CN116099548A - 一种用于制备高比例反反氢化双酚a的负载型催化剂的制备方法及应用 - Google Patents
一种用于制备高比例反反氢化双酚a的负载型催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明属于酚类加氢领域,公开一种用于制备高比例反反氢化双酚A的负载型催化剂的制备方法及应用。通过尿素热解法制备Ce或Mn元素掺杂的钴铝类水滑石,通过结构拓扑变换得到含有Ce或Mn元素掺杂的金属复合氧化物,再利用液相化学还原法制备负载型催化剂。以双酚A为原料,在高压釜式反应器中制备氢化双酚A,反应转化率99.9%,选择性99.9%,(trans,trans)‑HBPA比例高达71%。本发明不仅实现了载体对贵金属的分散,还利用Ce或者Mn引入的氧空位缺陷实现了对酚类物质的活化,并且这些可还原性载体也有利于产生氢溢流效应,从而有效提高催化剂对酚类物质的加氢性能并且有效地降低了贵金属活性组分的负载量。
Description
技术领域
本发明属于酚类加氢领域,涉及一种用于制备高比例反反氢化双酚A的负载型催化剂的制备方法及应用。
背景技术
双酚A(4,4′-二羟基二苯基丙烷,BPA,Bisphenol A),是一种经过非常广泛深入研究的基础原料化学品,主要用作生产聚碳酸酯、环氧树脂、四溴双酚A和其他合成特种树脂等。聚碳酸酯塑料是BPA的主要用途,约占全球BPA产量的70%,环氧树脂占双酚A总用量的近30%。虽然聚碳酸酯和环氧树脂在各自的应用领域中发挥了很好的作用,但是由于BPA型聚合物中芳环的存在,也产生了一些不利影响。研究认为BPA通过与多种生物受体相互作用,对人体产生内分泌干扰作用,这些干扰作用对神经系统、代谢功能、免疫功能造成不利影响。此外,由于BPA单体的芳香族结构,当温度迅速升高,再加上辐射,会使环氧树脂变黄、光学性能损失。相比双酚A型材料,氢化双酚A型材料具有无毒性、化学稳定性、耐紫外线、热稳定性及耐候性等优点。基于BPA型材料不利因素的影响,有必要对BPA型聚合物进行改性,改性方法之一是对BPA单体中的苯环进行加氢。
氢化双酚A的制备一般是以双酚A为原料,将其溶解于适当的有机溶剂(低级醇、环己烷、乙酸乙酯等)之中,在催化剂的作用下进行加氢反应得到。
美国专利,公开号:US2118954A,采用负载型镍基催化剂用于双酚A液相加氢制备氢化双酚A,该专利采用间歇釜式加氢工艺,在200℃,10-20MPa下进行反应,但该方法反应时间长,收率低。
美国专利,公开号:US4885409A,公开了一种活性炭载体上负载钯用于双酚A加氢的方法,采用间歇釜式加氢工艺,在反应温度为140℃,压力l0MPa的条件下反应12h,氢化双酚A的选择性高于99%,产物中反反异构体含量高于55%,但是该方法需要的反应时间长,反应压力高。
中国专利,公开号:CN106866365A,采用列管式固定床反应器在140-180℃,5-9MPa的条件下进行双酚A加氢,通过对加氢产物进行部分循环,使得反反异构体的比例达到60%,但是这种方法增加了生产周期和能耗,不利于工业化应用。
查阅文献可知,BPA加氢后会产生三种同分异构体,由于反反氢化双酚A((trans,trans)-HBPA)的结构对称性,其聚合物机械性能更好。双酚A催化加氢制氢化双酚A主要难点在加氢工艺催化剂的选择上,现有工业催化剂对(trans,trans)-HBPA的选择性大致在30-45%。目前我国氢化双酚A产品主要依靠国外进口,国内行业处于萌芽阶段,规模小、价格高、品质低,因此掌握高比例(trans,trans)-HBPA的生产技术,取得自主知识产权,具有重要的意义。
发明内容
