CN115090283B - 一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用 - Google Patents

一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用 Download PDF

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CN115090283B
CN115090283B CN202210876553.8A CN202210876553A CN115090283B CN 115090283 B CN115090283 B CN 115090283B CN 202210876553 A CN202210876553 A CN 202210876553A CN 115090283 B CN115090283 B CN 115090283B
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shell
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朱坚
应思斌
王平
罗功禹
谢国玲
余彭亮
张鲁忆
兰昭洪
刘刚
叶浩
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Ningxia Xinhua Chemical Co ltd
ZHEJIANG XINHUA CHEMICAL CO Ltd
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ZHEJIANG XINHUA CHEMICAL CO Ltd
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Abstract

本发明公开了一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用。所述催化剂具有如下通式:xM@yShell/ZT,其中M、Shell和ZT分别代表活性金属、氧化物壳层以及载体,质量组成:x为1~30wt%,y为0~40wt%,余量为ZT,所述活性金属选自Ru、Pd、Pt、Ni、Co、Fe、Cu、Ag、Zn、Ga、In中的至少一种;所述的氧化物壳层由偶联剂焙烧后形成,所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、锆酸酯偶联剂中的至少一种。本发明提供的负载型核壳催化剂具有制备简单、结构稳定、反应活性高、等诸多优点。

Description

一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内 酯加氢中应用
技术领域
本发明是涉及一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用,属于催化技术领域。
技术背景
3-环己基丙酸烯丙酯又称菠萝酯,具有温和的菠萝香味,用作赋香剂,主要用于配制菠萝等水果型香精。菠萝酯生产工艺是以环己基丙酸与烯丙醇进行酯化反应,或者环己基丙酸酯与烯丙醇进行酯交换反应。例如中国专利CN85102572A报道了以雷尼镍为催化剂,催化环己烯基丙酸甲酯加氢生成环己基丙酸甲酯,随后进行酯化制备菠萝酯,但该工艺存在环己烯基丙酸甲酯来源困难的问题,目前还未能实现工业化。
中国专利CN101041618A同样以肉桂酸甲酯作为原料,雷尼镍为催化剂,加氢制得得到环己基丙酸甲酯,随后进行酯交换制备菠萝酯,这也是目前香料行业生产环己基丙酸甲酯的主流工艺,但该工艺存在原料成本高的问题。
