CN110479305B - 一种核壳型柠檬醛选择性加氢催化剂的合成方法 - Google Patents
一种核壳型柠檬醛选择性加氢催化剂的合成方法 Download PDFInfo
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Abstract
本发明公开了一种核壳型柠檬醛选择性加氢催化剂的合成方法,包括:以Co‑MOF负载的贵金属M为前驱体,通过热解前驱体的方法得到核壳型催化剂M/Co@C。在所述催化剂中,贵金属M为Pt、Ir、Pd、Ru或Au,且质量分数为0.5‑10 wt%,Co的质量分数在20‑80%;其以MOFs为前驱体制备金属物种高度分散且具有强磁性的催化剂,其金属活性物种为M/Co(M为Pt、Ir、Pd、Ru或Au)纳米合金,被介孔碳包裹形成核壳状,使得活性物种在催化反应过程中不易聚集,展示出较好的活性及循环使用性能。
Description
技术领域
本发明涉及化学材料技术领域,尤其涉及一种核壳型柠檬醛选择性加氢催化剂的合成方法。
背景技术
香叶醇和橙花醇作为一种精细化学品中间体,在化学化工领域有着举足轻重的地位,尤其在香精香料、医疗药物等方面具有不可替代的经济价值。柠檬醛作为一种重要的α,β-不饱和醛,主要来源于枫茅油和山苍子油,其选择性加氢生产香叶醇和橙花醇已被证实是最具有经济价值的合成路线之一。虽然将不饱和醛直接氢化产生饱和的羰基化合物相对容易实现,但是转化为不饱和醇的挑战性较大,原因在于热力学角度共轭的碳碳双键氢化所需的活化能低于碳氧双键氢化所需的活化能,导致了碳碳双键更易氢化从而直接生成饱和的羰基化合物。
目前,用于柠檬醛选择性加氢生成不饱和醇所采用的催化剂基本为多相的负载型催化剂,催化载体主要包括:二氧化硅、活性炭、碳纳米管和三氧化二铝;催化活性金属主要含有Ru(钌)、Pt(铂)、Ir(铱)、Pd(钯)、Co(钴)等金属元素。例如,美国专利US4100180公开的技术方案中,在催化剂PtO/Fe/Zn的作用下,柠檬醛的转化率为70%时,目标产物香叶醇和橙花醇的总选择性达到85.5%。在中国专利CN101157028A公开的一种铂碳纳米管催化剂中,将活性组分铂纳米颗粒均匀分散在碳纳米管载体上,催化柠檬醛加氢制备香茅醛,转化率可达90%,选择性85%,但未有催化剂循环反应及滤出实验测试。中国专利CN101747152公开了一种负载在FeO上的Pt催化剂,在柠檬醛选择性加氢过程中,实现了对香叶醇和橙花醇的选择性调控。当柠檬醛的转化率为14.2%的时候,香叶醇和橙花醇的总选择性为58.9%。中国专利CN106824182A公开了一种以钌改性的Ir/C催化剂,在柠檬醛选择性加氢过程中,当柠檬醛的转化率为100%的时候,香叶醇和橙花醇的选择性能达到98%。中国专利CN102151575A公开了一种具有磁性的碳纳米管负载Pd/Fe3O4的催化剂,该催化剂因为其磁性能与液相体系高效分离,表现出良好的循环使用性能,但是催化剂活性中心颗粒大小不均一且磁性颗粒易脱落。
综上,虽然这些催化剂能够很大程度的催化柠檬醛选择性加氢制备香叶醇和/或橙花醇,但是普遍存在柠檬醛加氢过程中活性组分易团聚、活性组分易流失不易分离等问题,导致催化剂不能循环使用,而这些恰恰是催化剂是否能够应用的关键。
发明内容
本发明的目的是提供一种核壳型柠檬醛选择性加氢催化剂的合成方法,采用介孔碳包裹纳米金属合金活性组分,从而有效解决现有柠檬醛加氢过程中存在的催化剂活性组分易团聚、活性组分易流失、不易分离等问题。
本发明提供的技术方案如下:
一种核壳型柠檬醛选择性加氢催化剂的合成方法,包括:
以Co-MOF负载的贵金属M为前驱体,通过热解前驱体的方法得到核壳型催化剂M/Co@C;在所述催化剂中,贵金属M为Pt、Ir、Pd、Ru或Au,且质量分数为0.5-10 wt%,Co的质量分数在20-80%;
进一步包括:
S11取定量的2,5-二羟基对苯二甲酸和六水合硝酸钴放入容器中后,取定量的贵金属盐冲洗入容器中,其中,2,5-二羟基对苯二甲酸、六水合硝酸钴和贵金属盐的质量比为1:2-5:0.036-0.08;
S12 往容器中加入体积比为1:1的无水乙醇和N,N'-二甲基甲酰胺,加入的无水乙醇和N,N'-二甲基甲酰胺与配体2,5-二羟基对苯二甲酸的质量比为150:1;
S13待固体完全溶解,将混合溶液加入聚四氟水热反应釜中,并放入电热恒温鼓风干燥箱中进行反应;
S14 聚四氟水热反应釜中反应完成并降至常温后,对反应后的混合溶液进行离心处理;
S15 将离心后的混合溶液放入干燥箱中进行干燥得到前驱体M@Co-MOF;
S16 将M@Co-MOF前驱体放入管式炉热解,以5℃/min的加热速率从30℃加热到目标温度并保持2-24 h,所述目标温度为400-1000℃;当反应结束且温度降为室温,取出制备得到的固体催化剂Pt/Co@C并做好真空保存防止氧化。
本发明还提供了一种柠檬醛选择性加氢过程中制备不饱和醇的方法,应用于由上述核壳型柠檬醛选择性加氢催化剂的合成方法得到的核壳型催化剂M/Co@C,包括:
S20 称定量的催化剂于加氢反应釜的聚四氟乙烯内衬中,并通过乙醇将催化剂沉入内衬底部;
S30 加入定量的柠檬醛和十二烷,并取少量均匀的混合溶液过油膜制得空白样;
S40 安装加氢反应釜,并排除其内部空气;
S50 往加氢反应釜中充入氢气并设定反应条件,待反应结束后将反应釜中氢气排出并取少量混合液体过油膜待测试;
S60 将反应釜中剩余的混合液体和催化剂进行磁性分离,得到制备的不饱和醇,并对干燥后的催化剂进行循环测试。
进一步优选地,在步骤S40中,通过依次在氮气和氢气的压力下充放气排除加氢反应釜内部空气。
进一步优选地,在步骤S50中,往加氢反应釜中充入0.5-3Mpa氢气,设定反应温度为80-120℃,反应时间为60-180min。
金属有机框架材料(MOFs)是一类由金属节点和有机配体通过配位作用连接形成的一种新型晶态多孔材料,与传统无机多孔材料相比,超高的比表面积和孔隙率,多变的结构及灵活的可修饰、可裁剪的特性使其在诸多领域表现出了优异的性能。此外,由MOFs中的金属节点具备被有机配体均匀有序间隔的特点,其在作为模板或前驱体使用时,可转变为比MOFs材料更加稳定的金属基/导电碳多孔材料,同时也最大限度的保留了原始MOFs材料的特性,包括大的比表面积、金属活性物种高度分散性、定制的孔隙度等。考虑到大多数MOFs材料均是由过渡金属(Fe、Mn、Co、Cu、Ni等)和含有C、H、O、N、S等元素的有机配体构成,通常是催化体系中必不可少的元素,且导电碳/金属基多孔材料既保留母材料的特性也弥补了MOFs材料稳定性差的问题,在催化应用方面显示出了巨大的优势。
在本发明提供的核壳型柠檬醛选择性加氢催化剂的合成方法中,以MOFs为前驱体制备金属物种高度分散且具有强磁性的催化剂,其金属活性物种为M/Co(M为Pt、Ir、Pd、Ru或Au)纳米合金,被介孔碳包裹形成核壳状且具有磁性,使得活性物种在催化反应过程中不易聚集,展示出较好的活性及循环使用性能,具备广阔的应用前景,适用于但不限于柠檬醛选择性加氢反应中。
附图说明
下面将以明确易懂的方式,结合附图说明优选实施方式,对上述特性、技术特征、优点及其实现方式予以进一步说明。
图1为实施例1催化剂2%Pt/Co@C-700和实例3催化剂Co@C-700的X射线衍射图;
图2为实施例1中催化剂的透射电镜图,(a)为2%Pt/Co@C-700的透射电镜图,右下角插入图为催化剂的粒径分布;(b)为2%Pt/Co@C-700的高清透射电镜图;
图3为实施例1中催化剂2%Pt/Co@C-700的循环图(a)和滤出实验图(b)。
具体实施方式
下面结合附图和实例进一步说明本发明的实质内容,但本发明的内容并不限于此。
实施例1
1)采用水热法来合成前驱体H2PtCl6@Co-MOF:
首先称取2.216g(克)的2,5-二羟基对苯二甲酸和10.77g的六水合硝酸钴于2500mL(毫升)的烧杯中;之后称取0.345g的六水合氯铂酸,并用300mL的去离子水冲洗到烧杯中;接着依次加入300mL的无水乙醇和300mL的N,N'-二甲基甲酰胺(混合溶液有少量的放热现象),并将溶液在室温下搅拌至均匀透明的深红色混合溶液。这个过程中,若存在少量固体未溶解,将其放入超声机进行超声处理直至完全溶解。固体完全溶解后,将均匀透明的混合溶液加入2000mL的聚四氟水热反应釜中,然后放入电热恒温鼓风干燥箱,在120℃下反应24h。当聚四氟水热反应釜中的温度降至室温时取出,将混合溶液在转速9000r/min(转/分钟)的条件下离心5min(分钟)后进行超声处理,并分别用甲醇和N,N'-二甲基甲酰胺各洗三次。最后,在真空干燥箱中80℃的条件下保持6h得到淡黄色的前驱体H2PtCl6@Co-MOF。
2)制备催化剂2%Pt/Co@C-700:
首先,将适量前驱体H2PtCl6@Co-MOF加入石英管中,石英玻璃管两端用石英棉固定,其中氮气通出的一端利用石英砂填充后再利用石英棉固定,防止前驱体H2PtCl6@Co-MOF在氮气氛围下随着气体冲出。之后,将石英管放入小型氮气热解炉中,为了将管中的空气排出,热解炉预先通气30min。接着,在氮气流速为50mL/min的气氛下,以5℃/min的加热速率从30℃加热到700℃并保持6h。当反应结束且温度降为温室,取出制备得到的纯黑色固体催化剂2%Pt/Co@C-700并做好真空保存防止氧化。
3)柠檬醛选择性加氢过程中制备不饱和醇,采用加氢反应釜进行反应,属于内部磁力搅拌的方式且温度的控制归为内部实际控温:
首先,称取0.8g的催化剂于1000mL的加氢反应釜的内衬中,并加入300mL的乙醇(溶剂)确保内衬壁的催化剂沉入内衬底部;之后,加入20mL的柠檬醛和1000uL的十二烷(内标),取少量均匀的混合溶液过油膜制得空白样。待反应物加入,安装加氢反应釜,先在氮气1MPa的压力下冲放气五次,后切换气路在1MPa氢气的压力下冲放气五次保证加氢反应釜内空气的排除。之后,在加氢反应釜内冲入1MPa的氢气,等待6min保证气压不变后,将反应温度设置为110℃和反应时间设置为60min。当反应结束后,将加氢反应釜放入到冰水混合液体中以便快速降温,待温度到达15℃以下时检查气压是否正常,防止其反应漏气。若反应后气压正常,则可以慢慢的将反应釜氢气放出室外,并取少量的混合液体过油膜待测试。最后,将反应釜中剩余的混合液体与催化剂磁性分离,并在真空干燥后进行催化剂循环测试。
通过安捷伦GC-7820A对混合液体进行定性和定量的分析,其色谱柱为HP-5(30m×0.25mm×0.25μm),检测器显示为FID(氢离子火焰),对柠檬醛选择性加氢合成不饱和醇的催化性能如表1所示;透射电镜图如图2所示,其中,图2(a)为透射电镜图,右下角的插入图为催化剂的粒径分布,图2(b)为高清透射电镜图;循环和稳定性测试如图3所示,其中,图3(a)为催化剂的循环图(循环次数1~4),图3(b)为滤出实验图,从图中可以看出,该催化剂可以循环使用,且性能稳定。
实施例2
1)采用水热法来合成前驱体RuCl3@Co-MOF:
首先称取2.216g的2,5-二羟基对苯二甲酸和10.77g的六水合硝酸钴于2500mL(毫升)的烧杯中;之后称取1.33g的三氯化钌,并用300mL的去离子水冲洗到烧杯中;接着依次加入300mL的无水乙醇和300mL的N,N'-二甲基甲酰胺(混合溶液有少量的放热现象),并将溶液在室温下搅拌至均匀透明的深红色混合溶液。这个过程中,若存在少量固体未溶解,将其放入超声机进行超声处理直至完全溶解。固体完全溶解后,将均匀透明的混合溶液加入2000mL的聚四氟水热反应釜中,然后放入电热恒温鼓风干燥箱,在120℃下反应24h。当聚四氟水热反应釜中的温度降至室温时取出,将混合溶液在转速9000r/min(转/分钟)的条件下离心5min(分钟)后进行超声处理,并分别用甲醇和N,N'-二甲基甲酰胺各洗三次。最后,在真空干燥箱中80℃的条件下保持6h得到淡黄色的前驱体RuCl3@Co-MOF。
