CN1216045C - 用于制备乙酰吡啶的方法和催化剂 - Google Patents
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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Abstract
揭示了在催化剂存在下，在气相中反应通式(II)所示吡啶羧酸酯和乙酸来制备通式(I)所示乙酰吡啶的方法，通式(II)中，R1是C1-6烷基。所述催化剂的活性材料包含二氧化钛和至少一种碱金属氧化物或碱土金属氧化物，且承载在氧化铝-二氧化硅载体上，所述载体的表观孔隙度至少为50%。所述方法的优点是仅形成少量的副产物(例如，吡啶)。
Description
本发明涉及制备通式(I)所示乙酰吡啶，尤其是3-乙酰吡啶的方法，本发明还涉及适用于本发明方法的催化剂。
3-乙酰吡啶在医药和精细化工中被认为是日益重要的中间体和结构单元。到目前为止，常使用从烟酸或者其它不能方便获得的原料(例如3-乙基吡啶)开始的多级工艺来制备3-乙酰吡啶。代替使用杂环芳香酸，可以使用其衍生物。当所述酸是不挥发和/或在更高温度下会分解时，这尤其有用。因此，在520℃下，烟酸乙酯和乙酸进行缩合反应，可提供37％产率的3-乙酰吡啶(Houben-Weyl，第VI/2a卷，第632-633页)。最近，制备3-乙酰吡啶的方法已经在EP-A-0352674中提到，所述方法使用以二氧化钛和碱金属或碱土金属的氧化物或氢氧化物为基础的催化剂。使用烟酸和乙酸的甲酯，以及包含98％二氧化钛(锐钛矿)和2％氧化钠的催化剂，其选择性为54-60％。作为烟酸酯脱羧反应的副产物，形成量为29-41％的吡啶。在EP-A-0352674中，已经提到了其它各种方法，这些方法均不能获得满意的效果。
本发明的目的是提高现阶段制备3-乙酰吡啶方法的选择性，这样可以避免或者降低因形成大量不想要的副产物而导致的损失。
本发明中，通过权利要求1所述的方法已经达到这一目的。
已经发现，在通式(II)所示的吡啶羧酸酯和乙酸反应形成乙酰吡啶(I)的气相反应中，EP-A-0352674中所述的二氧化钛基催化剂的选择性可以通过使用表观孔隙度至少为50％的高孔隙度氧化铝-二氧化硅载体充分提高，如通过Archimedes方法所确定的，在通式(II)中，R1是C1-6烷基。
本发明的方法宜使用烟酸C1-6烷基酯作为原料来进行，制得3-乙酰吡啶。
还发现通过使用沸点更高的吡啶羧酸酯(II)，可以使反应产物更容易分离。若所述转化率低于100％，低级酯(例如烟酸的低级酯)具有和那些所需产物类似的沸点，导致在蒸馏过程中难于分离。使用更高沸点(更加稳定)的酯可以大大避免这种问题。这样的例子为烟酸的丁酯、戊酯或者己酯(包括如异丁基、仲丁基、异戊基等的异构体)，来代替烟酸的甲酯、乙酯或者丙酯，其在大气压下的沸点分别仅和3-乙酰吡啶相差3-4K(乙基)和15-16K(甲基和丙基)。烟酸丁酯和3-乙酰吡啶在大气压下的沸点差为32K。
宜使用沸点(在大气压下)超过所述产物乙酰吡啶(I)20K以上的吡啶羧酸酯(II)作为原料。
所述优选的反应温度为350-450℃。
有利的是，所述反应使用过量的乙酸且在水存在下进行。
在催化剂载体中氧化铝和二氧化硅的重量比为70∶30至90∶10，宜为75∶25至85∶15。
所述催化剂载体的表观孔隙度为60-70％。
所述催化剂载体的堆积密度宜低于1000kg/m3，更好是600-800kg/m3。
所述催化剂的二氧化钛含量以所述载体的重量计宜为5-20重量％。
所述催化剂可以通过包括以下步骤的方法来制备：(i)将表观孔隙度至少为50％的氧化铝-二氧化硅载体用四氯化钛的盐酸水溶液浸渍，制得第一催化剂前体；(ii)干燥；(iii)煅烧；(iv)将所述煅烧后的第一催化剂前体用碱金属和/或碱土金属的氢氧化物和/或氧化物的溶液或悬浮液浸渍，制得第二催化剂前体；(v)干燥，并(vi)煅烧所述干燥的第二催化剂前体来制备所述最终催化剂。
所述载体的浸渍不限于使用四氯化钛。因此，可以使用钛的其它可溶性盐或均匀分散的二氧化钛浆液。也可以使用合适的前体来代替碱金属或碱土金属的氢氧化物或氧化物，例如所述在加热时会分解的金属盐。
在载体中氧化铝和二氧化硅的比为70∶30至90∶10，宜为75∶25至85∶15。
所述催化剂载体的表观孔隙度宜为60-70％。
所述催化剂中二氧化钛含量以所述载体的重量计宜为5-20重量％。
