CN105964300A - 一种生物柴油酯化非均相催化剂及其制备方法 - Google Patents
一种生物柴油酯化非均相催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种生物柴油酯化非均相催化剂及其制备方法,所述催化剂是一种以MIL‑100/AILs颗粒为核相材料,以ZIF‑8为壳相材料形成的具有核壳结构的MIL‑100/AILs@ZIF‑8催化剂,并对MIL‑100、AILs、MIL‑100/AILs和MIL‑100/AILs@ZIF‑8的制备方法进行了介绍;所述催化剂能够用于合成生物柴油。本发明所述催化剂具有催化活性高、不容易失活、易分离、可循环使用、环境友好和选择性高等优点。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种生物柴油酯化非均相催化剂及其制备方法。
背景技术
近年来,由于环境污染以及能源短缺等问题,大量非石油的可替代性燃料逐渐受到大家的重视。其中,生物柴油因具有简单降解、燃烧无排放和无温室效应气体等优势,作为清洁、可再生能源而备受关注。生物柴油由各种长链脂肪酸甲酯、乙酯组成,可通过长链脂肪酸与短链醇的酯化反应合成。当前,生物柴油工业的主要难题在于催化剂的选用。
在CN201010294014.0的专利中,介绍了一种酸化油生产生物柴油的复合酸催化剂,它由浓硫酸、浓磷酸和直链烷基苯磺酸组成,其采用强腐蚀性催化剂例如浓硫酸等来催化反应,这对生物柴油的发展起到了很大的作用,然而,它们却严重地腐蚀了反应设备,并且污染了周边环境。在CN201310441652.4的专利中,介绍了一种生物柴油酯化复合酸催化剂,由甲基磺酸等酸和磷酸单脂等抑蚀剂组成,然而其主要成分易于与生物柴油产品溶解,不易于分离。
因此,为了寻求更好地效果,一些新的催化剂被报道出来,例如树脂、介孔硅和磷钨酸,但是,这些新催化剂催化活性并不高、容易失活,甚至有些是有毒性的,这给实际生产带来了新的问题。生物柴油是环保的绿色燃料,然而生物柴油制备工艺使用的却是不环境友好的催化剂,这本身也是不符合绿色化学的设计。因此,设计高效、便捷、环境友好和高选择性的绿色催化剂,对生物柴油的未来发展是至关重要的。
发明内容
为了解决现有技术中存在的问题,本发明公开了一种生物柴油酯化非均相催化剂及其制备方法,旨在提供一种于催化活性高、不容易失活、易分离、可循环使用、环境友好和选择性高的生产生物柴油用催化剂。
为达到以上目的,本发明采用的技术方案为:
一种生物柴油酯化非均相催化剂,所述催化剂是一种以MIL-100/AILs颗粒为核相材料,以ZIF-8为壳相材料形成的具有核壳结构的MIL-100/AILs@ZIF-8催化剂。其中,所述MIL-100为一种MIL系列金属有机框架材料,MIL代表Material of Institut Lavoisier,它是由铁簇合物和均苯三甲酸配体组装而成;所述ZIF-8为一种ZIF系列金属有机框架材料,ZIF代表zeolitic imidazolate framework,即类沸石咪唑酯骨架材料,它是由锌簇合物和二甲基咪唑配体组装而成;所述AILs为分子式是[SO3H-(CH2)3-HIM][HSO4]的酸性离子液体,是一种新型的环境友好催化剂;所述MIL-100/AILs颗粒为MIL-100与AILs的复合物。
上述生物柴油酯化非均相催化剂的制备方法,可以通过如下步骤实现:
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌25-35min形成混合溶液,将所得混合溶液装入高压釜,在120-140℃下反应60-90h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.05-0.06g/mL,六水合氯化铁与苯三甲酸的质量比为(1.5-2.5)∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶(1-2),在50-80℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在60-80℃真空干燥6-24h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶(0.5-2),然后在60-80℃下反应6-24h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在80-100℃下真空干燥10-24h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行12-40h的浸渍处理,然后加入PVP搅拌2-6h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在60-100℃下真空干燥8-24h,得到MIL-100/AILs;
(4)MIL-100/A ILs@ZIF-8的制备
将步骤(3)制得的MIL-100/AILs分散于甲醇中,随后缓慢加入锌盐混合均匀,而后加入二甲基咪唑,室温下混合均匀后静置12-36h得到预产物,其中MIL-100/AILs、甲醇、锌盐与二甲基咪唑的质量比为1∶(0.5-2)∶6∶1,将预产物离心洗涤后,在60-100℃下真空干燥8-24h,得到MIL-100/AILs@ZIF-8。
优选地,所述锌盐为六水合硝酸锌、氯化锌、醋酸锌中的一种或多种。
上述生物柴油酯化非均相催化剂可以应用于合成生物柴油。
关于述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在85-95℃下加热3-5h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率(可以用SP-6890;SE-54capillary column:30m×0.25mm×0.3mm或其他型号的气相色谱分析油脂的产率),将固体层中的催化剂回收后重复使用。
较佳地,所述油脂为油酸或大豆油。
本发明的原理为:AILs(L:0.82nm;W:0.6nm)能够穿过MIL-100的窗口(~0.86nm),因此AILs能够分散到MIL-100的孔道中,得到了较好的浸渍效果。用聚乙烯吡咯烷酮(PVP)将MIL-100纳米晶表面修饰可以实现将具有不同拓扑结构的金属有机框架材料复合在一起。将具有介观结构的MIL-100纳米粒子作为“核”包埋在具有微孔结构的ZIF-8“壳”里,制备出MIL-100@ZIF-8复合物。由于ZIF-8的窗口的很小(~0.34nm),当浸渍了AILs的MIL-100被ZIF-8包埋后AILs分子不能出去,这也就保证了该催化剂的稳定性及循环使用性。
