CN1569809A - Process for synthesizing methyl carbonate by alcoholysis of methanol and urea - Google Patents
Process for synthesizing methyl carbonate by alcoholysis of methanol and urea Download PDFInfo
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- CN1569809A CN1569809A CN 200410018111 CN200410018111A CN1569809A CN 1569809 A CN1569809 A CN 1569809A CN 200410018111 CN200410018111 CN 200410018111 CN 200410018111 A CN200410018111 A CN 200410018111A CN 1569809 A CN1569809 A CN 1569809A
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- urea
- catalyzer
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- methyl alcohol
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Abstract
The invention discloses a process for synthesizing methyl carbonate from alcoholysis of methanol and urea in a high pressure reactor, wherein the catalyst is a amine salt type ionic liquid having a molecular formula of R1R2R3NHX-MaXb, the raw material methanol and urea are subject to alcoholysis reaction and methyl carbonate is synthesized in one step.
Description
Technical field
The present invention relates to a kind of method, belong to organic chemistry synthetic technical field by methyl alcohol and urea alcoholysis Synthesis of dimethyl carbonate.
Background technology
Methylcarbonate (DMC) is the important carbonyl and the methylating reagent that substitute the methyl-sulfate photoreactive gas of severe toxicity, is the intermediate that is used for synthesizing high carbon chain carbonic ether and carbamate that it also can be used on improves its octane value in the fuel.Methylcarbonate normally carries out oxidation carbonylation with compound for catalysis carbon monoxide, oxygen and the methyl alcohol of copper and palladium and makes.This kind method exists that raw materials cost height, equipment have high input, equipment corrosion is serious and shortcomings such as the toxicity of carbon monoxide and explosion hazard.In recent years, people begin that carbonic acid gas is made the raw material Synthesis of dimethyl carbonate and attempt.Many investigators use organo-tin compound, ZrO
2, H
3PO
4/ ZrO
2And CeO
2-ZrO
2, K
2CO
3And CH
3Catalyst Synthesis of dimethyl carbonate such as I are studied.But,, the chance water of the inertia of carbonic acid gas and catalyzer make the productive rate of conversion of methanol and product also very low because taking off to live by methyl alcohol and the direct Synthesis of dimethyl carbonate of carbonic acid gas.
The operational path of methyl alcohol and alcoholysis of urea catalytic synthesizing dimethyl carbonate has the advantage that raw material is inexpensive, be easy to get, particularly anhydrous generation in the reaction, avoided aforementioned several non-phosgene route need handle the separation problem of methyl alcohol-methylcarbonate-water complex system, especially attractive to existing fertilizer plant exploitation derived product.Current, the catalyzer that is used for this reaction system is organo-tin compound or alkali metal compound mostly.Chao etc. adopt catalyzer such as alkali metal compound or quaternary ammonium compounds, and with carbamate or urea and methyl alcohol reaction Synthesis of dimethyl carbonate, but yield is very low.It is catalyzer under 180 ℃, 2Mpa that the grand people of Teng Jing waits then with basic metal or its compound, with urea and methyl alcohol segmentation reaction, prepares methylcarbonate by the mode that steams product continuously.When making catalyzer with LiH, the methylcarbonate yield is 36.4%.Saleh etc. are catalyzer with Dibutyltin oxide, dibutyl dimethoxy tin, dibutyl methoxyl group isocyanate group tin etc., with Urethylane or urea and methyl alcohol reaction, by steaming the product methylcarbonate continuously, obtain higher yields and selectivity.(application number: 01130478.2) reported a kind of synthetic method of methylcarbonate, adopt organotin or organolithium compound is catalyzer to Chinese patent, and triphenyl phosphorus, boron trifluoride or 4-dimethylamino pyridine are promotor.By two-stage reaction, 120～190 ℃ 1～4 hour; 190～250 ℃ were reacted 4～18 hours, and the productive rate of product can reach 24.42%.(application number: what 01131680.2) reported is that carbonate or oxide compound with basic metal and alkaline-earth metal is catalyzer to Chinese patent, two-stage reaction, 120～180 ℃, 2～10 hours; 180～240 ℃, 2～20 hours.The productive rate of product is 26.56%.The Synthesis of dimethyl carbonate of Chinese patent CN 1421430A report is the device that adopts continuously feeding, the oxide compound of using basic metal and alkaline-earth metal is a catalyzer, 150～250 ℃ of temperature of reaction, reaction pressure are 0.1～10MPa, temperature is that 70～200 ℃, stripping section temperature are 70～200 ℃, the rectifying section temperature above the reactor is 70～200 ℃ at the bottom of the still below the reactor, and the productive rate of product is 40～49.7%.Another piece Chinese patent CN1416949A report is the mixed oxide ZnO-La for preparing by co-deposition method with methyl alcohol and the employed catalyzer of urea synthesis methylcarbonate
2O
3, design one can in time remove the special device of by product ammonia in reactor, is reflected at 180～250 ℃, and it is that 1.8MPa constantly emits ammonia that back pressure valve is constantly regulated pressure, reaction 6h, the productive rate of product is 38.5～49.7%.But productive rate had only about 22% when above-mentioned system was carried out in batch still.
