CN1173484A - 制备醛类化合物的方法 - Google Patents
制备醛类化合物的方法 Download PDFInfo
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- CN1173484A CN1173484A CN97111553A CN97111553A CN1173484A CN 1173484 A CN1173484 A CN 1173484A CN 97111553 A CN97111553 A CN 97111553A CN 97111553 A CN97111553 A CN 97111553A CN 1173484 A CN1173484 A CN 1173484A
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- Prior art keywords
- membrane filtration
- ligand
- preferred
- hydroformylation reaction
- reaction mixture
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- 238000005374 membrane filtration Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000011541 reaction mixture Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 47
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Abstract
本发明涉及制备醛类化合物的方法,该方法是在催化剂体系存在下,在均相中通过烯属不饱和化合物与氢和一氧化碳加氢甲酰化反应完成,所述催化剂体系含有有机金属配位化合物和这些配位化合物的过量摩尔的配位体,然后通过芳族聚酰胺半透膜压滤将催化剂体系从加氢甲酰化反应混合物中分离出来。在该方法中,所存在的过量配位体与制得的醛类化合物的摩尔质量比为9—30,优选10—25,特别优选10—15,所存在的过量配位体不是磺化、羧化或磷酸化芳族二膦的烷基铵盐或芳基铵盐。通过维持摩尔质量比,不但可在加氢甲酰化反应本身中获得高活化值和高选择值,而且可在膜过滤步骤中获得优良的催化剂体系保留值。
Description
本发明涉及醛类化合物的制备方法,所述方法是在催化剂体系存在下,在均相中通过烯属不饱和化合物与氢和一氧化碳反应完成,所述催化剂体系含有有机金属配位化合物和这些配位化合物的过量摩尔的配位体,然后通过芳族聚酰胺半透膜压滤将催化剂体系从反应产物中分离出来。
在大规模工业生产中进行的烯烃加氢甲酰化反应日益地在基于铑配位化合物的催化剂体系下进行,所述配位化合物含有叔膦或亚磷酸根作为配位体。由于配位体通常以过量存在,因此催化剂体系含有有机金属配位化合物和附加的纯配位体。根据这些催化剂体系在有机介质中的溶解性,加氢甲酰化反应在均相中进行。为了分离反应产物并回收均匀溶解在反应产物中的催化剂体系,一般是将产物从反应混合物中蒸馏出来。然而由于所形成的醛类化合物的热敏感性,上述分离方法只可能适用于分子中含直至约8个碳原子的低级烯烃的加氢甲酰化反应。在含官能团的长链烯烃或烯属化合物的加氢甲酰化反应中,形成了热敏感的产物或具有高沸点的产物,该产物不能通过蒸馏令人满意地从催化剂中分离出来:由于形成稠油,蒸馏物质的热应力会导致有用产物的大量损失,而且由于配位化合物的分解,会导致催化剂的损失。这就大大降低了上述方法的经济价值。
为了避免使用热方式分离催化剂体系,已研制出了不同的方法。