2)制备催化剂4%Ru/Co@C-700:
首先,将适量前驱体RuCl3@Co-MOF加入石英管中,石英玻璃管两端用石英棉固定,其中氮气通出的一端利用石英砂填充后再利用石英棉固定,防止前驱体RuCl3@Co-MOF在氮气氛围下随着气体冲出。之后,将石英管放入小型氮气热解炉中,为了将管中的空气排出,热解炉预先通气30min。接着,在氮气流速为50mL/min的气氛下,以5℃/min的加热速率从30℃加热到700℃并保持6h。当反应结束且温度降为温室,取出制备得到的纯黑色固体催化剂4%Ru/Co@C-700并做好真空保存防止氧化。
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例3
1)采用水热法来合成前驱体Co-MOF:
首先称取2.216g的2,5-二羟基对苯二甲酸和10.77g的六水合硝酸钴于2500mL(毫升)的烧杯中,再加入300mL的去离子水;接着依次加入300mL的无水乙醇和300mL的N,N'-二甲基甲酰胺(混合溶液有少量的放热现象),并将溶液在室温下搅拌至均匀透明的深红色混合溶液。这个过程中,若存在少量固体未溶解,将其放入超声机进行超声处理直至完全溶解。固体完全溶解后,将均匀透明的混合溶液加入2000mL的聚四氟水热反应釜中,然后放入电热恒温鼓风干燥箱,在120℃下反应24h。当聚四氟水热反应釜中的温度降至室温时取出,将混合溶液在转速9000r/min(转/分钟)的条件下离心5min(分钟)后进行超声处理,并分别用甲醇和N,N'-二甲基甲酰胺各洗三次。最后,在真空干燥箱中80℃的条件下保持6h得到淡黄色的前驱体Co-MOF。
2)制备催化剂Co@C:
首先,将适量前驱体Co-MOF加入石英管中,石英玻璃管两端用石英棉固定,其中氮气通出的一端利用石英砂填充后再利用石英棉固定,防止前驱体Co-MOF在氮气氛围下随着气体冲出。之后,将石英管放入小型氮气热解炉中,为了将管中的空气排出,热解炉预先通气30min。接着,在氮气流速为50mL/min的气氛下,以5℃/min的加热速率从30℃加热到700℃并保持6h。当反应结束且温度降为温室,取出制备得到的纯黑色固体催化剂Co@C并做好真空保存防止氧化。
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步,这里不做赘述。
实施例4
1)合成的前驱体H2PtCl6@Co-MOF过程同实施例1中的第(1)步,但H2PtCl6的加入量为0.08g;
2)制备催化剂0.5%Pt/Co@C-400的过程同实施例1中的第(2)步,但热解温度为400℃;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例5
1)合成的前驱体H2PtCl6@Co-MOF过程同实施例1中的第(1)步,但H2PtCl6的加入量为1.4g;
2)制备催化剂8%Pt/Co@C-400的过程同实施例1中的第(2)步,但热解温度为800℃;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例6
1)合成的前驱体H2PtCl6@Co-MOF过程同实施例1中的第(1)步,但H2PtCl6的加入量分别为1.4g;
2)制备催化剂8%Pt/Co@C-400-2h的过程同实施例1中的第(2)步,但热解温度为1000℃,保持2h;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例7
1)合成的前驱体H2PtCl6@Co-MOF过程同实施例1中的第(1)步,但六水合硝酸钴的加入量为4.43g;
2)制备催化剂2%Pt/Co@C-700-24h的过程同实施例1中的第(2)步,但热解温度为700℃,保持24h;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例8
