CN109174088B - 一种用于炔类化合物选择性加氢反应的多相催化剂及其应用 - Google Patents
一种用于炔类化合物选择性加氢反应的多相催化剂及其应用 Download PDFInfo
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- CN109174088B CN109174088B CN201811251289.9A CN201811251289A CN109174088B CN 109174088 B CN109174088 B CN 109174088B CN 201811251289 A CN201811251289 A CN 201811251289A CN 109174088 B CN109174088 B CN 109174088B
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Classifications
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Abstract
本发明公开了一种用于炔类化合物选择性加氢反应的多相催化剂及其应用,按重量百分数计,所述多相催化剂由1~10%的贵金属粒子、9~90%的钛氧化物和9~90%的多孔炭组成。与一般的商业活性炭负载Pd催化剂或二氧化钛负载Pd催化剂相比,本发明制备的多相催化剂用于催化炔烃化合物选择性加氢反应制备烯烃化合物时,具有明显的协同作用,多孔炭的引入不仅可以促进底物的扩散,同时进一步调控贵金属粒子和钛氧化物的相互作用,使贵金属粒子富电荷,从而提高炔类化合物加氢的催化活性和选择性。使用本发明的催化剂催化苯乙炔加氢反应制备苯乙烯时,苯乙烯的选择性大于95%,苯乙炔的转化率为100%。
Description
技术领域
本发明涉及催化剂领域,具体涉及一种用于炔类化合物选择性加氢反应的多相催化剂及其应用。
背景技术
炔烃选择性加氢合成的烯烃化合物构成许多天然产物和药物的骨架,是关键医药中间体合成过程中经常涉及的反应类型。β-胡萝卜素、维生素E、信息素、葫芦素、白藜芦醇、多元不饱和脂肪酸、多烯类抗真菌药等生物、医药活性分子都涉及到碳碳双键的合成,它们在调节人体的生育功能、预防心脑血管疾病、抑制炎症、抗肿瘤等方面起到重要的作用。因此实现炔烃的半加氢具有重要的应用价值和意义。
由于原子经济性和环境友好性,通过选择性催化碳碳三键加氢合成烯烃是一种直接有效的制备方法,该方法的关键在于控制催化剂的选择性。理想的炔烃半加氢催化剂通常是Pd催化剂,但是它们常常需要与改性剂一起使用以提高选择性。显然改性剂的引入(锡、汞、铅等金属离子或者喹啉、吡啶或其他含硫含氮化合物)对环境可能造成污染,同时威胁人类的健康。近期,通过调节活性金属的电子结构和几何结构,无需引入改性剂的贵金属催化剂被广泛用于功能化烯烃化合物的合成,纳米多孔Pd(Highly SelectiveSemihydrogenation of Alkynes to Alkenes by Using an Unsupported NanoporousPalladium Catalyst:No Leaching of Palladium into the Reaction Mixture.ACSCatal.2017,7,8296-8303)和三明治结构的TiO2/Pt/TiO2(Porous TiO2/Pt/TiO2 SandwichCatalyst for Highly Selective Semihydrogenation of Alkyne to Olefin.ACSCatal.2017,7,6567-6572)可实现炔烃的高效选择性加氢。由于上述催化剂的制备过程中必须加入价格高昂的含氮配体,并且制备工艺相较复杂,所以开发一种简单易得,对体系高活性、高选择性的催化剂具有重要的应用意义。
已知,碳材料由于其高的化学稳定性,高的比表面积,以及对绝大多数有机溶剂惰性等优异的性能,并且其容易通过煅烧除去,与氧化物材料在很多方面具有互补性,因此被广泛地应用于多相催化。活性炭负载Pd催化剂对于炔烃化合物有一定的催化活性,但催化选择性需进一步提高。二氧化钛和金属Pd之间的强相互作用使其在炔类化合物的选择性加氢中表现较高的催化活性,但是仍也有固有的弱点,如催化剂在空气中放置容易失活,反应选择性不高,作为催化剂经常需要添加助催化剂或者多步处理(Selectivity enhancementin acetylene hydrogenation over diphenyl sulphide-modified Pd/TiO2catalysts.J.Catal.2011,281,231)等,这些问题限制了这类催化剂的应用。
发明内容
针对现有技术存在的上述技术问题,本发明的目的在于提供一种用于炔类化合物选择性加氢反应的多相催化剂及其应用,通过特定的方法合成含贵金属粒子的多相催化剂,所述多相催化剂对空气、水热均稳定,将其应用于炔烃化合物选择性加氢反应中,表现出优异的催化活性和选择性。