EP-A-0374615描述了可通过使用选择性半透聚芳酰胺分离膜,从有机溶剂中无损分离有机金属配位化合物并回收,所谓无损就是催化活性金属化合物不分解。在这种情况下,可使用压差(压滤)或浓度差(渗析)作为该分离过程中的动力。该方法特别适用于从有机溶液中分离具有以磷(III)化合物作为配位体的有机金属配位化合物和/或羰基金属;在所述溶剂中,所述金属化合物被用作均相催化剂。用作EP-A-0374615提及的烯烃的均相加氢甲酰化反应的铑配位化合物为HRhCO[P(C6H5)3]3、RhCl[P(C6H5)3]3以及含有以下式的磺化或羧化三芳基膦的烷基铵盐或芳基铵盐为配位体的化合物:其中X为磺酸根(SO3)或羧酸根(COO),x1、x2和x3为0或1,R1和R2各自为相同或不同的C4-C12-烷基基团、C6-C12-芳基基团或C6-C12-环烷基基团以及R1可另为氢。
根据EP-A-0374615,在从二环戊二烯加氢甲酰化反应的粗产物中两步膜分离含三(间磺苯基)膦的铑盐和三异辛基铵盐的催化剂体系中,可保留99.5%的铑化合物和94.4%的磷(III)化合物。因此在有机加氢甲酰化反应产物中仍剩下5.6%的磷(III)化合物,只能通过复杂方法分离,所述复杂方法如具有相对大量产物损失的复杂蒸馏。在第一或第二膜过滤步骤中的最终膜过滤稳态流速分别仅为5或10l/m2h。
由此,本发明目的是提供一种在均相中进行烯属不饱和化合物的加氢甲酰化反应的方法,该方法得到高活性和选择性并能改善整个催化剂体系的分离。
该目的可通过制备醛类化合物的方法达到;该制备方法是在催化剂体系存在下,在均相中由烯属不饱和化合物与氢和一氧化碳加氢甲酰化反应,然后通过芳族聚酰胺半透膜压滤将催化剂体系从加氢甲酰化反应混合物中分离出来,上述催化剂体系含有有机金属配位化合物和这些配位化合物的过量摩尔的配位体,在该方法中,所存在的过量摩尔的配位体与制得的醛类化合物的摩尔质量比为9-30,优选10-25,特别优选10-15,所述配位体不是磺化、羧化或磷酸化芳族二膦的烷基铵盐或芳基铵盐。
通过该新方法,可在实际没有损失的条件下无变化地回收有机金属配位化合物和这些配合物的过量配位体,也就是说,它们没有分解或经历过其它转化反应。
本发明说明书中的有机金属配位化合物是指其中有机基团的碳原子与金属原子键合的化合物。所述金属还包括所谓的半金属,如硼和硅。根据本发明,其中金属与碳之间通过氮、氧或硫结合的在有机溶剂中溶解的化合物也被称为有机金属配位化合物。
有机金属配位化合物的金属优选元素周期表中的IVA、VA、VIA、VIIA、VIIIA或IB族元素,特别是锰、铁、钴、镍、钯、铂、钌、铑或依。
除了金属之外,有机金属配位化合物还含有配位体,如CO,氢,胺类,膦类,亚磷酸根类,乙酸根,苄腈,乙酰丙酮化物,丁二酮肟,π-烯烃如1,5-环辛二烯,或π-芳族化合物如环戊二烯基。
过量存在于催化剂体系中的配位体优选地为单齿配位体,其中在加氢甲酰化反应中的单齿配位体与有机金属配位化合物的摩尔比至少为50,优选60-120,特别优选80-100。
特别适用的单齿配位体为芳族膦类,特别是磺化或羧化三芳基膦的烷基铵盐和/或芳基铵盐。特别可使用三苯基膦三磺酸的二硬脂酰基铵盐。
另外,磺化吡啶、喹啉、2,2′-联吡啶、卟啉和哌啶基膦、奎宁、乙二肟、磺化亚磷酸根和烷基-和芳基-取代的乙酰丙酮化物、水杨酸盐和扁桃酸根已被证明可用作过量的配位体。
在100至140℃温度优选120至130℃下、0.5至27MPa压力优选20至25MPa下,烯烃与一氧化碳和氢反应。合成气体的组成(即一氧化碳和氢的体积比)可延伸至很宽的范围,并可以变化,例如可从1∶10变化至10∶1。一般地,所使用的气体混合物中的一氧化碳与氢的体积比为约1∶1或仅稍微偏离此值。
在本发明的方法中,含一个或多个双键的具有2至30个碳原子的烯烃不饱和化合物被反应。适用的物质为含6至30个碳原子的取代或未取代的烯烃、含4至10个碳原子的取代或未取代的二烯烃、环系中含5至12个碳原子的取代或未取代的环烯烃或二环烯烃、含3至20个碳原子的不饱和羧酸和含1至18个碳原子的脂族醇的酯、含2至20个碳原子的饱和羧酸和含2至18个碳原子的不饱和醇的酯、各含3至20个碳原子的不饱和醇或酯或含8至20个碳原子的芳脂族烯烃。
