CN113996340A - 一种用于氢甲酰化反应的新型催化剂体系及氢甲酰化反应方法 - Google Patents
一种用于氢甲酰化反应的新型催化剂体系及氢甲酰化反应方法 Download PDFInfo
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 26
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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Abstract
本发明提供一种用于氢甲酰化反应的新型催化剂体系及氢甲酰化反应方法，本发明提供的用于氢甲酰化反应的催化剂，包括铑金属化合物、双膦配体、单膦配体和含氟烯烃。本发明提供的催化剂体系在氢甲酰化反应中可以有效降低单膦配体用量，降低配体结晶析出导致局部堵塞的风险，并且有效降低反应过程中原料发生聚合产物含量，提高总体选择性。
Description
技术领域
本发明属于氢甲酰化反应领域，特别涉及一种用于氢甲酰化反应的催化剂体系以及利用这种催化剂的氢甲酰化反应方法。
背景技术
氢甲酰化反应是一种重要的增碳反应，工业上应用广泛。在工业上，氢甲酰化反应所采用的催化剂主要为Co、Rh两种金属的各种配位络合物，由于铑催化剂体系的活性及催化产物的选择性上与钴催化剂体系比较优势明显，因此，铑催化剂体系已逐步取代钴体系催化剂成为工业氢甲酰化反应的主流。然而由于金属铑价格昂贵，在工业生产上通常采用降低催化剂用量或催化剂多次循环套用的方式降低生产成本。
现有的铑催化剂体系中通常包括铑源、单膦配体、双膦配体三部分。其中双膦配体主要作用是起到调节正构产物与异构产物比例(正异比)的作用，双膦配体的结构选择至关重要，在专利CN01803426中有详细描述：单膦配体作用主要有两方面，其一、双膦配体价格昂贵且双膦配体用量达到一定比例之后调节正异比的作用不在明显，只使用双膦配体不利于降低生产成本。在体系内加入价格低廉的单膦配体不但可以起到稳定催化剂的作用，也能够降低双膦配体的用量。其二、仅使用铑源与双膦配体组成的催化体系催化速率快，在实际生产中反应速率过快会带来放热量过大，容易引起温度失控，造成生产安全风险。在加入单膦配体后反应速率会有所降低，从而降低风险。
在专利US4215077、US4238419中使用单膦配体摩尔用量为铑金属的50倍以上，实际上，工业生产中往往加入大量过量的单膦配体，一般保持单膦配体与铑金属摩尔用量比例在200以上。因加入的单膦配体大量过量带来的问题是单膦配体有结晶析出风险，通常铑催化剂溶液的返回保持一定水平，以避免TPP结晶，但仍存在局部堵塞风险，影响装置运行。
在氢甲酰化反应过程中，底物中的双键也会发生多种其他类型反应，如加氢反应，聚合反应。反应温度越高，副反应愈加明显。因此氢甲酰化反应液中常含有底物加氢产物及底物聚合产物，降低反应选择性。
发明内容
本发明为弥补现有技术中存在的不足，提供一种用于氢甲酰化反应的新型催化剂体系，利用该催化剂体系可以有效降低现有工艺中单膦配体用量，降低配体结晶析出导致局部堵塞的风险，并且有效降低反应过程中原料发生聚合的产物的含量，提高总体选择性。
本发明为达到其目的，采用的技术方案如下：
一种用于氢甲酰化反应的催化剂体系，包括铑金属化合物、双膦配体、单膦配体和含氟烯烃。
所述铑金属化合物选自铑的卤化物、铑与羰基化合物配位的配合物、铑与乙酰基化合物配位的配合物中的一种或多种；优选的，所述铑金属化合物选自RhCl3、Rh(CO)2acac、Rh4(CO)12或Rh6(CO)16中的一种或多种。
本发明所提供的催化剂体系，所述双膦配体和铑金属化合物(以铑金属化合物中铑原子物质的量计)的摩尔比为100:1-1:1，优选为10:1-1:1。所述双膦配体选自如下结构式中的至少一种：
本发明所提供的催化剂体系，所述单膦配体和铑金属化合物(以铑金属化合物中铑原子物质的量计)的摩尔比为500:1-1:1，优选为200:1-10:1。所述单膦配体优选三苯基磷、三(对甲基苯)磷、二苯基膦、三叔丁基磷的一种或多种；更优选的，所述单膦配体为三苯基磷。
所述含氟烯烃选自四氟乙烯、偏氟乙烯、氟乙烯、三氟氯乙烯、五氟丙烯、六氟丙烯中的一种或多种；更优选的，所述含氟烯烃选自四氟乙烯和/或六氟丙烯。
