CN101098842A - 2-丁烯-1,4-二醇的制备方法 - Google Patents

2-丁烯-1,4-二醇的制备方法 Download PDF

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CN101098842A
CN101098842A CNA200580046190XA CN200580046190A CN101098842A CN 101098842 A CN101098842 A CN 101098842A CN A200580046190X A CNA200580046190X A CN A200580046190XA CN 200580046190 A CN200580046190 A CN 200580046190A CN 101098842 A CN101098842 A CN 101098842A
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glycol
hydrogenation
catalyst
butylene
fiber
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艾瑞克·乔奈特
卢波夫·济韦-敏思凯
艾伯特·仁肯
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DSM IP Assets BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C07C33/035—Alkenediols
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond

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Abstract

在不存在溶剂的条件下，在结构化催化剂的存在下氢化2-丁炔-1，4-二醇，由此可以制备2-丁烯-1，4-二醇。

Description

2-丁烯-1，4-二醇的制备方法
本发明涉及2-丁烯-2，4-二醇的制备，而2-丁烯-2，4-二醇是维生素B6、药物和杀虫剂的制备中的重要的工业中间体。
2-丁烯-1，4-二醇通常通过在溶剂(例如水溶液)中将2-丁炔-1，4-二醇催化氢化来制备2-丁烯-1，4-二醇。为了便于回收催化剂，已有建议在2-丁炔-1，4-二醇水溶液的氢化中使用丝状纺织布作为催化剂载体，参见Chem.Engineering Science 57(2002)，3453-3460。
根据本发明，现已发现，在不存在溶剂的条件下，通过在结构化催化剂上对2-丁炔-1，4-二醇进行催化氢化，可以以高收率和高选择性制备2-丁烯-1，4-二醇。由于氢微溶于例如水的溶剂中，因此不存在这样的溶剂，则可使单位时间的转化率更高，从而提高氢化方法的经济性。此外，由于本发明的方法避免了溶剂的分离和回收过程，所以出于环保的考虑本发明的方法也是优选的。
因此，本发明涉及制备2-丁烯-1，4-二醇的方法，所述方法包括在存在结构化催化剂且不存在溶剂的条件下氢化2-丁炔-1，4-二醇。
本文所用术语“结构化催化剂”是指空间位置受控制的催化剂。结构化催化剂在本领域中是已知的，例如参见Chimia 56(4)，2002，159-163。结构化催化剂的例子是陶瓷载体构造和纤维结构，特别是丝状纺织布。所有类型的丝状纺织布均可用于本发明。纤维可由有机或无机物质制成。其例子是由活性炭纤维制成的织物，例如丙烯腈纤维、玻璃纤维、陶瓷纤维、金属纤维或羊毛复合氧化物的活性炭纤维。优选的是聚丙烯腈织物。丝状纺织布的单根纤维的直径优选为约2-100μm，特别地，所述直径不大于约20μm。适宜地，织物由纤维束构成的丝线所织成，织布的孔径小于约1mm。可以例如用硝酸对织物进行化学处理以调整比表面积，并且织物可以具有例如金属(如Al、Ti或Pb)涂层以改善选择性。
作为催化剂，可以使用可催化2-丁炔-2，4-二醇至2-丁烯-2，4-二醇的选择性氢化的任何氢化催化剂。这样的催化剂的例子是贵金属，例如钯、铂、铱、铑、钌或其组合。载体织物上存在的催化剂的量可达约10质量％，适宜地为1-10质量％。通过用催化剂前驱体(催化剂金属的盐)的溶液进行处理，随后在氢气氛中干燥和加热，实现载体织物的加载，并且可以通过加载溶液(loading solution)中催化剂前驱体的浓度来控制载体织物的加载。
本发明的氢化可以在用于氢化2-丁炔-2，4-二醇以制备至2-丁烯-2，4-二醇的常规条件下进行。适宜地，氢化在约0.1-6MPa的压力和约350-500K的温度下进行。氢化可以以间歇或连续方式进行。
以下实施例进一步阐明了本发明，但这些实施例并不限制本发明。
实施例
催化剂制备
将平纹织物形式的源自聚丙烯腈的活性炭纤维(Taiwan CarbonTechnology Co)用作制备催化剂的载体。织物由直径约为0.5mm的长丝线织成。这些丝线由3-5μm的单丝组成的束构成。如Chem.EngineeringScience 57(2002)，3453-3460中所述，通过与Na2PdCl4水溶液的离子交换将钯沉积在织物上。用原子吸收光谱测定钯的加载量为4质量％，并通过BET法来分析催化剂的比表面积和孔径分布。采用一氧化碳的脉冲化学吸附来确定Pd的分散，参见上面提到的Chem.Eng.Sci.。
实验装置
上面提到的Chem.Eng.Sci.中详细描述了实验装置。
反应在由加热夹套保持的等温条件下在间歇反应器(150ml高压釜，Buechiglas，Uster，CH)中进行。该高压釜具有定量气体供给系统。
纤维催化剂被置于两个固定在搅拌器上的金属丝网(20×40mm)之间。
置于反应器中的催化剂的量在150与35mg之间变化。搅拌速度被保持在1500rpm以避免质量传递限制。为了达到有效的气-液接触，使用自出气中空轴搅拌器。在等压反应条件下向高压釜中充入氢气(＞99.99％)。
装入纯的2-丁炔-1，4-二醇固体(熔点331K)，并在氩气氛下熔化以防止反应物降解。在达到所需温度之后，用氢气冲洗反应器，并将其加压至期望水平。在反应过程中，通过以氢气消耗的速率从储罐中供给氢气，将反应器中H2的压力维持恒定。连续监测H2储罐中的压力，从而对瞬时的氢消耗进行在线测量。
用以He作为载气的配备FID检测器的气相色谱仪(Auto SystemXL，PERKIN ELMER)对从环路中取出的液体样品进行分析。在20K/min的温升速度(373-493K)下，在30m的Perkin Elmer Elite系列的0.25mm的具有0.25μm涂层的毛细柱上，对产物进行分离。使用1，3-丁二醇作为GC定量分析的内标。
不同反应条件下的实验结果示于图1-3。
图1示出了反应温度为325K时的典型的浓度-时间曲线。如图2所示，在丁炔二醇(B3)的转化率达到90％时，测量和预测的丁烯二醇(B2)的选择性约为98％；而当丁炔二醇(B3)的转化率为99％时，测量和预测的丁烯二醇(B2)的选择性降至95％。从图3可以看出温度对反应速率的影响，图中示出了作为时间函数的反应物浓度。基于初始反应速率，可以计算转化频率对温度的依赖性。

