CN105348097A - Method for synthesis of dimethyl carbonate - Google Patents
Method for synthesis of dimethyl carbonate Download PDFInfo
- Publication number
- CN105348097A CN105348097A CN201510747870.XA CN201510747870A CN105348097A CN 105348097 A CN105348097 A CN 105348097A CN 201510747870 A CN201510747870 A CN 201510747870A CN 105348097 A CN105348097 A CN 105348097A
- Authority
- CN
- China
- Prior art keywords
- synthesis
- methylcarbonate
- propylene
- catalyst system
- dimethyl 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthesis of dimethyl carbonate. The invention discloses a method for catalytic synthesis of dimethyl carbonate from propylene carbonate and methanol. In the process, the catalyst system has the characteristics of high catalytic activity, easy separation and no inactivation after continuous use. Specifically, the method takes propylene carbonate and methanol as the raw materials to synthesize dimethyl carbonate under the catalyst system, which is a mixture of a monohydric alcohol salt and polyethylene glycol; the synthesis reaction is carried out under normal pressure and a temperature of 25-80DEG C for 10-120min.
Description
Technical field
The present invention relates to a kind of catalyst system used in the process for Material synthesis methylcarbonate with propylene carbonate and methyl alcohol, belong to field of fine chemical.
Background technology
Methylcarbonate (dimethylcarbonate, DMC), that one is nontoxic, environmental-protecting performance is excellent, purposes industrial chemicals comparatively widely, it is a kind of important organic synthesis intermediate, containing functional groups such as carbonyl, methyl and methoxyl groups in its molecular structure, and there is multiple reactivity worth, there is use safety, convenience aborning, pollute less, the easy feature such as transport.Because methylcarbonate toxicity is less, be a kind of development prospect " green " Chemicals widely.The synthetic method of methylcarbonate mainly contains phosgenation, oxidation carbonylation method and ester-interchange method.Although phosgenation operational path is ripe, eliminated gradually owing to using the phosgene of severe toxicity.Relative phosgenation and oxidative carbonylation, ester-interchange method has that condition is relatively gentle, low to equipment corrosion, material toxicity is relatively little and DMC selectivity advantages of higher and being universally accepted.
Compared with heterogeneous catalyst, because homogeneous catalyst catalysis productive rate is high, selectivity is good, technology maturation, therefore, synthesis of dimethyl carbonate via transesterification mainly uses homogeneous catalyst, but it has catalyzer and reaction system and is difficult to be separated with system still liquid polymer phase to the shortcoming such as more.Mainly carry out transesterify Synthesis of dimethyl carbonate with soluble alkali metal oxyhydroxide, alkoxide, alkaline carbonate, oxalate and organic bases as homogeneous catalyst at present.As far back as 1974, US Patent No. 3803201 was with regard to the catalyzer of proposition sodium methylate as the transesterification reaction of cyclic carbonate and methyl alcohol.Until today, sodium methylate remains catalyzer the most frequently used on synthesis of dimethyl carbonate.The alkalescence of sodium methylate is very strong, but has the shortcoming of following two aspects in the industrial production as transesterification catalyst: one is large to equipment corrosion; Two is the acidolysis occurred under sodium methylate is easy to the effect issuing unboiled water solution and carbonic acid gas in atmosphere in the effect of water.
People are seeking more stable catalyzer always and are carrying out alternative sodium methylate.Up to the present, have found the transesterification reaction of many catalyzer for propylene carbonate and methyl alcohol, as the compound containing zirconium, titanium and tin that Japanese Patent JP63041432 reports; Tertiary amine, quaternary ammonium salt, ion exchange resin, load alkali and alkaline earth metal ions salt etc. on silica that US Patent No. 4691041 is reported; The sulphur of the phosphine that US4734518 reports, arsine antimony, divalence and selenium compound; What US5214182 reported contains phosphine polymkeric substance; The rare-earth oxide of US5430170 report; The type A zeolite of the K exchange of US5436362u report; The sodium hydroxide etc. that the loading type alkaline earth metal halide of US5498743 report and Japanese Patent JP2003342209 report.But above-mentioned these catalyzer mentioned will be applied in suitability for industrialized production, a large amount of problems is still had to need to research and solve.
Summary of the invention
The object of this invention is to provide a kind of mistake being Material synthesis methylcarbonate with propylene carbonate and methyl alcohol
The catalytic activity used in journey is high, easily separated and use continuously the process for catalytic synthesis of non-inactivation.
