CN108620127A - 一种四氢糠醇氢解制1,5-戊二醇的催化剂及制备方法及其应用 - Google Patents

一种四氢糠醇氢解制1,5-戊二醇的催化剂及制备方法及其应用 Download PDF

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CN108620127A
CN108620127A CN201710177295.3A CN201710177295A CN108620127A CN 108620127 A CN108620127 A CN 108620127A CN 201710177295 A CN201710177295 A CN 201710177295A CN 108620127 A CN108620127 A CN 108620127A
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catalyst
tetrahydrofurfuryl alcohol
donor ligand
auxiliary agent
reaction
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CN201710177295.3A
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CN108620127B (zh
Inventor
胡江林
刘运海
黎源
姜庆梅
宋延方
杨洋
陈长生
丁可
曾伟
杨恒东
王坤
华卫琦
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to CN201710177295.3A priority Critical patent/CN108620127B/zh
Priority to JP2019572270A priority patent/JP6830555B2/ja
Priority to PCT/CN2017/078264 priority patent/WO2018170932A1/zh
Priority to EP17902164.7A priority patent/EP3603800B1/en
Priority to US16/489,599 priority patent/US10974233B2/en
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Abstract

本发明公开一种四氢糠醇氢解制备1,5‑戊二醇的方法。采用的催化剂是由含氮配体功能化的有机高分子或无机杂化材料载体负载贵金属、助剂制备而成。该催化剂用于四氢糠醇氢解制备1,5‑戊二醇时，反应活性好、选择性高，助剂与载体中的含氮配体通过配位作用被束缚在催化剂上，从而明显降低助剂的流失，使得催化剂具有很高的稳定性，多次套用或长时间连续寿命考察性能无明显变化，大大降低了整个工艺生产成本。

Description

一种四氢糠醇氢解制1,5-戊二醇的催化剂及制备方法及其 应用
技术领域
本发明涉及催化剂技术、有机合成领域，更具体的涉及一种含氮配体功能化的载体负载催化剂的制备以及利用生物质衍生物四氢糠醇氢解制备1,5-戊二醇的方法。
背景技术
1,5-戊二醇是一种具有奇数碳原子的二元伯醇，其主要用于生产聚酯多元醇以及合成润滑剂所用酯类、聚氨酯泡沫塑料和弹性体增塑剂、饱和/不饱和聚酯树脂、粉末涂料、油墨、香料等。
专利CN1565728报道了用戊二酸二甲酯为原料，铜锌铝催化剂作用下加氢反应制取1,5-戊二醇。专利CN102320923通过对混二酸二甲酯精制分离出丁二酸二甲酯、戊二酸二甲酯和己二酸二甲酯，然后戊二酸二甲酯与氢气在加氢反应器内加氢制备1,5-戊二醇粗品，将所述粗品分别经脱色并过滤后得到产品1,5-戊二醇。该方法中戊二酸二甲酯主要来源于己二酸制备中副产戊二酸酯化，不仅受限于己二酸产业，来源短缺，还需要经过精馏纯化、加氢、再分离精制等多个过程，流程较长。