Summary of the invention
The technical problem to be solved in the present invention is to release a kind of method by methyl alcohol and urea alcoholysis Synthesis of dimethyl carbonate, this method has following advantage: reaction conditions is gentle, temperature of reaction is 130～180 ℃, reaction process is simpler, and the applying high voltage reactor can be finished the synthetic of methylcarbonate through single step reaction.Its productive rate is 25～30%, and selectivity is 100%.
The present invention is resolved above-mentioned technical problem by following technical proposal: in high-pressure reactor, catalyzer: general molecular formula is R
1R
2R
3NHX-M
aX
bThe ion liquid catalysis of amine salt type under, material benzenemethanol and urea is through alcoholysis reaction, the one-step synthesis methylcarbonate.
Now describe technical scheme of the present invention in detail.A kind of method by methyl alcohol and urea alcoholysis Synthesis of dimethyl carbonate is a raw material with methyl alcohol and urea, it is characterized in that, the employing general molecular formula is R
1R
2R
3NHX-M
aX
bAmine salt type ionic liquid as catalyzer, R wherein
4, R
2, R
3Represent C respectively
2～C
10Alkyl or aryl, HX are a kind of mineral acid or organic acid, and wherein X is an acid group, M
aX
bBe a kind of inorganic or organic acid salt, wherein M is a metal ion, and a, b are 1～3, the catalytic synthesis process is as follows: in the stainless steel high-pressure reactor, the methyl alcohol that adds 100 parts of weight, the urea of 1～16.5 part of weight, the catalyzer of 1～40 part of weight, 130～180 ℃ and stir under, reacted 4～8 hours, then, with reaction mixture cooling, sedimentation, isolate catalyzer, obtain the product of 0.3～6.5 part of weight, methylcarbonate.
Reaction mixture is analyzed with GC and GC-MS, and productive rate is 25～30%, and selectivity is 100%.
Technical solution of the present invention is further characterized in that the add-on of catalyzer is 3～10 parts of weight, and the add-on of urea is 1～8 part of weight.
Being further characterized in that of technical scheme of the present invention, HX is following mineral acid: H
2SO
4, HCl, HNO
3, HF, HBr, HBF
4, HPF
6One of; M
aX
bBe following inorganic acid salt: M
a(SO
4)
b, M
aCl
b, M
a(NO
3)
b, M
aF
b, M
aBr
b, M
a(BF
4)
bAnd M
a(PF
6)
bOne of, wherein M is K
+, Na
+, NH
4 +, Cu
2+, Ba
2+, Al
3+, Zn
2+, Fe
3+
Being further characterized in that of technical scheme of the present invention, HX is following organic acid: R
1COOH, R
1Be C
1～C
4Stable hydrocarbon or unsaturated alkyl, CF
3One of COOH, oxalic acid, oxysuccinic acid and tartrate; M
aX
bBe following organic acid salt M
a(R
1COO)
b, M
a(CF
3COO)
b, one of oxalate, malate, tartrate, wherein M is K
+, Na
+, NH
4 +, Cu
2+, Ba
2+, Al
3+, Zn
2+, Fe
3+
Compare with background technology, the present invention has following outstanding effect:
1. reaction conditions gentleness, temperature of reaction is 130～180 ℃.
2. adopt the intermittent type single step reaction, reaction process is simple, processing ease, and the investment of equipment is little.
3. reaction raw materials is easy to get, and production cost is low.
