CN1035162C - α-卤代羧酸脱卤催化剂 - Google Patents
α-卤代羧酸脱卤催化剂 Download PDFInfo
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Abstract
本发明涉及一种由下述a和b的混合物组成的α-卤代羧酸脱卤催化剂，其中含有：
a)沉积于一种选自炭，氧化硅，碳化硅，氧化铝或碳化硼的惰性载体之上并且已在氢存在下用于脱除α-卤代羧酸中的卤素的第VIII族贵金属，
b)由沉积于所述惰性载体之上的第VIII族贵金属组成的新鲜催化剂的细小粒子。
本发明特别适用于再生提纯α-卤代羧酸，尤其是粗一氯乙酸所用的钯催化剂。
Description
本发明涉及α-卤代羧酸脱卤的催化剂。本发明更具体地涉及除去一氯乙酸(AMCA)中所含的二氯乙酸(ADCA)所用的催化剂。在工业规模上是通过乙酸氯化来合成一氯乙酸的，但不可避免地要生成二氯乙酸，有时还有少量三氯乙酸。因此，得到的是由一氯乙酸、二氯乙酸、少量三氯乙酸和未反应的乙酸组成的混合物，即粗一氯乙酸。考虑到AMCA的沸点(189℃)和ADCA(194℃)很接近，用蒸馏的方法实际上无法将它们分开。相反，对此混合物加氢，则很容易按照如下反应把ADCA转化为AMCA：
这步加氢反应并不完全是有选择性的，还观察到了由AMCA生成乙酸的退减反应：
这个反应在催化剂作用下进行，并生成副产物乙醛，它会有产生缩合产物的麻烦。
对粗一氯乙酸进行加氢也会产生像一氯乙酸羟基乙酸酯(MAAG)之类的重组分。
粗一氯乙酸的加氢是在沉积于碳、氧化铝或氧化硅上的钯存在下进行的。此方法在例如US2,863,917和GB1,188,745中已经叙述。在法国专利FR2,647,032中也叙述了在此钯催化剂中添加硫或硫化物。法国专利FR2,046,424叙述了此钯催化剂的再生方法。实际上，在其工作过程中此催化剂会失去活性和选择性，并产生更多的醛和重产物。按照法国专利2,046,424，在100～150℃下用气体氯对废催化剂进行氧化，将钯转化为其氯化物，然后用氢或其它还原剂进行还原，重新产生金属钯。
本申请人发现了一个很简单的再生该催化剂的方法，这然是说，由废催化剂得到具有新催化性能的催化剂。
因此，本发明是一种由下述a和b的混合物组成的α-卤代羧酸脱卤催化剂，其中含有：
a)沉积于一种选自炭，氧化硅，碳化硅，氧化铝或碳化硼的惰性载体之上并且已在氢存在下用于脱除α-卤代羧酸中的卤素的第VIII族贵金属，
b)由沉积于所述惰性载体之上的第VIII族贵金属组成的新鲜催化剂的细小粒子。
简单归纳地说，本发明包括在α-卤代羧酸脱卤的废催化剂中添加细的新催化剂，在羧酸流和氢气作用下此细粉和废催化剂混合，形成具有新催化剂性能的新催化剂。另外的优点是减少了生产停顿，排空反应器和更换催化剂的工序。
在a中叙述的产物是一种催化剂。元素周期表第VIII族中的贵金属有钌、铑、钯、饿、铱和铂。将这种金属沉积在载体(如炭、氧化硅、碳化硅、氧化铝或碳化硼)上。贵金属的量可占贵金属与载体总量的0.1-10％。
贵金属最好沉积在大表面积的炭上，比例是催化剂重量，即炭加金属重量的0.1-5％，而且它被分散在炭的表面上。所谓大表面积的炭，理解为比表面约600-1300米/克的炭。这种炭呈挤出的小柱状或粉状。所述贵金属最好是钯。
作为α-卤代羧酸的例子，可举出分子式如下的酸：
式中X是氯R1和R2可以相同或不同，并表示X、H、具有1-12个碳原子的直链或支链烷基、具有3-12个碳原子的环烷基。本发明也适用于式(I)酸的酯类。以具有1-10个碳的脂族酯为佳，具有1-5个碳的脂族酯更好。
a产物是一种用于使α-卤化羧酸脱卤的催化剂，这就是说，随着使用时间进程它要丧失其部分能力。这种失效更经常是由于活性下降而造成的，因此应该升高温度使得相同数量的催化剂有相同的产率。也观察到副产物增加了。还观察到贵金属的损失。本发明涉及已经使用过的催化剂a，由于其活性不足，或由于副产物太多而必须更换它。
b产物是和a一样的产物，可是其粒度比a小，使其在α-卤代羧酸及氢气流的作用下很容易与a混合并形成均匀的一体。最好b是活性的，比如细的新催化剂即小粒度的新催化剂。
本申请人发现，尽管a与b的混合物所含的贵金属量比处于新状态下的a要少，但它具有与新状态下的a相同的性能。
加入到a中的b的数量视被研究对象性能而不同。例如，如果想要得到与新状态的a具有相同性能和相同产率的催化剂，而废催化剂的a又是损失了其初始贵金属的40％，那么加入b的数量是初始a的数量的3-10％就可以了，这时其贵金属含量就与初始时相同了。既然使用的催化剂b中贵金属含量可以比新状态的a高或者低，那么此b的量就是变化的了。如果想让得到的催化剂的活性比新状态的a高或者低，那么就多加或少一些b，或者加入含贵金属多一点或少一点的催化剂b就可以了。如果a和b含有不同的贵金属或不同的贵金属混合物，并不超出本发明的范围。如果a是没完全作废的催化剂或者b是已用了一点的催化剂，或者这两种情况都有，都不超出本发明的范围。如果本发明的a和b的混合物中所含的贵金属比新状态的a中所含的还多也不超出本发明的范围。
实际上，如果呈新状态的a为10,000克，贵金属含量为1％，即100克，例如损失了40％，还剩下60克金属，加入5000克含量为1％即50克贵金属的b。因此，a＋b的混合物含有110g贵金属。因此可以看到，在10,000克已经使用过并已作废的初始催化剂中补充5000克新催化剂就能得到新的催化剂，使得用初始加入量一半的新催化剂代替了更换全部催化剂。
本发明具体可用于提纯不纯的α-卤代羧酸R1CHXCOOH，R1定义同前。在特定的CH3COOH和情况下，这类酸是通过相应的羧酸R1CH2COOH进行卤代而制备的，得到的是R1CHXCOOH、R2CX2COOH、没转化的R1CH2COOH酸和有时少量的CX3COOH的混合物。
可以首先将R1CH2COOH从此混合物中分离出去，但是先加氢是更简单的方法
然后再进行分离，然而不可避免地有一部分RCHXCOOH要按照下式发生退减反应生成酸：
然后蒸馏R1CHXCOOH、R1CH2COOH和HX的混合物就足可以得到比较纯的R1CHXCOOH。