专利CN101225022和CN101270032分别报道了用负载型Ni和Ru催化剂催化戊二醛加氢制取1,5-戊二醇。戊二醛目前是通过乙烯醚和丙烯醛进行催化缩合反应，再经水解得到的。乙烯醚非常不稳定，极易爆炸，安全风险高。另外，原料戊二醛资源不丰富且价格高。
生物质衍生物糠醛可由玉米芯和甘蔗渣等农作物废料制取，在我国华北及山东一带被大量生产，具有来源广泛、储量大等优势，以糠醛及其衍生物为原料合成各种化学品成本低且更为绿色环保，受到了越来越多的关注。近年来，采用便宜的糠醛及其衍生物糠醇、四氢糠醇通过催化氢解制备1,5-戊二醇的路线得到了较多的研究，具体如下：
1)糠醛经初步加氢得到糠醇，然后在高温高压条件下(175℃、10-15MPa)，使用亚铬酸铜催化加氢得到1,5-戊二醇，该反应对1,5-戊二醇收率较低约30％(J.Am.Chem.Soc.,1931,53,1091)；卢冠忠研究小组成功开发了以糠醛为原料，通过在温和条件下(140℃、1.5MPa)，使用Pt/Co2AlO4催化加氢，反应24h后,1,5-戊二醇收率低于40％，副产物繁杂(Chem.Comm.,2011,47,3924-3926和CN102134180)。专利CN102872897公开了采用氢型超稳Y分子筛(H-USY)负载Pt催化剂，助剂为盐酸，120℃、1.5MPa条件下反应24h后，1,5-戊二醇收率可达82.6％，但催化剂活性仍不够高，且存在盐酸导致腐蚀严重的问题。
2)糠醛完全加氢可以得到四氢糠醇，早期文献中，以四氢糠醇为原料合成1,5-戊二醇需经过三步：首先四氢糠醇在Al2O3作用下生成二氢吡喃，二氢吡喃经水解得到5-羟基戊醛，最后5-羟基戊醛在亚铬酸铜催化加氢下生成1,5-戊二醇。该方法尽管克服了产物选择性低的问题，但由于需要对各步反应产物进行分离提纯，反应步骤复杂(J.Am.Chem.Soc.,1946,68,1646)。日本Tomishige研究小组首次报道以四氢糠醇为原料，采用Re、Mo或W促进的Rh/SiO2或Ir/SiO2催化剂，间歇式釜式反应器中，120℃、8MPa条件下一步法氢解制备1,5-戊二醇，反应24h转化率能达到90％以上，1,5-戊二醇的选择性能高达90％，催化剂套用过程中活性明显下降，第1次使用转化率79％，而第5次使用降为64.5％(Chem.Commum.,2009,45,2035-2037，J.Catal.,2009,267,89-92，J.Catal.,2012,294,171-183)。专利CN103848719报道了V、Nb或Ta促进的Ir/SiO2催化剂有一定的四氢糠醇一步法氢解制1,5-戊二醇活性，固定床反应器中，80℃、6MPa反应条件下，转化率不高于60％，1,5-戊二醇的选择性90％左右。相比较上述其他工艺路线，四氢糠醇一步法氢解制1,5-戊二醇路线流程简单，原料转化率与目标产物1,5-戊二醇选择性高，不足的是该工艺路线采用的催化剂活性仍不够高，且促进剂(Re、Mo或W等)在使用过程中流失导致催化剂失活无法多次套用或长时间连续使用，整个工艺生产成本过高。专利CN103071512中采用Re、Mo或W促进的雷尼Co或Cu催化剂用于四氢糠醇一步法氢解制1,5-戊二醇，虽然不使用贵金属，但是在间歇釜中120℃、8MPa下反应24h后转化率不高于10％，1,5-戊二醇选择性为46.7％，催化剂性能差。
发明内容
本发明提供了一种四氢糠醇氢解制1,5-戊二醇的催化剂、制备方法及其使用方法。本发明的具体实施例中的所述催化剂具有稳定性好、寿命长的特点，且在四氢糠醇氢解制1,5-戊二醇反应中表现出高的活性和选择性。
本发明采用以下技术方案：
