CN114127040B - 在包括二齿亚磷酸酯配体的加氢甲酰化过程中减少重馏分形成和催化剂损失的方法的用途 - Google Patents
在包括二齿亚磷酸酯配体的加氢甲酰化过程中减少重馏分形成和催化剂损失的方法的用途 Download PDFInfo
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Abstract
在加氢甲酰化过程中减少重馏分形成和催化剂损失的方法的用途,所述方法包括以下步骤;a)在反应器组件(1)中采用至少一种催化剂和至少一种配体使烯烃和合成气反应,b)在蒸馏单元(2)中从醛、催化剂、配体和初期重馏分的混合物中分离出获得的醛,c)催化剂、配体、初期重馏分和残留醛的混合物进入具有至少一个最先的残留醛汽提段(3a)和至少一个最末的初期重馏分汽提段(3b)的短停留时间蒸发器单元(3),所述蒸发器单元(3)为降膜型和/或刮膜型,d)在汽提出初期重馏分后,催化剂/配体混合物从至少一个最末的初期重馏分汽提段(3b)的下端(3b1)立即进入冷却单元(4)。
Description
本发明涉及在连续加氢甲酰化过程中减少重馏分存在的方法的用途,其中烯烃或烯烃混合物在包括至少一种有机二亚磷酸酯配体的铑配合物催化剂存在下与一氧化碳和氢气反应以生产醛。所述用途包括连续或不连续去除初期重馏分。
加氢甲酰化,也称为羰基合成法,是一种重要的工业方法,它通过在过渡金属催化剂配合物的存在下使烯烃与一氧化碳和氢气反应来生成醛。众所周知,优选的方法包括连续加氢甲酰化和将含有金属-有机磷配体的配合物催化剂的催化剂溶液再循环,其中金属是VIII族过渡金属,优选铑。这样的技术例如由US 4148830、US 4717775和US 4769498例示。得到的醛具有广泛的应用,例如,作为氢化成脂肪醇(所谓的羰基合成醇)的中间体,用于胺化成脂肪胺,用于氧化成脂肪酸,和用于醛醇缩合以生产增塑剂组分。
在铑催化的低压加氢甲酰化反应中,铑催化剂需要用于稳定和/或活化铑的配体。铑与磷配体形成配合物,其中磷配体通常是有机膦和/或有机亚磷酸酯,是本领域公知的。众所周知,铑-二亚磷酸酯催化剂用于线性烯烃如丙烯、丁烯和己烯的加氢甲酰化,且它们具有提高活性和对直链反应产物选择性的效果。
加氢甲酰化通常伴随着一系列平行和次级反应。由于它们的高反应性,形成的醛会进行羟醛缩合反应、Tischenko反应和缩醛化反应,并产生高沸点副产物如二聚体、三聚体和四聚体。在加氢甲酰化过程中产生的这些高沸点副产物称为重馏分,它们会给过程带来很多问题,因为它们的积累会导致含铑和配体的溶液强制流失。重馏分的形成可能发生在反应器中,以及在类似蒸发器下端的高温场所。
参见附图1,本发明涉及在加氢甲酰化过程中减少重馏分形成和催化剂损失的方法的用途,所述方法包括以下步骤;
a)在反应器组件(1)中采用至少一种催化剂和至少一种配体使烯烃和合成气反应,
b)在蒸馏单元(2)中从醛、催化剂、配体和初期重馏分的混合物中分离出获得的醛,
c)催化剂、配体、初期重馏分和残留醛的混合物进入具有至少一个最先的残留醛汽提段(3a)和至少一个最末的初期重馏分汽提段(3b)的短停留时间蒸发器单元(3),所述蒸发器单元(3)为降膜型和/或刮膜型,
d)在汽提出初期重馏分后,催化剂/配体混合物从至少一个最末的初期重馏分汽提段(3b)的下端(3b1)立即进入冷却单元(4)。
术语“初期重馏分”应理解为因所生成的醛具有高反应性而通过例如醛醇缩合、Tischenko反应、缩醛化和氧化反应无意获得的高沸点反应产物。初期重馏分将随着时间的推移逐渐变成具有更高沸点的更复杂重馏分。因此,术语“初期重馏分”应理解为可以在蒸发器中在不足于导致所用有机亚磷酸酯配体热降解的温和条件下分离出来的重馏分。在本发明的实施例中,采用约170℃或以下的温度和3毫巴或以下的真空。