一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于按重量百分数计,所述多相催化剂由1~10%的贵金属粒子、9~90%的钛氧化物和9~90%的多孔炭组成。
所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于所述多相催化剂的制备方法为,包括以下步骤:
1)以碳水化合物和钛氧化物为原料,在惰性气体气氛中,在600~1200℃下煅烧0.5~6h,碳水化合物煅烧反应转化为多孔炭,钛氧化物和多孔炭交替层层结合,得到钛氧化物和多孔炭组成的复合载体;
2)步骤1)所得复合载体加入到水中超声后,加入预先配制的贵金属前驱体的水溶液超声混合,将贵金属前驱体吸附在复合载体上,然后加入还原剂继续超声,还原剂将贵金属前驱体还原成贵金属粒子,抽滤,滤渣水洗后干燥,即得所述多相催化剂。
所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于贵金属粒子为Pd、Pt或Ru粒子,优选为Pd;所述贵金属粒子的粒径为1~50nm,优选为1~15nm。
所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于所述碳水化合物为蔗糖、果糖、葡萄糖、半乳糖、壳聚糖、纤维素或氨基葡萄糖盐酸盐;所述钛氧化物为TiO2(B)、锐钛矿、金红石或二氧化钛P25。
所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于步骤1)中,碳水化合物与钛氧化物的质量比为1:0.1~15,优选为1:0.6~10;步骤2)中,贵金属前驱体和复合载体的质量比为1:5~70,优选为1:10~65;所述还原剂为硼氢化钠。
所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于步骤1)中,碳水化合物为纤维素,钛氧化物为TiO2(B),所述碳水化合物和钛氧化物的质量比为1:0.1~15;步骤2)中,贵金属前驱体为PdCl2,H2PtCl6或RuCl3。
所述的多相催化剂在炔类化合物选择性加氢反应中的应用,其特征在于炔类化合物与溶剂混合,混合后的反应液在多相催化剂的作用下,与氢气进行选择性加氢反应,生成烯类化合物;其中反应温度为0~150℃,反应压力为0.1~10MPa;所述的溶剂为水、乙醇、二氯甲烷、四氢呋喃、乙酸乙酯、二氧六环、N,N-二甲基甲酰胺、正己烷或甲苯。
所述的多相催化剂在炔类化合物选择性加氢反应中的应用,其特征在于所述炔类化合物为苯乙炔、取代苯乙炔或炔醇,所述取代苯乙炔的取代基选自烷基、氨基、羟基、芳杂环、卤素、氰基、醛基、酮基或酰胺基,所述取代苯乙炔的取代基数量为一个或多个。
所述的多相催化剂在炔类化合物选择性加氢反应中的应用,其特征在于所述多相催化剂的质量为炔类化合物质量的0.1~10%。
所述的多相催化剂在炔类化合物选择性加氢反应中的应用,其特征在于进行选择性加氢反应的温度为20~80℃,压力为0.1~2MPa,溶剂为水或乙醇。
由于上述技术方案的运用,本发明与现有技术相比具有以下优势:
1、本发明以碳水化合物和钛氧化物为原料,经一步煅烧原位生成了钛氧化物和多孔炭组成的多相催化剂载体,一步法合成过程中会形成钛氧化物和多孔炭交替层层结合的层状材料结构,经过高温煅烧会得到多孔炭和二氧化钛紧密结合的复合载体。与物理混合的活性炭和钛氧化物一起煅烧相比,这种强相互作用有利于金属在复合载体上的分散,以及制备的多相催化剂在选择性加氢反应过程中产物的扩散;常规的负载金属的方法有超声法、沉积-沉淀法、溶胶凝胶法等,本发明优选为简单高效的超声法。所述多相催化剂的载体与贵金属前驱体水溶液在还原剂的作用下,超声还原,通过温和条件将吸附在复合载体上的贵金属前驱体还原成贵金属粒子,制备方法简单、条件温和、时间短、耗能低、生产成本低廉,且产品结构易于调节。
2、由于贵金属粒子和复合载体之间的强相互作用以及超声协助还原法的有效性,本发明制备得到的多相催化剂贵金属粒子大小均一、分散性好,贵金属粒子颗粒平均直径可以达到1~10nm。所述多相催化剂对空气、水及热稳定,在空气中存在5个月后其催化苯乙炔加氢活性不减,金属价态保持不变。
3、与一般的商业活性炭负载Pd催化剂或二氧化钛负载Pd催化剂相比,本发明制备的多相催化剂用于催化炔烃化合物选择性加氢反应制备烯烃化合物时时,具有明显的协同作用,多孔炭的引入不仅可以促进底物的扩散,同时进一步调控金属Pd和二氧化钛的相互作用,使金属Pd富电荷,从而提高炔类化合物加氢的催化活性和选择性。以催化苯乙炔加氢反应制备苯乙烯为例,使用本发明的催化剂可获得大于95%的选择性,苯乙炔的转化率为100%。
具体实施方式
下面结合具体实施例对本发明作进一步说明,但本发明的保护范围并不限于此。