含6至30个碳原子的取代或未取代的烯烃可为在终端或中间位置具有双键的直链或支链烯烃。优选含6至18个碳原子的直链烯烃,如正己-1-烯、正庚-1-烯、正辛-1-烯、正壬-1-烯、正癸-1-烯、正十一碳-1-烯、正十二碳-1-烯、正十八碳-1-烯和无环萜烯。适用的物质还可以是支链烯烃,如二聚异丁烯(2,2,4-三甲基戊-1-烯)、三聚丙烯、四聚丙烯和dimersol(二聚丁烯)。
优选的含4至10个碳原子的未取代二烯的实例为1,3-丁二烯、1,5-己二烯和1,9-癸二烯。
在环系中含5至12个碳原子的取代和未取代环烯烃或二环烯烃的实例包括环己烯、环辛烯、环辛二烯、二环戊二烯和环萜烯如苎烯、蒎烯、樟脑烯和红没药烯。
含8至12个碳原子的芳脂族烯烃实例为苯乙烯。
上述含3至20个碳原子的不饱和羧酸和含1至18个碳原子的脂族醇形成的酯的实例为其中醇成分中含1至18个碳原子的丙烯酸酯和甲基丙烯酸酯。
含2-20个碳原子的饱和羧酸和含2-18个碳原子的不饱和醇形成的酯包括其中羧酸成分中含2-20个碳原子的乙烯基酯和烯丙基酯,如乙酸乙烯基酯。
不饱和醇和醚包括如烯丙基醇和乙烯基醚。
如果适当的话,本发明方法可在存在有机溶剂条件下进行,所述有机溶剂在加氢甲酰化反应条件下为惰性,另外,该熔剂在膜分离步骤中不腐蚀膜。适用的溶剂为芳烃,如甲苯、邻二甲苯、间二甲苯、对二甲苯、二甲苯异构体混合物、乙苯、1,3,5-三甲基苯,这些化合物的混合物,或者为脂肪烃。然而,也可使用更极性的溶剂,如苯乙酮、四氢呋喃、锍醇(sulfinol)、二元醇或聚二元醇。尽管如此,加氢甲酰化反应也可在不添加有机溶剂的条件下进行,此时烯烃起始化合物和所生成的加氢甲酰化反应产物被用作溶剂。但是,由于该类型的反应混合物的粘度通常较高,所以在膜过滤时一般只能达到相对低的流速。
在被称为预生成反应(preforming)的加氢甲酰化反应步骤上游步骤中或者在特别是连续步骤情况下的就地加氢甲酰化反应中由金属或一种金属化合物和配位体生成了催化剂体系。这两种情况描述在文件号为196 19527.6的德国专利申请中。
通过在常规反应器中将以液相和气相存在的反应组分反应可制得醛类化合物,该制备可连续进行或分批进行。
在加氢甲酰化反应完成之后,通常冷却反应混合物,通过减压释放气体成分并伴随惰性气体(如氮气)或由CO和H2的合成气体混合物。然后通过膜过滤分离混合物。然而,反应混合物也可在不经冷却的条件下送入膜过滤。
在用于膜过滤的加氢甲酰化反应混合物中,有机金属配位化合物的过量存在的配位体浓度为基于用于膜过滤的反应混合物重量的2.5-25%,优选5-15%。
在用于膜过滤的加氢甲酰化反应混合物中,有机金属配位化合物的浓度为基于用于膜过滤的反应混合物重量的2-400ppm,优选10-300ppm,特别优选50-150ppm。
在压力为0.1-15Mpa,优选0.5-5Mpa,特别优选1-2Mpa下,在聚芳酰胺膜上进行膜过滤。
膜过滤可以单步或以多步进行,优选以多步进行,特别优选两步。可利用平行分离步骤,也可利用串连分离步骤,优选串连分离步骤。在串连分离步骤中,保留物在每步中被分离出来,渗透物被送入下步分离步骤。这种串连方法允许特别有效地使用现存的压力系统,即使用上一方法步骤中的工作压力。
如果保留物总量为基于所使用的反应混合物的8-90%,优选10-70%,特别优选20-40%,膜过滤保留物中所分离的配位体的浓度至少为所使用的膜分离加氢甲酰化反应混合物中的3倍,则可获得特别高的分离效率。
在两步膜过滤中,进一步证明:第一过滤步骤的保留物量与第二过滤步骤的保留物量的比例约为1∶1是有用的。
当使用变换的上述方法时,可通过使用循环泵增加膜的泄出而进一步增加膜的分离效率。通过膜的线性流速通常为0.1-10m/sec,优选0.5-2.5m/sec。
合并含催化剂体系的分离步骤保留物并循环回加氢甲酰化反应中;如果需要的话,可补充加入金属和/或有机金属配位化合物和配位化合物的配位体。在两步膜过滤方法中,也可甚至在送入第二膜过滤步骤之前,将上述补充量加入到第一步骤的渗透物中去。在这种情况下,可在不显著损失催化剂体系所存在的活性和选择性的条件下,获得改善的分离结果并可在加氢甲酰化反应中多次重复使用催化剂体系。