4. the selectivity height of methylcarbonate is 100%, and productive rate is 25～30%.
5. the reaction times weak point was generally 4～6 hours, and efficient is higher.
6. catalyzer was easier to separating of reaction mixture.
Embodiment
[embodiment one]
Add 100g methyl alcohol, 3.4g catalyzer and 8.5g urea in high-pressure reactor, catalyzer is Et
3NHCl-AlCl
3, 120 ℃ and stir under, react 6 hours, cooling distills out the reaction liquid form mixt, must 3.33g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 25.96%.
[embodiment two]
Add 100 methyl alcohol, 7.0g catalyzer and 16.5g urea in high-pressure reactor, catalyzer is (ph) Et
2NHCl-FeCl
3, 150 ℃ and stir under, react 4 hours, cooling distills out the reaction liquid form mixt, must 6.22g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 25.15%.
[embodiment three]
Add 100g methyl alcohol, 1.7g catalyzer and 5.0g urea in high-pressure reactor, catalyzer is OcEt
2NHOOCCH
3-CuCl
2, wherein 0c represents octyl group, 180 ℃ and stir under, react 4 hours, cooling distills out the reaction liquid form mixt, must 1.93g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 25.74%.
[embodiment four]
Add 100g methyl alcohol, 5.0g catalyzer and 2.0g urea in high-pressure reactor, catalyzer is Et
3NHOOCC
3H
7-ZnSO
4, 180 ℃ and stir under, react 6 hours, cooling distills out the reaction liquid form mixt, must 0.81g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 26.84%.
[embodiment five]
Add 100g methyl alcohol, 12.0g catalyzer and 11.5g urea in high-pressure reactor, catalyzer is Et
3NHCl-NH
4NO
3, 170 ℃ and stir under, react 4 hours, cooling distills out the reaction liquid form mixt, must 4.73g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 27.44%.
[embodiment six]
Add 100 methyl alcohol, 2g catalyzer and 10.2g urea in high-pressure reactor, catalyzer is Et
3NHCl-BaBr
2, 180 ℃ and stir under, react 8 hours, cooling distills out the reaction liquid form mixt, must 4.33g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 28.33%.
[embodiment seven]
Add 100g methyl alcohol, 3g catalyzer and 3.5g urea in high-pressure reactor, catalyzer is Et
3NHCl-KBF
4, 160 ℃ and stir under, react 5 hours, cooling distills out the reaction liquid form mixt, must 1.42g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 27.10%.
[embodiment eight]
Add 100g methyl alcohol, 5.0g catalyzer and 1.0g urea in high-pressure reactor, catalyzer is Et
3NHCl-Na (OOCC
2H
5)
3, 180 ℃ and stir under, react 6 hours, cooling distills out the reaction liquid form mixt, must 0.42g product methylcarbonate.
Analyze through GC, with ureometer, the productive rate of methylcarbonate is 27.77%.
Claims (4)
1. the method by methyl alcohol and urea alcohol Synthesis of dimethyl carbonate is a raw material with methyl alcohol and urea, it is characterized in that the employing general molecular formula is R
1R
2R
3NHX-M
aX
bAmine salt type ionic liquid as catalyzer, R wherein
1, R
2, R
3Represent C respectively
2～C
10Alkyl or aryl, HX are a kind of mineral acid or organic acid, and wherein X is an acid group, M
aX
bBe a kind of inorganic or organic acid salt, wherein M is a metal ion, and a, b are 1～3, the catalytic synthesis process is as follows: in the stainless steel autoclave, the methyl alcohol that adds 100 parts of weight, the urea of 1～16.5 part of weight, the catalyzer of 1～40 part of weight, 120～180 ℃ and stir under, reacted 4～8 hours, then, with reaction mixture cooling, sedimentation, isolate catalyzer, obtain the product of 0.3～6.5 part of weight, methylcarbonate.
2. the method for Synthesis of dimethyl carbonate according to claim 1 is characterized in that, the add-on of catalyzer is 3～10 parts of weight, and the add-on of urea is 1～8 part of weight.