本发明特别适用于提纯一氯乙酸。
退减反应是提纯后的酸中的X离子数，也就是由HX产生的X离子数与理论上应将R1CX2COOH(以及任意的CX3COOH)转化成R1CHXCOOH而得到的X数之比。除了CX3COOH例外以外，最小退减反应是1。更经常是1.4～3.4。
这样高的退减反应表明，此反应不是选择性的，会得到醛类和重产物。
本申请人已证明，在废催化剂中加入细的新催化剂，即形成由本发明的a和b的混合物组成的新催化剂，可得到新催化剂的性能。
本发明也涉及提纯分子式为R1CHXCOOH(R1如前面所定义)的α-卤代羧酸的方法，其特征在于使用含有本发明的a和b的催化剂。
实例1
1)在一个内径26毫米的带夹套玻璃塔A中加入130克直径2毫米、长度4毫米、比表面大于700米2/克、表面上沉积有0.8％的钯(＞100米2/克钯)的挤出炭。
然后向此塔中通入由粗酸溶液(其组成按重量计为约80％的一氯乙酸、约4％的二氯乙酸、约16％的乙酸)和4标准升/小时的氢气流组成的混合料流。
将此塔升温至125℃，反应进行几小时后得到下面的结果(见表中新催化剂栏)
2)在反应进行数千小时以后，此催化剂成为废催化剂(见表中废催化剂栏)，因此这就是催化剂a。
新催化剂含钯0.8％，就是1040毫克。废催化剂重170克含钯0.39％，就是660毫克。
在下面表中，＂ADCA＂表示二氯乙酸，＂MAAG＂表示一氯乙酸羟基乙酸酯，＂-CHO＂表示每千克要提纯的粗酸中所含的醛类(用乙醛表示)的毫克数，Cl-/ADCA表示退减反应。
液体的空间速度是每小时、每立方米催化剂床流过粗酸的速度。
3)然后加入13克呈70微米细粉状的细新催化剂，此新催化剂由含有1％的钯的炭构成，这就是物质b。
已证实，有3.2克又从催化剂床中排出，有9.8克留在催化剂床中。进行此补加而不停止反应。
重新计算时间，将此时定为D，282小时以后测量结果(见表中＂加入细粉催化剂再生废催化剂＂栏)。
进行性能测试直到1200小时，这时已加入催化剂床中98毫克。因此，本发明混合物含贵金属为660毫克＋98毫＝758毫克。
已证实，可以降低床温，使其转化二氯乙酸的性能和以前所观察的相同，副产物乙醛和一氯乙酸羟基乙酸酯(MAAG)的含量与用无活性的废催化剂相比也大大下降，这样的活性在当时一直得以维持。
表
| 反应小时数 | 温度℃ | 液体空速kg/h/m3 | ADCA％入口/出口 | MAAG％ | CHOmg/kg | Cl-ADCA | ||
| 废催化剂 | 155160 | 249261 | 3,353,35 | 0,170,14 | 1,451,40 | 825985 | 2,673,13 | |
| 加入粉状催化剂再生废催化剂 | 2824346517421200 | 140140140140140 | 250234255242238 | 3,222,562,972,953,02 | 0,140,100,160,140,15 | 0,400,600,700,800,70 | 402,5340243254290 | 1,712,101,781,891,84 |
| 新催化剂 | 200250 | 135135 | 241272 | 3,293,09 | 0,170,13 | 0,330,40 | 354308 | 2,962,98 |
Claims (5)
1.一种由下述a和b的混合物组成的α-卤代羧酸脱卤催化剂，其中包括：
a)沉积于一种选自炭，氧化硅，碳化硅，氧化铝或碳化硼的惰性载体之上并且已在氢存在下用于脱除α-卤代羧酸中的卤素的第VIII族贵金属，
b)由沉积于所述惰性载体之上的第VIII族贵金属组成的新鲜催化剂的细小粒子。
2.根据权利要求1的催化剂，其特征在于所述贵金属a和b都是钯。
3.根据权利要求1或2的催化剂，其特征在于α-卤代羧酸的分子式为：
式中X为氯，R1与R2可相同或不同，代表X、H、含有3-12个碳原子的直链或支链烷基。
4.根据权利要求1-3中任何一项的α-卤代羧酸脱卤催化剂的用途，其中该催化剂用于提纯分子式R1CHXCOOH中R1为氯、氢、含有3-12个碳原子的直链或支链烷基的α-一卤代羧酸。
5.根据权利要求1-3中任何一项的α-卤代羧酸脱卤催化剂的用途，其中该催化剂用于提纯粗一氯乙酸。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9112915 | 1991-10-18 | ||
| FR9112915A FR2682616B1 (fr) | 1991-10-18 | 1991-10-18 | Catalyseurs de deshalogenation d'acides carboxyliques alphahalogenes. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1071603A CN1071603A (zh) | 1993-05-05 |
| CN1035162C true CN1035162C (zh) | 1997-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112351A Expired - Fee Related CN1035162C (zh) | 1991-10-18 | 1992-10-17 | α-卤代羧酸脱卤催化剂 |
Country Status (15)
| Country | Link |
|---|---|
| US (2) | US5356850A (zh) |
| EP (1) | EP0537838B1 (zh) |
| JP (1) | JPH0734864B2 (zh) |
| KR (1) | KR100242369B1 (zh) |
| CN (1) | CN1035162C (zh) |
| AT (1) | ATE116159T1 (zh) |
| CA (1) | CA2080708C (zh) |
| DE (1) | DE69201041T2 (zh) |