如果本发明方法在存在溶剂条件下进行,而且为了获得最大可能高的转化速率,加氢甲酰化反应步骤在很少溶剂中进行,为了降低粘度,膜步骤在大量溶剂下进行时,那么加氢甲酰化反应步骤和膜分离步骤均可获得特别高的效率。在加氢甲酰化反应步骤中,溶剂量为用溶剂稀释的反应混合物总重量的5-25%,优选7-13%是有用的;相反地,在膜过滤步骤中,溶剂量为用溶剂稀释的反应混合物总重量的30-70%,优选40-60%。通过利用蒸馏从合并的分离步骤中的渗透物中分离有机溶剂和再循环到膜过滤上游,可获得在用于膜过滤的反应混合物中的更高溶剂量。该溶剂再加回到有待分离的加氢甲酰化反应混合物中。这样将得到了用于获得高流速的适宜稀释溶液。
本发明使用的膜由芳族聚酰胺(也称为聚芳酰胺)组成。聚芳酰胺可通过在偶极非质子性溶剂中缩聚芳族二羧酸或二羧酸衍生物和芳族二胺而获得。适用的的羧酸成分包括对苯二酸、4,4′-联苯二羧酸、4,4′-二苯基醚二羧酸、4,4′-二苯基砜二羧酸或2,6-萘二羧酸。适用的二胺成分包括对亚苯基二胺、3,3′-二甲氧基联苯胺、3,3′-二氯联苯胺、3,3′-二甲基联苯胺、4,4′-二氨基二苯基甲烷、2,2-双(4-氨基苯基)丙烷或1,4-双(4-氨基苯氧基)苯。
对聚芳酰胺膜特别重要的是其除了含有羧酸成分,还含有不同的二胺作为单体。例如,由对苯二酸、对亚苯基二胺、1,4-双(4-氨基苯氧基)苯和3,3′-二甲基联苯胺制成的聚芳酰胺已被证明是有用的。胺可随机地分布在聚合物中,但是,聚酰胺也可具有嵌段共聚物结构。
聚芳酰胺的平均分子量可在很宽范围内变化,一般为5000至200,000。优选具有摩尔质量为10,000至50,000的聚芳酰胺。
为了制备本发明的膜,德国专利申请P3802030中描述的方法被证明是有用的。这里公开的膜是由共聚酰胺组成的,所述共聚酰胺是由三种不同的二胺和一种二羧酸制成的。将这种共聚酰胺的酰胺类(如N-甲基-2-吡咯烷酮)非质子极性溶剂的溶液以液体层铺展在平面载体上。该液体层被引入到沉淀剂液体特别是水中,该沉淀剂液体能与溶液中的溶剂混溶,而聚合物能以膜形式沉淀出来。沉淀剂液体被允许对沉淀膜产生作用,直至溶剂被沉淀剂液体完全替代。如果需要的话,该膜可进一步进行热处理。如果适当的话,可在先用甘油处理之后干燥膜。
由上述方法制备的膜在整体上是不对称的,该膜是本领域技术人员原则上公知的。该膜具有很薄的分离层和一多孔载体结构,所述分离层厚度为0.05μ至5μ。由分离层和载体结构组成的膜的厚度为10μ至400μ,优选50μ至200μ。
膜的形状可根据需要选择,可由碟状构成,特别是空心丝或毛细管形,也可是适合于所需用途的其它形状。为了得到满意的流量,关键因素是获得尽可能高的稳定性,且此外单位体积内尽可能大的表面积。
使用前可预处理膜。最简单方法是将膜浸入待分离的溶液中,也可使用其它处理方法。为贮存目的用甘油浸渍的膜先用水洗,然后置于80-100℃的热水中10分钟。通过将膜平置在异丙醇中,并重复更换该醇,从而用如异丙醇代替水。然后以相同的方法,用加氢甲酰化反应混合物代替异丙醇,待分离的有机金属配位化合物及其配位体被溶解。本发明进一步证明:为了获得最佳的分离效率,使膜在操作条件下试运转一段时间是有用的,也就是利用加氢甲酰化反应混合物进行膜过滤,但应重复合并所得的保留物和渗透物,并将其重复循环至膜过滤前的加氢甲酰化反应混合物中。通过所谓的压力处理,进一步使膜孔闭合,从而提高了膜分离效率。膜处理的类型和方法决定了本发明方法中维持的操作条件。
实施例
制备本发明方法中使用类型的膜的方法描述如下。膜制备
在作为溶剂的N-甲基吡咯烷酮中缩合下列成分可制得聚芳酰胺:97-99mol%对苯二酰二氯
25mol%对亚苯基二胺
25mol%1,4-双(4-氨基苯氧基)苯
50mol%3,3′-二甲基联苯胺对苯二酰二氯的用量以聚芳酰胺具有Staudinger指数为200至300ml/g为准,溶剂用量以形成含7%重量的缩聚物的溶液为准。在缩合进行之后,通过加入100mol%CaO中和与溶剂疏松键合的氯化氢。然后在反应混合物中搅拌溶解5%重量(基于聚合物溶液)的无水氯化钙。仔细加热溶液,然后过滤并脱气。产物可直接用于膜制备。
