CN1102863C - Catalyst for preparation of ethanediol by epoxyethane hydration and its process - Google Patents
Catalyst for preparation of ethanediol by epoxyethane hydration and its process Download PDFInfo
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- CN1102863C CN1102863C CN98114026A CN98114026A CN1102863C CN 1102863 C CN1102863 C CN 1102863C CN 98114026 A CN98114026 A CN 98114026A CN 98114026 A CN98114026 A CN 98114026A CN 1102863 C CN1102863 C CN 1102863C
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- China
- Prior art keywords
- catalyst
- reaction
- catalyzer
- hydration
- epoxy ethane
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Abstract
The present invention relates to a catalyst for preparing ethylene glycol for direct catalytic hydration of an epoxy ethane homogeneous phase method and a reaction process thereof. The catalyst is a compound of inorganic salts and heteropoly acid salts, and the general formula of the catalyst is YaPMbOc<*>nH2O(I)+BdX(II). The hydration reaction can be carried out in an intermittent kettle type reactor or a continuous tube type reactor under the mixed condition, the weight ratio of the catalyst II to the catalyst I is 1 to 10: 1, and CO2 media are not used. The molar ratio of water to epoxy ethane is reduced to 4 to 8: 1 from 25 to 28: 1 in the prior art, the conversion rate of the epoxy ethane is from 95.0 to 99.9%, and the selectivity of the ethylene glycol is from 88 to 96%.
Description
The present invention relates to a kind of catalyzer that is used for catalyzing epoxyethane hydration reaction preparing ethylene glycol, particularly relate to catalyzer and reaction process thereof that a kind of homogeneous catalysis hydration reaction prepares ethylene glycol.
Preparing ethandiol by catalyzing epoxyethane hydration, homogeneous catalysis hydration reaction are two kinds, and a kind of is direct catalytic hydration, i.e. oxyethane direct and water effect generation monoethylene glycol under catalyst action; Another kind is the ethylene carbonate method, promptly oxyethane under the effect of catalyzer, elder generation and CO
2Effect generates ethylene carbonate, and ethylene carbonate adds water and resolves into monoethylene glycol under the effect of catalyzer then.This method must have CO
2Condition under carry out, pressure is higher.The present invention adopts direct catalytic hydration technology, and directly catalytic hydration relates to patent such as WO85/04406, GB2083026A etc.Use catalyzer to be organometallic complex, as [(Ph
3P)
2N] VO
3, [(Ph
3P)
2N]
2WO
4, (PPN)
2MoO
4, (PPM)
2MoO
4Deng, these catalyzer need be dissolved in the organic solvent, as C
6H
5CH
3, C
2H
2Cl
2, C
6H
6Deng in.Its shortcoming is that consumption of organic solvent is big, and inflammable poisonous, pollutes.Among the GB2098985A, alkyl epoxide and CO have been narrated
2The technological process of prepared in reaction alkyl alcohol.Its introduce with halogenation season phosphonium salt be catalyzer, under substantially anhydrous situation, alkyl epoxide and CO
2Reaction generates alkyl carbonate, and the alkyl carbonate hydrolysis generates ethylene glycol.Present technique is used CO
2, the equipment complexity, uneconomical.U.S. Pat 4117250 has proposed the catalyzer of class ethylene oxide hydration reaction preparing ethylene glycol, and it can be that potassium compound is at H
+The K that produces in the medium
2CO
3And this technology must be at CO
2Medium in carry out.
The purpose of this invention is to provide a kind of CO that need not to add
2Medium can make oxyethane and one step of water directly act on the high reaction activity of generation ethylene glycol and the catalyzer and the process of high glycol selectivity.
The object of the present invention is achieved like this, and the present invention has done intensive screening to ethylene oxide hydration homogeneous reaction catalyzer, to carbonate series; Acid carbonate series; Heteropolyacid salt series and composite salt catalyst series, the main optionally influence of investigating the transformation efficiency and the ethylene glycol of oxyethane, selecting the high catalyzer of active highly selective through investigation is the mixture of a kind of inorganic salt and heteropolyacid salt, the general formula of catalyzer is:
Y
aPM
bO
cNH
2O (I)+B
dIn X (II) formula:
Y is H, Li, Na or K etc.; M is Mo, W or V etc.;
B is K or Na etc.; X is Cl
-, Br
-, I
-, CO
3 2-, HCO
3 -Or PO
4 3-Deng;
A is 3 or 7; B is 10～12; C is 40 or 42; N is 3～15; D is 1～3.
