CN1359893A - 一种乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法 - Google Patents
一种乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法 Download PDFInfo
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- 229940116333 ethyl lactate Drugs 0.000 title claims abstract description 21
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Abstract
一种乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法,它是将乳酸乙酯蒸汽与空气的混合气,在硅胶负载的银催化剂存在下,于250-300℃反应生成丙酮酸乙酯。本发明的方法催化剂制备容易,活性和选择性高,单程转化率高达80%以上,选择性达90%以上。
Description
一、技术领域
本发明涉及乳酸乙酯的催化氧化,具体地说是乳酸乙酯多相催化氧化制备丙酮酸乙酯。
二、技术背景
丙酮酸是合成L-氨基酸的前体[参见H.Yamada和H.Kumagai,Pure andApplied Chemistry:IUPAC Bulletin,vol.50,1989,p.117及S.Takao等,J.Ferment.Tech.,62(1984)329],还可以作为合成腈基丙烯酸酯粘合剂的原料。电子工业中它还用作光阻材料的溶剂[参见Japan Kokai,H4-36752,Feburary6,1992]。目前的生产工艺为1881年就报道的酒石酸脱水脱羧方法,该法需要过量的硫酸氢钾作脱水剂,收率大约为60%,主料的价格与辅料的消耗都较高,而且只能间歇式生产。
八十年代初出现了通过乳酸的氧化然后水解得到丙酮酸的专利报道[参见Jpn.Patent 56-19854(1981)及Jpn.Patent 57-24336(1982)]。后来又有H.Hiyashi等研究了其它一些过渡金属氧化物及以MoO3为主的混合氧化物的催化性能[参见H.Hiyashi等,J.Mol.Catal.,83(1993)207及H.Hiyashi等,Bull.Chem.Soc.Jpn.,66,1542(1993)]。一定的选择性下,丙酮酸乙酯的收率都在65%以下,并不理想。反应温度提高转化率上升,但是选择性剧降。
三、发明内容
本发明的目的是提供一种新的由乳酸乙酯制备丙酮酸乙酯的气固多相催化氧化方法,其以硅胶负载的银或银合金为催化剂,催化剂制备简单,转化率及选择性都较高。
银催化剂是工业上有重要应用的一类催化剂,例如,乙烯环氧化中的Ag/α-Al2O3,及甲醇氧化过程中的电解银催化剂。实际上银还是其它简单醇的很好的部分氧化催化剂[参见B.A.德鲁斯著,北京大学化学系有机催化教研室译,有机催化,中国工业出版社1963,p214及C.Kemball和D.A.Dowden,Catalysis,The Chemical Sosiety,Vol.3,1980,p91]。银催化剂与氧化物催化剂不同的特点是其工作状态下氧的覆盖度较低,表面酸碱性很弱,这就有效地避免了产物的深度氧化以及乳酸乙酯、丙酮酸乙酯的水解副反应,而水解反应生成的乳酸或丙酮酸在催化反应条件下极容易分解。
本发明的目的是通过如下的技术方案实现的。
负载银催化剂可以通过湿法浸渍制备。以硅胶为载体,一定浓度的AgNO3或银氨溶液浸渍后,不断搅拌下烘干、焙烧、还原。还原的方法有多种,最常用的是氢气还原法,甲醛还原法[参见Bell等,J.Catal.,38,440(1975)]。另外还可以通过高温焙烧使银盐分解为单质银。银合金催化剂用硝酸盐共浸渍或者分步浸渍(先浸渍其它金属的盐酸盐,还原后再按相同方法浸渍银盐)。
本发明采用硅胶负载的银或银合金作催化剂,在气相中将乳酸乙酯用空气氧化为丙酮酸乙酯。具体的技术方案如下:
一种乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法,它是将乳酸乙酯的蒸汽与空气的混合气在催化剂存在下于250-300℃反应生成丙酮酸乙酯,其中催化剂是硅胶负载的银催化剂。硅胶负载的银催化剂可以含有钯,钯的含量可以占金属原子总量的0-15atm%。硅胶负载的银催化剂中银和钯金属的总担载量为20-40wt%。乳酸乙酯蒸汽与空气的混合气中,空气与乳酸乙酯蒸气的比例为10-25∶1(V/V)。