实施例1基于TiO2-x和多孔炭(TiO2-x@C)负载Pd的多相催化剂
在100ml烧杯中加入0.5g纤维素(人工合成纤维素,粒径65μm,购于麦克林试剂公司)和50mL的去离子水,搅拌溶解随后加入TiO2(B)0.1g,搅拌至均匀混合液。加热搅拌至烧杯中的去离子水挥发完全,得到固体混合物,这种方法得到的固体可以使后期煅烧后钛氧化物和多孔炭密切、均一结合。此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为40wt%的TiO2-x(0<x<2)和60wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pd2+还原成单质Pd,然后抽滤,滤渣水洗多次,干燥后得到TiO2-x@C担载的Pd催化剂。
实施例2基于TiO2-x和多孔炭(TiO2-x@C)负载Pd的多相催化剂
在100ml烧杯中加入0.5g D-葡糖糖(购于Sigma试剂公司)和50mL的去离子水,搅拌溶解随后加入TiO2(B)0.2g,搅拌至均匀混合液。加热搅拌至烧杯中的去离子水挥发完全,得到固体混合物,此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为60wt%的TiO2-x(0<x<2)和40wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pd2+还原成单质Pd,抽滤,滤渣水洗多次,干燥后得到TiO2-x@C担载的Pd催化剂。
实施例3基于TiO2-x和多孔炭(TiO2-x@C)负载Pd的多相催化剂
在100ml烧杯中加入0.5g纤维素(人工合成纤维素,粒径65μm,购于麦克林试剂公司),50mL的去离子水,搅拌溶解随后加入TiO2(B)0.3g,搅拌至均匀混合液。加热搅拌至烧杯中的去离子水挥发完全,得到固体混合物,此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为70wt%的TiO2-x(0<x<2)和30wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),超声10min后,加入1mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为2mg/mL),将Pd2+还原成单质Pd,抽滤,滤渣水洗多次,干燥后得到TiO2-x@C担载的Pd催化剂。
实施例4实施例3中TiO2-x@C负载Pd催化剂的表征
通过高分辨透射电子显微镜(HRTEM)对催化剂进行表征,证实催化剂由二氧化钛、多孔炭和纳米金属Pd共同构成。Pd纳米粒子均匀分布在在载体上,和二氧化钛有密切的接触,说明Pd和二氧化钛之间存在着明显的相互作用。通过对150个纳米Pd金属粒子进行统计,得出Pd纳米粒子的平均粒径为2.8nm。
实施例5基于TiO2-x和多孔炭(TiO2-x@C)负载Pd的多相催化剂
在100ml烧杯中加入0.5g D-果糖(购于Sigma试剂公司),50mL的去离子水,搅拌溶解随后加入TiO2(B)0.5g,搅拌至均匀混合液。加热搅拌至去离子水挥发完全,得到固体混合物,此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为80wt%的TiO2-x(0<x<2)和20wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min后,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),继续超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pd2+还原成单质Pd,抽滤,滤渣水洗多次,干燥后得到TiO2-x@C担载的Pd催化剂。
实施例6基于P25和多孔炭(P25@C)负载Pt的多相催化剂
在100ml烧杯中加入0.5g D-氨基葡萄糖盐酸盐(购于Sigma试剂公司),50mL的去离子水,搅拌溶解随后加入二氧化钛P250.3g,搅拌至均匀混合液。加热搅拌至去离子水挥发完全,得到固体混合物,此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为70wt%的二氧化钛P25和30wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的H2PtCl6水溶液(H2PtCl6水溶液的浓度为10mg/mL),继续超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pt4+还原成单质Pt,抽滤,滤渣水洗多次,干燥后得到P25@C担载的Pt催化剂。
实施例7基于TiO2-x和多孔炭(TiO2-x@C)负载Ru的多相催化剂