以下非限制性的例子将说明本发明的方法和本发明催化剂的制备。
实施例1
催化剂的制备：
为了制备所述催化剂，可以使用多孔二氧化硅-氧化铝球体作为载体。合适的材料由Norton Chemical Process Products Corporation of Akron，Ohio提供，典型描述如下：
大小和形状：4mmφ球体
表面积： 12m2/g
表观孔隙度：65％
堆积密度： 710kg/m3
总孔体积(Hg porosimetry)：0.5ml/g
Al2O3：79-81％
SiO2； 17-19％
通过往15ml浓盐酸和60ml去离子水的混合物中加入23ml(40g，0.21mol)TiCl4，来制备四氯化钛水溶液(用TiO2表示为22％，0.21mol，16g)。将所述最终溶液搅拌几分钟，并冷却。
使用初期润湿技术在25-30℃下喷涂所述TiCl4，将上述二氧化硅-氧化铝球体(250g)浸渍在旋转玻璃容器或者金属圆桶中。之后在真空(环境温度：90-95℃)中干燥所述催化剂前体1小时，然后，在120℃下干燥12小时，最后在400℃下在空气流(500ml/min)中煅烧12小时。分析可知有7％的Ti。
将煅烧的球体再次置于旋转圆桶中，并用稀释的氢氧化钠溶液(1.5g NaOH的5％水溶液)喷涂。
在120℃下干燥所述催化剂12小时，然后在500℃下煅烧1小时。
实施例2
3-乙酰吡啶的制备
将15ml(12g)实施例1中制备的催化剂填充到内径为12mm的电加热管式反应器中。在12小时内，使用精密泵将17.9g烟酸丁酯、32g水和125g乙酸的混合物计量加入在410℃下操作的反应器中。从所述反应混合物中获得8.9g3-乙酰吡啶、0.9g吡啶和1.3g烟酸丁酯。烟酸丁酯转化率93％(选择性78％)，3-乙酰吡啶对应产率为73％。所述吡啶形成的选择性为11％。
对比例1
使用EP-A-0352674中所述的催化剂制备3-乙酰吡啶
将15ml(≈15g)EP-A-0352674的实施例1中制备的催化剂填充到内径为12mm的电加热管式反应器中。在60小时内，使用精密泵将78g烟酸丁酯、149g水和523g乙酸的混合物计量加入在410℃下操作的反应器中。从所述反应混合物中获得30.5g 3-乙酰吡啶、8.5g吡啶和9.0g烟酸甲酯。烟酸丁酯转化率为88％(选择性50％)，3-乙酰吡啶对应产率为45％。所述吡啶形成的选择性为19％。
对比例2
使用EP-A-0352674中所述的催化剂制备3-乙酰吡啶
将15ml(≈15g)EP-A-0352674的实施例1中制备的催化剂填充到内径为12mm的电加热管式反应器中。在63小时内，使用精密泵将104g烟酸丁酯、162g水和606g乙酸的混合物计量加入在405℃下操作的反应器中。从所述反应混合物中获得30g 3-乙酰吡啶、3g吡啶和26g烟酸丁酯。烟酸丁酯转化率为75％(选择性58％)，3-乙酰吡啶对应产率为43％。所述吡啶形成的选择性为5％。
实施例3
3-乙酰吡啶的制备
将270ml(≈227g)实施例1制备的催化剂填充到内径为23.5mm的管式反应器中。使用精密泵将烟酸丁酯(30g/h)、水(54g/h)和乙酸(210g/h)的混合物经蒸发器加入用盐浴加热的管式反应器中。少量氮气流(11/h)确保蒸汽的传送。所述盐浴的温度为410℃。所述反应蒸汽在水循环系统中冷凝。在总共运行35小时之后，收集反应溶液。将这种对应于710g烟酸丁酯的溶液部分进行分离。81％烟酸丁酯转化成了293g 3-乙酰吡啶，对应选择性为75％，产率为61％。吡啶形成的选择性为4％。
Claims (15)
1.制备通式(I)所示乙酰吡啶的方法，所述乙酰吡啶通过在催化剂存在下，在气相中反应通式(II)所示吡啶羧酸酯和乙酸来制备；
在通式(II)中，R1是C1-6烷基；所述催化剂的活性原料包含二氧化钛和至少一种碱金属或碱土金属的氧化物，其特征在于，所述催化剂包含表观孔隙度至少为50％的氧化铝-二氧化硅载体。
2.权利要求1所述的方法，其特征在于，所制备的乙酰吡啶(I)为3-乙酰吡啶，所述吡啶羧酸酯(II)为烟酸C1-6烷基酯。
3.权利要求1或2所述的方法，其特征在于，所述吡啶羧酸酯(II)在大气压下的沸点比所述乙酰吡啶(I)的沸点高20K以上。
4.权利要求1或2所述的方法，其特征在于所述反应温度为350-450℃。
5.权利要求1或2所述的方法，其特征在于，在所述催化剂载体中氧化铝和二氧化硅的重量比为70∶30-90∶10。