本发明同现有技术相比,具有以下优点和有益效果:
(1)本发明通过较为简便的方法合成了核壳结构的MIL-100/AILs@ZIF-8,该催化剂活性高、不容易失活、易分离和环境友好,同时控制原料配比和实验条件,实现活性组分AILs的有效封装,实现了催化剂的稳定性及循环使用性;
(2)MIL-100/AILs@ZIF-8具有比表面积大、孔隙率好、密度低等优点,在MIL-100/AILs表面包覆ZIF-8,提高了催化剂的稳定性,带来了巨大的比表面积,增加了活性位点,充分地发挥了催化剂的催化性能。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。
实施例1
一种生物柴油酯化非均相催化剂,所述催化剂是一种以MIL-100/AILs颗粒为核相材料,以ZIF-8为壳相材料形成的具有核壳结构的MIL-100/AILs@ZIF-8催化剂。
上述生物柴油酯化非均相催化剂的制备方法,是通过如下步骤实现的:
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌25min形成混合溶液,将所得混合溶液装入高压釜,在120℃下反应90h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.05g/mL,六水合氯化铁与苯三甲酸的质量比为1.5∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶1,在50℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在60℃真空干燥24h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶0.5,然后在60℃下反应24h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在80℃下真空干燥24h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行12h的浸渍处理,然后加入PVP搅拌6h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在60℃下真空干燥24h,得到MIL-100/AILs;
(4)MIL-100/A ILs@ZIF-8的制备
将步骤(3)制得的MIL-100/AILs分散于甲醇中,随后缓慢加入六水合硝酸锌混合均匀,而后加入二甲基咪唑,室温下混合均匀后静置12h得到预产物,其中MIL-100/AILs、甲醇、六水合硝酸锌与二甲基咪唑的质量比为1∶0.5∶6∶1,将预产物离心洗涤后,在60℃下真空干燥24h,得到MIL-100/A ILs@ZIF-8。
上述生物柴油酯化非均相催化剂可以应用于合成生物柴油。
关于述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在85℃下加热5h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率,将固体层中的催化剂回收后重复使用。
实施例2
一种生物柴油酯化非均相催化剂,所述催化剂是一种以MIL-100/AILs颗粒为核相材料,以ZIF-8为壳相材料形成的具有核壳结构的MIL-100/AILs@ZIF-8催化剂。
上述生物柴油酯化非均相催化剂的制备方法,是通过如下步骤实现的∶
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌35min形成混合溶液,将所得混合溶液装入高压釜,在140℃下反应60h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.06g/mL,六水合氯化铁与苯三甲酸的质量比为2.5∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶2,在80℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在80℃真空干燥6h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶2,然后在80℃下反应6h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在100℃下真空干燥10h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行40h的浸渍处理,然后加入PVP搅拌2h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在100℃下真空干燥8h,得到MIL-100/AILs;
(4)MIL-100/A ILs@ZIF-8的制备
将步骤(3)制得的MIL-100/AILs分散于甲醇中,随后缓慢加入氯化锌混合均匀,而后加入二甲基咪唑,室温下混合均匀后静置36h得到预产物,其中MIL-100/AILs、甲醇、氯化锌与二甲基咪唑的质量比为1∶2∶6∶1,将预产物离心洗涤后,在100℃下真空干燥8h,得到MIL-100/AILs@ZIF-8。
上述生物柴油酯化非均相催化剂可以应用于合成生物柴油。
关于述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在95℃下加热3h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率,将固体层中的催化剂回收后重复使用。
实施例3
一种生物柴油酯化非均相催化剂,所述催化剂是一种以MIL-100/AILs颗粒为核相材料,以ZIF-8为壳相材料形成的具有核壳结构的MIL-100/AILs@ZIF-8催化剂。
上述生物柴油酯化非均相催化剂的制备方法,是通过如下步骤实现的:
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌32min形成混合溶液,将所得混合溶液装入高压釜,在132℃下反应80h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.056g/mL,六水合氯化铁与苯三甲酸的质量比为2.2∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶1.2,在68℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在70℃真空干燥15h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶1.7,然后在68℃下反应16h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在93℃下真空干燥14h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行26h的浸渍处理,然后加入PVP搅拌5h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在87℃下真空干燥14h,得到MIL-100/AILs;
