CN1204109C - Method for synthesizing methyl carbonate by using urea and carbinol - Google Patents
Method for synthesizing methyl carbonate by using urea and carbinol Download PDFInfo
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- CN1204109C CN1204109C CN 01130478 CN01130478A CN1204109C CN 1204109 C CN1204109 C CN 1204109C CN 01130478 CN01130478 CN 01130478 CN 01130478 A CN01130478 A CN 01130478A CN 1204109 C CN1204109 C CN 1204109C
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- CN
- China
- Prior art keywords
- urea
- reaction
- methyl alcohol
- temperature
- primary catalysts
- 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.)
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 83
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000004202 carbamide Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 7
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 title abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical group 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000007039 two-step reaction Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- LHTZCYHRTBUGOI-UHFFFAOYSA-N 3-n,4-n-dimethylpyridine-3,4-diamine Chemical compound CNC1=CC=NC=C1NC LHTZCYHRTBUGOI-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing methyl carbonate by using urea and methanol, which is characterized in that the urea and the methanol are put into a reaction kettle, and a main catalyst or a main catalyst and an auxiliary catalyst are added into the reaction kettle; the temperature is raised to 120 to 190 DEG C, and the reaction is carried out for 1 to 4 hours; then, the temperature is raised to 190 to 250 DEG C, and the reaction is carried out for 4 to 18 hours; in addition, the temperature can also be raised to 190 to 250 DEG C for one time, and the reaction is carried out for 4 to 18 hours; after the reaction temperature is reduced to room temperature, a product is prepared by separation, wherein the molar ratio of the urea to the methanol is 1: 2 to 10, and the weight ratio of the main catalyst to the auxiliary catalyst to the urea is 1: 0 to 5: 1 to 20. The present invention has the advantages of low cost of raw materials, secure reaction processes, simple technology, easy operation, etc.
Description
Technical field:
Methylcarbonate (Dimethyl carbonate is called for short DMC) is a kind of environmental friendliness chemical products, and its application more and more is subject to people's attention.It can replace traditional phosgene, methyl-sulfate to produce polycarbonate, isocyanic ester etc., makes quality product raising, production process not have burn into simplified equipment, public hazards minimizing; It can be used for synthesizing the specialty chemicals of high added value, is applied to medicine, agricultural chemicals, lubricated wet goods field; It is the solvent of excellent property, is used for the electrolytic solution of battery; It can also be used for boosting of octane rating as the additive of gasoline.
Use phosgenation to synthesize DMC the earliest, but since phosgene hypertoxicity is arranged and, is eliminated gradually the severe corrosive of equipment; That oxidative carbonylation of methanol method exists is big to equipment corrosion, catalyst life weak point, unstripped gas price height, CO have problems such as toxicity, and development is restricted; The raw material oxyethane that ester-interchange method is used or the price of propylene oxide are expensive and inflammable and explosive, and its development is subjected to the potential influence.
Summary of the invention:
It is low to the purpose of this invention is to provide a kind of cost, the method by urea and methyl alcohol Synthesis of dimethyl carbonate of reaction process safety.
The directly synthetic DMC of urea and methyl alcohol is synthetic DMC of two steps in the presence of catalyzer with urea and methyl alcohol, and reaction formula is expressed as follows:
Two-step reaction all is little thermo-negative reaction, and high temperature is beneficial to reaction, and wherein the first step reaction is easier to, and (140～190 ℃) just can react under relatively low temperature, and second step then needed higher temperature (more than 190 ℃).Two-step reaction all produces gas NH3, and two-step reaction all needs catalyzer, and is available with a kind of catalyzer.Because the raw material that uses is urea, thereby makes cost of the present invention low, reaction process safety.
