CN1102639A - C3-C5α，β-单烯不饱和醛、羧酸或腈的制备 - Google Patents
C3-C5α，β-单烯不饱和醛、羧酸或腈的制备 Download PDFInfo
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Abstract
制备C3-C5α，β-单烯不饱和醛、羧酸或腈的方法，该方法是通过在装有催化活性多金属氧化物的多管反应器中，将欲制备的化合物的还原态催化气相氧化或气相氨氧化来制备目标化合物的，其中，催化填料的体积活性沿催化管在流动方向上突然地、逐步地和/或连续地降低。
Description
本发明涉及制备C3-C5α，β-单烯不饱和醛、羧酸或腈的方法，该方法是通过在升高的温度下，在装有催化活性多金属氧化物的多管反应器中，将欲制备的α、β-单烯不饱和化合物的还原态进行催化气相氧化或气相氨氧化来制备标题化合物的，且起始化合物的单程转化率大于90mol%。
在升高的温度下，在装有催化活性多金属氧化物材料的多管反应器中，由C3-C5α，β-单烯不饱和醛、羧酸或腈的适当还原态（特别是由相应的单烯）开始，气相催化，氧化或氨氧化制备这些化合物的方法是本领域公知的（例如参见DE-A2，004，251，EP-A83，198，EP-A835，EP-A178，364，DE-A2，203，709，DE-A，2，513，405，DE-A2，635，031，EP-A293，859，DE-A2，251，364，和DE-A2，626，887）按此方法制备并由相应的C3或C4化合物开始反应是特别重要的，所述C3或C4化合物是：丙烯醛（例如通过丙烯氧化）、甲基丙烯醛（例如通过异丁烯或叔丁醇氧化）、丙烯酸（例如通过丙烯醛氧化）、甲基丙烯酸（例如通过甲基丙烯醛氧化）、丙烯腈（例如通过丙烯或丙烯醛氨氧化）和甲基丙烯腈（例如通过异丁烯或叔丁醇氨氧化）。适于这些反应的许多多金属氧化物催化剂可以归入下面通式（Ⅰ）：
其中变量具有下列意义：
X1：镍和/或钴，
X2：铊、碱金属和/或碱土金属，
X3：磷、砷、硼、锑、锡、铈、铅和/或钨，
X4：硅、铝、钛和/或锆，
其中：
a是从0.5至5，
b是从0.01至3，
c是从3至10，
d是从0.02至2，
e是从0至5，
f是从0至10，
n是由出现的不同于氧的元素的价态和数目决定的数字。
它们可用已知方法获得（例如参见在先申请DE-A 4，023，239（O.Z.0050/41774），通常模制成固体球、环或柱体，但也可以壳型催化剂形式使用，即预制的惰性支撑芯涂布活性物质。当然，它们也可以粉末状催化剂形式使用。
所用的氧化剂是氧（氨氧化要求还存在氨），反应物用惰性气体例如N2、循环反应废气和/或蒸汽稀释是有利的。从这方面来讲，已证明使用空气作为氧源是特别有利的。通常，反应是按固定床氧化或固定床氨氧化来进行的。有关的细节是本领域公知的。
这些气相催化的氧化或氨氧化制备方法的特征在于一方面：它们要求升高的反应温度（通常在200℃至600℃范围内），另一方面是高度放热的。因此，一般来讲，含有活性多金属氧化物的催化剂管被作为调节介质的循环液（例如熔盐）所包围。
另外，这些气相催化的氧化或氨氧化制备方法的特征还在于目标反应伴随多种可能的竞争反应（例如平行或后继反应），这阻碍了靶产物的形成。因此，为了最具选择性地形成靶产物，需要对反应加以控制。对于给定的尽可能高的离析物转化率，能使对靶产物的选择性增高的特别有利的方法是本领域技术人员已知的，它包括使催化填料的体积活性（即每单位体积反应空间的活性）沿催化管在流动方向上增加，以使得体积活性从气体入口向气体出口方向增加（例如参见DE-A3，006，894，EP-A441，312或DE-AS2，056，614）。
我们现已惊奇地发现，当催化填料的体积活性沿催化管在流动方向突然地、逐步地和/或连续地降低时，在升高的温度下，在装有催化活性多金属氧化物的多管反应器中，将欲制备的α，β-单烯不饱和化合物的还原态（特别是相应的单烯）通过催化气相氧化或气相氨氧化可以制备C3-C5α，β-单烯不饱和醛、羧酸或腈，这种方法可以获得产量改进的靶产物，且起始物的单程转化率大于90mol%，这是与本领域技术人员的一般看法相反的。上述方法特别适用于使用适当的起始化合物，特别是当使用的金属氧化物材料是通式（Ⅰ）的一种，且循环调节液的温度为200℃至600℃时，气相催化氧化制备相应的C3或C4化合物以及氨氧化制备（甲基）丙烯腈;所述C3或C4化合物是丙烯醛（由丙烯制得）、丙烯酸（由丙烯醛制得）、甲基丙烯醛（由异丁烯或叔丁醇制得）、甲基丙烯酸（由甲基丙烯醛制得）。降低体积活性例如可以通过减少活性材料的浓度或用具有较低体积活性的催化剂代替具有较高体积活性的催化剂（例如通过改变多金属氧化物材料的组成）来达到。