本发明的乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法,原料成本低,制备方法简易,单程转化率高达80%以上,且生成丙酮酸乙酯的选择性好,可达90%以上。催化剂制备容易,活性和选择性都较高,能连续生产。以下通过实施例进步说明本发明。
四、具体实施方法
实施例1:
1.1催化剂制备
将5克烟雾状硅胶(Cab-O-Sil)加入到10毫升含1.57克AgNO3的水溶液中,室温静置半小时,然后在搅拌下用红外灯烘干,再在120℃干燥24小时。干燥的粉末于350℃静态空气中焙烧3小时,然后在350℃用氢气还原5小时备用。
1.2催化反应过程
反应在固定床直型反应管中进行,反应管内径为10毫米。所用催化剂为500毫克20-40目的20wt%Ag/Cab-O-Sil。反应前升温至350℃用氢气还原1小时,降温到300℃时切换为空气与乳酸乙酯的混合气,乳酸乙酯流量为0.6克/小时,空气∶乳酸乙酯=15∶1。经过催化剂的反应混合物进行气相色谱在线分析(色谱柱为15%PEG6000/GDX103)。反应4小时后达到稳态,转化率为88.2%,选择性90.5%。
实施例2:
按照实施例1中所述步骤、条件反应,选择担载量为40wt%的Ag/Cab-O-Sil催化剂,反应转化率为95.0%,选择性为88.0%。
实施例3:
按照实施例1中所述步骤、条件反应,反应温度为260℃,乳酸乙酯的流量为0.4克/小时,反应转化率为81.4%,选择性为92.7%。
实施例4:
5克Cab-O-Sil加入到10毫升含200毫克PdCl2·2H2O的水溶液中,室温静置半小时,在红外灯下烘干,烘干时要不停搅拌,以保证均匀浸渍。然后在120℃干燥24小时,250℃还原10小时,再将得到的粉末加到10毫升含0.63克AgNO3的水溶液中,搅拌下滴入3毫升20%甲醛溶液,过滤,120℃干燥,压片过筛。按照实施例1中所述条件步骤反应,反应温度改为280℃,转化率85.5%,选择性93.5%。
Claims (4)
1.一种乳酸乙酯气相催化氧化制备丙酮酸乙酯的方法,其特征是将乳酸乙酯的蒸汽与空气的混合气在催化剂存在下于250-300℃反应生成丙酮酸乙酯,其中催化剂是硅胶负载的银催化剂。
2.根据权利要求1所述的制备丙酮酸乙酯的方法,其特征是硅胶负载的银催化剂中含有钯,钯占金属原子总量的0-15atm%。
3.根据权利要求1或2所述的制备丙酮酸乙酯的方法,其特征是硅胶负载的银催化剂银和钯金属的总担载量为20-40wt%。
4.根据权利要求1或2所述的制备丙酮酸乙酯的方法,其特征是乳酸乙酯蒸汽与空气的混合气中,空气与乳酸乙酯蒸气的比例为10-25∶1(V/V)。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101318903B (zh) * | 2008-06-27 | 2011-03-30 | 烟台海岸带可持续发展研究所 | 一种制备丙酮酸乙酯的方法 |
WO2016199174A1 (en) | 2015-06-10 | 2016-12-15 | Council Of Scientific & Industrial Research | Oxidative dehydrogenation of lactate esters to pyruvate esters |
CN106928059A (zh) * | 2017-03-23 | 2017-07-07 | 南京师范大学 | 一种催化氧化合成丙酮酸乙酯的方法 |
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CN101318903B (zh) * | 2008-06-27 | 2011-03-30 | 烟台海岸带可持续发展研究所 | 一种制备丙酮酸乙酯的方法 |
WO2016199174A1 (en) | 2015-06-10 | 2016-12-15 | Council Of Scientific & Industrial Research | Oxidative dehydrogenation of lactate esters to pyruvate esters |
CN106928059A (zh) * | 2017-03-23 | 2017-07-07 | 南京师范大学 | 一种催化氧化合成丙酮酸乙酯的方法 |
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