一种四氢糠醇氢解制备1,5-戊二醇所用的催化剂，所述催化剂包括载体和负载在所述载体上的活性组分和助剂；其中，载体为接枝了含氮配体的聚苯乙烯或接枝了含氮配体的硅胶；所述活性组分为Rh、Ir、Pt、Pd、Ru、Au等金属元素中的任意一种或多种；所述助剂为Re、Mo、W、V、Nb、Ta、Mn、Sn等金属元素中的任何一种或多种。所述接枝了含氮配体的聚苯乙烯中的含氮配体为咪唑、吡啶、联吡啶、1,10-邻菲罗啉中的任意一种；所述接枝了含氮配体的硅胶中的含氮配体为咪唑、吡啶、联吡啶、1,10-邻菲罗啉中的任意一种。以催化剂的总重计，所述活性组分的负载量为0.05～10wt％，优选为1-5wt％；所述活性组分、助剂及含氮配体的摩尔比为1：(0.01-2)：(0.05-4)，优选为1：(0.05-1)：(0.1-2)。
优选地，所述接枝了含氮配体的聚苯乙烯结构式如下：
其中，m＝500～2000，n＝200～1000，优选m＝800～1500，n＝300～800。
优选地，所述的接枝了含氮配体的硅胶结构式如下：
其中，x＝5000～10000，y＝200～1000，优选x＝6000～8000，y＝300～800。
一种制备所述催化剂的方法，将载体加入活性组分的可溶性盐溶液中进行等体积浸渍，然后在在80～120℃干燥6～24小时，再用助剂的可溶性盐溶液等体积浸渍，在80～120℃干燥6～24小时，得到所述催化剂。
活性组分的可溶性盐选自氯化铑、氯铱酸、氯铂酸、氯化钯、氯化钌、氯金酸中的一种或多种，助剂的可溶性盐选自铼酸铵、钼酸铵、偏钨酸铵、钒酸铵、酒石酸铌、酒石酸钽、醋酸锰、氯化锡中的一种或多种。
一种使用所述的催化剂进行四氢糠醇氢解制备1,5-戊二醇的方法，所述催化剂在使用前需在氢气中原位还原才具有催化活性，还原条件为氢气压力0.1～1MPa，优选为0.2～0.4MPa；每100g氢解催化剂采用的H2流速为0.2～10L/min，优选为1～5L/min；还原温度50～200℃，优选为100～180℃；还原时间为1～10小时，优选为2～6小时。当所述反应在间歇釜中进行，四氢糠醇水溶液质量百分浓度为5～100％，催化剂用量为四氢糠醇质量的1～10wt％，反应温度50～150℃，优选为60～120℃，氢气压力1～20MPa(表压)，优选为2～10MPa；反应时间2～24小时，优选为2～6小时。当所述反应在固定床反应器中进行，四氢糠醇水溶液浓度为5～100％，反应温度50～150℃，优选为60～120℃，氢气压力1～20MPa(表压)，优选为2～10MPa；固定床反应器四氢糠醇液料/催化剂质量空速为0.5～4h-1，优选为1～3h-1；氢气/催化剂体积空速为500～1500h-1，优选为800～1200h-1。
所述的催化剂在四氢糠醇氢解制备1,5-戊二醇的方法中的用途。
本发明的具体实施例中的催化剂具有以下有益效果：
该催化剂用于四氢糠醇氢解制备1,5-戊二醇时，反应活性好、选择性高，助剂与载体中的含氮配体通过配位作用被束缚在催化剂上，从而明显降低助剂的流失，使得催化剂具有很高的稳定性，多次套用或长时间连续寿命考察性能无明显变化，大大降低了整个工艺生产成本。
具体实施方式
下面结合实施例对本发明作进一步的说明，需要说明的是，实施例并不构成对本发明要求保护范围的限制。
原料四氢糠醇购买于淄博华澳化工有限公司，活性组分的可溶性盐-下文也称为贵金属M的可溶性盐(氯化铑、氯铱酸、氯铂酸、氯化钯、氯化钌、氯金酸)和助剂P的可溶性盐(铼酸铵、钼酸铵、偏钨酸铵、钒酸铵、氯化钌、酒石酸铌、酒石酸钽、醋酸锰、氯化锡)购买于国药集团化学试剂有限公司。载体S,也就是接枝了含氮配体(咪唑、吡啶、联吡啶、1,10-邻菲罗啉)的聚苯乙烯和硅胶购买自Sigma-Aldrich试剂公司(货号分别依次为549363(m＝1240，n＝320)，192074(m＝960，n＝400)，589993(m＝1070，n＝530),561878(m＝1150，n＝670)；56760(x＝7300，y＝390),537985(x＝6500，y＝460),537950(x＝8000，y＝710),569798(x＝7100，y＝650))。
