CN105879907A - 一种固载化离子液体催化剂及其在合成酯类润滑油制备中的应用 - Google Patents
一种固载化离子液体催化剂及其在合成酯类润滑油制备中的应用 Download PDFInfo
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Abstract
本发明公开了一种固载化离子液体催化剂,该催化剂通过以下方法制备得到:1)将离子液体、无水乙醇、正硅酸四乙酯在40 oC~70 oC恒温搅拌至离子液体溶解、溶液澄清,然后加入盐酸溶液,继续搅拌1 h~3 h后静置陈化12 h~24 h,即得介孔二氧化硅固载化离子液体催化剂的初产物;2)将所述介孔二氧化硅固载化离子液体催化剂的初产物在80 oC~100 oC真空干燥3 h~6 h,即得介孔二氧化硅固载化离子液体催化剂。本发明还公开了该催化剂在合成酯类润滑油制备中的应用。本发明涉及的催化剂合成方法简单,催化剂活性高,大大加快了其工业化应用的进程。
Description
技术领域
本发明涉及一种固载化离子液体催化剂及其在合成酯类润滑油制备中的应用。
背景技术
合成酯类基础油由于其具有优异的高低温性能、润滑性能及其它良好的综合性能,一直作为航空润滑油料的关键组分在航空领域发挥着不可或缺的作用;同时又由于其具有性能可调、原料来源可再生、环境友好等特点,从而在汽车、冶金、水泥等行业具有重要潜在应用。国际方面在合成酯构效关系、制备工艺、性能及应用等方面开展了大量的研究工作,但其研究深度和系统性等方面仍需进一步加深和完善。国内合成酯基础理论与关键技术匮乏,合成酯工业基本处于空白,制约了我国航空等高新技术工业的突破和交通运输等行业节能技术的发展。因此,发展符合要求的高性能合成酯类润滑基础油是解决上述问题关键因素。
合成酯是有机醇与有机酸通过酯化反应得到的产物,酯化反应本身简单,反应物在热和催化剂的作用下生成酯类化合物和水。酯化反应可以在无催化剂下进行,但反应速度较慢,所以在生产实践中,酯化反应一般都有加入催化剂。在酯类润滑油的发展过程中催化剂起着至关重要的作用,然而用于酯化反应的无机强酸、固体酸以及酸性离子交换树脂等传统酸催化剂均存在一些不足之处,如腐蚀设备、难分离、易失活等,效果均不十分理想。酸性离子液体作为一种新型环境友好液体酸催化剂,它同时拥有液体酸的高密度反应活性位点和固体酸的不挥发性,其分子结构和酸性可调,与产物易分离,热稳定性高,是真正意义上可设计的催化剂。然而均相的离子液体在催化的过程中也存在着很多缺点:用量大且具有一定的腐蚀性、能耗大、成本高,从而限制了离子液体作为一类新型高效的催化剂在工业中的应用。
与均相催化剂相比,固载化的离子液体催化剂具有分离和再生简单、腐蚀性小、成本低等优点,因此本发明将离子液体固载化,使得均相的离子液体转变为多相的状态。本发明选择介孔二氧化硅作为离子液体的载体,通过溶胶-凝胶的方法将离子液体成功负载到载体二氧化硅上。介孔材料负载的多相催化剂具有大的比表面积和孔容、丰富的纳米孔结构,有利于催化反应过程中底物和产物的扩散和传输,进而大大提高催化剂的催化活性,因此多相化的离子液体催化剂具有重要的应用前景。
发明内容
本发明的目的是提供一种固载化离子液体催化剂及其在合成酯类润滑油制备中的应用。本发明以正硅酸四乙酯为硅源、无水乙醇为溶剂、离子液体为催化剂活性物种、盐酸溶液为成胶剂,采用溶胶-凝胶的方法制备得到介孔二氧化硅固载的离子液体催化剂,并将该催化剂用于季戊四醇多元醇酯润滑油的合成。
一种固载化离子液体催化剂,其特征在于该催化剂通过以下方法制备得到:
1)将离子液体、无水乙醇、正硅酸四乙酯在40 oC
~ 70 oC恒温搅拌至离子液体溶解、溶液澄清,然后加入盐酸溶液,继续搅拌1 h ~
3 h后静置陈化12 h ~ 24 h,即得介孔二氧化硅固载化离子液体催化剂的初产物;
2)将所述介孔二氧化硅固载化离子液体催化剂的初产物在80 oC
~ 100 oC真空干燥3 h ~ 6 h,即得介孔二氧化硅固载化离子液体催化剂。
所述离子液体为1-丁基磺酸-3-甲基咪唑硫酸氢盐、1-丁基磺酸-3-甲基咪唑磷酸二氢盐或1-丁基磺酸-3-甲基咪唑三氟乙酸盐。
所述无水乙醇与正硅酸四乙酯的摩尔比为 1 ~ 8:1。
所述离子液体与正硅酸四乙酯的质量比为 7:500 ~