由于氢甲酰化过程中单膦配体具有调控反应速率及稳定催化体系的作用，生产中单膦配体用量远高于双膦配体用量，这样过量使用的单膦配体在控反应速率的同时也降低了反应的产物正异比，使得正构产物减少，异构产物增加，并且增加配体析出堵塞管道的风险。本发明的优选方案中，在催化剂中还进一步包括含氟烯烃；在本发明的催化剂中引入含氟烯烃，通过和其他组分联合作用，不但可以调控反应速率，而且大大降低单膦配体用量，起到提高正异比的作用。在调控速率方面含氟烯烃与铑金属化合物的比例及用量至关重要。优选的，所述含氟烯烃与铑金属化合物(以铑金属化合物中铑原子物质的量计)二者的摩尔比为1:1-1:50；在稳定催化体系方面，发现使用具有烯烃结构的氟化合物具有明显优势，推测是含氟烯烃中氟原子能够抑制铑簇生成从而起到稳定催化剂的作用并且稳定的含氟双键结构能够抑制氧自由基生成，避免双膦配体因氧化而失去活性。
本发明的催化剂体系中，还优选包括起溶解作用的溶剂。在催化剂用于催化反应之前，可以将铑金属化合物和双膦配体、单膦配体溶于溶剂中；在优选方案中，进一步含有含氟烯烃，可在铑金属化合物和双膦配体、单膦配体溶解后，将含氟烯烃加入其中，制成催化剂溶液。溶剂的具体用量以达到溶解目的为最低限度。进行溶解操作的时候，优选在无水无氧氛围下进行。作为一种示例，在一种具体实施方式中，催化剂溶液的具体配置操作可以这样进行：在无水无氧氛围下，将铑金属化合物和双膦配体、单膦配体溶于溶剂中，室温搅拌，时间可以为0.5-24h；然后再向其中加入含氟烯烃，室温搅拌，时间可以是0.5-24h。优选的，所述溶剂为在氢甲酰化反应中表现出惰性的溶剂；进一步优选的，所述溶剂为烷烃、芳烃、卤代烃、醚类或脂类溶剂中的一种或多种；更优选的，所述溶剂为正己烷、甲苯、四氢呋喃或二氯甲烷中的一种或多种，更进一步优选甲苯。
本发明第二方面提供一种氢甲酰化反应方法，在上述的催化剂体系存在下，使反应底物与一氧化碳和氢气发生氢甲酰化反应，所述反应底物为烯烃、烯醇中的一种或多种。
铑金属化合物(以铑金属化合物中铑原子物质的量计)为底物摩尔量的0.01‰-0.5‰。
本发明的优选方案中，所述烯烃或烯醇的碳数在6以下；优选的，所述烯烃选自碳数为6以下的端位烯烃中的一种或多种；更优选的，所述烯烃选自丙烯、丁烯、异丁烯、戊烯中的至少一种。优选的，所述烯醇选自碳数为6以下的端位烯醇中的一种或多种，更优选的，所述烯醇选自甲基烯丙醇、3-甲基-3-丁烯-1-醇、烯丙醇中的至少一种。
本发明的优选方案中，所述氢甲酰化反应的反应温度为60-150℃，优选为70-110℃；反应时间为0.5-24h；反应压力为0.1-6MPa，优选为0.5-2MPa。
本发明的优选方案中，所述一氧化碳和氢气的摩尔比为2:1-1:2，更优选1:1。
本发明优选的，所述氢甲酰化反应在无氧氛围下进行，氧气含量优选小于20ppm(v/v)。氢甲酰化反应最好在惰性气体氛围中进行，惰性气体包括但不限于氮气、氩气。
本发明的优选方案中，反应体系中还存在溶剂以使氢甲酰化反应在均相条件下进行。该溶剂可以和催化剂溶液中的溶剂相同或不同。优选的，所述溶剂为在氢甲酰化反应中表现出惰性的溶剂；进一步优选的，所述溶剂为烷烃、芳烃、卤代烃、醚类或脂类溶剂中的一种或多种；更优选的，所述溶剂为正己烷、甲苯、四氢呋喃或二氯甲烷中的一种或多种，更进一步优选甲苯。
本发明的优选方案中，基于反应体系中投入的原料总质量，所述反应底物在反应体系中的质量浓度为5-100％，优选为10-40％。
本发明提供的技术方案具有如下有益效果：
本发明的催化剂体系不但可以有效调控反应速率，降低单膦配体用量，起到提高正异比的作用；而且优选后的含有含氟烯烃的体系能够达到稳定催化剂的作用。该催化剂体系较之前体系，贵金属用量降低，利于降低生产成本，特别适用于工业化生产应用。
具体实施方式
为了更好的理解本发明的技术方案，下面结合实施例进一步阐述本发明的内容，但本发明的内容并不仅仅局限于以下实施例。
以下实施例中所用到的部分仪器或原料说明如下：
气相毛细管柱(30m DB-WAX,ID.:0.32mm,FD.:0.25μm)；初始温度80℃，以3℃/min升温速率升温至230℃；所得反应产物在反应溶液中的浓度(在每种情况下的单位是重量％)是通过GC分析使用内标确定。
实施例中部分原料来源：
XANTPHOS、DIOP、DPPB：99wt％，武汉朋和科技有限公司；