针对现有技术所存在的问题,本发明采用廉价易得的环戊基丁内酯作为原料,采用负载型核壳催化剂,可直接加氢得到3-环己基丙酸烯丙酯,也可加氢得到中间体环己基丙酸或环己基丙酸酯。
发明内容
为了克服上述现有技术中的不足,本发明提供一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用。
本发明公开了一种负载型核壳催化剂,利用两亲性偶联剂的双向桥联作用(即一端能金属发生络合,另一端的与载体表面的羟基发生自发的缩聚反应)将活性金属锚附在载体上,所述催化剂具有如下通式:xM@yShell/ZT,其中,M、Shell和ZT分别代表活性金属、氧化物壳层以及表面具有羟基的载体,按质量分数计,x为1~30wt%,y为0~40wt%,余量为ZT;所述活性金属选自Ru、Pd、Pt、Ni、Co、Fe、Cu、Ag、Zn、Ga、In中的至少一种;所述的氧化物壳层由偶联剂焙烧后形成,所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、锆酸酯偶联剂中的至少一种。
优选的,所述表面具有羟基的载体选自氧化钛,氧化硅、氧化锆、氧化铈、铈锆固溶体、氧化铝、分子筛、羟基磷灰石、铌酸、氧化钒、氧化钨、活性炭中的至少一种。
优选的,所述的硅烷偶联剂选自氨基硅烷偶联剂,选自3-氨丙基三乙氧基硅烷,2-氨乙基-3-氨丙基甲基二甲氧基硅烷、2-氨乙基-3-氨丙基三甲氧基硅烷、2-氨乙基-3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、苯基-3-氨丙基三甲氧基硅烷中的至少一种;所述的钛酸酯偶联剂选自异丙氧基三(乙二胺基-N-乙氧基)钛酸酯,新烷氧基三(对氨基苯氧基)钛酸酯,新烷氧基三(乙二胺基N-乙氧基)钛酸酯、双三乙醇胺二异丙基钛酸酯中的至少一种;所述的锆酸酯偶联剂选自四(三乙醇胺)锆,新烷氧基三(对氨基苯氧基)锆酸酯,新烷氧基三(乙二胺基N-乙氧基)锆酸酯中的至少一种。
本发明提供一种负载型核壳催化剂的制备方法,利用两亲性偶联剂的双向桥联作用将活性金属锚附在载体上,具体如下步骤:
1)在有机溶剂中加入活性金属和偶联剂,使活性金属和偶联剂发生络合;
2)在1)制备的溶液中加入载体,使偶联剂与载体表面羟基发生缩聚反应,锚定偶联剂,即制得催化剂前体;
3)对2)制备的催化剂前体进行烘干、焙烧、还原处理,即制得负载型核壳催化剂。
优选的,步骤1)中,有机溶剂选自甲醇、乙醇、异丙醇、丙酮、甲苯中的至少一种,活性金属来源于硝酸盐、醋酸盐、乙酰丙酮盐中的至少一种,偶联剂与活性金属的摩尔比为0.1~10。
优选的,步骤1)中,所述反应温度为0~60℃,所述反应时间为1~24小时,步骤2)中所述反应温度为0~80℃,所述反应时间为1~48小时;步骤3)中所述焙烧温度为250~800℃,焙烧气氛为氮气或者空气,所述还原温度为300~600℃,还原气为氢气体积浓度为5~100%氢氮混合气。
本发明提供一种负载型核壳催化剂的应用,其用于环戊基丁内酯加氢反应。
优选的,若加氢反应在无醇体系中进行,则产物为环己基丙酸;加氢反应过程在含醇体系中进行,则主要产物为环己基丙酸酯。
优选的,所述含醇体系,醇选自甲醇、乙醇、丙醇、异丙醇、丁醇、烯丙醇中的至少一种,产物为对应的环己基丙酸甲酯、环己基丙酸乙酯、环己基丙酸丙酯、环己基丙酸异丙酯、环己基丙酸丁酯,所述产物与烯丙醇进行酯交换则得到菠萝酯。当所述含醇体系为烯丙醇时,产物则为菠萝酯。
优选的,加氢反应可在反应釜中进行间歇加氢反应,也可在固定床中进行连续加氢反应,其中,
所述间歇加氢条件为:加氢温度优选100~300℃,加氢压力优选0.5~10MP,催化剂投料量与环戊基丁内酯的质量比优选0.1~20%;