1)合成的前驱体H2PtCl6@Co-MOF过程同实施例1中的第(1)步,但H2PtCl6的加入量分别为1.8g;
2)制备催化剂10%Pt/Co@C-400-2h的过程同实施例1中的第(2)步,但热解温度为1000℃,保持2h;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例1中的第(3)步。
实施例9
1)合成的前驱体RuCl3@Co-MOF过程同实施例2中的第(1)步;
2)制备催化剂4%Ru/Co@C-500-24h的过程同实施例2中的第(2)步,但热解温度为500℃,保持24h;
3)柠檬醛选择性加氢过程中制备不饱和醇过程同实施例2中的第(3)步。
表1:实施例1-8制备催化剂对柠檬醛选择性加氢合成不饱和醇的催化性能
应当说明的是,上述实施例均可根据需要自由组合。以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种核壳型柠檬醛选择性加氢催化剂的合成方法,其特征在于,包括:
以Co-MOF负载的贵金属M为前驱体,通过热解前驱体的方法得到核壳型催化剂M/Co@C;在所述催化剂中,贵金属M为Pt、Ir、Pd、Ru或Au,且质量分数为0.5-10wt%,Co的质量分数在20-80%;
以Co-MOF负载的贵金属M为前驱体,通过热解前驱体的方法得到核壳型催化剂M/Co@C中进一步包括:
S11取定量的2,5-二羟基对苯二甲酸和六水合硝酸钴放入容器中后,取定量的贵金属盐冲洗入容器中,其中,2,5-二羟基对苯二甲酸、六水合硝酸钴和贵金属盐的质量比为1:2-5:0.036-0.08;
S12往容器中加入体积比为1:1的无水乙醇和N,N'-二甲基甲酰胺,加入的无水乙醇和N,N'-二甲基甲酰胺与配体2,5-二羟基对苯二甲酸的质量比为150:1;
S13待固体完全溶解,将混合溶液加入聚四氟水热反应釜中,并放入电热恒温鼓风干燥箱中进行反应;
S14聚四氟水热反应釜中反应完成并降至常温后,对反应后的混合溶液进行离心处理;
S15将离心后的混合溶液放入干燥箱中进行干燥得到前驱体M@Co-MOF;
S16将M@Co-MOF前驱体放入管式炉热解,以5℃/min的加热速率从30℃加热到目标温度并保持2-24h,所述目标温度为400-1000℃;当反应结束且温度降为室温,取出制备得到的固体催化剂Pt/Co@C并做好真空保存防止氧化。
2.如权利要求1所述的核壳型柠檬醛选择性加氢催化剂的合成方法,其特征在于,在步骤S14中,对反应后的混合溶液进行离心处理之后,还包括对离心后的混合溶液进行超声处理及分别使用甲醇和N,N'-二甲基甲酰胺对超声后的混合溶液进行清洗。
3.一种柠檬醛选择性加氢过程中制备不饱和醇的方法,其特征在于,应用于如权利要求1或2所述的核壳型柠檬醛选择性加氢催化剂的合成方法得到的核壳型催化剂M/Co@C,包括:
还包括:
S20称定量的催化剂于加氢反应釜的聚四氟乙烯内衬中,并通过乙醇将催化剂沉入内衬底部;
S30加入定量的柠檬醛和十二烷,并取少量均匀的混合溶液过油膜制得空白样;
S40安装加氢反应釜,并排除其内部空气;
S50往加氢反应釜中充入氢气并设定反应条件,待反应结束后将反应釜中氢气排出并取少量混合液体过油膜待测试;
S60将反应釜中剩余的混合液体和催化剂进行磁性分离,得到制备的不饱和醇,并对干燥后的催化剂进行循环测试。
4.如权利要求3所述的柠檬醛选择性加氢过程中制备不饱和醇的方法,其特征在于,在步骤S40中,通过依次在氮气和氢气的压力下充放气排除加氢反应釜内部空气。
5.如权利要求3所述的柠檬醛选择性加氢过程中制备不饱和醇的方法,其特征在于,在步骤S50中,往加氢反应釜中充入0.5-3Mpa氢气,设定反应温度为80-120℃,反应时间为60-180min。
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