三苯基磷，99wt％，阿拉丁科技有限公司；
Rh(CO)2acac，98wt％，湖北巨胜科技有限公司；
烯丙醇，99wt％，扬州韦德化工有限公司。
实施例1
在无水无氧氛围下，将0.1mmol Rh(CO)2acac与0.4mmol XANTPHOS及2mmol三苯基磷溶于580g甲苯中，室温搅拌0.5h，得到溶液a。
将高压釜用氮气置换6次后，将溶液a泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通合成气至压力为1MPa。向溶液a加入0.01mmol四氟乙烯，室温搅拌0.5h。高压釜升至内温90℃后将2mol(约116g)烯丙醇泵入高压釜。加热搅拌6h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：烯丙醇0.92％、丙醇0.23％、丙醛0.32％、烯丙醇聚合物0.02％、正构羟基丁醛86.53％、异构羟基丁醛10.43％，其他1.55％。
实施例2
在无水无氧氛围下，将0.025mmol Rh4(CO)12与0.8mmol DIOP及2mmol三苯基磷溶于360g甲苯中，室温搅拌0.5h，得到溶液b。
将高压釜用氮气置换6次后，将溶液b泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通入合成气至压力为2MPa。向溶液加入0.03mmol五氟丙烯，室温搅拌0.5h。高压釜升至内温80℃后将2mol(约116g)烯丙醇泵入高压釜。加热搅拌8h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：烯丙醇0.95％、丙醇0.25％、丙醛0.35％、烯丙醇聚合物0.03％、正构羟基丁醛84.32％、异构羟基丁醛12.46％，其他1.64％。
实施例3
在无水无氧氛围下，将0.16mmol Rh6(CO)16与1.0mmol DPPB及4mmol三(对甲基苯)磷溶于980g甲苯中，室温搅拌0.5h，得到溶液c。
将高压釜用氮气置换6次后，将溶液c泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通合成气至压力为4MPa。向溶液加入0.05mmol四氟乙烯，室温搅拌0.5h。高压釜升至内温60℃后将2mol(约116g)烯丙醇泵入高压釜。加热搅拌12h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：烯丙醇0.89％、丙醇0.26％、丙醛0.41％、烯丙醇聚合物0.02％、正构羟基丁醛82.79％、异构羟基丁醛14.03％，其他1.60％。
实施例4
在无水无氧氛围下，将1.0mmol RhCl3与1.0mmol DIOP及20mmol二苯基膦溶于800g正己烷中，室温搅拌0.5h，得到溶液d。
将高压釜用氮气置换6次后，将溶液d泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通入合成气至压力为6MPa。向溶液加入0.5mmol六氟丙烯，室温搅拌0.5h。高压釜升至内温150℃后将2mol(约112g)异丁烯泵入高压釜。加热搅拌1h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：异丁烯0.13％、异丁烷0.09％、异丁烯聚合物0.33％、异戊醛98.06％、其他1.39％。
实施例5
在无水无氧氛围下，将0.5mmol Rh(CO)2acac与1.0mmol XANTPHOS及30mmol三叔丁基磷溶于500g正己烷中，室温搅拌0.5h，得到溶液e。
将高压釜用氮气置换6次后，将溶液e泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通入合成气至压力为5MPa。向溶液加入0.1mmol偏氟乙烯，室温搅拌0.5h。高压釜升至内温120℃后将2mol(约112g)异丁烯泵入高压釜。加热搅拌3h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：异丁烯1.26％、异丁烷0.31％、异丁烯聚合物0.27％、异戊醛97.04％、其他1.12％。
对比例1