3. the method for Synthesis of dimethyl carbonate according to claim 1 and 2 is characterized in that, HX is following mineral acid: H
2SO
4, HCl, HNO
3, HF, HBr, HBF
4, HPF
6One of; M
aX
bBe following inorganic acid salt: M
a(SO
4)
b, M
aCl
b, M
a(NO
3)
b, M
aF
b, M
aBr
b, M
a(BF
4)
bAnd M
a(PF
6)
bOne of, wherein M is K
+, Na
+, NH
4 +, Ca
2+, Ba
2+, Al
3+, Zn
2+, Fe
3+
4. the method for Synthesis of dimethyl carbonate according to claim 1 and 2 is characterized in that, HX is following organic acid: R
1COOH, R
1Be C
1～C
4Stable hydrocarbon or unsaturated alkyl, CF
3One of COOH, oxalic acid, oxysuccinic acid and tartrate; M
aX
bBe following organic acid salt M
a(R
1COO)
b, M
a(CF
3COO)
b, one of oxalate, malate, tartrate, wherein M is K
+, Na
+, NH
4 +, Ca
2+, Ba
2+, Al
3+, Zn
2+, Fe
3+
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018111 CN1280254C (en) | 2004-05-08 | 2004-05-08 | Process for synthesizing methyl carbonate by alcoholysis of methanol and urea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018111 CN1280254C (en) | 2004-05-08 | 2004-05-08 | Process for synthesizing methyl carbonate by alcoholysis of methanol and urea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569809A true CN1569809A (en) | 2005-01-26 |
| CN1280254C CN1280254C (en) | 2006-10-18 |
Family
ID=34479352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410018111 Expired - Fee Related CN1280254C (en) | 2004-05-08 | 2004-05-08 | Process for synthesizing methyl carbonate by alcoholysis of methanol and urea |
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|---|---|
| CN (1) | CN1280254C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962602B (en) * | 2006-11-22 | 2010-05-12 | 陕西师范大学 | Process for preparing dimethyl carbonate by reacting methanol, carbon monoxide and oxygen |
| WO2011013880A2 (en) * | 2009-07-31 | 2011-02-03 | Korea Research Institute Of Chemical Technology | Method for preparing dialkyl carbonate |
| CN104418732A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Method of synthesizing dimethyl carbonate by use of reaction of urea and methanol |
| EP3135662A1 (en) | 2015-08-31 | 2017-03-01 | Yashentech Corporation | Process for producing dimethyl carbonate |
| CN115007206A (en) * | 2022-07-01 | 2022-09-06 | 中国科学院山西煤炭化学研究所 | Ionic liquid catalyst for catalyzing alcoholysis of urea and methanol, preparation method and application thereof |
-
2004
- 2004-05-08 CN CN 200410018111 patent/CN1280254C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962602B (en) * | 2006-11-22 | 2010-05-12 | 陕西师范大学 | Process for preparing dimethyl carbonate by reacting methanol, carbon monoxide and oxygen |
| WO2011013880A2 (en) * | 2009-07-31 | 2011-02-03 | Korea Research Institute Of Chemical Technology | Method for preparing dialkyl carbonate |
| WO2011013880A3 (en) * | 2009-07-31 | 2011-09-29 | Korea Research Institute Of Chemical Technology | Method for preparing dialkyl carbonate |
| CN102471221A (en) * | 2009-07-31 | 2012-05-23 | 浦项产业科学研究院 | Method for preparing dialkyl carbonate |
| US8629295B2 (en) | 2009-07-31 | 2014-01-14 | Research Institute Of Industrial Science & Technology | Method for preparing dialkyl carbonate |
| CN102471221B (en) * | 2009-07-31 | 2014-12-03 | 浦项产业科学研究院 | Method for preparing dialkyl carbonate |
| CN104418732A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Method of synthesizing dimethyl carbonate by use of reaction of urea and methanol |
| CN104418732B (en) * | 2013-09-03 | 2016-09-28 | 中国科学院化学研究所 | A kind of method that carbamide and methanol are synthesized dimethyl carbonate |
| EP3135662A1 (en) | 2015-08-31 | 2017-03-01 | Yashentech Corporation | Process for producing dimethyl carbonate |
| CN115007206A (en) * | 2022-07-01 | 2022-09-06 | 中国科学院山西煤炭化学研究所 | Ionic liquid catalyst for catalyzing alcoholysis of urea and methanol, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280254C (en) | 2006-10-18 |
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Granted publication date: 20061018 Termination date: 20110508 |