CN112108175A - 一种芳香族烯烃的制备方法 - Google Patents
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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Abstract
本发明提供一种芳香族烯烃的制备方法,包括:在氢气气氛下,以Y分子筛封装的纳米钯为催化剂,对芳香族炔烃进行催化加氢,制得芳香族烯烃。本发明以Y分子筛封装的纳米钯对芳香族炔烃进行催化加氢,能够使芳香族炔烃以端点吸附的构像吸附在钯颗粒表面,而非平躺的吸附构像。该端点吸附构像使得芳香族炔烃在钯颗粒表面的吸附能大于对应产物芳香族烯烃的吸附能,进而使得催化剂展现了良好的催化选择性。
Description
技术领域
本发明属于化工技术领域,特别涉及一种芳香族烯烃的制备方法。
背景技术
炔烃选择性加氢制备烯烃在石油化工和精细化工领域具有举足轻重的地位,其对合成各种高附加值化学品和各种高分子化合物都有十分重要的意义。
工业上炔烃选择性加氢制备烯烃常用的是林德拉催化剂(Lindlar catalyst),它是由钯负载在碳酸钙或硫酸钡载体上,同时引入一定量的醋酸铅或喹啉而组成。林德拉催化剂在炔烃加氢使用中可展现较好的催化选择性,但是催化的活性一般较低。此外,林德拉催化剂中一般含有铅重金属物质(Pb或PbO),导致在实际使用中会对环境或者产品造成污染。随着环保的要求越来越严格,寻找可替代林德拉催化剂的负载型钯催化剂已经迫在眉睫。
目前,提高负载型钯催化剂催化选择性的方法包括非金属元素表面修饰法和合金法等。非金属元素表面修饰法主要是利用硫或磷等元素对负载型钯催化剂进行表面吸附,进而可调控钯金属表面价电子状态,从而影响催化选择性。郑南峰课题组报道了利用硫醇修饰可显著提高负载型钯催化剂的选择性,对某些内炔的催化选择性能接近100%(Chem,2018,4:1080-1091)。需要指出,修饰的硫醇在催化反应过程中可能会流失到反应体系,造成产物和环境的污染。日本Kaneda等报道了核壳型Pd@Ag合金催化剂在炔烃选择性加氢中展现了非常好的催化选择性,以正辛炔加氢为例,Pd@Ag催化剂的选择性可接近100%(ACSCatalysis,2016,6:666-670)。但是合金催化剂在合成过程中制备工艺复杂,尤其工业大规模制备时合金的比例和形貌结构控制难度较大。巩金龙课题组将Pd颗粒封装进SOD型分子筛(Pd@SOD),利用氢溢流效应,结合乙炔分子不能扩散进入SOD笼从而可阻止其与Pd颗粒相接触的特征,实现了乙炔选择性加氢制备乙烯接近95%的选择性(Angew.Chem.Int.Ed.,2019,58:7668-7672)。该Pd@SOD催化剂在气相乙炔加氢制备乙烯反应中展现了良好的选择性,而对液相反应中的炔烃加氢选择性没有研究。同时在液相体系中,分子筛封装贵金属催化剂通过氢溢流能否提升炔烃加氢选择性在理论上也有待进一步验证。
因此,发展一种绿色、无毒、高效、易于大规模制备且可适用于液相炔烃选择性加氢的催化剂体系是当前该研究领域的热点和难点。
发明内容
本发明的目的在于提供一种芳香族烯烃的制备方法,提高芳香族炔烃加氢生成芳香族烯烃的选择性,以解决上述技术问题。
为了实现上述目的,本发明采用如下技术方案:
一种芳香族烯烃的制备方法,包括:在氢气气氛下,以Y分子筛封装的纳米钯为催化剂,对芳香族炔烃进行催化加氢,制得芳香族烯烃。
进一步的,对芳香族炔烃进行催化加氢的温度为40~80℃。
进一步的,对芳香族炔烃进行催化加氢的温度为50~70℃。
进一步的,氢气的压力为0.5~1.5MPa。
进一步的,氢气的压力为1MPa。
进一步的,对芳香族炔烃进行催化加氢的时间为15~90min。
进一步的,所述催化剂重量为芳香族烯烃重量的2-20倍。
进一步的,所述催化剂中纳米钯的含量为0.1wt%~1wt%。
进一步的,所述催化剂中纳米钯的平均粒径为0.5~2nm。
进一步的,芳香族炔烃的芳环上还包含一个或多个取代基,所述取代基为苯环、醛基、氟或溴。
进一步的,Y分子筛封装的纳米钯的制备方法包括:乙醇溶剂中分散Y型分子筛,然后再与分散于乙醇溶剂中的乙酰丙酮钯混合形成混合液,然后混合液在氢气气氛下还原,制得Y分子筛封装的纳米钯。