可制备不含载体的膜或在作为载体的聚酯纤维网上制备膜。制备不含载体的膜的方法描述如下。利用刀片将温热的聚芳酰胺取出置于玻璃板上,形成约150μ的均匀膜,然后浸渍在2℃的水浴中。20分钟后,将膜从玻璃板上揭开,置于100℃热水中5分钟。将膜置于异丙醇中,以用该醇代替多孔液体水。然后用甲苯清洗膜,此处理后即可适用于进行分离。在所有的操作中,必须注意保证膜不被干透。实施例2-6和比较实施例1、7和8
利用含三苯基膦三磺酸(TPPTS)的铑盐和各种铵盐的催化剂体系进行二环戊二烯(DCP)的加氢甲酰化反应:a) 制备TPPTS的二硬脂酰基铵盐
在氮气下将253g Na-TPPTS溶液加入到搅拌烧瓶中,加热至65℃。加入250.3g二硬脂酰基胺于595g甲苯中形成的溶液。在60分钟内,搅拌加入90ml浓度为20%的硫酸,直至pH达到2.6,混合物再进行2.5小时的反应。为改善相分离,加入170g异丙醇。15分钟后分离出1037.5g的含TPPTS的二硬脂酰基铵盐的有机相,所述铵盐中每摩尔胺含0.33mol TPPTS。有机相含126mmol磷(III)/kg。
根据上述说明的类似方法可制备TPPTS的其它铵盐(实施例2-7和比较实施例1)。实施例3和比较实施例7和8中使用的Jeffamine为Texaco化学公司的商业产品,它们具有下列结构:Jeffamin M 600:(摩尔质量=600g/mol)Jeffamin D 2000:(摩尔质量=2000g/mol)Jeffamin T 3000:(摩尔质量=3000g/mol)b) 利用TPPTS的二硬脂酰基铵盐进行二环戊二烯的分批加氢甲酰化反应。
利用氮气冲洗2.15升的搅拌高压釜。在具有氮气夹套的玻璃容器中溶解由a)中获得的212.8g配位体溶液和0.29mmol以2-乙基己酸盐形式存在的铑(60重量ppm的Rh;P/Rh比为100),在氮气下将500g甲苯转入至高压釜中。在搅拌条件下,通过送入合成气体建立起27MPa的压力。当反应温度达到130℃后,进行两小时的预生成反应。然后在1小时内向高压釜中泵入500g二环戊二烯。通过空气鼓风冷却,使温度维持在130℃。二环戊二烯进料完成后,混合物再进行3小时的反应。然后将高压釜冷却至室温并泄压。利用残余压力将高压釜中的内容物转入至安装有浸渍分管的2升三颈烧瓶中并称量。通过重量的增加计算二环戊二烯的转化率。
利用类似的方法,通过使用实施例3-6和比较实施例1、7和8的TPPTS的铵盐进行二环戊二烯的加氢甲酰化反应。所得结果总结在表1中。c) 单步膜过滤
将由上述b)得到的特定反应产物应用在实验室的膜过滤装置上。所用的膜为Hoechst AG(UF-PA(PET 100))聚芳酰胺膜。首先在80℃水中将膜加热10分钟,然后利用循环泵以200l/h速率使膜泄出,建立起1MPa的压力。在40℃的操作温度下,将表1所示量的加氢甲酰化反应产物作为渗透物流过膜。催化剂成分的量在渗透物中确定,由此可得到表1所示的保留值,该值为基于所用的加氢甲酰化反应混合物。
由表1可以看出,只有维持摩尔质量比〔摩尔质量(配位体)∶摩尔质量(醛)〕=9-30,才能不但获得加氢甲酰化反应中的优良选择性,而且获得膜过滤中的突出保留值。实施例9
利用氮气仔细冲洗5升搅拌高压釜,该高压釜安装有用于气体进入和产物排出的浸渍分管及气体出口阀门。
使用超压氮气从储罐中将872g含磷(III)量138mmol/kg的TPPTS的二硬脂酰基铵盐的甲苯溶液和120mg以2-乙基己酸铑形式存在的铑转入到高压釜中。
然后催化剂在27MPa和125℃下进行预生成反应2小时。接着在1小时内,通过浸渍管从储罐中泵入1,500g丙烯(Rh为80ppm,基于丙烯;P∶Rh摩尔比=100)。通过反应器中的冷却旋管去除反应热。允许反应再进行1小时,然后冷却。使高压釜泄压,利用Schlenk接头将混合物转入至一个三颈烧瓶中并称量(3028g)。转化率为95%,n/i比为63/37。
将反应产物转入至实验室的膜过滤装置上并以两步过滤。转移膜(transmembrane)的压力为1.5MPa。使用Hoechst AG的UF-PA5(PET100)膜。获得了表2所示的保留值和流速。
