CN1049493A - α-羟基酮的氢化 - Google Patents
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- 239000012429 reaction media Substances 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical group OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000007788 liquid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- OOJRTGIXWIUBGG-UHFFFAOYSA-N 2-methylpropane-1,2,3-triol Chemical compound OCC(O)(C)CO OOJRTGIXWIUBGG-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- -1 chromous acid ketone Chemical class 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000007868 Raney catalyst Substances 0.000 claims 1
- 229910000564 Raney nickel Inorganic materials 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 12
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 238000004845 hydriding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
- C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
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- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
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Abstract
本发明涉及在含羧酸的多相液相反应介质中催
化氢化工a-羟基酮为相应的醇的方法。羧酸可以是简
单的羧酸或羟基羧酸。
羧酸的存在既提高了醇产物的收率,又改进了其
选择性。
Description
本发明涉及把α-羟基酮,特别是二羟基丙酮氢化成相应的醇的改进方法。
用均相或多相催化剂体系把酮氢化为相应的醇是众所周知的。其中US-A-4024193描述了用均相催化剂体系把纯的二羟基丙酮氢化成甘油。
再有,在我们的公开的EP-A-306215中描述了通过甲醛自缩合形成的二羟基丙酮的氢化来合成甘油的方法。在这份文献中,描述了均相和多相氢化两种技术。
前面所述的氢化方法一般涉及到使用一种溶剂,通常是醇。
但是,现已发现,在一种羧酸存在下进行氢化反应,可以大大增加该反应生成所需醇产物的选择性。
因此,本发明涉及在液相反应介质中,在多相氢化催化剂和氢存在下,氢化α-羟基酮为相应的醇的方法,其特征在于氢化反应在羧酸存在下进行。
此方法中可被氢化的α-羟基酮的例子是可生成甘油的二羟基丙酮。
α-羟基酮有多种来源,例如来自一种醛或相应醛的混合物的自缩合或相互缩合。我们的公开EP-A-306215中描述了一种该方法。在J.A.C.S.,1984,106卷4829-4832页中由Matsumoto,T.等人叙述了另一种合成方法。
EP-A-245976中描述了合成α-羟基酮的又一方法。
α-羟基酮是在多相催化剂存在下,用氢氢化成相应的醇。
在合成α-羟基酮,例如二羟基丙酮的过程中,此方法的副产物是eruthrulose水合物。后者也能由本发明的方法氢化成甲基甘油,一种非常类似于甘油的产品。
适宜的多相氢化催化剂是分割成细粉状的或载体金属。这些催化剂的例子可以是载于在该反应条件下惰性的载体比如碳或石墨上的第八族金属,例如镍、阮内镍或钌,或亚铬酸酮类型的催化剂。
在商业范围内,氢是易于获得的。可以使用从商业上获得的氢,或如果需要可以将氢进一步纯化。合适的氢的分压范围可以从10~30,000千帕,优选范围是从100~10,000千帕。
氢化过程适宜在高温下完成,合适的范围是从环境温度到150℃,优选是40~150℃,最优选是40~120℃。
氢化步骤合适的液体反应介质是能溶解氢化反应试剂的溶剂。合适的溶剂包括醇、水、醚和它们中的一种或多种的混合物,但并不仅限于此。
反应介质最好是含至少40% W/W水的水介质。反应介质可以含有C1-C6脂肪醇,例如丁醇和甲基戊醇;也可以含来自早期氢化反应或,如从外源加入的甘油产物。
本发明的特征是羧酸存在下进行氢化。优选的羧酸是脂肪族羧酸,更优选的是C1-C4饱和脂肪族羧酸或羟基羧酸,最优选的是醋酸、乳酸、柠檬酸。此外,甚至例如在二羟基丙酮污染了少量甲醛的情况下,也能观察到此种改进。如果二羟基丙酮是由甲醛自缩合制备,就会存在此种污染,此污染大大抑制二羟基丙酮氢化中对甘油的选择性。但是,在氢化过程中醋酸的加入恢复了对甘油的选择性,就象不存在污染一样。
适合本发明液相氢化反应介质的羧酸的量是能保持反应体系的PH值范围为2~6,优选为2.9~5.5。
氢化反应可以分批进行,或连续进行,优选的是连续进行。