(4)MIL-100/A ILs@ZIF-8的制备
将步骤(3)制得的MIL-100/AILs分散于甲醇中,随后缓慢加入醋酸锌混合均匀,而后加入二甲基咪唑,室温下混合均匀后静置27h得到预产物,其中MIL-100/AILs、甲醇、醋酸锌与二甲基咪唑的质量比为1∶1.2∶6∶1,将预产物离心洗涤后,在73℃下真空干燥18h,得到MIL-100/AILs@ZIF-8。
上述生物柴油酯化非均相催化剂可以应用于合成生物柴油。
关于述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在88℃下加热4h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率,将固体层中的催化剂回收后重复使用。
实施例4
一种生物柴油酯化非均相催化剂的制备方法,是通过如下步骤实现的:
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌30min形成混合溶液,将所得混合溶液装入高压釜,在130℃下反应72h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.054g/mL,六水合氯化铁与苯三甲酸的质量比为2∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶1.5,在65℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在70℃真空干燥15h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶1.2,然后在70℃下反应16h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在90℃下真空干燥18h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行30h的浸渍处理,然后加入PVP搅拌4h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在80℃下真空干燥17h,得到MIL-100/AILs;
上述生物柴油酯化非均相催化剂可以应用于合成生物柴油。
关于述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在90℃下加热4h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率,将固体层中的催化剂回收后重复使用。
实施例1-4中的所制生物柴油酯化非均相催化剂以及其他催化剂的催化性能及重复性实验,结果如表1所示。
表1实施例1-4所制生物柴油酯化非均相催化剂以及其他催化剂的催化性能及重复性实验。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (6)
1.一种生物柴油酯化非均相催化剂,其特征在于:所述催化剂是一种以MIL-100/AILs颗粒为核相材料,以ZIF-8为壳相材料形成的具有核壳结构的MIL-100/AILs@ZIF-8催化剂。
2.一种如权利要求1所述生物柴油酯化非均相催化剂的制备方法,其特征在于是通过如下步骤实现的:
(1)MIL-100的制备
将六水合氯化铁充分溶于去离子水后,加入均苯三甲酸搅拌25-35min形成混合溶液,将所得混合溶液装入高压釜,在120-140℃下反应60-90h后冷却到室温,用甲醇洗净后,在沸甲醇中煮12h,150℃真空干燥12h,得到MIL-100,其中,六水合氯化铁与去离子水的质量体积比为0.05-0.06g/mL,六水合氯化铁与苯三甲酸的质量比为(1.5-2.5)∶1;
(2)AILs的制备
将咪唑与1,3-丙烷磺内酯加入到无水乙醇溶剂中,其中咪唑、1,3-丙烷磺内酯与乙醇的摩尔比为1∶1∶(1-2),在50-80℃下搅拌回流直至得到微黄色固体沉淀,将微黄色固体沉淀真空抽滤后用无水乙醇洗净,在60-80℃真空干燥6-24h得到中间体;将所述中间体和98%的浓硫酸依次加入到去离子水中,其中中间体、浓硫酸与蒸馏水的摩尔比为1∶1∶(0.5-2),然后在60-80℃下反应6-24h,得粗离子液体产物,将所述粗离子液体产物用乙酸乙酯洗净后,在80-100℃下真空干燥10-24h,得酸性离子液体AILs;
(3)MIL-100/AILs的制备
将步骤(2)制得的AILs充分溶解于甲醇中形成均一溶液,将步骤(1)制得的MIL-100置于上述溶液中进行12-40h的浸渍处理,然后加入PVP搅拌2-6h,其中MIL-100、AILs、甲醇与PVP的质量比为1∶1∶0.5∶0.2,将所得物质进行离心洗涤后,在60-100℃下真空干燥8-24h,得到MIL-100/AILs;
(4)MIL-100/AILs@ZIF-8的制备
将步骤(3)制得的MIL-100/AILs分散于甲醇中,随后缓慢加入锌盐混合均匀,而后加入二甲基咪唑,室温下混合均匀后静置12-36h得到预产物,其中MIL-100/AILs、甲醇、锌盐与二甲基咪唑的质量比为1∶(0.5-2)∶6∶1,将预产物离心洗涤后,在60-100℃下真空干燥8-24h,得到MIL-100/AILs@ZIF-8。
3.根据权利要求2所述催化剂的制备方法,其特征在于:所述锌盐为六水合硝酸锌、氯化锌、醋酸锌中的一种或多种。
4.如权利要求1-3中任一所述生物柴油酯化非均相催化剂应用于合成生物柴油。
5.如权利要求4所述述生物柴油酯化非均相催化剂应用于合成生物柴油的方法,其特征在于包括如下步骤:
(1)将乙醇、油脂和生物柴油酯化非均相催化剂同时混合,在85-95℃下加热3-5h,所得产物为生物柴油的混合物,其中乙醇和油脂的物质的量之比为10∶1,生物柴油酯化非均相催化剂的加入量为油脂质量的10.0%;
(2)将产物离心获得液体层和固体层,液体层利用气相色谱分析后计算油脂的产率,将固体层中的催化剂回收后重复使用。
6.如权利要求5所述方法,其特征在于:所述油脂为油酸或大豆油。
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