| DK (1) | DK0537838T3 (zh) |
| ES (1) | ES2066552T3 (zh) |
| FI (1) | FI924705A (zh) |
| FR (1) | FR2682616B1 (zh) |
| GR (1) | GR3015215T3 (zh) |
| NO (1) | NO300620B1 (zh) |
| TW (1) | TW280781B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0728730B1 (de) * | 1994-12-02 | 2001-03-07 | Salzgitter Anlagenbau GmbH | Verfahren zur Herstellung von Monochloressigsäure |
| DE19546080A1 (de) | 1995-12-11 | 1997-06-12 | Hoechst Ag | Verfahren zur Darstellung einer besonders reinen Monochloressigsäure |
| EP1900719A1 (en) * | 2006-09-01 | 2008-03-19 | BUSS ChemTech AG | Manufacture of substantially pure monochloroacetic acid |
| DE102008019338A1 (de) * | 2008-04-16 | 2009-10-22 | Qiagen Gmbh | Verfahren zur Isolierung von Polypeptiden |
| US9357997B2 (en) | 2011-07-08 | 2016-06-07 | Smith & Nephew, Inc. | Suture passer and method |
| BR112014008207B1 (pt) | 2011-10-20 | 2019-09-10 | Akzo Nobel Chemicals Int Bv | processo para a purificação de uma alimentação líquida |
| AU2012324958B2 (en) | 2011-10-20 | 2016-03-17 | Akzo Nobel Chemicals International B.V. | Process for the hydrodechlorination of a liquid feed comprising dichloroacetic acid |
| CN107948656B (zh) | 2011-10-28 | 2021-06-01 | 太阳专利托管公司 | 图像解码方法及图像解码装置 |
| RU2711661C2 (ru) | 2015-03-17 | 2020-01-20 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Способ очистки монохлороуксусной кислоты |
| AR104892A1 (es) | 2015-06-12 | 2017-08-23 | Akzo Nobel Chemicals Int Bv | Proceso para la hidrodecloración de una alimentación que comprende ácido dicloroacético |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803054A (en) * | 1971-02-08 | 1974-04-09 | Hoechst Ag | Process for preparing sulfited platinum on carbon catalysts |
| US3864281A (en) * | 1972-08-17 | 1975-02-04 | Hoechst Ag | Process for the manufacture of a dehalogenation catalyst |
| US4888316A (en) * | 1988-11-21 | 1989-12-19 | Phillips Petroleum Company | Preparation of hydrotreating catalyst from spent catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1920806C3 (de) * | 1969-04-24 | 1974-07-04 | Knapsack Ag, 5033 Huerth-Knapsack | Verfahren zur Regenerierung eines Dehalogenierungskatalysators |
| US4422954A (en) * | 1982-03-31 | 1983-12-27 | Allied Corporation | Method to restore the metal content of a noble metal hydrogenation catalyst |
| DE3782213T2 (de) * | 1986-07-10 | 1993-03-11 | Chiyoda Chem Eng Construct Co | Verfahren zur enthalogenierung eines halogenids und katalysator hierfuer. |
| FR2645531B1 (fr) * | 1989-04-07 | 1991-06-07 | Atochem | Procede et catalyseur de deshalogenation d'acides carboxyliques alphahalogenes |
-
1991
