CN101628908A - Method for synthesizing propylene carbonate - Google Patents
Method for synthesizing propylene carbonate Download PDFInfo
- Publication number
- CN101628908A CN101628908A CN200810045551A CN200810045551A CN101628908A CN 101628908 A CN101628908 A CN 101628908A CN 200810045551 A CN200810045551 A CN 200810045551A CN 200810045551 A CN200810045551 A CN 200810045551A CN 101628908 A CN101628908 A CN 101628908A
- Authority
- CN
- China
- Prior art keywords
- propylene carbonate
- reaction
- acrylic ester
- propylene
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing propylene carbonate, which has a process route for synthesizing the propylene carbonate in the presence of organic alkali and inorganic alkali catalyst by using o-chloropropanol and CO2 intermediates of industrially-prepared propylene oxide as raw materials. The molar ratio of the organic alkali to the o-chloropropanol is 0.5-5:1, the molar ratio of the inorganic alkali catalyst to the o-chloropropanol is 0-1:1, the reaction pressure is 0.2 to 10MPa, the reaction temperature is between 50 and 140 DEG C, and the reaction time is 0.5 to 20 hours. The method has the characteristics of mild reaction condition, short reaction time, high yield and easy separation of a product.
Description
Technical field
The invention belongs to a kind of method of synthesizing acrylic ester.
Background technology
Propylene carbonate is a kind of organic solvent of excellent property, is widely used in weaving, the carbonic acid gas in battery, makeup, gas delivery and Sweet natural gas and the syngas for synthetic ammonia and the fields such as absorption of hydrogen sulfide.Propylene carbonate also is a kind of important organic chemicals, is the important source material of dimethyl carbonate production by transesterification.
The existing synthetic method of propylene carbonate mainly contains phosgenation, methanol oxidation carbonyl process, alcoholysis of urea, carbonic acid gas and 1,2-propylene glycol synthesis method, carbonic acid gas and propylene oxide additive process.Wherein, phosgenation uses the phosgene of severe toxicity as raw material, is eliminated just gradually.The methanol oxidation carbonyl process is to the seriously corroded (CN Patent 1197792) of equipment, and existing catalyzer is the cost height not only, and owing to the life-span reason is difficult to satisfy industrial requirement.Alcoholysis of urea as raw material, is a cleaning route that does not rely on oil with urea cheap and easy to get, but because technical reason, this route still is in the pilot scale stage (princes and dukes should wait for Zhao Yanmin, Chen Tong, fine chemistry industry, 2005,22 (8), 638～640).Carbonic acid gas and 1, the direct synthesizing acrylic ester of 2-propylene glycol are the shortest routes of technical process in all routes, and no coupling product generates, and meet Green Chemistry and Atom economy notion, but this is reflected at normal pressure, and the equilibrium constant in the time of 25 ℃ has only 7.0 * 10
-5Even pressure rises to 10MPa, equilibrium conversion also has only about 8%, therefore is subjected to the restriction of chemical equilibrium, the yield of this route propylene carbonate very low (Zhao Tiansheng, Han Yizhuo, Sun Yuhan etc., gas chemical industry, 1998,23 (5): 52～56), be difficult to industrialization.Carbonic acid gas and propylene oxide additive process especially at home, account for more than 90% of propylene carbonate overall throughput (Feng Jianmin, Si Jinming, chemical engineering abstracts, 2004,4,25～26) in industrial being most widely used.
Adjacent propylene chlorohydrin is the intermediate of industrial production propylene oxide, and propylene and chlorine water generate adjacent propylene chlorohydrin through chlorohydrination, prepare propylene oxide with the lime saponification then, and the propylene oxide for preparing in this processing method of industrial application accounts for more than 90% of total amount.Adjacent propylene chlorohydrin comprises 1-chloro-2-propanol and 2-chloro-1-propanol, and both shared ratios are 4～9: 1.
Carbonic acid gas is to be final product behind the fossil oil oxidizing fire of representative with coal and oil, since the mankind enter suitability for industrialized production, because a large amount of fuel energies that use, the concentration of carbonic acid gas in atmosphere is increased gradually, become main greenhouse gases, directly cause temperature of the earth to rise and climatic anomaly, existent environment of people in serious threat.On the other hand, CO
2Be the abundantest Cl resource, the CO in atmosphere, water
2Carbon content is oil, Sweet natural gas, coal carbon content 10 times.Therefore, rationally utilize CO
2, not only to improving environment for human survival, and to utilizing cheap Cl resource, the significance of having increased economic efficiency
Summary of the invention
This patent relates to the adjacent propylene chlorohydrin of a kind of intermediate with industrial preparation propylene oxide and carbonic acid gas and reacts and prepare the method for propylene carbonate.This technology is to have reaction conditions gentleness, technical process is short, product yield the is high method for preparing propylene carbonate.