重复循环第一和第二步骤的保留物,再在高压釜中与丙烯反应。通过加入2-乙基己酸铑和/或TPPTS的二硬脂酰基铵盐溶液,适当补充损失很少的铑和磷(III)。该补充加入到第一步骤的渗透物中。
催化剂重复循环共10次,转化率(90-95%)、选择性(n/i比63/37)或保留值(参见表2)没有显著变化。在表2所示的流速值中,第一个值为各个膜过滤步骤中的初值,而第二个值表征了平衡状态。
表2表明:在重复使用时,由于稠油聚集浓缩,流速开始时降低,而在较低水平时稳定,也就是说,稠油也可以渗透,因此分离催化剂成分和稠油是可能的。
表2进一步表明:本发明方法第一次使得能够很好地从产物(包括稠油)中分离出金属配合物和过量的配位体,并且可重复循环。表1
*M(TCD-dial)=192.26g/mol表2:含TPPTS二硬脂酰基铵盐为配位体的Rh-催化剂体系在丙烯加氢甲酰化反应中的膜分离和重复循环。
实施例 | TPPTS铵盐中的胺 | TPPTS铵盐中的摩尔质量M1[mg/mol] | 摩尔质量比M1 | 加氢甲酰化反应 | 渗透量[起始量的%] | 流速[l/m2h] | 保留值[起始量的%] | |||
转化率[%] | 二醛/单烯醛选择性 | Rh | 配位体[P] | 胺[N] | ||||||
M(TCD-dial)* | ||||||||||
1(V) | 三异辛胺 | 1563.5 | 8.1 | 99.9 | 99/1 | 15 | 64 | 89.3 | 69.8 | 16.5 |
2 | 二硬脂酰基胺 | 2068.47 | 10.8 | 99.4 | 97/3 | 66 | 61 | 97.5 | 96.1 | 78.3 |
3 | Jeffamine M600 | 2302.47 | 12.0 | 98.8 | 23 | 9 | 99.7 | 98.7 | 63.9 | |
4 | 三鲸蜡基胺 | 2573.43 | 13.4 | 98.7 | 96/4 | 22 | 44 | 95.0 | 90.0 | 73.3 |
5 | 三-正十八烷基胺 | 2825.91 | 14.7 | 98.5 | 91/9 | 53 | 49 | 93.0 | 87.0 | 88.7 |
6 | 三(二十二烷基)胺 | 3330.87 | 17.3 | 99.7 | 90/10 | 48.8 | 29 | 96.5 | 94.7 | 81.9 |
7 | Jeffamine D2000 | 6502.47 | 33.8 | 98.1 | 69/31 | 29 | 22 | 99.5 | 89.4 | 93.9 |
8(v) | Jeffamine T300 | 9502.47 | 49.4 | 98.4 | 63/37 | 56 | 31 | 99.7 | 97.7 | 91.4 |
加氢甲酰化反应 | 膜过滤 | |||||||
反应时间 | 温度[℃] | 重量循环次数 | 渗透量[起始量的%] | 保留值[起始量的%] | 流速[l/m2/h] | |||
第一步骤 | 第二步骤 | Rh | P[总量] | 第一步骤 | 第二步骤 | |||
222222.32.52222.5 | 125125125125125125127128126128125 | 012345678910 | 8785858884828384838381 | 8694969394909593949493 | 95.9699.2399.7198.8599.3099.5798.6199.5299.0999.0798.80 | 89.392.799.399.299.498.999.097.297.797.698.2 | 103-1097-1692-1782-1576-1772-1767-1367-1263-1058-1056-12 | 136-51115-4082-2975-2468-2856-1566-1889-3074-1676-2262-21 |
Claims (16)