- 1991-10-18 FR FR9112915A patent/FR2682616B1/fr not_active Expired - Fee Related
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1992
- 1992-10-01 NO NO923834A patent/NO300620B1/no not_active IP Right Cessation
- 1992-10-06 AT AT92203075T patent/ATE116159T1/de not_active IP Right Cessation
- 1992-10-06 EP EP92203075A patent/EP0537838B1/fr not_active Expired - Lifetime
- 1992-10-06 ES ES92203075T patent/ES2066552T3/es not_active Expired - Lifetime
- 1992-10-06 DE DE69201041T patent/DE69201041T2/de not_active Expired - Fee Related
- 1992-10-06 DK DK92203075.4T patent/DK0537838T3/da active
- 1992-10-16 US US07/961,809 patent/US5356850A/en not_active Expired - Fee Related
- 1992-10-16 FI FI924705A patent/FI924705A/fi unknown
- 1992-10-16 CA CA002080708A patent/CA2080708C/fr not_active Expired - Fee Related
- 1992-10-17 KR KR1019920019124A patent/KR100242369B1/ko not_active IP Right Cessation
- 1992-10-17 CN CN92112351A patent/CN1035162C/zh not_active Expired - Fee Related
- 1992-10-19 JP JP4306007A patent/JPH0734864B2/ja not_active Expired - Lifetime
- 1992-10-20 TW TW081108340A patent/TW280781B/zh active
-
1994
- 1994-06-24 US US08/264,878 patent/US5475135A/en not_active Expired - Fee Related
-
1995
- 1995-02-28 GR GR950400419T patent/GR3015215T3/el unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803054A (en) * | 1971-02-08 | 1974-04-09 | Hoechst Ag | Process for preparing sulfited platinum on carbon catalysts |
| US3864281A (en) * | 1972-08-17 | 1975-02-04 | Hoechst Ag | Process for the manufacture of a dehalogenation catalyst |
| US4888316A (en) * | 1988-11-21 | 1989-12-19 | Phillips Petroleum Company | Preparation of hydrotreating catalyst from spent catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2682616A1 (fr) | 1993-04-23 |
| EP0537838A1 (fr) | 1993-04-21 |
| DE69201041D1 (de) | 1995-02-09 |
| CN1071603A (zh) | 1993-05-05 |
| US5475135A (en) | 1995-12-12 |
| GR3015215T3 (en) | 1995-05-31 |
| DE69201041T2 (de) | 1995-08-03 |
| ES2066552T3 (es) | 1995-03-01 |
| NO923834D0 (no) | 1992-10-01 |
| NO300620B1 (no) | 1997-06-30 |
| FI924705A (fi) | 1993-04-19 |
| ATE116159T1 (de) | 1995-01-15 |
| NO923834L (no) | 1993-04-19 |
| CA2080708A1 (fr) | 1993-04-19 |
| US5356850A (en) | 1994-10-18 |
| CA2080708C (fr) | 1999-02-16 |
| JPH0734864B2 (ja) | 1995-04-19 |
| EP0537838B1 (fr) | 1994-12-28 |
| FR2682616B1 (fr) | 1993-12-10 |
| DK0537838T3 (da) | 1995-06-06 |
| FI924705A0 (fi) | 1992-10-16 |
| JPH05301045A (ja) | 1993-11-16 |
| TW280781B (zh) | 1996-07-11 |
| KR100242369B1 (ko) | 2000-02-01 |
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