醇具有挥发性低、溶解性好等优点，可以作为溶剂，溶解许多高分子聚合物、醇酸树脂、醋酸纤维及橡胶等物质。
由环己烯为原料制备环己醇，主要是通过环己烯水合反应来制备环己醇。环己烯水合反应是典型的酸催化反应，在液体酸催化剂上如浓硫酸，主要是通过烷基酸酯中间物的生成，再进一步通过水解得到烷基醇的过程。早期使用硫酸作为催化剂，常温下催化环己烯水合制备环己醇，但由于硫酸工艺中存在产物回收复杂，能耗高、易腐蚀等缺陷；第二代水合催化剂被开发，使用离子交换树脂催化环己烯的水合反应，离子交换树脂解决了产品回收问题，但仍存在催化剂本身热稳定性差和寿命短、在有机溶剂中发生溶胀、价格高等不足，这些限制了这类催化剂在工业应用中的进一步发展。
分子筛催化剂是目前工业上应该较多的固体酸催化剂，其制备简单、性质稳定、易分离再生、机械强度高、抗热性能好等优点，纳米级的分子筛催化剂外表面积显著增加，吸附能力更强，有利用提高反应活性，孔道长度缩短，降低分子在孔道内的扩散阻力，有利于产物分子的快速脱除，使用寿命延长。负载型纳米级分子筛催化剂在性能上具有更优异的特性，可以提高催化剂的疏水性，使活性组分在反应过程中不易流失。在工业上为了达到客观的反应速率需要大量催化剂，开发更高效的水合催化剂具有重要意义。
发明内容
本发明提供了一种纳米级环己烯水合制备环己醇催化剂的合成方法，不采用模板剂，不需要经过高温焙烧过程，生产成本更低，生产工艺简单，更具有市场竞争力。在本发明方法中，所合成的催化剂是一种活性、选择性高，易分离，损失小，可重复使用。
本发明采用的技术方案如下：
(1)分别配制水玻璃溶液A，硫酸铝溶液B及硫酸溶液C，向水玻璃溶液A中滴加硫酸铝溶液B，测PH后，搅拌20分钟，再滴加硫酸溶液C，测PH值，搅拌30分钟，再测PH值，备用。三种溶液体积比为A:B:C＝6:5:6,控制硅铝摩尔比为25～30。
(2)将第一步所配好的浆料，打入晶化釜，微波合成，开动搅拌，结束后冷却到50℃。
(3)晶化后的母液打入板框压滤机，压去母液，母液排掉，空气吹干，用纯水洗涤至一定电导率用空气吹干，洗涤温度保持50℃。
(4)向酸洗罐的酸液中加入洗好的催化剂进行酸洗，交换2小时，再去压滤洗涤，反复5次，干燥，获得载体催化剂ZSM-5。
(5)称取一定量的四水硫酸锆(ZS)配置成溶液，加入载体催化剂ZSM-5，搅拌24小时，80℃缓慢蒸干溶剂，烘箱内至干燥完全，获得负载型纳米级分子筛催化剂。
具体实施方式
首先分别配制1.2立的硫酸铝溶液B和1.5立硫酸溶液C以及0.6立的水玻璃溶液A，装罐，备用；按照体积比A：B：C＝6:5:6，像A溶液中滴加B溶液，再滴加C溶液，滴加后搅拌30分钟，测PH；
将配好的浆料，打入晶化釜，开动搅拌，微波合成，晶化结束后通入冷却水降温至50℃，晶化后的母液经浆料泵打入板框压滤机，压去母液，母液直接排掉，空气吹干；通入高水洗涤至一定电导率后用空气吹干，洗涤水直接排放；通入低水洗涤至一定的电导率后用空气吹干，洗涤水会高水罐；通入去离子水洗涤至一定的电导率，吹干，洗涤水去低水罐。整个过程洗涤温度为50℃。
将酸洗罐当中加入酸液，保持40℃，开动搅拌状态下，逐渐加入洗好的催化剂，加完后，交换2小时，然后去压滤机压滤，压滤后用纯水适当洗涤；如此反复5次。酸洗合格的物料，压滤后，空气吹干，待用。
称取一定量量的四水硫酸锆(ZS)分别配置成溶液，加入载体催化剂ZSM-5，搅拌24小时，80℃缓慢蒸干溶剂，烘箱内至干燥完全，获得负载型纳米级分子筛催化剂。
将合成的纳米级分子筛催化剂用于催化环己烯水合制备环己醇的反应中，将混合物(比例为：环己烯120g，水150g，催化剂40g)加入水合反应器，搅拌，反应温度：120～125℃，反应时间：0.6小时。
效果对比：
将使用本发明方法合成的催化剂与工业成熟应用的旭化成催化剂进行性能对比，可以发现：
(1)本发明催化剂环己烯转化率与旭化成催化剂相当(转化率决定产量)；
(2)环己醇选择性可达到99％以上(选择性决定原料的利用率)；
(3)反应后油水混合物分离快，油相清澈，基本接近无色(分离效果决定了工艺的可操作性)；
(4)通过显微镜观察，纳米级分子筛催化剂粒径分布合理，过滤时催化剂损失小(粒度分布决定了反应过程催化剂的流失量)；
本发明提出的一种纳米级环己烯水合制备环己醇催化剂的合成方法，已通过较佳的实施例子进行了描述，其中未详细述及的部分均为本领域技术人员的公知常识。本发明的保护范围以权利要求的内容为准，所有基于本发明的技术启示或类似的替换和改动，都被视为包括在本发明精神、范围和内容中。
Claims (4)
1.一种纳米级环己烯水合制备环己醇的催化剂，其特征是将活性组分锆负载于纳米级催化剂载体ZSM-5，载体ZSM-5使用硫酸铝、硫酸及水玻璃溶液制备。
2.根据权利要求1所述的一种纳米级环己烯水合制备环己醇催化剂的合成方法，其特征为分别配置三种反应物的溶液，采用微波法合成载体ZSM-5。
3.根据权利要求1所述的一种纳米级环己烯水合制备环己醇催化剂的合成方法，其特征为采用浸渍法，将金属锆盐负载于ZSM-5，获得负载型纳米催化剂。
4.根据权利要求1所述的一种环己烯水合制备环己醇催化剂的合成方法，其特征步骤如下：
a)按溶液体积比Na2SiO3：Al2(SO4)3：H2SO4＝6:5:6的比例混合，混合过程开启搅拌，并测PH值，采用微波法合成，经过过滤，酸洗，干燥获得载体ZSM-5；
b)称取一定量的金属锆盐配置溶液，加入载体ZSM-5，搅拌，恒温蒸干溶剂，得到负载型纳米催化剂。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538051A (zh) * | 2009-05-06 | 2009-09-23 | 北京化工大学 | 一种zsm-5沸石催化剂的制备方法 |
| CN102584537A (zh) * | 2011-12-30 | 2012-07-18 | 中国天辰工程有限公司 | 一种合成环己醇的方法 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538051A (zh) * | 2009-05-06 | 2009-09-23 | 北京化工大学 | 一种zsm-5沸石催化剂的制备方法 |
| CN102584537A (zh) * | 2011-12-30 | 2012-07-18 | 中国天辰工程有限公司 | 一种合成环己醇的方法 |
Non-Patent Citations (2)
| Title |
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| ZHAOXIA SONG等: ""Production of Propylene from Ethanol Over ZSM-5 Zeolites"", 《CATAL LETT》 * |
| 卢永斌等: ""纳米ZSM-5分子筛的合成及应用"", 《天然气化工（C1化学与化工）》 * |
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