它们的结构式分别如下所示：
在以下实施例中，如无特别注明，所采用的“％”均为“摩尔百分数”。
以下实施例使用的测试仪器为：气相使用岛津GC-2010型气相色谱仪(氢火焰检测器，氮气作为载气)进行分析，使用DB-5型毛细管色谱柱(5％Phenyl Methyl Siloxan，30m×0.32mm×0.25μm)，氢火焰检测器(FID)。进样器和检测器温度均为280℃；柱温采用程序升温控制：柱温初始100℃保持0.5分钟，15℃/min升温至260℃，保持5分钟。柱压力8.5868psi，流速1.5mL/min。进样量：0.2μL。转化率和选择性采用面积归一法进行计算。
实施例1～24：催化剂制备
采用分步等体积浸渍法进行制备，首先将贵金属M(Rh、Ir、Pt、Pd、Ru、Au)的可溶性盐(氯化铑、氯铱酸、氯铂酸、氯化钯、氯化钌、氯金酸)分别配制成水溶液，按照表1的比例加入载体S粉末，搅拌混合均匀，室温下浸渍12h，在120℃干燥12h；再将助剂P(Re、Mo、W、V、Nb、Ta、Mn、Sn)的可溶性盐(铼酸铵、钼酸铵、偏钨酸铵、钒酸铵、酒石酸铌、酒石酸钽、醋酸锰、氯化锡)分别配制成的水溶液，按照表1的比例加入至上述已浸渍贵金属M组分后的载体S中，搅拌混合均匀，室温下浸渍12h，在120℃干燥12h，制得不同活性组分含量的催化剂。
表1催化剂制备
实施例28～54：催化剂评价——间歇釜
本发明的催化剂评价在间歇釜反应器中进行，反应器容积为5000mL，材质为不锈钢。将一定量的催化剂加入反应器中，反应前对催化剂原位还原，还原温度150℃，H2压力为0.3MPa，H2流速1.5L/min，还原4小时。还原结束后降至反应温度，加入3000g一定浓度的四氢糠醇水溶液，调节温度至反应温度，充入一定压力的氢气，开始反应，一定时间后结束，具体反应条件如表2所示，降温泄压后取液体样品，用上述配有DB-5毛细管柱且有火焰离子(FID)检测器的气相色谱进行分析。
本发明的催化剂在间歇釜反应器中进行套用，上一釜反应结束后，反应液通过反应釜内置过滤器除去，催化剂留在反应釜内，再次加入3000g一定浓度的四氢糠醇水溶液，调节温度至反应温度，充入一定压力的氢气，开始反应，一定时间后结束，具体条件与上一釜反应相同。
表2间歇釜反应器中反应条件及结果
从表2可以看出，不同的氢解催化剂对四氢糠醇氢解反应均表现出好的活性和1,5-戊二醇选择性，在相对短的时间内即可获得高的转化率，特别地，接枝了含氮配体的载体使得催化剂稳定性极好，10次套用后活性基本保持。
实施例55～81：催化剂评价——固定床
本发明的催化剂评价在固定床反应器中进行，反应器为外径40mm，内径20mm，长1000mm的不锈钢管。将50g催化剂装填至反应器中，反应前对催化剂原位还原，还原温度150℃，H2压力为0.3MPa，H2流速1.5L/min，还原4小时。还原结束后降至反应温度，设定氢气/催化剂体积空速为1000h-1，调节四氢糠醇水溶液流速至所需的四氢糠醇液料/催化剂质量空速，调节压力至所需反应压力，具体反应条件如表2所示，在线取液体样品，用上述配有DB-5毛细管柱且有火焰离子(FID)检测器的气相色谱进行分析。
表3固定床反应器中反应条件及结果
从表3可以看出，固定床反应器中，不同的氢解催化剂对四氢糠醇氢解反应同样表现出好的活性和1,5-戊二醇选择性，200h寿命考察显示出接枝了含氮配体的载体使得催化剂稳定性极好。
对比实施例1～10：聚苯乙烯和硅胶负载催化剂制备
为了更好地体现出本申请中催化剂的优点，直接采用聚苯乙烯和硅胶作为载体制备了10款有代表性的未接枝含氮配体载体负载的催化剂，即金属和助剂含量、制备方法与实施例分别与1#、2#、10#、11#、13#、19#、21#、23#、26#和27#催化剂相同。
表4对比催化剂制备
对比实施例11～20：聚苯乙烯和硅胶负载催化剂性能评价