A kind of method for the synthesis of methylcarbonate of the present invention, with propylene carbonate and methyl alcohol for raw material, unitary
The mixture of alkoxide and polyoxyethylene glycol is under catalyst system, in normal pressure, reacts 10 ~ 120min and namely obtain product methyl-carbonate at 25 ~ 80 DEG C.
As a further improvement on the present invention, the unitary alkoxide in catalyst system and the mass ratio of polyoxyethylene glycol are 1:2 ~ 1:8.
As preferred version of the present invention, the unitary alkoxide in catalyst system is sodium methylate.
Improve further as the present invention, the add-on of catalyst system is 1% ~ 10% of oxide spinel propylene and methanol quality sum; The add-on of preferred catalyst systems is 3% ~ 6% of oxide spinel propylene and methanol quality sum.
Adopt technique scheme, with propylene carbonate and methyl alcohol for raw material carries out building-up reactions, obtain methylcarbonate, catalyzer of the present invention is the mixture of sodium methylate and polyoxyethylene glycol, because sodium methylate belongs to monohydroxy-alcohol, and less stable, be easy to inactivation, add polyoxyethylene glycol can with sodium methylate complexing, effectively slow down the inactivation of sodium methylate, thus avoid catalyst deactivation and slagging scorification to such an extent as to the problem of blocking pipe.
In sum, with use merely compared with monohydroxy-alcohol salt in prior art, the catalyst system adopted in technical scheme of the present invention have catalytic activity high, use non-inactivation continuously, can Reusability, not to be soluble in methylcarbonate and than being easier to the features such as separation, not only solve alkaline residue blocking in production and produce the problem of pipeline, further reduces production cost, optimize the production technique of methylcarbonate.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
embodiment 1
Oxide spinel propylene and methyl alcohol are added in the there-necked flask of 1000ml according to the ratio of 1:5, adds catalyzer by 5% of raw material total amount, namely add propylene carbonate 100g, methyl alcohol 500g, sodium methylate 30g, PEG120g, mixing, be placed in 1000ml heating jacket to heat, utilize reactive distillation column to carry out building-up reactions, reflux when having cut to occur 20min, then discharging, when still temperature is 78 DEG C, stopped reaction.Top sample component is methyl alcohol 68.6%, and methylcarbonate is 31.37%; Still sample component is methyl alcohol is 46.85%, and methylcarbonate is 0.63%, and propylene glycol is 49.13%, and propylene carbonate is 3.84%.
Distilled by reactor liquid in embodiment 1, reclaim catalyst system, carry out recycling experiment under identical experiment condition, after 7 round-robin tests, top sample component is methyl alcohol 69.52%, and methylcarbonate is 30.47%; Still sample component is methyl alcohol is 48.44%, and methylcarbonate is 0.42%, and propylene glycol is 47.12%, and propylene carbonate is 4%.
embodiment 2
Get sodium methylate 20g, polyoxyethylene glycol 100g, other conditions with embodiment 1, when still temperature is 80 DEG C, stopped reaction.Top sample component is methyl alcohol 76.42%, and methylcarbonate is 23.57%; Still sample component is methyl alcohol is 45.5%, and methylcarbonate is 0.27%, and propylene glycol is 50.13%, and propylene carbonate is 2.96%.
embodiment 3
Get sodium methylate 25g, polyoxyethylene glycol 125g, other conditions with embodiment 1, when still temperature is 90 DEG C, stopped reaction.Top sample component is methyl alcohol 70.12%, and methylcarbonate is 29.87%; Still sample component is methyl alcohol is 40.95%, and methylcarbonate is 0.36%, and propylene glycol is 56.92%, and propylene carbonate is 1.66%.
embodiment 4
Get sodium methylate 24g, polyoxyethylene glycol 100g, other conditions with embodiment 1, when still temperature is 80 DEG C, stopped reaction.Top sample component is methyl alcohol 68.21%, and methylcarbonate is 31.87%; Still sample component is methyl alcohol is 43.59%, and methylcarbonate is 0.29%, and propylene glycol is 54.52%, and propylene carbonate is 1.6%.
embodiment 5
Get sodium methylate 20g, polyoxyethylene glycol 120g, other conditions with embodiment 1, when still temperature is 100 DEG C, stopped reaction.Top sample component is methyl alcohol 83.39%, and methylcarbonate is 19.07%; Still sample component is methyl alcohol is 49.38%, and methylcarbonate is 0.34%, and propylene glycol is 47.83%, and propylene carbonate is 2.25%.