6.权利要求1或2所述的方法，其特征在于，在所述催化剂载体中氧化铝和二氧化硅的重量比为75∶25-85∶15。
7.权利要求1或2所述的方法，其特征在于，所述催化剂载体的表观孔隙度为60-70％。
8.权利要求1或2所述的方法，其特征在于，所述催化剂载体的堆积密度为600-1000kg/m3。
9.权利要求1或2所述的方法，其特征在于，所述催化剂载体的堆积密度为600-800kg/m3。
10.权利要求1或2所述的方法，其特征在于，以所述载体的重量计，所述催化剂的二氧化钛含量为5-20重量％。
11.一种用于权利要求1所述方法中的催化剂，所述催化剂由以下步骤制得：
(i)表观孔隙度至少为50％的氧化铝-二氧化硅载体用四氯化钛的盐酸水溶液浸渍，制得第一催化剂前体；
(ii)干燥；
(iii)煅烧；
(iv)所述煅烧后的第一催化剂前体用碱金属和/或碱土金属的氢氧化物和/或氧化物的溶液或悬浮液浸渍，制得第二催化剂前体；
(v)干燥，并
(vi)煅烧所述干燥的第二催化剂前体。
12.权利要求11所述的催化剂，其特征在于，所述载体中氧化铝和二氧化硅的重量比为70∶30-90∶10。
13.权利要求11所述的催化剂，其特征在于，所述载体中氧化铝和二氧化硅的重量比为75∶25-85∶15。
14.权利要求11或12所述的催化剂，其特征在于，所述催化剂载体的表观孔隙度为60-70％。
15.权利要求11或12所述的催化剂，其特征在于，以所述载体的重量计，所述催化剂的二氧化钛含量为5-20重量％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01103953 | 2001-02-19 | ||
| EP01103953.4 | 2001-02-19 | ||
| US33254601P | 2001-11-26 | 2001-11-26 | |
| US60/332,546 | 2001-11-26 |
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| Publication Number | Publication Date |
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| CN1491214A CN1491214A (zh) | 2004-04-21 |
| CN1216045C true CN1216045C (zh) | 2005-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN028051440A Expired - Fee Related CN1216045C (zh) | 2001-02-19 | 2002-02-14 | 用于制备乙酰吡啶的方法和催化剂 |
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| Country | Link |
|---|---|
| EP (1) | EP1363886B1 (zh) |
| JP (1) | JP2004525901A (zh) |
| CN (1) | CN1216045C (zh) |
| AT (1) | ATE397589T1 (zh) |
| AU (1) | AU2002250937B2 (zh) |
| CA (1) | CA2437704A1 (zh) |
| CZ (1) | CZ20032193A3 (zh) |
| HU (1) | HUP0303277A2 (zh) |
| PL (1) | PL363280A1 (zh) |
| WO (1) | WO2002066433A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101524A1 (en) * | 2003-05-19 | 2004-11-25 | Lonza Ag | Polyglycerol esters of pyridinecarboxylic acids |