Claims (11)

1.制备2-丁烯-1，4-二醇的方法，所述方法包括在存在结构化催化剂且不存在溶剂的条件下氢化2-丁炔-1，4-二醇。
2.如权利要求1的方法，其中所述结构化催化剂的载体是丝状纺织布。
3.如权利要求2的方法，其中所述丝状纺织布由活性炭纤维制成。
4.如权利要求2的方法，其中所述活性炭纤维由聚丙烯腈纤维制成。
5.如权利要求2-4中任何一项的方法，其中所述纤维的直径为约2-100μm。
6.如权利要求2-5中任何一项的方法，其中所述纤维的直径不大于20μm 。
7.如权利要求2-6中任何一项的方法，其中所述纺织布的孔径小于1mm 。
8.如权利要求2-7中任何一项的方法，其中所述催化剂为钯催化剂。
9.如权利要求1-8中任何一项的方法，其中所述载体上的催化剂加载量为约1-10质量％。
10.如权利要求1-9中任何一项的方法，其中所述氢化在约0.1-6MPa的压力下进行。
11.如权利要求1-10中任何一项的方法，其中所述氢化在约350-500K的温度下进行。
CNA200580046190XA 2005-01-07 2005-12-29 2-丁烯-1,4-二醇的制备方法 Pending CN101098842A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295530A (zh) * 2011-08-11 2011-12-28 浙江启明药业有限公司 一种3-丁烯-1-醇的合成方法
CN109622049A (zh) * 2018-12-21 2019-04-16 万华化学集团股份有限公司 用于炔丙基醇部分加氢制备烯丙基醇的催化剂及其制法

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US9975827B2 (en) * 2014-07-23 2018-05-22 Fundacion Tecnalia Research & Innovation Method for manufacturing 2,3-butanediol

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DE4333293A1 (de) * 1993-09-30 1995-04-06 Basf Ag Verfahren zur selektiven Hydrierung von Butindiol-1,4 zu Buten-2-diol-1,4 und dafür geeigneter Katalysator
DE19962907A1 (de) * 1999-12-23 2001-07-05 Basf Ag Verfahren zur Herstellung von C¶10¶-C¶30¶-Alkenen durch partielle Hydrierung von Alkinen an Festbett-Palladium-Trägerkatalysatoren

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295530A (zh) * 2011-08-11 2011-12-28 浙江启明药业有限公司 一种3-丁烯-1-醇的合成方法
CN102295530B (zh) * 2011-08-11 2013-11-06 浙江启明药业有限公司 一种3-丁烯-1-醇的合成方法
CN109622049A (zh) * 2018-12-21 2019-04-16 万华化学集团股份有限公司 用于炔丙基醇部分加氢制备烯丙基醇的催化剂及其制法

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EP1833779A2 (en) 2007-09-19
US20080312475A1 (en) 2008-12-18
US7541501B2 (en) 2009-06-02
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KR101226317B1 (ko) 2013-01-24
JP4960886B2 (ja) 2012-06-27

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