Claims (5)
1. for the synthesis of a method for methylcarbonate, with propylene carbonate and methyl alcohol for raw material, in catalyst body
The lower Synthesis of dimethyl carbonate of system, is characterized in that described catalyst system is the mixture of unitary alkoxide and polyoxyethylene glycol; Described building-up reactions, in normal pressure, reacts 10 ~ 120min at 25 ~ 80 DEG C.
2. a kind of method for the synthesis of methylcarbonate according to claim 1, is characterized in that described catalysis
Unitary alkoxide in system and the mass ratio of polyoxyethylene glycol are 1:2 ~ 1:8.
3. a kind of method for the synthesis of methylcarbonate according to claim 1, urges described in it is characterized in that
Unitary alkoxide in change system is sodium methylate.
4. a kind of method for the synthesis of methylcarbonate according to claim 1,2 or 3, its feature exists
Add-on in described catalyst system is 1% ~ 10% of oxide spinel propylene and methanol quality sum.
5. a kind of method for the synthesis of methylcarbonate according to claim 1,2 or 3, its feature exists
Add-on in described catalyst system is 3% ~ 6% of oxide spinel propylene and methanol quality sum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510747870.XA CN105348097A (en) | 2015-11-06 | 2015-11-06 | Method for synthesis of dimethyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510747870.XA CN105348097A (en) | 2015-11-06 | 2015-11-06 | Method for synthesis of dimethyl carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105348097A true CN105348097A (en) | 2016-02-24 |
Family
ID=55324185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510747870.XA Pending CN105348097A (en) | 2015-11-06 | 2015-11-06 | Method for synthesis of dimethyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105348097A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569807A (en) * | 2003-07-22 | 2005-01-26 | 中国寰球工程公司 | Process for combined production of methyl carbonate and propylene glycol |
-
2015
- 2015-11-06 CN CN201510747870.XA patent/CN105348097A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569807A (en) * | 2003-07-22 | 2005-01-26 | 中国寰球工程公司 | Process for combined production of methyl carbonate and propylene glycol |
Non-Patent Citations (3)
| Title |
|---|
| 于丽等: ""PEG对催化剂活性影响的研究"", 《广州化工》 * |
| 王桂珍等: ""酯交换法合成碳酸二甲酯工艺探讨"", 《广州化工》 * |
| 王玉兰等: "酯交换法合成碳酸二甲酯催化剂评述", 《精细与专用化学品》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | A review on transesterification of propylene carbonate and methanol for dimethyl carbonate synthesis | |
| CN111423326B (en) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method | |
| CN100395019C (en) | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application | |
| CN102126956B (en) | Catalytic method for preparing dimethyl cabonate along with ethylene glycol | |
| EP3950660A1 (en) | Method for preparing dimethyl carbonate | |
| CN101613259B (en) | Method for preparing electronic grade propylene glycol monomethyl ether | |
| CN100388978C (en) | Complex catalyst for synthesizing carbonate ester by using homogeneous oxidation carbonylation of alcohol (S), its prepn. tech. and use | |
| EP3643698A1 (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN101412674A (en) | Method for synthesizing diphenyl carbonate by heterogeneous interesterification | |
| CN113929813B (en) | Multifunctional metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate | |
| CN102464587A (en) | Method for preparing small molecular carbonated dialkyl ester through ester exchange | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN110078702A (en) | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate | |
| CN106084197A (en) | A kind of preparation method of narrow ditribution polyethers | |
| CN113185407A (en) | Method for synthesizing dimethyl carbonate through ester exchange reaction | |
| CN105348097A (en) | Method for synthesis of dimethyl carbonate | |
| CN104043480A (en) | Ionic liquid catalyst and dimethyl carbonate synthesis method | |
| CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst | |
| CN104072376B (en) | A kind of by CO 2with the method for methanol-fueled CLC methylcarbonate | |
| US10696619B2 (en) | Method for preparing dialkyl carbonate | |
| CN111701618A (en) | Ionic liquid catalyst and preparation method and application thereof | |
| CN110922577A (en) | Preparation method of polyether carbonate polyol | |
| CN108727193B (en) | Preparation method of diphenyl carbonate compound | |
| CN109603802A (en) | For by urea and the composite catalyst of methanol-fueled CLC dimethyl carbonate and its preparation method and application | |
| EP2660237B1 (en) | Tertiary amine preparation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160224 |