所述连续加氢条件为:加氢温度优选100~300℃,加氢压力优选0.5~10MP,环戊基丁内酯与氢气的摩尔比优选为1:(1~100),环戊基丁内酯的质量空速优选为0.3~5h-1
本发明的有益效果:
与现有技术相比,本发明有较好的、较优的环戊基丁内酯转化率,以及环己基丙酸甲酯选择性,环戊基丁内酯转化率>98%,环己基丙酸烯丙酯选择性>86%,环己基丙酸选择性>12%,环己基丙酸甲酯和环己基丙酸的总选择性>98%,且在600小时的反应过程中未出现失活迹象,表现出优异的反应活性和稳定性。
附图说明
图1是本发明实施例3金属Pt作为活性组分,二氧化钛作为载体,3-氨丙基三乙氧基硅烷作为偶联剂的催化剂固定床反应性能。
具体实施方式
下面结合实施例对本发明的技术方案作进一步说明。
实施例1
1)称取3-氨丙基三乙氧基硅烷56g溶解于450g异丙醇中,室温下超声溶解30分钟,随后加入10.5g氯铂酸,室温下超声处理30分钟,随后静置12小时,使3-氨丙基三乙氧基硅烷与铂充分络合。
2)室温下,在步骤1)制备的溶液中加入100g二氧化钛,充分搅拌3小时,使3-氨丙基三乙氧基硅烷锚定在二氧化钛表面。随后,通过旋蒸去除异丙醇,得到淡黄色固体。
3)将步骤2)得到的淡黄色固体置于马弗炉中,空气气氛下,550℃焙烧4小时,降至室温后取出。随后在管式炉中进行还原处理,氢气气氛下,300℃还原4小时,即得到负载型核壳催化剂。
步骤1)中硅烷偶联剂的氨基可与活性金属发生络合反应,随后在步骤2)中乙氧基与二氧化钛表面羟基发生缩聚反应,锚定活性金属。步骤3)中硅烷偶联剂在空气中焙烧,形成二氧化硅壳层,包裹在活性金属Pt表面,此后经还原活性金属Pt为还原态。经等离子体电感耦合原子吸收光谱分析,制备的负载型核壳催化剂中Pt的质量百分数为4.5%,Si的质量百分数为5.8%,所得负载型核壳催化剂记为:Pt@SiO2/TiO2
催化剂性能检测
将10g实施例1制备的负载型核壳催化剂,600g环戊基丁内酯,600g甲醇投入2L不锈钢反应釜中,用氮气置换5次后,氢气充压至6MPa,密闭后将反应釜升温至180℃,机械搅拌(1000转/min),控制反应釜压力在6.0MPa反应,反应12小时。采用过滤的方法将催化剂与反应液分离,反应液的定量分析在安捷伦7890气相色谱仪上进行,采用色谱柱HP-INNOWax和FID检测器进行检测。
参照上述实验和检测步骤,分别替换对应的偶联剂、金属或载体,可制得不同壳层的负载型核壳催化剂、不同活性组分的负载型核壳催化剂或不同载体的负载型核壳催化剂,其他参数不变。
表1为金属Pt作为活性组分,二氧化钛作为载体,不同硅烷偶联剂作为壳层的催化剂反应性能。
表1不同硅烷偶联剂作为壳层的催化剂Pt@SiO2/TiO2反应性能
在反应过程中生成的环己基丙酸具有较强的酸性,易与活性金属发生反应,造成金属流失,降低催化剂活性,而氧化物壳层与金属之间的强作用力以及氧化物壳层包裹在活性金属表面可有效避免活性金属的流失。由表1可知,制备的以SiO2作为壳层的催化剂性能差别不大,环戊基丁内酯转化率>95%,环己基丙酸甲酯选择性>90%,环己基丙酸选择性>5%,环己基丙酸甲酯和环己基丙酸的总选择性>97%,说明SiO2作为壳层均可有效避免Pt的流失。
表2二氧化钛作为载体,3-氨丙基三乙氧基硅烷作为偶联剂,不同金属作为活性组分的催化剂反应性能。
表2不同金属作为活性组分的催化剂M@SiO2/TiO2反应性能
由于环戊基丁内酯加氢需要断裂C-O键,由表2可知,C-O键活化能力强的活性金属Pt、Ni、Co、Fe均有较好的、较优的环戊基丁内酯转化率,以及环己基丙酸甲酯选择性,而C-O键活化能力相对较弱的活性金属Ru、Pd、Cu、Ag、Zn、Ga、In环戊基丁内酯转化率以及环己基丙酸甲酯选择性相对较差。