针对现有技术的不足,本发明提供了一种用于制备高比例反反氢化双酚A((trans,trans)-HBPA)的负载型催化剂。首先通过尿素热解法制备Ce或者Mn元素掺杂的钴铝类水滑石(CoAl-LDHs),且在该领域内首次采用含有Ce或者Mn元素掺杂的金属复合氧化物(MMOs)作为催化剂载体;该载体通过Ce或者Mn元素产生的氧空位缺陷可以实现酚类物质的活化,然后利用贵金属Ru或者Pt对氢气的优异解离能力实现双酚A的催化加氢。此外这些可还原性载体也可以产生氢溢流效应,这有效地降低了贵金属活性组分Ru或者Pt的负载量。
为实现上述目的,本发明的技术方案如下:
一种用于制备高比例反反氢化双酚A的负载型催化剂的制备方法,步骤如下:
(1)首先按照(Co+Al+Ce):CO(NH2)2=1:4称取钴盐、铝盐、铈盐、尿素或按照(Co+Al+Mn):CO(NH2)2=1:4称取钴盐、铝盐、锰盐、尿素,溶解于去离子水中搅拌30min形成均匀溶液,控制金属离子总浓度为0.2mol/L;然后将该溶液转移至带内衬的水热釜中,最后将水热釜放入90-130℃的烘箱中恒温24h;待水热釜冷却至室温后,取出水热釜内衬,对里面的固体物质用去离子水洗涤至中性,然后将该固体烘干并且研磨成粉得到催化剂前体,最后将该催化剂前体置于400℃-650℃的管式炉中进行焙烧得到金属复合氧化物载体;
(2)采用液相化学还原法制备单金属或双金属负载型催化剂;向Ru单金属溶液、Pt单金属溶液、RuPd混合溶液或RuPt混合溶液中加入纯净水搅拌30min,向上述溶液中加入金属复合氧化物载体,搅拌3h,水浴升温至60-90℃后加入还原剂硼氢化钠反应3h-6h,最后对固体进行洗涤和真空干燥,得到负载型催化剂。
所述钴盐包括Co(NO3)2.6H2O或CoCl2.6H2O,优选Co(NO3)2.6H2O;铝盐包括Al(NO3)3.9H2O或AlCl3.9H2O,优选Al(NO3)3.9H2O;铈盐为Ce(NO3)3.6H2O;锰盐为Mn(NO3)2.4H2O。其中钴盐、铝盐、铈盐摩尔比为Co:Al:Ce=2:1:(0.1-1.25)或钴盐、铝盐、锰盐摩尔比为Co:Al:Mn=2:1:(0.1-1.25),水热温度为110℃,催化剂前体焙烧温度为550℃。
所述贵金属活性组分Ru、Pt、RuPd或RuPt,贵金属负载量为0.5-1.5wt%,优选1.25wt%,其中Ru:Pd(摩尔比)=4:1-1:3,优选Ru:Pd(摩尔比)=3:1,Ru:Pt(摩尔比)=7:1-1:4,优选Ru:Pt(摩尔比)=3:1,水浴温度为80℃。
一种双酚A催化加氢制氢化双酚A的方法,包括以下步骤:
将双酚A溶解在有机溶剂中,配置成质量浓度为1%-25%的双酚A溶液置于间歇高压反应釜,然后加入经过H2还原处理的负载型催化剂,进行氮气充压置换,打开加热装置进行反应;反应温度为100-140℃,氢压为2-5MPa,搅拌速度为800r/min,反应时间为1-6h,反应结束后对反应液进行离心分离回收催化剂用于下一次加氢反应,剩余反应液蒸发脱除溶剂,使用乙酸乙酯对得到的粗产物进行重结晶处理。
所述有机溶剂是环己烷、异丙醇、乙酸乙酯中的一种,有机溶剂和双酚A的质量比为200-3:1。优选地,有机溶剂为乙酸乙酯。
所述双酚A与负载型催化剂的质量比为1:1-10:1。
优选反应温度为120-130℃,氢压为3-4MPa,反应时间为3-4h。
在上述氢化双酚A的制备方法中,合适负载量的加氢负载型催化剂能够实现低贵金属负载量下达到99.9%以上的转化率,氢化双酚A选择性可达99.9%,其中反反氢化双酚A((trans,trans)-HBPA)比例为63%-71%。
本发明的有益效果:本发明将双酚A溶液与合适的负载型贵金属催化剂(单贵金属Ru、Pt或者RuPd、RuPt双金属)投入高压反应釜中,加氢获得高性能的氢化双酚A产品,氢化双酚A选择性99.9%,无其它副反应发生,其中(trans,trans)-HBPA比例为63%-71%。本发明所制备的双酚A催化加氢制氢化双酚A负载型催化剂的加氢活性良好,反应条件温和,极大降低了贵金属的用量同时又能保证催化活性,有效降低了氢化双酚A的生产成本,对于双酚A的非均相催化发展具有重要意义。