The ethylene oxide hydration reaction can be carried out in tank reactor intermittently or successive tubular reactor.Water and oxyethane are added in the reactor by 1～10: 1 (weight) by 4～8: 1 (mol ratio) catalyst I I: I, reactor heats in oil bath, system system temperature is 100～150 ℃, reaction times is 8～30 minutes, reaction terminating, reaction solution ethylene glycol content is 40～50%, and the oxyethane transformation efficiency reaches 95.0～99.9%, and glycol selectivity reaches 88～96%.
The catalyzer that the present invention selects has advantages of high catalytic activity and higher selectivity to oxyethane and water reaction.Compare with existing technology, the catalysis of this class can make oxyethane and water directly act on generation ethylene glycol under the condition of gentleness, reached the purpose that reduces the hydration ratio, keeping high oxyethane transformation efficiency and monoethylene glycol optionally under the condition, hydration can be compared by 25～28 of existing technology: 1 reduces to 4～8: 1 (mol ratio), the oxyethane transformation efficiency reaches 95～99.9%, glycol selectivity 88～96%.Do not using CO
2Under the ambient condition, still keep less catalyst levels, and do not use poisonous, inflammable organic solvent.Catalyzer can directly be bought from market, and raw material is cheap and easy to get.Ethylene oxide hydration reaction water composition and division in a proportion reduces, and energy consumption reduces, and it is more economical reasonable that it is produced.
The present invention will be further described below in conjunction with embodiment:
Embodiment 1: take by weighing oxyethane 20 grams, H
2O 40.8 grams, catalyzer KHCO
31 gram, K
3[P (Mo
3O
10)
4] 7H
2O 0.15 gram adds in the white steel autoclave of 100ml, reactor is placed in the oil bath add, and temperature of reaction is controlled at 130 ℃, 20 minutes reaction times.Stopped reaction takes out reactor with reaction solution, with cold water cooling, sampling analysis oxyethane transformation efficiency 96.4%, glycol selectivity 94.0%.
Embodiment 2: take by weighing oxyethane 100 grams, water 204 grams, catalyzer KHCO
35 grams, H
3[P (Mo
3O
10)
4] 7H
2O 0.5 gram is made into reaction soln, in the stainless steel cylinder of the 2L that packs into, uses volume pump to the continuous tubular reactor feeding, flow reactor is long 1.5m, and the stainless steel tube of diameter phi 3mm places oil bath, the reacting by heating temperature is controlled at 120 ℃, reaction pressure 1.5MPa, and the reaction times is 15 minutes.Stopped reaction, reaction solution cools off sampling analysis, oxyethane transformation efficiency 99.9%, glycol selectivity 94.5% with cold water after the reducing valve decompression.
Embodiment 3: take by weighing oxyethane 44 grams, water 72 grams, catalyst n aHCO
32.5 gram, H
3[P (Mo
3O
10)
4] 7H
2O 0.25 gram adds in the white steel autoclave, and reactor is gone in oil bath to heat, and temperature of reaction is controlled at 120 ℃, 15 minutes reaction times, stopped reaction.With cold water cooling, sampling analysis, oxyethane transformation efficiency 98.5%, glycol selectivity 90.9%.
Embodiment 4: take by weighing oxyethane 44 grams, water 144 grams, catalyzer KHCO
33.0 gram, H
3[P (W
3O
10)
4] 7H
2O 0.60 gram adds in the white steel autoclave, reactor is placed in the oil bath heats, and temperature of reaction is controlled at 130 ℃, and in 15 minutes reaction times, stopped reaction is with cold water cooling, sampling analysis, oxyethane transformation efficiency 97.9%, glycol selectivity 89.4%.