表3为金属Pt作为活性组分,3-氨丙基三乙氧基硅烷作为偶联剂,不同载体的催化剂反应性能。由表3可知制备的负载型核壳催化剂均有较优的环戊基丁内酯转化率,以及环己基丙酸甲酯选择性。
表3不同载体催化剂Pt@SiO2/ZT反应性能
表4为金属Pt作为活性组分,3-氨丙基三乙氧基硅烷作为偶联剂,二氧化钛作为载体的负载型核壳催化剂用于不同含醇体系的环戊基丁内酯加氢。由表4可知,在不同含醇体下,环戊基丁内酯加氢可得到相应的环己基丙酸酯,且随着醇类碳链数的增加,转化率和环己基丙酸酯选择性降低。
表4不同含醇体系的反应性能
对比例1
1)室温下,称取10.5g氯铂酸,15g二氧化硅,100g二氧化钛置于450g去离子水中,充分搅拌3小时,随后100℃烘干,得到淡黄色固体。
2)将步骤1)得到的淡黄色固体置于马弗炉中,空气气氛下,550焙烧4小时,降至室温后取出。随后在管式炉中进行还原处理,氢气气氛下,300℃还原4小时,即得到负载型催化剂,记为Pt/SiO2-TiO2。经等离子体电感耦合原子吸收光谱分析,制备的负载型催化剂中Pt的质量百分数为4.7%,Si的质量百分数为10.7%。
实施例2
参照实施例1制备步骤,表5为金属Pt作为活性组分,二氧化钛作为载体,不同钛酸酯偶联剂及锆酸酯偶联剂作为壳层的催化剂反应性能。
采用固定床反应器考察实施例1制备的催化剂用于环戊基丁内酯无醇体系加氢反应性能。反应条件:反应温度280℃,反应压力6MPa,环戊基丁内酯的质量空速为0.5h-1,氢气与环戊基丁内酯的摩尔比为20。对比实施例1和实施例2的反应条件可以看出,在无醇体系中反应温度明显高于含醇体系,这主要是因为在含醇体系中,生成的环己基丙酸会与醇反应,促进了反应的进行。反应后产物定量分析在安捷伦7890气相色谱仪上进行,采用色谱柱HP-INNOWax和FID检测器进行检测。
由表5可知,制备的负载型核壳催化剂均有较优的环戊基丁内酯转化率,以及环己基丙酸甲酯选择性。由表5可知,环戊基丁内酯转化率>98%,环己基丙酸烯丙酯选择性>86%,环己基丙酸选择性>12%,环己基丙酸甲酯和环己基丙酸的总选择性>98%,且在600小时的反应过程中未出现失活迹象,表现出优异的反应活性和稳定性。
表5不同钛酸酯偶联剂作为壳层的催化剂反应性能
实施例3
采用固定床反应器考察实施例1制备的催化剂用于环戊基丁内酯在烯丙醇体系中的加氢反应性能。反应条件:反应温度180℃,反应压力6MPa,环戊基丁内酯的质量空速为0.5h-1,氢气与环戊基丁内酯的摩尔比为20,烯丙醇与与环戊基丁内酯的摩尔比为2.5。反应后产物定量分析在安捷伦7890气相色谱仪上进行,采用色谱柱HP-INNOWax和FID检测器进行检测。
结果见图1,环戊基丁内酯转化率>98%,环己基丙酸烯丙酯选择性>88%,环己基丙酸的选择性>10%,且在600小时的反应过程中未出现失活迹象,表现出优异的反应活性和稳定性。
实施例4
将10g对比例1制备的负载型催化剂,600g环戊基丁内酯,600g甲醇投入2L不锈钢反应釜中,用氮气置换5次后,氢气充压至6MPa,密闭后将反应釜升温至180℃,机械搅拌(1000转/min),控制反应釜压力在6.0MPa反应,反应12小时。由表6可知,对比例1制备的负载型催化剂效果明显差于实施例1制备的负载型核壳催化剂。由表7可知,对比例1制备的负载型催化剂反应后Pt负载量降低明显,说明反应过程中Pt流失严重。
表6对比例催化剂反应性能
表7催化剂反应前后金属含量变化
最后有必要在此说明的是:以上实施例只用于对本发明的技术方案作进一步详细地说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。