对于分批操作,氢化反应过程将随氢化催化剂的类型和浓度,氢的分压,以及被氢化产物的性质。既无论是粗的或纯的或就地产生的而变化。氢化如二羟基丙酮形成的甘油产物可用现有技术中已知的方法纯化和回收。适宜的纯化方法是真空蒸馏。如果需要,可以使用本专业人员已知的现有技术进行后处理。这种处理包括,但不限于此,通过碳床和用漂白剂处理。
和迄今使用的各种合成方法比较,本发明的方法显然操作更简单和成本更低廉,并对所需的醇产物具有更高的选择性。原料易得,产物易于分离和纯化。
参考下列实施例对本发明作进一步说明。
实施例1和比较实验1
用氮气吹扫300ml不锈钢高压釜,加入催化剂(64% W/W镍,载于含商品名称为Harshaw NI5132P的铝的载体上-1g)和适量的反应剂溶液,密封并反复用氢加压和减压,直到压力达到10,000千帕。在实施例1和比较实验1中,此反应剂溶液为浓度8%的DHA去离子水溶液。把0.4g醋酸加到实施例1的物料中,使其PH值为2.96。
开始加热并搅拌(5℃/分,1100转/分),直到达到110℃,保持此温度4.5小时,并不断搅拌。此阶段后,停止加热/搅拌,并使高压釜冷却至室温。从液体产物取样并用高效液相色谱(HPLC)分析,结果列在下面的表1中。
在不加羧酸的比较实验1中,对甘油的选择性为76.4%。在实施例1中,醋酸的存在使选择性增加到97.3%。
实施例2-7
用氮气吹扫300ml不锈钢高压釜,然后加入催化剂(54% W/W镍,载于含商品名称为Sudchemie G134的铝的载体上-1g)和列于下面表2中的适宜的反应剂溶剂。使用柠檬酸和柠檬酸钠混合物以获得指定的PH值。然后密封高压釜并用氢增压以吹出氮气。最后高压釜用氢增压到25巴。
开始加热和搅拌(5℃/分,1000转/分)直到达到110℃,保持此温度3小时并不停搅拌。此阶段过后。停止加热/搅拌,并使高压釜冷却至室温。如实施例1那样分析液体产物。表2列出了每个加料组份和实验结果。这些结果表明柠檬酸的存在对用Sudchemie G134催化剂氢化二羟基丙酮是有益的。
实施例8-10
除了规定的反应剂的量,所有这些实施例中的实验步骤如上述的实施例1。使用的配料和反应条件及获得的结果列在下面的表3中。
这些结果表明了用Harshaw Ni5132催化剂氢化二羟基丙酮时加到反应介质中的羧酸的效应。
实施例11-17和对比实验2和3
除了规定的反应剂量,所有这些实施例和比较实验中的实验步骤和上述实施例1所用的相同。使用的配料和反应条件及获得的结果列在下面的表4和表5中。
比较实验2和实施例11的结果表明,在氢化反应过程中根据本发明使用羧酸调节PH值,即使作为杂质的甲醛存在也是有益的。
表1 在10,000千帕下,醋酸对DHA水溶液氢化的影响
序号 | pH | 最终DHAwt% | 最终甘油wt% | 对甘油的选择性 | DHA的转化 | 加入的CH3COOH(克) |
比较实验1实施例1 | 6.52.96 | 0.10.1 | 6.17.8 | 76.4297.39 | 98.7598.75 | 0.00.4 |
DHA-二羟基丙酮
高压釜装料:8%浓度DHA去离子水溶液(比较实验92克,实施例191.6克),1克催化剂(Harshaw Ni 5132P)条件:10,000千帕H2,110℃,1100转/分,4.5小时。
表2 柠檬酸对二羟基丙酮氢化为甘油选择性的影响
实施例序号 | 物料 | ||
水溶液20℃时的pH | 缓冲水(克) | 二羟基丙酮(克) | |
234567 | 234567 | 180180180180180180 | 202020202020 |
产物分析
实施例序号 | 进料二羟基丙酮(% W/W) | 甘油(% W/W) |
234567 | 000000 | 0.41.51.80.70.60.0 |
Claims (9)
1、在液体反应介质中,在多相氢化催化剂和氢存在下氢化α-羟基酮为相应的醇的方法,其特征在于氢化是在羧酸存在下进行的。
2、按照权利要求1的方法,其中α-羟基酮是二羟基丙酮和/或eruthrulose,以及相应的醇分别是甘油和/或甲基甘油。
3、按照权利要求1或2的方法,其中氢化催化剂选自载于反应条件下是惰性的载体上的第八族金属和亚铬酸酮类型的催化剂。
4、按照权利要求3的方法,其中催化剂是阮内镍,在氧化铝上的Harshaw镍或在碳上的钌。
5、按照前述权利要求的任一种方法,其中氢化反应是在氢分压从10-30000千帕和温度从环境温度到150℃下进行。
6、按照前述权利要求的任一方法,其中羧酸是C1-C4的饱和脂肪族羧酸或羟基羧酸。
7、按照权利要求6的方法,其中羧酸是醋酸,乳酸或柠檬酸。
8、按照前述权利要求的任一种方法,其中液体介质中存在的羧酸的量保持反应体系PH值的范围为2-6。
9、按照前述权利要求的任一种方法,其中液体反应介质含有至少40%W/W的水。
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Application Number | Priority Date | Filing Date | Title |
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GB898914991A GB8914991D0 (en) | 1989-06-29 | 1989-06-29 | Hydrogenation of hydroxy ketones |
GB8914991.8 | 1989-06-29 |
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CN1049493A true CN1049493A (zh) | 1991-02-27 |