1.一种制备醛类化合物的方法,该方法是在催化剂体系存在下,在均相中通过烯属不饱和化合物与氢和一氧化碳加氢甲酰化反应完成,所述催化剂体系含有有机金属配位化合物和这些配位化合物的过量摩尔的配位体,然后通过芳族聚酰胺半透膜压滤将催化剂体系从加氢甲酰化反应混合物中分离出来,其中所存在的过量配位体与制得的醛类化合物的摩尔质量比为9-30,优选10-25,特别优选10-15,所存在的过量配位体不是磺化、羧化或磷酸化芳族二膦的烷基铵盐或芳基铵盐。
2.根据权利要求1的方法,其中有机金属配位化合物的金属为元素周期表中的IVA、VA、VIA、VIIA或IB族元素,特别是锰、铁、钴、镍、钯、铂、钌、铑或依。
3.根据权利要求1或2的方法,其中过量存在的配位体为单齿配位体,加氢甲酰化反应中的单齿配位体与有机金属配位化合物的摩尔比至少为50,优选60-120,特别优选80-100。
4.根据权利要求1-3中一项或多项的方法,其中过量存在的配位体为磺化吡啶、喹啉、2,2′-联吡啶、卟啉和哌啶基膦、奎宁、乙二肟、磺化亚磷酸根或烷基-和芳基-取代的乙酰丙酮化物、水杨酸根或扁桃酸根。
5.根据权利要求1-4中一项或多项的方法,其中烯烃与一氧化碳和氢的反应是在100至140℃温度优选120至130℃下、0.5至27MPa压力优选20至25MPa下进行。
6.根据权利要求1-5中一项或多项的方法,其中对于加氢甲酰化反应,含一个或多个双键的具有2至30个碳原子的烯属不饱和化合物被反应。
7.根据权利要求1-6中一项或多项的方法,其中反应在有机溶剂存在下进行。
8.根据权利要求1-7中一项或多项的方法,其中在用于膜过滤的加氢甲酰化反应混合物中,有机金属配位化合物的过量存在的配位体浓度为基于用于膜过滤的反应混合物重量的2.5-25%,优选5-15%。
9.根据权利要求1-8中一项或多项的方法,其中在用于膜过滤的加氢甲酰化反应混合物中,有机金属配位化合物的浓度为基于用于膜过滤的反应混合物重量的2-400ppm,优选10-300ppm,特别优选50-150ppm。
10.根据权利要求1-9中一项或多项的方法,其中膜过滤是在压力为0.1-15MPa,优选0.5-5MPa,特别优选1-2MPa下,在聚芳酰胺膜上进行;该膜过滤可以单步或以多步进行,优选两步。
11.根据权利要求1-10中一项或多项的方法,其中膜过滤是利用串连分离步骤进行。
12.根据权利要求1-11中一项或多项的方法,其中膜过滤保留物总量为所使用的加氢甲酰化反应混合物的8-90%,优选10-70%,特别优选20-40%,膜过滤保留物中所分离的配位化合物的配位体的浓度至少为用于膜过滤的加氢甲酰化反应混合物中的3倍。
13.根据权利要求1-12中一项或多项的方法,其中在两步膜过滤中,第一过滤步骤的保留物量与第二过滤步骤的保留物量的比例约为1∶1。
14.根据权利要求1-13中一项或多项的方法,其中含催化剂体系的膜过滤分离步骤保留物重复循环回加氢甲酰化反应中,可补充或不补充加入金属和/或有机金属配位化合物和配位化合物的配位体。
15.根据权利要求14的方法,其中在两步膜过滤方法中,补充加入的金属和/或有机金属配位化合物和配位化合物的配位体甚至可在送入第二膜过滤步骤之前加入到第一步骤的渗透物中去。
16.根据权利要求1-15中一项或多项的方法,其中溶剂通过蒸馏从合并的膜过滤分离步骤中的渗透物中分离出来,再循环至膜过滤上游中并加入至膜过滤之前的加氢甲酰化反应混合物中。
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DE19619527.6 | 1996-05-15 | ||
DE19632602.8 | 1996-08-13 | ||
DE19632602A DE19632602A1 (de) | 1996-08-13 | 1996-08-13 | Verfahren zur Herstellung von Aldehyden |
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CN103288610A (zh) * | 2012-02-23 | 2013-09-11 | 赢创奥克森诺有限责任公司 | 用于工业加氢甲酰基化异丁烯并分离产物混合物的方法和装置 |
