CN101121642A - Catalytic method used for cyclic carbonates hydrolysis - Google Patents
Catalytic method used for cyclic carbonates hydrolysis Download PDFInfo
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- CN101121642A CN101121642A CNA200610089231XA CN200610089231A CN101121642A CN 101121642 A CN101121642 A CN 101121642A CN A200610089231X A CNA200610089231X A CN A200610089231XA CN 200610089231 A CN200610089231 A CN 200610089231A CN 101121642 A CN101121642 A CN 101121642A
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- cyclic carbonate
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- phosphoric acid
- acid salt
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Abstract
The present invention relates to a method for catalyzing and hydrolyzing orbicular carbonic acid esters, which is characterized in that: the method uses phosphate as a catalyzer to make the hydrolyzing reaction for the orbicular carbonic acid esters; under the condition of low water ratio, common pressure, low temperature and warm situation, the hydrolyzing effect can reach the best.
Description
Technical field: the invention belongs to the ester-type hydrolysis technical field, specifically refer to a kind of novel method of cyclic carbonate catalytic hydrolysis.
Background technology:
The hydrolysis of ester class is a kind of important chemical reaction, is widely used in the every field of petrochemical iy produced, and cyclic carbonate wherein has very important fundamental position especially as the hydrolysis of NSC 11801 (EC), propylene carbonate (PC) etc.
The hydrolysis of NSC 11801 (EC) is the important step of being produced ethylene glycol (EG) by oxyethane (EO) catalytic hydration two-step approach.Ethylene glycol (EG) is a kind of important Organic Chemicals, is mainly used to produce trevira, frostproofer, unsaturated polyester resin, nonionogenic tenside, thanomin and explosive etc.The technology that ethylene glycol is produced mainly is divided into petrochemical industry route and non-petrochemical industry route.Direct catalytic hydration of EO and NSC 11801 method (EC) route are arranged in the petrochemical industry route.The key of this technology of EO catalytic hydration system EG is a catalyzer, roughly is divided into homogeneous catalysis hydration method and heterogeneous catalysis hydration method.NSC 11801 method (EC) route is the CO that discharges when utilizing oxidation of ethylene system EO
2Generating EC for raw material and EO react under the effect of catalyzer, is that the intermediate product catalytic hydrolysis is produced EG then with EC, is the industrialization direction of EO system EG from now on.
The hydrolysis of propylene carbonate (PC) is to be that the starting ester exchange process is produced DMC coproduction 1 simultaneously with propylene carbonate (PC) and methyl alcohol, and 2-propylene glycol process guarantees 1, and the effective ways of 2-propylene glycol product purity have very high industrial application value.
Being used for this class annular carbonic acid esters hydrolysis catalysts at present mainly contains: alkaline carbonate, alkali metal hydrocarbonate, compounds such as alkaline earth metal carbonate, basic zeolite, quaternary ammonium type strongly basic anion exchange resin, IIIA family metal oxide, zinc, manganese, lead, contain the polymkeric substance of phosphine groups etc., but these catalyst system more or less exist, and catalytic activity is low, stability is not high, severe reaction conditions, poor water resistance, problem such as the catalysis cost is higher.
Summary of the invention:
The present invention is the method that a kind of cyclic carbonate catalytic hydrolysis generates correspondent alcohol, the applied catalyzer of this method can make the hydrolysis of cyclic carbonate carry out under low water ratio, normal pressure and lesser temps, and obtains the very high cyclic carbonate ester conversion rate and the selectivity of correspondent alcohol.
Reaction expression of the present invention is:
R
1＝H，C
nH
2nCl，C
6H
5，C
nH
2n+1，CnH
2n-1；R
2＝H，C
mH
2mCl，C
6H
5，C
mH
2m+1，C
mH
2m-1(n，m＝1～6)
The catalytic hydrolysis method of cyclic carbonate provided by the present invention comprises: under the condition that the phosphoric acid salt catalyzer exists, cyclic carbonate generation catalytic hydrolysis reaction generates corresponding alcohol.
Said phosphoric acid salt comprises: alkalies and alkaline earth phosphoric acid salt, alkalies and alkaline earth hydrophosphate are with the pyrophosphate salt of, alkalies and alkaline earth dihydrogen phosphate and alkalies and alkaline earth, and the best is alkali-metal phosphoric acid salt; In the hydrolysis reaction, the ratio of water and cyclic carbonate (mol ratio) is 1: 1～1: 20, and the best is 1: 1～1: 4; Catalyst levels is 0.1～2.0mol% of cyclic carbonate amount of substance, and the best is 1.0mol%; Reaction conditions, normal pressure～1.0MPa, temperature of reaction 333.15～393.15K, the best is 378.15K; In 0～6 hour reaction times, the best is 0.1～2 hour.The cyclic carbonate ester structure is:
R
1＝H，C
nH
2nCl，C
6H
5，C
nH
2n+1，C
nH
2n-1；R
2＝H，C
mH
2mCl，C
6H
5，C
mH
2m+1，C
mH
2m-1(n，m＝1～6)
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Take by weighing EC (NSC 11801) and H at 1: 1 according to mol ratio
2O puts into flask, and takes by weighing catalyzer K by 1.0% of EC mole number
3PO
4Add in the above-mentioned mixed solution; Flask is put into 105 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the ethylene carbonate ester conversion rate is 97.55%, and glycol selectivity is 98.63%.