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CN90106537A Pending CN1049493A (zh) | 1989-06-29 | 1990-06-29 | α-羟基酮的氢化 |
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EP (1) | EP0405956A1 (zh) |
JP (1) | JPH0338536A (zh) |
KR (1) | KR910000585A (zh) |
CN (1) | CN1049493A (zh) |
AU (1) | AU5781490A (zh) |
CA (1) | CA2020007A1 (zh) |
GB (1) | GB8914991D0 (zh) |
NO (1) | NO902891L (zh) |
NZ (1) | NZ234262A (zh) |
ZA (1) | ZA904895B (zh) |
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CN101801896B (zh) * | 2007-09-19 | 2013-09-18 | 三井化学株式会社 | 醇的制造方法以及酸处理阮内催化剂 |
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---|---|---|---|---|
DE4138792A1 (de) * | 1991-11-26 | 1993-05-27 | Basf Ag | Verfahren zur herstellung von 1,2-propylenglykol |
JP5797108B2 (ja) * | 2011-12-26 | 2015-10-21 | エア・ウォーター株式会社 | 2−インダノールの製造方法 |
JP6486020B2 (ja) * | 2014-05-30 | 2019-03-20 | 三菱ケミカル株式会社 | 2,3−ブタンジオールの製造方法 |
EP3173398B1 (en) | 2014-07-23 | 2020-12-09 | Fundación Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1222216A (en) * | 1967-07-10 | 1971-02-10 | Ici Ltd | Hydrogenation process |
GB8720491D0 (en) * | 1987-08-29 | 1987-10-07 | Bp Chem Int Ltd | Synthesis of glycerol |
-
1989
- 1989-06-29 GB GB898914991A patent/GB8914991D0/en active Pending
-
1990
- 1990-06-22 ZA ZA904895A patent/ZA904895B/xx unknown
- 1990-06-25 AU AU57814/90A patent/AU5781490A/en not_active Abandoned
- 1990-06-25 JP JP2164369A patent/JPH0338536A/ja active Pending
- 1990-06-27 NZ NZ234262A patent/NZ234262A/en unknown
- 1990-06-27 EP EP90307051A patent/EP0405956A1/en not_active Withdrawn
- 1990-06-27 CA CA002020007A patent/CA2020007A1/en not_active Abandoned
- 1990-06-28 KR KR1019900009665A patent/KR910000585A/ko not_active Application Discontinuation
- 1990-06-28 NO NO90902891A patent/NO902891L/no unknown
- 1990-06-29 CN CN90106537A patent/CN1049493A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101801896B (zh) * | 2007-09-19 | 2013-09-18 | 三井化学株式会社 | 醇的制造方法以及酸处理阮内催化剂 |
Also Published As
Publication number | Publication date |
---|---|
NO902891L (no) | 1991-01-02 |
NO902891D0 (no) | 1990-06-28 |
EP0405956A1 (en) | 1991-01-02 |
AU5781490A (en) | 1991-01-03 |
CA2020007A1 (en) | 1990-12-30 |
ZA904895B (en) | 1992-02-26 |
JPH0338536A (ja) | 1991-02-19 |
GB8914991D0 (en) | 1989-08-23 |
NZ234262A (en) | 1991-07-26 |
KR910000585A (ko) | 1991-01-29 |
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