本发明方法的用途有利且优选地用于在至少一种VIII族过渡金属如钌、钯、锇、铱、铂和铑的催化剂或催化剂前体的存在下,将至少一种C2-C6烯烃如乙烯、丙烯、包括1-丁烯和顺式-或反式-2-丁烯的丁烯、戊烯和/或己烯进行加氢甲酰化。
至少一个最末的初期重馏分汽提段(3b)适宜具有短路径且在0.1-3毫巴范围和130-170℃范围的温度下操作。
根据本发明的一个实施方案,蒸馏单元(2)具有至少一个最先和最末段(分别为2a和2b),其中所有段(分别为2a和2b)具有用于醛的上出口(分别为21a和21b),用于醛、催化剂、配体和初期重馏分的混合物的中入口(分别为25a和25b)和用于残留醛、催化剂、配体和初期重馏分的混合物的下出口(分别为22和23)。最末段(2b)预设为将残留醛、催化剂、配体和初期重馏分的混合物从最末段(2b)下出口(23)进料至重馏分分离器入口(3a1)。
冷却单元(4)具有出口(41),通过该出口将回收的、经过程纯化的催化剂/配体混合物送回反应器组件(1)。
来自最末段(2b)下出口(23)的残留醛、催化剂、配体和初期重馏分料流的混合物部分送回反应器组件,部分通过重馏分分离器入口(3al)进入蒸发器单元(3)。
这样的设置将允许更小且更具成本效益的初期重馏分分离蒸发器单元。更小的蒸发器单元也将允许更短的停留时间和更短的路径,这是非常期望的特性,以不引起配体的热分解。通过计算和过程模拟表明,允许低至10%以下甚或1%的回流到反应器的催化剂/配体去通过重馏分汽提段就足以将初期重馏分从过程中分离出来。
根据本发明的一个实施方案,回收的催化剂和配体混合物从冷却单元(4)出口(41)借助蒸馏单元(2)的最末段(2b)返回入口(26)送回至反应器组件(1)。
催化剂是选自以下组成的组的过渡金属:钴和铑,而配体是亚磷酸酯配体,优选有机二亚磷酸酯配体。
在本发明最优选的实施方案中,配体是式I的有机二磷酸酯配体:
且催化剂混合物是铑有机亚磷酸酯配体配合物。
根据本发明的一个实施方案,通过分析催化剂/配体混合物料流中重馏分的存在,以规则的间隔不连续地进行初期重馏分的分离,分析操作可以手动或通过自动化进行。
根据本发明的另一个实施方案,初期重馏分的分离可以连续进行。初期重馏分的连续分离因此可以通过统计制程指导的手段进行指导,其中对催化剂/配体混合物料流中重馏分的存在的分析是调节通过蒸发器单元(3)的流量即公斤/小时,以及至少是初期重馏分汽提塔段(3b)的温度。
烯烃适合是C2-C6烯烃。
根据本发明的优选实施方案,烯烃是1-丁烯和可能的顺式-和/或反式-2-丁烯。
实验-重馏分分析
已在生产醛的加氢甲酰化过程中使用超过6个月之久的催化剂/配体混合物,即铑/二亚磷酸酯配体A4N3(CAS 198979-98-5),就重馏分含量进行分析。因此,因加氢甲酰化过程中产生的醛具有高反应性,重馏分确实有足够的时间通过羟醛缩合、Tischenko反应、缩醛化和氧化反应而累积。分析结果如表1所示。
表1
*)远比C20更重的重馏分由于其复杂性而难以分析。
实验-重馏分分离。
实验在实验室装置中进行,采用上述催化剂/配体混合物模拟1-丁烯和合成气的连续加氢甲酰化反应。在蒸发器中蒸馏出醛类,并在降膜蒸发器中以短停留时间和短路径将重馏分从剩余催化剂/配体和重馏分的混合物中分离出来。表2中列出了压力、温度和重馏分的分离量
表2
*)远比C20更重的重馏分由于其复杂性而难以分析。
观察和结论;
可以看到,在这些相对温和的条件下,较轻的重馏分很容易很高程度地从催化剂/配体混合物中分离。我们还观察到从催化剂/配体混合物中分离出较轻的配体降解产物。已知这样的配体降解产物会对完整配体的降解起催化剂作用。因此,本文所述的发明将不仅能避免昂贵的铑催化剂通过与复杂的重馏分一起流失而损失,还将提高脆弱的有机亚磷酸酯配体的寿命。由于复杂重馏分的大幅减少,生产中断也将更少发生。复杂重馏分得以大幅减少是通过从反应/产物溶液料流中连续或周期性地分离出初期重馏分来实现的,因为复杂的、>C20->>C20重馏分的形成需要花费数天、数周甚至数月的时间,所有都取决于生产参数。