23:330。
所述盐酸溶液的摩尔浓度为 3 ~ 8 mol/L;盐酸溶液与无水乙醇的体积比为2:15 ~ 5:4。
如上所述催化剂在合成酯类润滑油制备中的应用,其特征在于以季戊四醇、有机酸为原料,以介孔二氧化硅固载化离子液体为催化剂,以甲苯为除水剂,在155oC ~ 170 oC反应10 h后经离心分离、旋转蒸发即得季戊四醇多元醇酯。
所述季戊四醇与有机酸的摩尔比为4:1。
所述介孔二氧化硅固载化离子液体与季戊四醇的质量比为1:9。
所述有机酸为正戊酸、正己酸、正庚酸、正辛酸、正壬酸或正癸酸。
与现有技术相比,本发明具有以下优点:本发明采用溶胶-凝胶的方法通过改变离子液体的用量调控二氧化硅固载离子液体催化剂的孔容、孔径和比表面积,使得其孔容在0.9 ~
4 cm3/g、孔径在7 ~ 35 nm、比表面积在300 ~ 700 m3/g范围内可调。
本发明涉及的催化剂合成方法简单,催化剂活性高,大大加快了其工业化应用的进程。
通过表征发现,该催化剂孔径分布在7 ~ 35 nm之间,是典型的介孔材料。
本发明中催化合成季戊四醇多元醇酯润滑油是按照在化学计量比进行的,该催化反应可在较低的反应温度和较短的反应时间内完成,且可得到高纯产物。
附图说明
图1为本发明实施例5制得的IL1/SiO2-5%催化剂的氮气吸附等温线。
图2为本发明实施例5制得的IL1/SiO2-5%催化剂的TG/DTA图。
图3 为本发明实施例5制得的IL1/SiO2-5%催化剂的透射电镜图。
具体实施方式
下面通过实施例对本发明作进一步说明,其目的在于更好的理解本发明的研究内容。
实施例1
1-丁基磺酸-3-甲基咪唑硫酸氢盐([BHSO3MIm]HSO4)的合成
步骤一. 将1 mol甲基咪唑、等摩尔的4-丁烷磺内酯和100 mL丙酮混合于三口烧瓶中,25 oC下用机械搅拌反应3天。有白色固体析出时将反应温度提高到50 oC,继续反应3天,有大量的白色固体析出,过滤所得白色固体即为BMImSO3,蒸馏后可以再次结晶出BMImSO3,将产物用丙酮洗涤纯化。
步骤二. 在冰浴搅拌的条件下,将1 mol上述产物缓慢滴加到1.02 mol浓硫酸(98%)中,生成液体产物,将产物中的水蒸干,得到无色粘稠液体 [BHSO3MIm]+[HSO4]-。
实施例2
1-丁基磺酸-3-甲基咪唑磷酸二氢盐的合成
在冰浴搅拌的条件下,将1 mol实施例1步骤一中产物缓慢滴加到1.18 mol浓磷酸(85%)中,生成液体产物,将产物中的水蒸干,得到无色粘稠液体[BHSO3MIm]+[H2PO4]-。
实施例3
1-丁基磺酸-3-甲基咪唑三氟乙酸盐的合成
在冰浴搅拌的条件下,将1 mol实施例1步骤一中产物缓慢滴加到等摩尔量的三氟乙酸中,生成固体产物,将产物中的水蒸干,得到白色固体[BHSO3MIm]+[CF3CO2]-。
实施例4
分别量取4 mL无水乙醇、5 mL正硅酸四乙酯于100 mL圆底烧瓶中,60 oC水浴中搅拌至溶液澄清。量取2.5 mL已配置好的6
mol/L的盐酸溶液慢慢滴加至上述溶液中成胶,滴加完毕继续搅拌1 h后陈化。陈化24 h后80 oC真空干燥4 h即可得到二氧化硅,标记为SiO2,产率为90%,
实施例 5
首先将0.066 g离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐加入到100 mL圆底烧瓶中,再加入4 mL无水乙醇磁力搅拌下将离子液体溶解后,取5 mL正硅酸四乙酯滴加到上述溶液中,60 oC水浴中继续搅拌30
min至溶液澄清。量取2.5 mL已配置好的6
mol/L的盐酸溶液慢慢滴加至上述溶液中成胶,滴加完毕继续搅拌1 h后陈化。陈化24 h后80 oC真空干燥4 h即可得到负载量为5%(质量分数)离子液体催化剂,标记为IL1/SiO2-5%,产率为80%,孔径在35 nm,比表面积为700 m3/g。
图1是本发明实施例5制得的IL1/SiO2-5%催化剂的氮气吸附等温线。如图1所示,该材料具有明显的IV型吸附等温线,说明材料具有典型的介孔结构。
图2是本发明实施例5制得的IL1/SiO2-5%催化剂TG/DTA图。从图中可以看出该催化剂的热分解分为两个部分,首先,从室温到200 oC范围内的失重对应于催化剂吸附的水分和其表面羟基缩和所失去的水的质量。其次,200-490 ºC 范围内的失重则对应于硅胶孔内表面与羟基直接相互作用的离子液体层的受热分解和硅胶中离子液体聚集主体的热分解阶段。