实施例
A）多金属氧化物催化剂A的制备
将组成为Mo12Bi1Co5Fe2，5W2Si1，6K0，1Ox的细碎多金属氧化物材料压模成长为3mm，外径5mm，壁厚1.5mm的空心柱体。
B）多金属氧化物催化剂B的制备
将按A法获得的细碎多金属氧化物材料以400mm的层厚度施用于直径5mm的惰性支撑球（由滑石组成）上。
C）丙烯制备丙烯醛的催化气相氧化
1.在盐浴加热的管式反应器（V2A，壁厚2mm，内径25mm）中装入体积为1200ml的多金属氧化物催化剂A，并使已含5vol%丙烯、45vol%空气和50vol%氮气的气态混合物以2400L/小时（S.T.P）的速度通过其中。使用330℃的恒定盐浴温度，以92mol%的选择率获得96mol%的丙烯转化率，以上是基于所生成的作为主要产物的丙烯醛和作为进一步的目标产物的少量丙烯酸的重量和来计算的。（在所述丙烯醛氧化形成丙烯酸之前将制备丙烯醛作为第一氧化步骤是特别重要的）。
2.在相同于C）1中所使用的管式反应器中填入体积为1200ml的多金属氧化物催化剂B，使反应气如C）1中一样通过其中。在96mol%的相同的丙烯转化率，使用340℃的恒定盐浴温度，以相同基准计算，所获得的选择率为91.5mol%。
为获得相同的丙烯转化率所需的较高盐浴温度证明：含有多金属氧化物催化剂B的填料的体积活性比含有多金属氧化物催化剂A的填料的体积活性低。
3.在相同于C）1中所使用的管式反应器中，沿流动方向首先填入体积为800ml的多金属氧化物催化剂B，接着立即填入体积为400ml的多金属氧化物催化剂A，使反应气如C）1中一样通过其中。在96mol%的相同的丙烯转化率，使用329℃的恒定盐浴温度，以相同基准计算，得到91.8mol%的选择率。
4.在相同于C）1中所使用的管式反应器中，按照本发明，首先沿流动方向填入体积为800ml的多金属氧化物催化剂A，接着填入体积为400ml的多金属氧化物催化剂B，使反应气如C）1中一样通过其中。在96mol%的相同的丙烯转化率，使用330℃的恒定盐浴温度，以相同基准计算，得到93mol%的选择率。
Claims (1)
- 制备C3-C5α，β-单烯不饱和醛、羧酸或腈的方法，该方法是通过在升高的温度下，在装有催化活性多金属氧化物的多管反应器中将欲制备的α，β-单烯不饱和化合物的还原态进行催化气相氧化或气相氨氧化来制备C3-C5α，β-单烯不饱和醛、羧酸或腈的，且起始化合物的单程转化率大于90mol%；其中，催化填料的体积活性沿催化管在流动方向突然地、逐步地和/或连续地降低。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4307509A DE4307509A1 (de) | 1993-03-10 | 1993-03-10 | Verfahren zur Herstellung von 3 bis 5 C-Atome aufweisenden alpha,beta-monoethylenisch ungesättigten Aldehyden, Carbonsäuren oder Nitrilen |
| DEP4307509.6 | 1993-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1102639A true CN1102639A (zh) | 1995-05-17 |
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ID=6482399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94102720A Pending CN1102639A (zh) | 1993-03-10 | 1994-03-10 | C3-C5α，β-单烯不饱和醛、羧酸或腈的制备 |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0614868B1 (zh) |
| JP (1) | JPH06321841A (zh) |
| CN (1) | CN1102639A (zh) |
| CA (1) | CA2115973A1 (zh) |