Claims (10)
1.在加氢甲酰化过程中减少重馏分形成和催化剂损失的方法,所述方法包括以下步骤;
a)在反应器组件(1)中采用至少一种催化剂和至少一种配体使烯烃和合成气反应,
b)在蒸馏单元(2)中从醛、催化剂、配体和初期重馏分的混合物中分离出获得的醛,
c)催化剂、配体、初期重馏分和残留醛的混合物部分进入具有至少一个最先的残留醛汽提段(3a)和至少一个最末的初期重馏分汽提段(3b)的短停留时间蒸发器单元(3),所述蒸发器单元(3)为降膜型和/或刮膜型,其中所述至少一个最末的初期重馏分汽提段(3b)具有短路径并且在0.1-3毫巴范围和在130-170℃范围的温度下操作,
d)在汽提出初期重馏分后,催化剂/配体混合物从至少一个最末的初期重馏分汽提段(3b)的下端(3b1)立即进入冷却单元(4),
蒸馏单元(2)具有至少一个最先段(2a)和最末段(2b),其中所有段(2a和2b)具有用于醛的上出口(21a和21b),用于醛、催化剂、配体和初期重馏分的混合物的中入口(25a和25b)和用于残留醛、催化剂、配体和初期重馏分的混合物的下出口(22和23),最末段(2b)预设为将残留醛、催化剂、配体和初期重馏分的混合物从最末段(2b)下出口(23)进料至重馏分分离器入口(3a1),且其中来自最末段(2b)下出口(23)的残留醛、催化剂、配体和初期重馏分料流的混合物部分送回所述反应器组件,部分通过所述重馏分分离器入口(3al)进入所述蒸发器单元(3),
其中所述催化剂是铑催化剂,
其中所述配体是有机二亚磷酸酯配体。
2.根据权利要求1的方法,其中所述冷却单元(4)具有出口(41),通过该出口将回收的、经纯化的催化剂/配体混合物送回所述反应器组件(1)。
3.根据权利要求2的方法,其中所述回收的催化剂和配体混合物从冷却单元(4)出口(41)借助蒸馏单元(2)的最末段(2b)返回入口(26)送回至反应器组件(1)。
4.根据权利要求1的方法,其中所述配体是式I的有机二亚磷酸酯配体:
5.根据权利要求1或3任一项的方法,其中通过分析催化剂/配体混合物料流中重馏分的存在,以规则的间隔不连续地进行初期重馏分的分离。
6.根据权利要求1或3任一项的方法,其中初期重馏分的分离连续进行。
7.根据权利要求6的方法,其中初期重馏分的连续分离可通过统计制程指导的手段进行指导,其中对催化剂/配体混合物料流中重馏分的存在的分析是调节通过蒸发器单元(3)的流量以及至少是初期重馏分汽提塔段(3b)的温度。
8.根据权利要求1的方法,其中烯烃是C2-C6烯烃。
9.根据权利要求1的方法,其中烯烃是1-丁烯。
10.根据权利要求1的方法,其中烯烃是包括1-丁烯和顺式和/或反式2-丁烯的丁烯。
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US5672766A (en) * | 1994-12-12 | 1997-09-30 | Mitsubishi Chemical Corporation | Method for producing aldehydes |
US5744650A (en) * | 1995-12-06 | 1998-04-28 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-Ligand complex catalyzed processes |
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