CN1004132B - 酯化反应新方法 - Google Patents
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Abstract
发明属于醇酸直接酯化反应。一种新型酯化催化剂,其特征在于它是一种由天然丝光沸石经过化学处理成为一种以缺铝氢型丝光沸石为基础的固体酸催化剂,其化学组成为SiO↓[2]65~90%,Al↓[2]O↓[3]2~5%。本发明详细介绍此种催化剂在酯化反应中的应用技术。
Description
本发明属于醇酸酯化反应。
醇酸酯化是人们熟知的平衡反应,为了提高酯的收率对于旨在破坏平衡,促进酯化的各种催化剂已进行过许多研究,迄今为止,最常用的催化剂有酸(主要是硫酸)重金属盐以及离子交换树脂等,目前国内酯类产品的生产,仍然沿用硫酸作酯类生产的催化剂,因为酯类对离子交换树脂有溶涨作用,催化剂易被破坏而未能推广应用,重金属盐对食品是一种讳忌物很难通过食品检验。而硫酸法酯化虽然有适应性广等优点,但对于 能溶于水的醇和酸其转化率一般只能达到60~70%左右,而且有后处理工艺冗长、腐蚀设备、三废污染环境等缺点,为解决上述问题,我们采用丝光沸石分子筛(Mordenite)进行酯化反应,实验结果表明,采用等克分子或醇或酸过量的情况下,酯化转化率达95%以上,获得满意结果。使用分子筛进行裂解、异构化、烷基化、加氢脱氢、氧化、煤的液化、卤化(主要是氯化)、废水处理、吸收等反应及工艺的研究报导极多,但用作酯化催化剂国内外文献报导也不多见,1970年苏联格列利奇科等人用合成分子筛和活性炭作催化剂把邻苯二甲酸酐与相应的醇反应合成增塑剂邻苯二甲酸酯得到100%产率,1974年印度ThakarH.P等用磷酸-硅胶作催化剂酯化得到84%醋酸丁酯,1975年日本Onada TaKeru等用先后经Pd,Sb盐类和K,2n的醋酸盐浸渍烘焙过的载体SiO2做催化剂由烯烃、氧和醋酸经气相催化反应合成酯,1979年苏联G.N娜斯列娃等在试验中发现经Ti及B交换的分子筛是最有效的催化剂,得到了94~98%癸二酸辛二酯,1980年苏联V.SKrasnobaeva用Ku-2,Ku-3,Nar,Nax,CaA和Cax等合成分子筛作催化剂合成了烯丙基酯,证明用分子筛比离子交换树脂或硫酸作催化剂有较好的酯化结果,并确定了酯化的最适条件,1983~84年我国兰州大学化学系王秋莹等人,使用HY型、HZSM-5型826HM及SD-261等固体酸催化剂合成了丙烯酸酯类系列产品,但该文在使用HM(丝光沸石)作催化剂时,效果不理想,丙烯酸酯产率只有48%,国内的兰大王秋莹等在筛选固体酸催化剂时使用过这种催化剂。但他们的处理方法获得的沸石分子筛效果并不理想,本发明采用的处理沸石分子筛的方法,对于饱和一元羧酸和十碳以下的伯醇酯化均有良好的效果,其酯化转化率达95%以上,本发明由于革除硫酸作催化剂,因而免去了冗长的后处理工艺,并避免了由于使用硫酸而引起的设备腐蚀和三废污染环境,从而降低成本缩短工时,尤其对于食用酯类的生产,应更有安全感,故是目前较为理想的酯化方法。
本发明采用天然丝光沸石经过一定的化学处理成为一种缺铝氢型丝光沸石,天然丝光沸石产于浙江省缙云县岱石口矿,有效含量70%,经过特殊处理其化学组成为:
SiO2 65~90%
Al2O3 2~5%
同样,合成丝光沸石经过特殊化学处理也可以成为如上所述的性能良好的催化剂,下面以实施例形式,分别阐述催化剂的制备和应用方案。
实例一 催化剂的制备
A.天然丝光沸石的处理方法
把天然丝光沸石破碎后(直径1~3mm)的颗粒1000克,用0.5N~4N的盐酸(或硫酸)溶液4千克,在强力搅拌下控温90~100℃加热处理1小时,然后倾去上层清液,再次加入4千克的0.2-2N酸溶液重复处理2~5次,洗净烘干后在400~600℃下焙烧4小时,重复酸处理过程和焙烧过程,将经处理的催化剂置于洁净器皿中备用。
B.合成丝光沸石的处理方法
把合成丝光沸石(粉状)1000克加入0.1~5N(最好是0.5N)的盐酸或(硫酸)溶液4千克,在强力搅拌下控温90~100℃加热处理1小时,然后倾去上层清液再次加入4千克的0.2-2N酸溶液,重复处理2~5次,洗净烘干后在400~600℃下焙烧4小时,重复酸处理和焙烧过程,将经处理的催化剂置于洁净皿中备用。
实例二 丙酸丁酯的制备
在一个装有回流冷凝器、分水器、温度计和搅拌马达的100毫升三口烧瓶中,加入丙酸29.65克,丁醇29.64克和实例一中经处理后的丝光沸石30%~50%,反应烧瓶置于一带有自动温度控制器的加热套上在猛烈的搅拌下于120℃~150℃下,加热回流4小时,当分水器中分出的水不再增加时除去加热套待物料冷却至室温时,停止搅拌记取分出的水量,当沸石催化完全下沉之后,倾出上层清液取样分析称取上层粗产品约50克,产率96%,同样可以制取一系列水溶性低或水不溶的醇和酸的酯如丙酸异丁酯、丁酸丙酯、丁酸异丙酯、丁酸丁酯、丁酸戊酯等,同类型反应的实施例试验数据列于表一中。(第5页)