The method for preparing propylene carbonate that the present invention proposes is to be raw material with adjacent propylene chlorohydrin, carbonic acid gas, is undertaken by catalyzed reaction, and concrete steps are as follows:
Adjacent propylene chlorohydrin (1-chloro-2-propanol massfraction 75%, 2-chloro-1-propanol massfraction 20%) and organic bases are added in the autoclave, add catalyzer again, use CO
2Behind the air three times, charge into CO in the gas replacement reaction kettle
2To specified pressure, stir and heat up, after certain temperature, keep certain hour, stop to stir, be cooled to room temperature, filter and obtain product.Product carries out qualitative analysis with GC-MS (HP6890/5973, hewlette-packard), does quantitative analysis with GC (GC112A, Shanghai analytical instrument factory).
Adjacent propylene chlorohydrin of the present invention comprises 1-chloro-2-propanol and 2-chloro-1-propanol.
Catalyzer of the present invention is selected from a kind of in salt of wormwood, yellow soda ash, the magnesiumcarbonate, and the mol ratio of carbonate and adjacent propylene chlorohydrin is 0～1: 1, is preferably 0.01～0.09: 1.
Organic bases of the present invention is selected from a kind of in diethylamine, triethylamine, tripropyl amine, the Tributylamine, and the mol ratio of organic bases and adjacent propylene chlorohydrin is 0.5～5: 1, is preferably 1～1.1: 1.
Temperature of reaction of the present invention in 50～140 ℃ of scopes, preferred 80～120 ℃.
Carbonic acid gas original pressure of the present invention in 0.2MPa～10MPa scope, preferred 1.0～2.0MPa.
Reaction times of the present invention in 0.5h～20h scope, preferred 1h～4h.
Advantage of the present invention:
The present invention is with adjacent propylene chlorohydrin of the intermediate of industrial preparation propylene oxide and CO
2Be raw material, shortened technical process, the reaction conditions gentleness, the reaction times is short, and yield height, product are easy to separate.
Embodiment
Further specify the present invention below by embodiment, enforcement of the present invention is not limited to following examples.
Embodiment 1:
In reactor, add the adjacent propylene chlorohydrin (0.211mol) of 21.005g successively, 21.001g (0.208mol) triethylamine and 1.435g (0.010mol) salt of wormwood, sealed reactor, air is three times in the usefulness carbon dioxide replacement reactor, charges into the carbonic acid gas of 2.0MPa, be warming up to 100 ℃, reaction 3h postcooling is to room temperature, filter product 25.069g, product contains 1-chloro-2-propanol 0.503% by analysis, 2-chloro-1-propanol 0.806%, propylene carbonate 80.366%.Adjacent propylene chlorohydrin transformation efficiency 98.4%, propylene carbonate selectivity 95.1%, propylene carbonate yield 93.6%.
Embodiment 2
In reactor, add the adjacent propylene chlorohydrin (0.215mol) of 21.379g successively, 21.370g (0.211mol) triethylamine and 1.439g (0.010mol) salt of wormwood, sealed reactor, air is three times in the usefulness carbon dioxide replacement reactor, charges into the carbonic acid gas of 2.0MPa, be warming up to 80 ℃, reaction 3h postcooling filters and obtains product 26.206g to room temperature, and product contains 1-chloro-2-propanol 0.549% by analysis, 2-chloro-1-propanol 1.664%, propylene carbonate 77.604%.Adjacent propylene chlorohydrin transformation efficiency 97.1%, propylene carbonate selectivity 95.5%, propylene carbonate yield 92.7%.
Embodiment 3
In reactor, add the adjacent propylene chlorohydrin (0.217mol) of 21.596g successively, 21.600g triethylamine (0.213mol) and 1.441g (0.010mol) salt of wormwood, sealed reactor, air is three times in the usefulness carbon dioxide replacement reactor, charges into the carbonic acid gas of 1.5MPa, be warming up to 100 ℃, reaction 3h postcooling filters and obtains product 27.065g to room temperature, and product contains 1-chloro-2-propanol 0.839% by analysis, 2-chloro-1-propanol 1.164%, propylene carbonate 75.914%.Adjacent propylene chlorohydrin transformation efficiency 97.4%, propylene carbonate selectivity 95.3%, propylene carbonate yield 92.8%.