在无水无氧氛围下，将1mmol Rh(CO)2acac与4mmol XANTPHOS及80mmol三苯基磷溶于580g甲苯中，室温搅拌0.5h，得到催化剂溶液。
将高压釜用氮气置换6次后，将催化剂溶液泵入高压釜，通入合成气(CO：H2＝1：1，摩尔比)置换6次，通入合成气至压力为1MPa。高压釜升至内温90℃后将2mol(约116g)烯丙醇泵入高压釜。加热搅拌4h，降温至室温后泄压。有机产品取样气相色谱分析，反应液组成为：烯丙醇0.91％、丙醇0.55％、丙醛1.12％、烯丙醇聚合物2.36％、正构羟基丁醛75.53％、异构羟基丁醛17.57％，其他1.96％。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (10)
1.一种用于氢甲酰化反应的催化剂体系，其特征在于，包括铑金属化合物、双膦配体、单膦配体和含氟烯烃。
2.根据权利要求1所述的催化剂体系，其特征在于，所述双膦配体和铑金属化合物(以铑金属化合物中铑原子物质的量计)的摩尔比为100:1-1:1，优选为10:1-1:1；
所述单膦配体和铑金属化合物(以铑金属化合物中铑原子物质的量计)的摩尔比为500:1-1:1，优选为200:1-10:1；
所述含氟烯烃与铑金属化合物(以铑金属化合物中铑原子物质的量计)的摩尔比为1:1-1:50。
3.根据权利要求1或2所述的催化剂体系，其特征在于，所述铑金属化合物选自铑的卤化物、铑与羰基化合物配位的配合物、铑与乙酰基化合物配位的配合物中的一种或多种；优选的，所述铑金属化合物选自RhCl3、Rh(CO)2acac、Rh4(CO)12或Rh6(CO)16中的一种或多种。
4.根据权利要求1或2所述的催化剂体系，其特征在于，所述双膦配体选自以下化合物中的至少一种：
5.根据权利要求1或2所述的催化剂体系，其特征在于，所述单膦配体选自三苯基磷、三(对甲基苯)磷、二苯基膦、三叔丁基磷的一种或多种。
6.根据权利要求1或2所述的催化剂体系，其特征在于，所述含氟烯烃选自四氟乙烯、偏氟乙烯、氟乙烯、三氟氯乙烯、五氟丙烯、六氟丙烯中的一种或多种；优选的，所述含氟烯烃选自四氟乙烯、六氟丙烯。
7.根据权利要求1-6任一项所述的催化剂体系，其特征在于，还包括溶剂；优选的，所述溶剂为烷烃、芳烃、卤代烃、醚类或脂类溶剂中的一种或多种；更优选的，所述溶剂为正己烷、甲苯、四氢呋喃或二氯甲烷中的一种或多种。
8.一种氢甲酰化反应方法，其特征在于，在权利要求1-7任一项所述的催化剂体系存在下，使反应底物与一氧化碳和氢气发生氢甲酰化反应，所述反应底物为烯烃、烯醇中的一种或多种。
9.根据权利要求8所述的氢甲酰化反应方法，其特征在于，所述烯烃或烯醇的碳数在6以下；优选的，所述烯烃选自碳数为6以下的端位烯烃中的一种或多种，更优选的，所述烯烃选自丙烯、丁烯、异丁烯、戊烯中的至少一种；优选的，所述烯醇选自碳数为6以下的端位烯醇中的一种或多种，更优选的，所述烯醇选自甲基烯丙醇、3-甲基-3-丁烯-1-醇、烯丙醇中的至少一种。
10.根据权利要求8-9任一项所述的氢甲酰化反应方法，其特征在于，铑金属化合物(以铑金属化合物中铑原子物质的量计)为底物摩尔量的0.01‰-0.5‰；
所述氢甲酰化反应的反应温度为60-150℃，反应时间为0.5-24h，反应压力为0.1-6MPa。
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| CN114931961A (zh) * | 2022-06-10 | 2022-08-23 | 万华化学集团股份有限公司 | 一种氢甲酰化催化剂及其应用 |
| CN114931961B (zh) * | 2022-06-10 | 2024-02-27 | 万华化学集团股份有限公司 | 一种氢甲酰化催化剂及其应用 |
| CN115433065A (zh) * | 2022-08-22 | 2022-12-06 | 万华化学集团股份有限公司 | 一种1,3-丁二醇的制备方法 |
| CN115433065B (zh) * | 2022-08-22 | 2023-08-11 | 万华化学集团股份有限公司 | 一种1,3-丁二醇的制备方法 |
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