实例三 己酸乙酯的合成
A.在一装有回流冷凝器、温度计、加料漏斗及电动马达的四口烧瓶中加入己酸34.86克,乙醇18.4克,再生合成沸石分子筛催化剂30%~50%,反应瓶置于一个带有自动控温的加热套上,在强力搅拌下于90~150℃加热回流,不时地从加料漏斗中补充等体积的新鲜乙醇,加入速度与分水器中醇-水混合液的馏出速度相一致,直至反应混合物从开始回流时的80℃~90℃,逐步升高到128℃~135℃,使加入己酸基本上完全反应为止,补加醇的量约35克,反应时间约14~20小时,待反应完成之后,继续蒸出多余的乙醇,回收的乙醇经处理后重用,除去加热套冷却反应混合物,停止搅拌待催化剂完全下沉之后,倾出上层清液,少量的酸经碱中和后蒸馏即得纯品己酸乙酯35克,收率80.72%。
B.固定床流通式连续酯化操作方法
在一长1100mm,直径25mm的圆玻璃柱中装填入338克φ1~3mm的实例一中经处理过的天然沸石分子筛。柱外两端分别装上0~250℃温度计各两支。填充管置于一绕有电热丝或水夹套的加热套管中,加热套管接一电表及调压变压器以控制加热温度。如用水夹套加热则用一恒温水浴控制加热温度,当内管温度升至150~158℃时,从装有配成一定比例的己酸和乙醇混合料的恒压加料漏斗上以120~180ml/小时的滴加速度,通过不锈钢针型阀或注射泵均匀地从底部加入混合物料至反应管中,柱顶馏出物用一装有回流冷凝器的两口烧瓶承接,反应生成物用气相色谱测定其转化率,取出合格的物料,分去反应生成的水层后,用-50cm的填充柱分馏,即可获得纯度99.99%(色谱含量)的产品。单程转化率一般可达95%以上,纯品总收率可达90%以上,固定床流通式连续酯化适用于水溶性大的乙醇酯类,如丙酸乙酯、丁酸乙酯、己酸乙酯、庚酸乙酯等十碳以下的脂肪酸乙醇酯类的生产,实验结果见表二、表三和表四。
实例四 乳酸乙酯的合成
在一个带有实例二装置的反应烧瓶中加入乳酸27.02克,乙醇13.8克,甲苯10毫升和经实例一B处理过的沸石分子筛催化剂30%~50%,并把反应瓶置于能自动控温的加热套上,在强力搅拌下于90~110℃加热4小时,当分水器中分出的水不再增加时,除去加热套并停止搅拌记下分出的水量,并蒸出残余的甲苯,待催化剂完全下沉之后,倾出上层清液称取重量结果得乳酸乙酯粗品29克,产率81.9%,同样可以制备乳酸甲酯、乙酸乙酯、三乙酸甘油酯、二乙酸乙二醇酯等一系列产品。
实例五 催化剂的再生
实例一中所述的催化剂,经长期反应失效后,可以再生活化后恢复活性再使用,其再生方法是把失效的催化剂置于400~600℃的马弗炉中煅烧4~6小时,待所有的有机沉积物燃烧殆尽即可得到再生,继续使用。
表一 丝光沸石分子筛催化酯化反应结果
表二 固定床流通式乙酯类酯化反应的结果
表三 丙酸乙酯二次反应结果
表四 流通式己酸乙酯批量生产模拟试验
Claims (7)
1、一种使用缺铝氢型丝光沸石固体酸催化剂的直接酯化方法,其特征在于:
①流通式连续酯化方法:在一圆玻璃柱中,装入经处理的天然丝光沸石催化剂,柱外两端分别装有两支温度计,填充管置于-绕有电热丝的加热套管中,加热套管接一电表和变压器以控制温度,当内管温度升高至80~170℃时,可将酸和醇的混合物从底部加入反应管中柱顶馏出物冷凝后回收,经分馏后可得产品。
②锅式酯化反应:在一个装有回流冷凝器、分水器、温度计、加热漏斗和搅拌马达的容器中加入经处理的天然或合成丝光沸石催化剂和醇、酸反应物反应器置于一个带有自动控制的加热套上,在强力搅拌下加热回流温度至110~180℃。冷却反应物,经分馏后即得产品。
2、根据权利要求1①中所述的方法,其特征为圆玻璃柱长度为1100mm,直径为25mm。
3、根据权利要求1①中所述的方法,其特征为酸和醇混合液中酸和醇克分子比为1∶1~2.1,醇酸混合物以120~180ml/小时的速度均匀地从底部加入反应管中。
4、根据权利要求1②中所述的方法,其特征为反应物中醇和酸比例为1∶1,催化剂加入量为总物料量的30~50%。
5、根据权利要求1中所述的方法,其特征为沸石分子筛催化剂组成中二氧化硅为65~90%,三氧化二铝为2.0%~5%(重量百分比)。
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CN100344371C (zh) * | 2004-08-31 | 2007-10-24 | 中国石油化工股份有限公司 | 一种固体超强酸催化材料的制备方法 |
CN104117378B (zh) * | 2014-06-29 | 2016-03-02 | 陈昆 | 酯化反应催化剂的制备方法 |
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