| CN111705548B (zh) * | 2020-05-26 | 2021-12-31 | 仙鹤股份有限公司 | 一种装饰原纸的制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT302983B (de) * | 1969-04-02 | 1972-11-10 | Shell Int Research | Verfahren zur Epoxydation von olefinischen Verbindungen |
| US3979400A (en) * | 1974-12-11 | 1976-09-07 | Reilly Tar & Chemical Corporation | Production of pyridyl ketones |
| EP0352672A3 (de) * | 1988-07-28 | 1990-08-08 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Alkenylaromaten |
| US4950763A (en) * | 1988-07-29 | 1990-08-21 | Basf Aktiengesellschaft | Preparation of ketones |
| CN1128792C (zh) * | 1997-05-05 | 2003-11-26 | 阿科化学技术公司 | 采用改进的非均质催化剂组合物的环氧化方法 |
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2002
- 2002-02-14 CA CA002437704A patent/CA2437704A1/en not_active Abandoned
- 2002-02-14 AT AT02719829T patent/ATE397589T1/de not_active IP Right Cessation
- 2002-02-14 EP EP02719829A patent/EP1363886B1/en not_active Expired - Lifetime
- 2002-02-14 CN CN028051440A patent/CN1216045C/zh not_active Expired - Fee Related
- 2002-02-14 CZ CZ20032193A patent/CZ20032193A3/cs unknown
- 2002-02-14 AU AU2002250937A patent/AU2002250937B2/en not_active Ceased
- 2002-02-14 PL PL02363280A patent/PL363280A1/xx not_active Application Discontinuation
- 2002-02-14 HU HU0303277A patent/HUP0303277A2/hu unknown
- 2002-02-14 WO PCT/EP2002/001533 patent/WO2002066433A1/en active IP Right Grant
- 2002-02-14 JP JP2002565950A patent/JP2004525901A/ja active Pending
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| Publication number | Publication date |
|---|---|
| CZ20032193A3 (cs) | 2003-12-17 |
| PL363280A1 (en) | 2004-11-15 |
| AU2002250937B2 (en) | 2006-08-03 |
| CA2437704A1 (en) | 2002-08-29 |
| HUP0303277A2 (hu) | 2004-01-28 |
| JP2004525901A (ja) | 2004-08-26 |
| ATE397589T1 (de) | 2008-06-15 |
| EP1363886B1 (en) | 2008-06-04 |
| CN1491214A (zh) | 2004-04-21 |
| EP1363886A1 (en) | 2003-11-26 |
| WO2002066433A1 (en) | 2002-08-29 |
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