| CZ (1) | CZ49394A3 (zh) |
| DE (2) | DE4307509A1 (zh) |
| ES (1) | ES2091646T3 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4045693B2 (ja) | 1999-04-27 | 2008-02-13 | 住友化学株式会社 | メタクリル酸の製造方法 |
| JP3631406B2 (ja) * | 1999-12-28 | 2005-03-23 | 株式会社日本触媒 | 接触気相酸化反応用の多管式反応器 |
| JP4426069B2 (ja) | 2000-06-12 | 2010-03-03 | 株式会社日本触媒 | アクリル酸の製造方法 |
| US6960684B2 (en) * | 2002-03-29 | 2005-11-01 | Nippon Shokubai Co., Ltd. | Production process for unsaturated aldehyde |
| US7045657B2 (en) | 2002-04-03 | 2006-05-16 | Nippon Shokubai Co., Ltd. | Catalytic gas phase oxidation process |
| FR2912742B1 (fr) * | 2007-02-16 | 2010-03-05 | Arkema France | Procede de synthese d'acrylonitrile a partir de glycerol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0784400B2 (ja) * | 1990-04-03 | 1995-09-13 | 株式会社日本触媒 | 不飽和アルデヒドおよび不飽和酸の製造方法 |
| DE4023239A1 (de) * | 1990-07-21 | 1992-01-23 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von propen oder iso-buten zu acrolein oder methacrolein |
-
1993
- 1993-03-10 DE DE4307509A patent/DE4307509A1/de not_active Withdrawn
-
1994
- 1994-02-18 CA CA002115973A patent/CA2115973A1/en not_active Abandoned
- 1994-03-04 CZ CZ94493A patent/CZ49394A3/cs unknown
- 1994-03-05 DE DE59400709T patent/DE59400709D1/de not_active Expired - Lifetime
- 1994-03-05 EP EP94103357A patent/EP0614868B1/de not_active Expired - Lifetime
- 1994-03-05 ES ES94103357T patent/ES2091646T3/es not_active Expired - Lifetime
- 1994-03-07 JP JP6035937A patent/JPH06321841A/ja not_active Withdrawn
- 1994-03-10 CN CN94102720A patent/CN1102639A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ES2091646T3 (es) | 1996-11-01 |
| EP0614868B1 (de) | 1996-09-25 |
| JPH06321841A (ja) | 1994-11-22 |
| EP0614868A1 (de) | 1994-09-14 |
| CA2115973A1 (en) | 1994-09-11 |
| DE4307509A1 (de) | 1994-09-15 |
| DE59400709D1 (de) | 1996-10-31 |
| CZ49394A3 (en) | 1994-11-16 |
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