CN104011108A (zh) * | 2011-12-13 | 2014-08-27 | 巴斯夫欧洲公司 | 包含聚醚多元醇的反应混合物的后处理方法 |
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EP0823282B1 (de) * | 1996-05-15 | 2001-11-14 | Celanese Chemicals Europe GmbH | Verfahren zur Herstellung von Aldehyden |
US6252123B1 (en) * | 1998-07-09 | 2001-06-26 | Union Carbide Chemicals & Plastics Technology Corporation | Membrane separation process for metal complex catalysts |
EP1112964B1 (en) | 1999-05-12 | 2017-02-22 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
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US9649625B1 (en) | 2016-06-24 | 2017-05-16 | Eastman Chemical Company | Catalysts and processes for producing aldehydes |
RU2646763C1 (ru) * | 2016-12-30 | 2018-03-07 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Фосфинсодержащие каликсареновые лиганды, способ их получения и применения |
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DE3842819A1 (de) * | 1988-12-20 | 1990-06-21 | Hoechst Ag | Verfahren zur abtrennung von metallorganischen verbindungen und/oder metallcarbonylen aus ihren loesungen in organischen medien |
DE4316180A1 (de) * | 1992-09-16 | 1994-11-17 | Basf Ag | Verfahren zur Herstellung von Aldehyden |
DE19619527A1 (de) * | 1996-05-15 | 1997-11-20 | Hoechst Ag | Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden |
DE19609337C2 (de) * | 1996-03-11 | 1998-11-19 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden mittels eines Rhodium und substituierte Diphenyldiphosphane enthaltenden Katalysatorsystems |
EP0823282B1 (de) * | 1996-05-15 | 2001-11-14 | Celanese Chemicals Europe GmbH | Verfahren zur Herstellung von Aldehyden |
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