为了更好地体现出本申请中催化剂的优点，采用间歇釜考察了对比实施例中催化剂1-1#～1-10#，评价条件与实施例28～54中1#、2#、10#、11#、13#、19#、21#、23#、26#和27#催化剂相同。
表5间歇釜反应器中反应条件及结果
从表5中可以看出，没有接枝含氮配体的聚苯乙烯和硅胶直接负载催化剂在活性和选择性上明显差于本申请中制备的催化剂，套用中活性下降较快，稳定性差。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种四氢糠醇氢解制备1,5-戊二醇所用的催化剂，其特征在于：所述催化剂包括载体和负载在所述载体上的活性组分和助剂；其中，载体为接枝了含氮配体的聚苯乙烯或接枝了含氮配体的硅胶；所述活性组分为金属元素Rh、Ir、Pt、Pd、Ru、Au中的任意一种或多种；所述助剂为金属元素Re、Mo、W、V、Nb、Ta、Mn、Sn中的任何一种或多种。
2.根据权利要求1所述的催化剂，其特征在于：所述接枝了含氮配体的聚苯乙烯中的含氮配体为咪唑、吡啶、联吡啶、1,10-邻菲罗啉中的任意一种；所述接枝了含氮配体的硅胶中的含氮配体为咪唑、吡啶、联吡啶、1,10-邻菲罗啉中的任意一种。
3.根据权利要求2所述的催化剂，其特征在于：所述接枝了含氮配体的聚苯乙烯结构式如下：
其中，m＝500～2000，n＝200～1000，优选m＝800～1500，n＝300～800。
4.根据权利要求2所述的催化剂，其特征在于：所述的接枝了含氮配体的硅胶结构式如下：
其中，x＝5000～10000，y＝200～1000，优选x＝6000～8000，y＝300～800。
5.根据权利要求1-4中任一项所述的催化剂，其特征在于：以催化剂的总重计，所述活性组分的负载量为0.05～10wt％，优选1-5wt％；所述活性组分、助剂及含氮配体的摩尔比为1：(0.01-2)：(0.05-4)，优选1：(0.05-1)：(0.1-2)。
6.一种制备权利要求1-5中任意一项所述的催化剂的方法，其特征在于：将载体加入活性组分的可溶性盐溶液中进行等体积浸渍，然后在在80～120℃干燥6～24小时，再用助剂的可溶性盐溶液等体积浸渍，在80～120℃干燥6～24小时，得到所述催化剂。
7.根据权利要求6所述的催化剂的制备方法，其特征在于：所述活性组分的可溶性盐选自氯化铑、氯铱酸、氯铂酸、氯化钯、氯化钌、氯金酸中的一种或多种；所述助剂的可溶性盐选自铼酸铵、钼酸铵、偏钨酸铵、钒酸铵、酒石酸铌、酒石酸钽、醋酸锰、氯化锡中的一种或多种。
8.一种使用权利要求1-5中任意一项所述的催化剂进行四氢糠醇氢解制备1,5-戊二醇的方法，其特征在于：所述反应在间歇釜中进行，四氢糠醇水溶液质量百分浓度为5～100％，催化剂用量为四氢糠醇质量的1～10wt％，反应温度50～150℃，优选为60～120℃，氢气压力1～20MPa，优选为2～10MPa；反应时间2～24小时，优选为2～6小时。
9.一种使用权利要求1-5中任意一项所述的催化剂进行四氢糠醇氢解制备1,5-戊二醇的方法，其特征在于：所述反应在固定床反应器中进行，四氢糠醇水溶液质量百分浓度为5～100％，反应温度50～150℃，优选为60～120℃，氢气压力1～20MPa，优选为2～10MPa；流动相反应器四氢糠醇液料/催化剂质量空速为0.5～4h-1，优选为1～3h-1；氢气/催化剂体积空速为500～1500h-1，优选为800～1200h-1。
10.根据权利要求8或9所述的方法，其特征在于：所述催化剂在使用前需在氢气中进行原位还原，还原条件为氢气压力0.1～1MPa，优选为0.2～0.4MPa；每100g所述催化剂采用的H2流速为0.2～10L/min，优选为1～5L/min；还原温度50～200℃，优选为100～180℃；还原时间为1～10小时，优选为2～6小时。
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