图3 是本发明实施例5制得的IL1/SiO2-5%催化剂透射电镜图。从图中可以看出,该催化材料具有丰富的孔道且分布比较均匀,与BET表征的结果一致,而丰富的纳米多孔结构有利于物质的扩散和传输,进一步提高了本发明制备催化剂的催化活性。
实施例6
除了将离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐的用量改为0.14 g,其它的步骤与实施例5相同,得到是离子液体负载量为10%(质量分数)的催化剂,标记为IL1/SiO2-10%,产率为85%,孔径在26 nm,比表面积600 m3/g。
实施例7
除了将离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐的用量改为0.22 g,其它的步骤与实施例5相同,得到是离子液体负载量为15%(质量分数)的催化剂,标记为IL1/SiO2-15%,产率为85%,孔径在15 nm,比表面积400 m3/g。
实施例8
除了将离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐的用量改为0.32 g,其它的步骤与实施例5相同,得到是离子液体负载量为20%(质量分数)的催化剂,标记为IL1/SiO2-20%,产率为85%,孔径在8 nm,比表面积300 m3/g。
实施例 9
除了将离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐改为1-丁基磺酸-3-甲基咪唑磷酸二氢盐,其它的步骤与实施例5相同,得到是离子液体负载量为5%(质量分数)的催化剂,标记为IL2/SiO2-5%,产率为85%。
实施例 10
除了将离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐改为1-丁基磺酸-3-甲基咪唑三氟乙酸盐,其它的步骤与实施例5相同,得到是离子液体负载量为5%(质量分数)的催化剂,标记为IL3/SiO2-5%,产率为85%。
实施例11
分别称取5.01 g异丙醇铝、25.5
g异丙醇、2.7 g十六烷基三甲基溴化铵和0.066
g离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐于100 mL圆底烧瓶中,经搅拌均匀后向其中滴加13 mL
3 mol/L的盐酸溶液,滴加完毕后25 oC继续搅拌4 h,然后升温至80 oC搅拌2 h,110 oC真空干燥12 h即可得到氧化铝负载离子液体催化剂的初产物,将上述进一步在550 oC焙烧5 h即可得到最终产物即氧化铝负载离子液体催化剂(负载质量百分数为5%),标记为IL1/Al2O3-5%,产率为75%。
实施例12
称取2.3 g正丙醇锆溶液(质量分数为70%)、0.032 g离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐于100 mL圆底烧瓶中,再加入3.1 mL无水乙醇40 oC水浴中搅拌至离子液体溶解后,向其中滴加2 mol/L的硝酸溶液,继续搅拌1 h后陈化24 h,150 oC真空干燥即可得到氧化锆负载离子液体催化剂的初产物。将上述初产物在550 oC条件下焙烧5 h即可得到最终产物(离子液体负载量为5%),标记为IL1/ZrO2-5%,产率为85%。
实施例13
首先称取0.066 g 离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐于100 mL圆底烧瓶中,量取26 mL无水乙醇将其搅拌溶解,然后将5.30 g钛酸四丁酯加入其中60 oC搅拌。分别量取5 mL去离子水、25 mL无水乙醇和8.5 mL乙酸于滴液漏斗中,混合均匀后滴加入烧瓶中,滴加完毕继续搅拌1 h,静置陈化24 h,80 oC真空干燥 4 h即可得到二氧化钛固载离子液体催化剂的初产物。将上述初产物550 oC焙烧5 h即可得到二氧化钛固载离子液体催化剂(负载质量百分数为5%),标记为IL1/TiO2-5%,产率为80%。
实施例14