Claims (2)
1, a kind of catalyzer of hydrating epoxy ethane to prepare ethandiol is characterized in that this catalyzer is the mixture of inorganic salt and heteropolyacid salt, and the catalyzer general formula is: Y
aPM
bO
cNH
2O (I)+B
dX (II), wherein Y is H, Li, Na or K; M is Mo, W or V; B is K or Na; X is Cl
-, Br
-, I
-, CO
3 2-, HCO
3 -Or PO
4 3-A is 3 or 7; B is 10～12; C is 40 or 42; N is 3～15; D is 1～3; And II: I=1～10: 1 (weight).
2, a kind of process of hydrating epoxy ethane to prepare ethandiol, it is characterized in that using the described catalyst for hydration of epoxy ethane to prepare ethandiol of claim 1, be reflected in autoclave intermittently or the successive tubular reactor and carry out, water: oxyethane=4～8: 1 (mol ratio), temperature of reaction is 100～150 ℃, and the reaction times is 8～30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114026A CN1102863C (en) | 1998-05-28 | 1998-05-28 | Catalyst for preparation of ethanediol by epoxyethane hydration and its process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114026A CN1102863C (en) | 1998-05-28 | 1998-05-28 | Catalyst for preparation of ethanediol by epoxyethane hydration and its process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1237481A CN1237481A (en) | 1999-12-08 |
| CN1102863C true CN1102863C (en) | 2003-03-12 |
Family
ID=5223710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114026A Expired - Fee Related CN1102863C (en) | 1998-05-28 | 1998-05-28 | Catalyst for preparation of ethanediol by epoxyethane hydration and its process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1102863C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305820C (en) * | 2003-09-23 | 2007-03-21 | 中国石化集团天津石油化工公司 | Technical method for producing dihydric alcohol by catalytic hydration of epoxy compound |
| SG191979A1 (en) | 2011-01-24 | 2013-08-30 | Shell Int Research | Process for the production of ethylene oxide |
| AU2012210661B2 (en) | 2011-01-24 | 2015-04-30 | Shell Internationale Research Maatschappij B.V. | Process for the production of ethylene oxide |
| CN103012063B (en) * | 2011-09-28 | 2014-12-03 | 中国石油化工股份有限公司 | Preparation method of propylene glycol |
| CN103212425A (en) * | 2013-03-14 | 2013-07-24 | 中山职业技术学院 | Preparation raw material of sulfonated wood active carbon, preparation method and application thereof |
| CN112717847A (en) * | 2020-12-17 | 2021-04-30 | 南京延长反应技术研究院有限公司 | Micro-interface reaction system and method for preparing ethylene glycol by ethylene oxide method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117250A (en) * | 1977-12-22 | 1978-09-26 | Union Carbide Corporation | Continuous process for producing alkylene glycols from alkylene carbonates |
| WO1985004406A1 (en) * | 1984-03-28 | 1985-10-10 | Union Carbide Corporation | Organosalts of metalate anions and process for the production of alkylene glycols therewith |
| CN1117039A (en) * | 1994-05-20 | 1996-02-21 | 罗纳·布朗克化学公司 | Heteropolyacid-based catalysts and use thereof for the preparation of aliphatic carboxylic acids |
-
1998
- 1998-05-28 CN CN98114026A patent/CN1102863C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117250A (en) * | 1977-12-22 | 1978-09-26 | Union Carbide Corporation | Continuous process for producing alkylene glycols from alkylene carbonates |
| WO1985004406A1 (en) * | 1984-03-28 | 1985-10-10 | Union Carbide Corporation | Organosalts of metalate anions and process for the production of alkylene glycols therewith |
| CN1117039A (en) * | 1994-05-20 | 1996-02-21 | 罗纳·布朗克化学公司 | Heteropolyacid-based catalysts and use thereof for the preparation of aliphatic carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1237481A (en) | 1999-12-08 |
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| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: China Petroleum & Natural Gas Co., Ltd. Applicant after: Fushun Petrochemical Company Applicant before: Inst. under Fushun Petro-Chemical Corp. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: INST. UNDER FUSHUN PETRO-CHEMICAL CORP. TO: FUSHUN PETROLEUM AND CHEMICALBRANCH OF CHINA NATIONAL PETROLEUM CORP. |
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| CF01 | Termination of patent right due to non-payment of annual fee |