Claims (8)

1.一种负载型核壳催化剂的应用,其特征在于:所述负载型核壳催化剂用于环戊基丁内酯加氢反应,所述负载型核壳催化剂具有如下通式:xM@yShell/ZT,其中,M、Shell和ZT分别代表活性金属、氧化物壳层以及表面具有羟基的载体,按质量分数计,x为1~30wt%,y为0~40wt%,余量为ZT;所述活性金属选自Ru、Pd、Pt、Ni、Co、Fe、Cu、Ag、Zn、Ga、In中的至少一种;所述氧化物壳层为二氧化硅、二氧化钛、二氧化锆中的至少一种;所述表面具有羟基的载体选自氧化钛、氧化硅、氧化锆、氧化铈、铈锆固溶体、氧化铝、分子筛、羟基磷灰石、铌酸、氧化钒、氧化钨、活性炭中的至少一种。
2.如权利要求1所述的应用,其特征在于:若加氢反应在无醇体系中进行,则产物为环己基丙酸;加氢反应过程在含醇体系中进行,则产物为环己基丙酸酯。
3.如权利要求2所述的应用,其特征在于:所述含醇体系,醇选自甲醇、乙醇、丙醇、异丙醇、丁醇、烯丙醇中的至少一种。
4.如权利要求2所述的应用,其特征在于:加氢反应可在反应釜中进行间歇加氢反应,也可在固定床中进行连续加氢反应;其中,
所述间歇加氢条件为:加氢温度为100~300℃,加氢压力为0.5~10MP,所述负载型核壳催化剂投料量与环戊基丁内酯的质量比为0.1~20%;
所述连续加氢条件为:加氢温度为100~300℃,加氢压力为0.5~10MP,环戊基丁内酯与氢气的摩尔比为1:(1~100),环戊基丁内酯的质量空速为0.3~5h-1
5.如权利要求1所述的应用,其特征在于:所述的氧化物壳层由偶联剂焙烧后形成,所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、锆酸酯偶联剂中的至少一种,其中所述的硅烷偶联剂选自氨基硅烷偶联剂、3-氨丙基三乙氧基硅烷、2-氨乙基-3-氨丙基甲基二甲氧基硅烷、2-氨乙基-3-氨丙基三甲氧基硅烷、2-氨乙基-3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、苯基-3-氨丙基三甲氧基硅烷中的至少一种;所述的钛酸酯偶联剂选自异丙氧基三(乙二胺基-N-乙氧基)钛酸酯、新烷氧基三(对氨基苯氧基)钛酸酯、新烷氧基三(乙二胺基N-乙氧基)钛酸酯、双三乙醇胺二异丙基钛酸酯中的至少一种;所述的锆酸酯偶联剂选自四(三乙醇胺)锆、新烷氧基三(对氨基苯氧基)锆酸酯、新烷氧基三(乙二胺基N-乙氧基)锆酸酯中的至少一种。
6.权利要求1所述的应用,其特征在于:利用两亲性偶联剂的双向桥联作用将活性金属锚附在载体上即制得所述负载型核壳催化剂,具体如下步骤:
1)在有机溶剂中加入活性金属和偶联剂,使活性金属和偶联剂发生络合;
2)在1)制备的溶液中加入载体,使偶联剂与载体表面羟基发生缩聚反应,锚定偶联剂,即制得催化剂前体;
3)对2)制备的催化剂前体进行烘干、焙烧、还原处理,即制得负载型核壳催化剂。
7.如权利要求6所述的应用,其特征在于:步骤1)中,有机溶剂选自甲醇、乙醇、异丙醇、丙酮、甲苯中的至少一种,活性金属选自硝酸盐、醋酸盐、乙酰丙酮盐中的至少一种,偶联剂与活性金属的摩尔比为0.1~10。
8.如权利要求6所述的应用,其特征在于:步骤1)中反应温度为0~60℃,反应时间为1~24小时,步骤2)中反应温度为0~80℃,反应时间为1~48小时;步骤3)中所述焙烧温度为250~800℃,焙烧气氛为氮气或者空气,所述还原温度为300~600℃,还原气为氢气体积浓度为5~100%氢氮混合气。
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