Embodiment 4
In reactor, add 21.002 adjacent propylene chlorohydrins (0.211mol) successively, 20.805g (0.206mol) triethylamine and 1.143g (0.011mol) sodium carbonate catalyst, all the other conditions are with case study on implementation 1, filtration obtains product 24.622g, product contains 1-chloro-2-propanol 2.749% by analysis, 2-chloro-1-propanol 1.332%, propylene carbonate 78.243%.Adjacent propylene chlorohydrin transformation efficiency 95.0%, propylene carbonate selectivity 94.2%, propylene carbonate yield 89.5%.
Embodiment 5
In reactor, add the adjacent propylene chlorohydrin (0.211mol) of 21.005g successively, 20.935g (0.207mol) triethylamine and 1.152g (0.014mol) magnesiumcarbonate catalyzer, all the other conditions are with case study on implementation 1, filtration obtains product 23.560g, product contains 1-chloro-2-propanol 6.553% by analysis, 2-chloro-1-propanol 2.585%, propylene carbonate 76.744%.Adjacent propylene chlorohydrin transformation efficiency 89.1%, propylene carbonate selectivity 94.1%, propylene carbonate yield 83.8%.
Embodiment 6
In reactor, add the adjacent propylene chlorohydrin (0.211mol) of 20.994g successively, 14.886g (0.206mol) diethylamine and 1.435g (0.010mol) salt of wormwood catalyzer, all the other conditions are with case study on implementation 1, filtration obtains product 21.272g, product contains 1-chloro-2-propanol 1.330% by analysis, 2-chloro-1-propanol 2.821%, propylene carbonate 63.356%.Adjacent propylene chlorohydrin transformation efficiency 95.6%, propylene carbonate selectivity 65.5%, propylene carbonate yield 62.6%.
Embodiment 7
In reactor, add the adjacent propylene chlorohydrin (0.211mol) of 21.009g successively, 22.965g (0.227mol) triethylamine, sealed reactor, air is three times in the usefulness carbon dioxide replacement reactor, charges into the 2.0MPa carbonic acid gas, be warming up to 100 ℃, reaction 3h postcooling filters and obtains product 26.842g to room temperature, and product contains 1-chloro-2-propanol 1.818% by analysis, 2-chloro-1-propanol 0.939%, propylene carbonate 70.561%.Adjacent propylene chlorohydrin transformation efficiency 96.3%, propylene carbonate selectivity 91.3%, propylene carbonate yield 87.9%.
Claims (5)
1. the method for a synthesizing acrylic ester is characterized in that with adjacent propylene chlorohydrin and CO
2Be raw material, under organic bases and inorganic base catalyst effect, at certain reaction condition synthesizing acrylic ester.
2. the method for a kind of synthesizing acrylic ester as claimed in claim 1, it is characterized in that described reaction conditions is, the mol ratio 0.1～100: 1 of carbonic acid gas and adjacent propylene chlorohydrin, the mol ratio 0～1: 1 of inorganic base catalyst and adjacent propylene chlorohydrin, the mol ratio of organic bases and adjacent propylene chlorohydrin is 0.5～5: 1,50～140 ℃ of temperature of reaction, reaction pressure 0.2MPa～10MPa, reaction times 0.5h～20h.
3. the method for a kind of synthesizing acrylic ester as claimed in claim 1 is characterized in that described organic bases is diethylamine, triethylamine, tripropyl amine or Tributylamine.
4. the method for a kind of synthesizing acrylic ester as claimed in claim 1 is characterized in that described inorganic base catalyst is the carbonate of alkali-metal carbonate or alkaline-earth metal.