在100ml烧杯中加入0.5g壳聚糖(低粘度,<200mPa.s,购买于Sigma),50mL的去离子水,搅拌溶解随后加入TiO2(B)0.3g,搅拌至均匀混合液。加热搅拌至去离子水挥发完全,得到固体混合物,此固体混合物在氮气炉中程序升温至650℃煅烧1h后,即得到组成为70wt%的TiO2-x(0<x<2)和30wt%的多孔炭的复合载体。取0.1g所述复合载体,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的RuCl3水溶液(RuCl3水溶液的浓度为10mg/mL),继续超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Ru3+还原成单质Ru,抽滤,滤渣水洗多次,干燥后得到TiO2-x@C担载的Ru催化剂。
实施例8以实施例1制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例1制备的多相催化剂和10mL的二氯甲烷加入到50mL的不锈钢高压釜中后,不锈钢高压釜中内用氢气充排气3次之后(即通过氢气对不锈钢高压釜内的空气进行置换,排空不锈钢高压釜内的空气,以下实施例等同),充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为46%,2-甲基-3-丁烯-2-醇的选择性为97%。
实施例9以实施例2制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例2制备的的多相催化剂和10mL的四氢呋喃加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为67%,2-甲基-3-丁烯-2-醇的选择性为96%。
实施例10以实施例3制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例3制备的的多相催化剂和10mL的乙醇加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为90%,2-甲基-3-丁烯-2-醇的选择性为95%。
实施例11以实施例5制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例5制备的的多相催化剂和10mL的乙醇加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为64%,2-甲基-3-丁烯-2-醇的选择性为96%。
实施例8-11说明并不是二氧化钛含量越多催化活性越好,也并不是多孔炭含量越多催化活性越好,而是二氧化钛和多孔炭的含量存在一个最优比例。
实施例12以实施例6制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例6的催化剂和10mL的N,N-二甲基甲酰胺加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为57%,2-甲基-3-丁烯-2-醇的选择性为95%。
实施例13以实施例7制备的多相催化剂催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg实施例7的催化剂和10mL的二氧六环加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为50%,2-甲基-3-丁烯-2-醇的选择性为98%。
实施例14以实施例3制备的催化剂放置5个月后催化炔醇加氢制备烯醇
将900mg的2-甲基-3-丁炔-2-醇、10mg放置5个月之后的实施例3制备的催化剂和10mL的乙醇加入到50mL的不锈钢高压釜中,不锈钢高压釜中内用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,进行选择性加氢反应,反应0.5h。停止反应后将不锈钢高压釜中残余的氢气小心排出,取出反应液。采用离心的方法将多相催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为89%,2-甲基-3-丁烯-2-醇的选择性为96%。通过实施例14和实施例10进行对比,可以看出实施例3所得的催化剂稳定性很好,对空气和水分都很惰性。
实施例15~35
实施例15~35为使用实施例3制备的多相催化剂催化各种炔类化合物加氢反应制备功能化烯类化合物的实施例,实施例15~35的操作步骤同实施例10。表1给出了实施例的反应条件以及对应的反应收率。
表1
从实施例15-35可以看出,催化剂具有很好的普适性,不同取代基在反应过程中都可以很好的保留,炔基可以选择性的转化为双键。除了苯乙炔,不管是含有给电子取代基,还是吸电子取代基的炔烃化合物,在催化剂的作用下,都可以高效地转化为相应的烯烃化合物。另外,具有卤素(F、Cl、Br、I)取代的苯乙炔,卤素也可以很好的保留。这在工业上是非常重要的,因为如果卤素脱掉,卤化氢会大大腐蚀设备,从而限制其在工业上的应用。同时不管是对于端基炔还是分子内炔基,催化剂都具有很高的催化性能。也就是说,Pd/TiO2-x@C在炔烃化合物的催化加氢中是一种高活性、高选择性的催化剂。