附图说明
图1为尿素均匀热解法制备得到的载体前体和载体的X射线衍射图像。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1:本发明制备的Ru/CoAlCe-MMOs或者Ru/CoMnAl-MMOs
取0.7g经过550℃焙烧的载体CoAlCe-MMOs或者CoMnAl-MMOs在100℃下烘干,冷却到室温后待用,以氯化钌溶液为贵金属活性组分前驱体溶液,活性组分Ru的负载量定为1wt%,制备负载型催化剂Ru/CoAlCe-MMOs或者Ru/CoMnAl-MMOs。具体实验步骤如下:取1381μL的RuCl3.nH2O(1.3519gRuCl3.nH2O/100mL)溶液于100mL圆底烧瓶中,向其中加入35mL纯净水,磁力搅拌30min,取0.7g载体CoAlCe-MMOs或者CoMnAl-MMOs,在搅拌条件下缓慢加入到上述分散好的活性组分前驱体溶液中,磁力搅拌3h;水浴升温至80℃,加入一定量的硼氢化钠,水浴恒温3h,反应结束后过滤洗涤、80℃真空烘箱中干燥12h得到催化剂;随后将一定量的催化剂置于H2氛围中在300℃还原2h,得到负载型催化剂Ru/CoAlCe-MMOs或者Ru/CoMnAl-MMOs。类似地,可制备Pt/CoAlCe-MMOs和Pt/CoMnAl-MMOs。
实施例2:本发明制备的Ru3Pd1/CoAlCe-MMOs或者Ru3Pd1/CoMnAl-MMOs
取0.7g经过550℃焙烧的载体CoAlCe-MMOs或者CoMnAl-MMOs在100℃下烘干,冷却到室温后待用,以氯化钌、氯化钯溶液为贵金属活性组分前驱体溶液,活性组分Ru和Pd的总负载量定为1wt%,制备负载型催化剂Ru3Pd1/CoAlCe-MMOs或者Ru3Pd1/CoMnAl-MMOs。具体实验步骤如下:取1022μL的RuCl3.nH2O(1.3519gRuCl3.nH2O/100mL)溶液和303μL的PdCl2(1.0003gPdCl2/100mL)于100mL圆底烧瓶中,向其中加入35mL纯净水,磁力搅拌30min,取0.7g载体CoAlCe-MMOs或者CoMnAl-MMOs,在搅拌条件下缓慢加入到上述分散好的活性组分前驱体溶液中,磁力搅拌3h;水浴升温至80℃,加入一定量的硼氢化钠,水浴恒温3h,反应结束后过滤洗涤、80℃真空烘箱中干燥12h得到催化剂;随后将催化剂置于H2氛围中在300℃还原2h,得到负载型催化剂Ru3Pd1/CoAlCe-MMOs或者Ru3Pd1/CoMnAl-MMOs。类似地,可制备其他不同比例的RuPd双金属催化剂和RuPt双金属催化剂。
实施例3
在高压釜式反应器中测试Ru/CoAlCe-MMOs催化剂的催化性能。
将1.0g双酚A溶解在30mL异丙醇中,取0.25g在管式炉中经过400℃还原2h后的上述加氢负载型催化剂加入到反应釜中,用氮气置换3次后,在高压反应釜中进行催化加氢反应。反应条件为:温度100-140℃,氢气压力4MPa,反应时间6h。反应结束后,催化剂离心分离回收再利用,蒸发烘干溶剂后,向其中加入一定量的乙酸乙酯进行重结晶处理,反应结果列于表1中。
实验考察不同反应温度对双酚A催化加氢的影响(所用催化剂为1.25%Ru/CoAlCe-MMOs)。
表1
温度/℃ | 转化率/% | (trans,trans)-HBPA选择性/% |
140 | 99.9 | 63 |
130 | 99.9 | 65 |
120 | 99.9 | 67 |
110 | 99.9 | 69 |
100 | 99.9 | 71 |