5. the method for a kind of synthesizing acrylic ester as claimed in claim 2 is characterized in that described alkaline carbonate, alkaline earth metal carbonate are salt of wormwood, yellow soda ash or magnesiumcarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810045551A CN101628908A (en) | 2008-07-14 | 2008-07-14 | Method for synthesizing propylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810045551A CN101628908A (en) | 2008-07-14 | 2008-07-14 | Method for synthesizing propylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101628908A true CN101628908A (en) | 2010-01-20 |
Family
ID=41574205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810045551A Pending CN101628908A (en) | 2008-07-14 | 2008-07-14 | Method for synthesizing propylene carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101628908A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624231A (en) * | 2015-02-12 | 2015-05-20 | 常州大学 | Catalyst for synthesizing propylene carbonate and preparation method of catalyst |
| WO2021083022A1 (en) * | 2019-10-30 | 2021-05-06 | 吴剑华 | Method for producing propylene carbonate or ethylene carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923842A (en) * | 1974-06-28 | 1975-12-02 | Phillips Petroleum Co | Preparation of oxirane compound from the corresponding olefin via the cyclic carbonate ester |
| CN1696123A (en) * | 2005-06-03 | 2005-11-16 | 中国科学院长春应用化学研究所 | Method for synthesizing cyclic carbonate |
| CN1817877A (en) * | 2006-03-17 | 2006-08-16 | 中国科学院过程工程研究所 | Synthesis of cyclic carbonic ester |
-
2008
- 2008-07-14 CN CN200810045551A patent/CN101628908A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923842A (en) * | 1974-06-28 | 1975-12-02 | Phillips Petroleum Co | Preparation of oxirane compound from the corresponding olefin via the cyclic carbonate ester |
| CN1696123A (en) * | 2005-06-03 | 2005-11-16 | 中国科学院长春应用化学研究所 | Method for synthesizing cyclic carbonate |
| CN1817877A (en) * | 2006-03-17 | 2006-08-16 | 中国科学院过程工程研究所 | Synthesis of cyclic carbonic ester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624231A (en) * | 2015-02-12 | 2015-05-20 | 常州大学 | Catalyst for synthesizing propylene carbonate and preparation method of catalyst |
| WO2021083022A1 (en) * | 2019-10-30 | 2021-05-06 | 吴剑华 | Method for producing propylene carbonate or ethylene carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Aresta et al. | Utilisation of CO 2 as a chemical feedstock: opportunities and challenges | |
| CA2756416C (en) | Rendering natural gas as an environmentally carbon dioxide neutral fuel and a regenerative carbon source | |
| CA2756753C (en) | Rendering coal as an environmentally carbon dioxide neutral fuel and a regenerative carbon source | |
| CN101743659A (en) | Process for producing energy preferably in the form of electricity and/or heat using carbon dioxide and methane by catalytic gas reaction and a device for performing the process | |
| US20180362426A1 (en) | Methods and catalysts for the selective production of methanol from carbon dioxide and hydrogen gas for chemical synthesis and gas purification | |
| US20080287555A1 (en) | Novel process and catalyst for carbon dioxide conversion to energy generating products | |
| WO2010011101A3 (en) | Catalyst for synthesizing methanol from synthesis gas and preparation method thereof | |
| WO2013164172A1 (en) | Process for the production of chemical compounds from carbon dioxide | |
| CN101992115B (en) | High selective catalyst | |
| CN102212009B (en) | Process for co-producing dimethyl carbonate and dimethyl ether by urea alcoholysis method | |
| CN103721697B (en) | The catalyst of a kind of synthesizing acrylic ester and preparation method and application | |
| EP3402911B1 (en) | Process for producing oxalic acid | |
| CN101628908A (en) | Method for synthesizing propylene carbonate | |
| KR101545257B1 (en) | Method of preparation of glycerol carbonate by using the zirconium containing metal organic frameworks as catalysts | |
| CN103933961A (en) | Catalyst for synthesizing propylene carbonate as well as preparation method and application of catalyst | |
| CN102127051B (en) | Method for synthetizing cyclic carbonate by using olefin as raw material | |
| CN101934232B (en) | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas | |
| CN110683511A (en) | Methane cracking hydrogen production coupling CO2Reduced chemical looping process | |
| CN101624186B (en) | Method for synthesizing carbon monoxide by selective hydrogenation of carbon dioxide | |
| CN101698670B (en) | Method for preparing phenyl iso-propenyloxysilane | |
| CN104961720A (en) | Preparation method of propylene carbonate | |
| CN103252239B (en) | Catalyst for synthesizing glycerol carbonic, preparation method for catalyst and application of catalyst | |
| CN101314570A (en) | Catalysis synthesis method for paranitrophenetole | |
| CN102020626A (en) | Method for synthesizing propylene carbonate | |
| CN106955715B (en) | A kind of biomass gasifying hydrogen making catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100120 |