Embodiment 2
Take by weighing EC and H at 1: 1 according to mol ratio
2O puts into flask, and takes by weighing catalyzer K by 1.0% of EC mole number
2HPO
4Add in the above-mentioned mixed solution; Flask is put into 105 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the ethylene carbonate ester conversion rate is 92.32%, and glycol selectivity is 98.27%.
Embodiment 3
Take by weighing EC and H at 1: 1 according to mol ratio
2O puts into flask, and takes by weighing catalyzer KH by 1.0% of EC mole number
2PO
4Add in the above-mentioned mixed solution; Flask is put into 95 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the ethylene carbonate ester conversion rate is 62.45%, and glycol selectivity is 56.34%.
Embodiment 4
Take by weighing EC and H at 1: 1.5 according to mol ratio
2O puts into flask, and by with the EC mol ratio be that 0.01 amount takes by weighing catalyzer K
3PO
4Add in the above-mentioned mixed solution; Flask is put into 105 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the ethylene carbonate ester conversion rate is 99.68%, and glycol selectivity is 97.32%.
Embodiment 5
Take by weighing EC and H at 1: 2.1 according to mol ratio
2O puts into flask, and by with the EC mol ratio be that 0.01 amount takes by weighing catalyzer K
3PO
4Add in the above-mentioned mixed solution; Flask is put into 105 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the ethylene carbonate ester conversion rate is 96.84%, and glycol selectivity is 99.33%.
Embodiment 6
Take by weighing PC (alkene ester in the carbonic acid) and H at 1: 1 according to mol ratio
2O puts into flask, and takes by weighing catalyzer K by 1.0% of PC mole number
3PO
4Add in the above-mentioned mixed solution; Flask is put into 105 ℃ of oil baths heat condensing reflux.Reaction pressure is a normal pressure, and in 1 hour reaction times, the propylene carbonate ester conversion rate is 90.45%, 1, and 2-propylene glycol selectivity is 75.22%.
Claims (7)
1. the catalytic hydrolysis method of a cyclic carbonate is characterized in that with alkalies and alkaline earth phosphoric acid salt be catalyzer, realizes the hydrolysis of cyclic carbonate under mild conditions.
2. according to claim 1, alkali metal phosphate is phosphoric acid salt, hydrophosphate, dihydrogen phosphate and the pyrophosphate salt of K, Na etc., and alkali earth metal phosphate is phosphoric acid salt, hydrophosphate, dihydrogen phosphate and the pyrophosphate salt of Ca, Mg etc.
3. according to claim 1, what preferentially select is alkali-metal phosphoric acid salt.
4. according to claim 1, catalyst levels is 0.1～2.0mol% of cyclic carbonate amount of substance.
5. according to claim 1, reactants water is 1: 1～1: 20 than (water/NSC 11801, mol ratio).
6. according to claim 1, the cyclic carbonate ester structure is:
R
1＝H，C
nH
2nCl，C
6H
5，C
nH
2n+1，C
nH
2n-1；R
2＝H，C
mH
2mCl，C
6H
5，C
mH
2m+1，C
mH
2m-1(n，m＝1～6)
7. according to claim 1, reaction conditions is: normal pressure～1.0MPa, temperature of reaction 333.15～393.15K, 0～6 hour reaction times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610089231XA CN101121642A (en) | 2006-08-10 | 2006-08-10 | Catalytic method used for cyclic carbonates hydrolysis |
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|---|---|---|---|
| CNA200610089231XA CN101121642A (en) | 2006-08-10 | 2006-08-10 | Catalytic method used for cyclic carbonates hydrolysis |
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Family
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085187A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparation of glycol by ethylene carbonate hydrolysis |
| CN107353225A (en) * | 2017-05-04 | 2017-11-17 | 南京齐正化学有限公司 | A kind of preparation method of 2 isopropylidene amino ethoxy-ethanol |
| CN107915577A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method of ethylene carbonate hydrolysis ethylene glycol |
| CN112513137A (en) * | 2018-06-22 | 2021-03-16 | 科思创知识产权两合公司 | Process for producing polyols |
-
2006
- 2006-08-10 CN CNA200610089231XA patent/CN101121642A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085187A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparation of glycol by ethylene carbonate hydrolysis |
| CN105085187B (en) * | 2014-05-14 | 2017-08-11 | 中国石油化工股份有限公司 | The method of preparing ethyl glycol by hydrolysis of ethylene carbonate |
| CN107915577A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method of ethylene carbonate hydrolysis ethylene glycol |
| CN107353225A (en) * | 2017-05-04 | 2017-11-17 | 南京齐正化学有限公司 | A kind of preparation method of 2 isopropylidene amino ethoxy-ethanol |
| CN112513137A (en) * | 2018-06-22 | 2021-03-16 | 科思创知识产权两合公司 | Process for producing polyols |
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