实施例4
在高压釜式反应器中测试不同载体负载的单金属催化剂和不同摩尔比例的RuPd双金属负载型催化剂(总负载量为1.25wt%)的催化性能。
表2
综上所述,本发明首次采用Ce或者Mn元素掺杂的金属复合氧化物作为载体制备了新型的负载型单金属催化剂和双金属催化剂,利用Ce元素或者Mn元素产生的氧空位缺陷活化酚类物质,提高了催化剂对双酚A的加氢性能并且有效降低了贵金属活性组分的负载量,从而降低了催化剂的制备成本。
上面以示例性而非限制性的方式描述了本发明及其若干实施例。本领域的普通技术人员在阅读本说明书后能够联想到其他可替代的实施方案,这些实施方案也在本发明的范围之内。
Claims (8)
1.一种用于制备高比例反反氢化双酚A的负载型催化剂的制备方法,其特征在于,步骤如下:
(1)首先按照(Co+Al+Ce):CO(NH2)2=1:4称取钴盐、铝盐、铈盐、尿素或按照(Co+Al+Mn):CO(NH2)2=1:4称取钴盐、铝盐、锰盐、尿素,溶解于去离子水中搅拌30min形成均匀溶液,控制金属离子总浓度为0.2mol/L;然后将该溶液转移至带内衬的水热釜中,最后将水热釜放入90-130℃的烘箱中恒温24h;待水热釜冷却至室温后,取出水热釜内衬,对里面的固体物质用去离子水洗涤至中性,然后将该固体烘干并且研磨成粉得到催化剂前体,最后将该催化剂前体置于400℃-650℃的管式炉中进行焙烧得到金属复合氧化物载体;
(2)采用液相化学还原法制备单金属或双金属负载型催化剂;向Ru单金属溶液、Pt单金属溶液、RuPd混合液或RuPt混合液中加入纯净水搅拌30min,向上述溶液中加入金属复合氧化物载体,搅拌3h,水浴升温至60-90℃后加入还原剂硼氢化钠反应3h-6h,最后对固体进行洗涤和真空干燥,得到负载型催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述的钴盐、铝盐、铈盐摩尔比为Co:Al:Ce=2:1:(0.1-1.25),所述的钴盐、铝盐、锰盐摩尔比为Co:Al:Mn=2:1:(0.1-1.25)。
3.根据权利要求2所述的制备方法,其特征在于,所述钴盐包括Co(NO3)2.6H2O或CoCl2.6H2O;铝盐包括Al(NO3)3.9H2O或AlCl3.9H2O;铈盐为Ce(NO3)3.6H2O;锰盐为Mn(NO3)2.4H2O。
4.根据权利要求1所述的制备方法,其特征在于,所述单金属或双金属负载型催化剂中活性组分为Ru、Pt、RuPd或RuPt,活性组分的负载量为0.5-1.5wt%;其中Ru:Pd的摩尔比=4:1-1:3,Ru:Pt的摩尔比=7:1-1:4。
5.根据权利要求1-4任一所述的制备方法,其特征在于,步骤(2)中的水浴温度为80℃;步骤(1)中的水热温度为110℃,催化剂前体焙烧温度为550℃。
6.一种双酚A催化加氢制氢化双酚A的方法,其特征在于,包括以下步骤:
将双酚A溶解在有机溶剂中,配置成质量浓度为1%-25%的双酚A溶液置于间歇高压反应釜,然后加入负载型催化剂,进行氮气充压置换,打开加热装置进行反应;反应温度为100-140℃,氢压为2-5MPa,搅拌速度为800r/min,反应时间为1-6h,反应结束后对反应液进行离心分离回收催化剂用于下一次加氢反应,剩余反应液蒸发脱除溶剂,使用乙酸乙酯对得到的粗产物进行重结晶处理;
其中,双酚A与负载型催化剂的质量比为1:1-10:1;
有机溶剂和双酚A的质量比为200-3:1。
7.根据权利要求6所述的方法,其特征在于,所述有机溶剂是环己烷、异丙醇、乙酸乙酯中的一种。
8.根据权利要求6或7所述的方法,其特征在于,所述的反应温度为120-130℃,氢压为3-4MPa,反应时间为3-4h。
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