进一步的,混合液中钯占Y分子筛的质量分数为0.5%~2%;在氢气气氛下进行还原的条件是40~70℃的反应温度,且氢气压力为1~2.5大气压,还原时间为24~36小时。
进一步的,所述乙醇溶剂中分散的Y型分子筛浓度为5mg/ml。
进一步的,催化加氢以乙醇为溶剂,乙醇的重量为芳香族炔烃重量的50~200倍。
相对于现有技术,本发明具有以下有益效果:
本发明以Y分子筛封装的纳米钯对芳香族炔烃进行催化加氢,能够使芳香族炔烃以端点吸附的构像吸附在钯颗粒表面,而非平躺的吸附构像。该端点吸附构像使得芳香族炔烃在钯颗粒表面的吸附能大于对应产物芳香族烯烃的吸附能,进而使得催化剂展现了良好的催化选择性。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为Pd@Y催化剂的XRD图谱;
图2为Pd@Y催化剂的透射电镜图。
具体实施方式
下面将参考附图并结合实施例来详细说明本发明。需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。
以下详细说明均是示例性的说明,旨在对本发明提供进一步的详细说明。除非另有指明,本发明所采用的所有技术术语与本申请所属领域的一般技术人员的通常理解的含义相同。本发明所使用的术语仅是为了描述具体实施方式,而并非意图限制根据本发明的示例性实施方式。
实施例1
本实施例在氢气气氛下,以Y分子筛封装的纳米钯为催化剂,对芳香族炔烃进行催化加氢,制得芳香族烯烃,包括如下步骤:
(1)制备催化剂
取干燥的HY分子筛50mg,加入10mL无水乙醇,超声混合均匀。称取2.74mg乙酰丙酮钯溶于1.12mL无水乙醇中,超声至乙酰丙酮钯粉末完全溶解,将溶解后溶液缓慢逐滴加入HY分子筛乙醇溶液中,室温或水浴(25-30℃)搅拌过夜。
取搅拌过夜后样品,离心弃上清液,加入10mL无水乙醇洗涤样品,重复三遍,之后加入10mL无水乙醇超声分散,水浴60℃缓慢搅拌、0.1MPa H2条件下还原24h。取还原后样品,离心弃上清液,加入无水乙醇、去离子水各5mL后超声洗涤,重复此洗涤步骤三遍,将样品置于真空干燥箱中干燥过夜。得到Y分子筛封装钯颗粒的催化剂Pd@Y。
Pt@Y催化剂的XRD图如图1所示。XRD分析表明钯颗粒的引入没有影响Y分子筛的自身结构,同时XRD没有观察到钯颗粒的特征峰,表明封装的钯颗粒粒径较小,没有大范围团聚的现象。进一步结合Pd@Y催化剂的电镜图片(图2)可以观察到,钯颗粒均匀分布在Y分子筛中,且合成的铂颗粒粒径较均匀,且平均粒径约为1.6nm。负载的钯纳米颗粒在催化剂中的质量分数为0.4%(质量分数算法:负载后催化剂中钯纳米颗粒质量除以催化剂总重)。
(2)制备芳香族炔烃
取0.1mmol的4-乙基苯乙炔14uL,按2%的摩尔比例加入Pd@HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,置于高压釜中经氢气置换釜内空气三次,以50℃、1MPa的H2条件催化反应进行35min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Pd@Y催化4-乙基苯乙炔加氢制备4-乙基苯乙烯的转化率和选择性分别为100%和94%。
实施例2
取0.1mmol的4-氟苯乙炔11.5uL,按2%的摩尔比例加入实施例1制备的Pd@HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,置于高压釜中经氢气置换釜内空气三次,以50℃、1MPa的H2条件催化反应进行35min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Pd@HY催化4-氟苯乙炔加氢制备4-氟苯乙烯的转化率和选择性分别为100%和89%。
实施例3
取0.1mmol的4-溴苯乙炔18.10mg,按2%的摩尔比例加入实施例1制备的Pd@HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,置于高压釜中经氢气置换釜内空气三次,以50℃、1MPa的H2条件催化反应进行45min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Pd@HY催化4-乙基苯乙炔加氢制备4-乙基苯乙烯的转化率和选择性分别为100%和85%。