催化反应:以季戊四醇和正己酸酯化反应得到季戊四醇四正己酸酯为模型反应,按照化学计量比4:1(摩尔比)分别称取1.8 g季戊四醇和6.13 g正己酸于100 mL三口烧瓶中以,加入0.2 g固载化的离子液体催化剂,2 mL 甲苯作为除水剂,158 oC反应10 h,产物经离心分离、旋转蒸发后参考国标GB/T4945-2002测量产物酸值,通过酸值对产物的酯化程度进行分析。其中酯化率的计算公式如下:
酯化率(%)= [ (
1 – 产物酸值/初始酸值) × 酸醇摩尔比 ÷ 4 ] × 100%
表格1 不同催化剂催化季戊四醇与正己酸酯化反应性能测试
表格1中给出了不同载体负载的离子液体催化剂的催化活性区别,从表格中我们可以知道在二氧化硅负载的[BHSO3MIm]HSO4、[BSO3HMIm]H2PO4、[BSO3HMIm]CF3CO2这三种离子液体催化剂中,离子液体[BHSO3MIm]HSO4即IL1具有相对较好的催化活性,因此选用IL1作为活性中心对催化剂的载体进行筛选,结果表明载体二氧化硅固载的IL1催化剂具有最好的催化活性。
实施例15
催化反应:按照季戊四醇与正戊酸的摩尔比为4:1分别称取1.8 g季戊四醇和5.45 g正戊酸于100 mL三口烧瓶中,加入0.2 g IL1/SiO2,2 mL 甲苯作为除水剂,155 oC反应10 h,产物经离心分离、旋转蒸发后加入一定质量的三苯甲烷作为内标,通过核磁共振对产物进行定量分析。
实施例16
催化反应:除了将正戊酸改为等摩尔量的正己酸,反应温度为158 oC,其它均与实施例15相同。
实施例17
催化反应:除了将正戊酸改为等摩尔量的正庚酸,反应温度为160 oC,其它均与实施例15相同。
实施例18
催化反应:除了将正戊酸改为等摩尔量的正辛酸,反应温度为160 oC,其它均与实施例15相同。
实施例19
催化反应:除了将正戊酸改为等摩尔量的正壬酸,反应温度为165 oC,其它均与实施例15相同。
实施例20
催化反应:除了将正戊酸改为等摩尔量的正癸酸,反应温度为170 oC,其它均与实施例15相同。
表格2 离子液体催化剂IL1/SiO2催化合成酯类润滑基础油性能研究
表格2中列出了IL1/SiO2催化合成几种酯类基础润滑油的测试结果。从表格中我们看到该催化剂对于催化合成多元醇酯类基础润滑油表现出了优异的性能,在相对较低反应温度及较短时间内获得高于92%的酯化反应收率,且催化剂较易分离。对于其它结构季戊四醇酯的合成也表现出较好的催化性能,产物收率最高可达98%。
Claims (8)
1.一种固载化离子液体催化剂,其特征在于该催化剂通过以下方法制备得到:
1)将离子液体、无水乙醇、正硅酸四乙酯在40 oC~70 oC恒温搅拌至离子液体溶解、溶液澄清,然后加入盐酸溶液,继续搅拌1 h ~ 3 h后静置陈化12 h ~ 24 h,即得介孔二氧化硅固载化离子液体催化剂的初产物;所述的离子液体为1-丁基磺酸-3-甲基咪唑硫酸氢盐、1-丁基磺酸-3-甲基咪唑磷酸二氢盐或1-丁基磺酸-3-甲基咪唑三氟乙酸盐;
2)将所述介孔二氧化硅固载化离子液体催化剂的初产物在80 oC ~ 100 oC真空干燥3 h ~ 6 h,即得介孔二氧化硅固载化离子液体催化剂。
2.如权利要求1所述的催化剂,其特征在于所述无水乙醇与正硅酸四乙酯的摩尔比为 1 ~ 8:1。
3.如权利要求1所述的催化剂,其特征在于所述离子液体与正硅酸四乙酯的质量比为 7:500 ~ 23:330。
4.如权利要求1所述的催化剂,其特征在于所述盐酸溶液的摩尔浓度为 3 ~ 8 mol/L;盐酸溶液与无水乙醇的体积比为2:15 ~ 5:4。
5.如权利要求1至4任一项所述催化剂在合成酯类润滑油制备中的应用,其特征在于以季戊四醇、有机酸为原料,以介孔二氧化硅固载化离子液体为催化剂,以甲苯为除水剂,在155 oC ~ 170 oC反应10 h后经离心分离、旋转蒸发即得季戊四醇多元醇酯。
6.如权利要求5所述的应用,其特征在于所述季戊四醇与有机酸的摩尔比为4:1。
7.如权利要求5所述的应用,其特征在于所述介孔二氧化硅固载化离子液体与季戊四醇的质量比为1:9。
8.如权利要求5所述的应用,其特征在于所述有机酸为正戊酸、正己酸、正庚酸、正辛酸、正壬酸或正癸酸。
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