对比例1基于二氧化钛P25负载Pd的催化剂用于炔醇加氢制备烯醇
催化剂制备:取0.1g二氧化钛P25,加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),继续超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pd2+还原成单质Pd,抽滤,滤渣水洗多次,干燥后得到P25担载的Pd催化剂。
催化反应过程:将900mg的2-甲基-3-丁炔-2-醇、10mg上述制备的P25担载的Pd催化剂和10mL的乙醇加入到50mL的不锈钢高压釜中,用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,反应0.5h。停止反应后将残余的氢气小心排出,取出反应液。采用离心的方法将催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为42%,2-甲基-3-丁烯-2-醇的选择性为96%。
对比例2基于商业活性炭负载Pd的催化剂用于炔醇加氢制备烯醇
催化剂制备:取0.1g商业活性炭(椰壳活性炭,200目-300目,购于九鼎化学科技有限公司),加入到50mL去离子水中,超声10min,加入0.15mL预先配置好的PdCl2水溶液(PdCl2水溶液的浓度为10mg/mL),继续超声10min后,加入5mL新鲜配置的硼氢化钠水溶液继续超声(硼氢化钠水溶液的浓度为1mg/mL),将Pd2+还原成单质Pd,抽滤,滤渣水洗多次,干燥后得到C担载的Pd催化剂。
催化反应过程:将900mg的2-甲基-3-丁炔-2-醇、10mg上述制备的商业活性炭负载Pd的催化剂和10mL的乙醇加入到50mL的不锈钢高压釜中,用氢气充排气3次之后,充氢气至0.2MPa并密封,于25℃水浴加热,磁力搅拌,反应0.5h。停止反应后将残余的氢气小心排出,取出反应液。采用离心的方法将催化剂和反应液分离,反应液用气相色谱检测,检测计算得到2-甲基-3-丁炔-2-醇的转化率为18%,2-甲基-3-丁烯-2-醇的选择性为93%。
通过对比例可以看出,单独的商业活性炭或者单独的二氧化钛P25为载体负载纳米金属Pd时,其催化活性和选择性都不及实施例3所得的催化剂,证实钛氧化物的多孔炭之间存在明显的协同作用。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式,本发明的保护范围也仅仅于本领域技术人员根据本发明构思所能够想到的等同技术手段。
Claims (6)
1.一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于所述多相催化剂的制备方法为,包括以下步骤:
1)以碳水化合物和钛氧化物为原料,在惰性气体气氛中,在600~650℃下煅烧0.5~6h,碳水化合物煅烧反应转化为多孔炭,钛氧化物和多孔炭交替层层结合,得到钛氧化物和多孔炭组成的复合载体;
2)步骤1)所得复合载体加入到水中超声后,加入预先配制的贵金属前驱体的水溶液超声混合,将贵金属前驱体吸附在复合载体上,然后加入还原剂继续超声,还原剂将贵金属前驱体还原成贵金属粒子,抽滤,滤渣水洗后干燥,即得所述多相催化剂;
步骤1)中,碳水化合物为纤维素,钛氧化物为TiO2(B),碳水化合物与钛氧化物的质量比为1:0.6~10;步骤2)中,贵金属前驱体和复合载体的质量比为1:10~65;
步骤2)中,贵金属前驱体为PdCl2,贵金属粒子为Pd,贵金属粒子的粒径为1~15nm。
2.根据权利要求1所述的一种用于炔类化合物选择性加氢反应的多相催化剂,其特征在于步骤2)中,所述还原剂为硼氢化钠。
3.根据权利要求1所述的多相催化剂在炔类化合物选择性加氢反应中的应用,其特征在于炔类化合物与溶剂混合,混合后的反应液在多相催化剂的作用下,与氢气进行选择性加氢反应,生成烯类化合物;其中反应温度为0~150℃,反应压力为0.1~10MPa;所述的溶剂为水、乙醇、二氯甲烷、四氢呋喃、乙酸乙酯、二氧六环、N,N-二甲基甲酰胺、正己烷或甲苯。
4.根据权利要求3所述的应用,其特征在于所述炔类化合物为苯乙炔、取代苯乙炔或炔醇,所述取代苯乙炔的取代基选自烷基、氨基、羟基、芳杂环、卤素、氰基、醛基、酮基或酰胺基,所述取代苯乙炔的取代基数量为一个或多个。
5.根据权利要求3所述的应用,其特征在于所述多相催化剂的质量为炔类化合物质量的0.1~10%。
6.根据权利要求3所述的应用,其特征在于进行选择性加氢反应的温度为20~80℃,压力为0.1~2MPa,溶剂为水或乙醇。
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