实施例4
取0.1mmol的4-乙炔苯甲醛13.02mg,按2%的摩尔比例加入实施例1制备的Pd@HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,置于高压釜中经氢气置换釜内空气三次,以50℃、1MPa的H2条件催化反应进行30min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Pd@HY催化4-乙基苯乙炔加氢制备4-乙基苯乙烯的转化率和选择性分别为99%和91%。
实施例5
取0.1mmol的9-乙炔基菲20.22mg,按2%的摩尔比例加入实施例1制备的Pd@HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,置于高压釜中经氢气置换釜内空气三次,以50℃、1MPa的H2条件催化反应进行38min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Pd@HY催化4-乙基苯乙炔加氢制备4-乙基苯乙烯的转化率和选择性分别为100%和90%。
对比例1
本对比例将Pd@Y催化剂替换成Pd/Y催化剂,对4-乙基苯乙炔进行催化加氢,具体包括如下步骤:
(1)制备Pd/Y催化剂
称取1.18mg氯钯酸钠粉末溶于300ul的去离子水中,超声分散,待完全溶解后逐滴加入100mg HY分子筛中使分子筛完全均匀浸渍于氯钯酸钠溶液中达到湿润状态,静置过夜后将样品置于烘箱中,100℃空气环境干燥4h,升温、降温时间均为30min。待样品冷却后取干燥样品置于马弗炉中,空气环境300℃焙烧4h,升温速率为0.5℃/min。经焙烧后得到浸渍法制备样品,命名为Imp-Pd/HY。
(2)4-乙基苯乙炔催化加氢
取0.1mmol的4-乙基苯乙炔14uL,按2%的摩尔比例加入Imp-Pd/HY粉末50mg,加入2.5mL无水乙醇,超声使体系分散均匀,以50℃、0.1MPa的H2条件下催化,反应进行15min后,离心取上清液稀释后使用GC-MS进行检测,由检测结果可知Imp-Pd/HY催化4-乙基苯乙炔加氢制备4-乙基苯乙烯的转化率和选择性仅为100%和21%。
由技术常识可知,本发明可以通过其它的不脱离其精神实质或必要特征的实施方案来实现。因此,上述公开的实施方案,就各方面而言,都只是举例说明,并不是仅有的。所有在本发明范围内或在等同于本发明的范围内的改变均被本发明包含。
Claims (10)
1.一种芳香族烯烃的制备方法,其特征在于:包括:
在氢气气氛下,以Y分子筛封装的纳米钯为催化剂,对芳香族炔烃进行催化加氢,制得芳香族烯烃。
2.根据权利要求1所述的制备方法,其特征在于:对芳香族炔烃进行催化加氢的温度为40~80℃。
3.根据权利要求1所述的制备方法,其特征在于:氢气的压力为0.5~1.5MPa。
4.根据权利要求1所述的制备方法,其特征在于:对芳香族炔烃进行催化加氢的时间为15~90min。
5.根据权利要求1所述的制备方法,其特征在于:所述催化剂重量为芳香族烯烃重量的2-20倍。
6.根据权利要求1所述的制备方法,其特征在于:所述催化剂中纳米钯的含量为0.1wt%~1wt%。
7.根据权利要求1所述的制备方法,其特征在于:所述催化剂中纳米钯的平均粒径为0.5~2nm。
8.根据权利要求1所述的制备方法,其特征在于:芳香族炔烃的芳环上还包含一个或多个取代基,所述取代基为苯环、醛基、氟或溴。
9.根据权利要求1所述的制备方法,其特征在于:Y分子筛封装的纳米钯的制备方法包括:乙醇溶剂中分散Y型分子筛,然后再与分散于乙醇溶剂中的乙酰丙酮钯混合形成混合液,然后混合液在氢气气氛下还原,制得Y分子筛封装的纳米钯。
10.根据权利要求9所述的制备方法,其特征在于:混合液中钯占Y分子筛的质量分数为0.5%~2%;在氢气气氛下进行还原的条件是40~70℃的反应温度,且氢气压力为1~2.5大气压,还原时间为24~36小时。
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