Synthetic method of the present invention is: urea and methyl alcohol are put into reactor, add Primary Catalysts or Primary Catalysts and promotor, be warmed up to 120-190 ℃, reacted 1-4 hour, and be warming up to 190-250 ℃ again, reacted 4-18 hour, or once be warmed up to 190-250 ℃, reacted 4-18 hour, temperature of reaction is reduced to room temperature, separates to make product;
Wherein the ratio of each component is: urea and methyl alcohol mol ratio are urea: methyl alcohol=1: 2-10
The weight ratio of Primary Catalysts, promotor and urea is a Primary Catalysts: promotor: urea=1: 0-5: 1-20.
Aforesaid Primary Catalysts is organometallic compound C
4H
9Li, R
2SnX
2, R
2SnO; Wherein X represents Cl, R ' O, R ' COO, and it is the alkyl of 2-12 that R, R ' represent carbon number.
Aforesaid promotor is Lewis Acids and Bases ph
3P, BF
3, 4-dimethylamino pyridine etc.
The analytical procedure of product of the present invention is: product of distillation is produced GC-920 with sea, Shanghai glad chromatogram company limited and is analyzed.Chromatographic condition is as follows: chromatographic column: external diameter 3mm, the stainless steel column of long 2m; Monomer: GDX-203 (60～80 order): detector: thermal conductivity cell; Sampler temperature: 220 ℃; Column and programmed temperature: 100 ℃ of initial temperature, 7 minutes time; 20 ℃ of heat-up rate per minutes; Temperature is 200 ℃ eventually, 20 minutes time; Sample size: 1 μ L.
The present invention compared with prior art has following advantage:
(1) raw materials cost is low.
(2) reaction process safety.
(3) technology is simple, and is easy to operate.
Embodiment:
Embodiment 1:
Take by weighing urea 15 grams, measure 40 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is 4: 1, takes by weighing tBu again
2SnO, ph
3Each 4 gram of P, the autoclave magneton of putting into 75 milliliters stirs, and is heated rapidly to 140 ℃ from room temperature, keeps reheat to 190 ℃ reaction 9 hours 3 hours.Reaction stops the cooling back and goes out volatile component with air distillation, steams the productive rate (is standard substance with urea) that thing calculates DMC with gas chromatographic analysis, and analytical results is listed in table 1.
Embodiment 2:
Take by weighing urea 7.5 grams, measure 30 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is about 6: 1, takes by weighing tBu again
4Sn 4 gram, the autoclave magneton of putting into 75 milliliters stirs, and is heated rapidly to 150 ℃ from room temperature, keeps 4 hours, and reheat to 215 ℃ kept 6 hours.Reaction stops the cooling back and goes out volatile component with air distillation, steams the productive rate (is standard substance with urea) that thing calculates DMC with gas chromatographic analysis, and analytical results is listed in table 1.
Embodiment 3:
Take by weighing urea 15 grams, measure 20 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is about 2: 1, takes by weighing tBu again
2Sn (OC
2H
5)
20.5 gram, 4-dimethylamino pyridine 4 gram, the autoclave magneton of putting into 75 milliliters stirs, and from 140 ℃ of room temperature rapid heating, keeps 2 hours, and reheat to 210 ℃ kept 8 hours.Reaction stops the cooling back and goes out volatile component with air distillation, steams the productive rate (is standard substance with urea) that thing calculates DMC with gas chromatographic analysis, and analytical results is listed in table 1.
Embodiment 4:
Take by weighing urea 7.5 grams, measure 40 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is 8: 1, takes by weighing tBu again
2SnO 4 grams, BF
3O (C
2H
5)
22 grams, the autoclave magneton of putting into 75 milliliters stirs, and is heated rapidly to 220 ℃ of reactions 10 hours from room temperature.Reaction stops the cooling back and goes out volatile component with air distillation, steams the productive rate (is standard substance with urea) that thing calculates DMC with gas chromatographic analysis, and analytical results is listed in table 1.
Embodiment 5:
Take by weighing urea 7.5 grams, measure 40 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is about 8: 1, takes by weighing tBu again
2Sn (OC
2H
5)
20.5 gram, ph
3The P2 gram, the autoclave magneton of putting into 75 milliliters stirs, and is heated rapidly to 235 ℃ from room temperature, keeps 15 hours.Reaction stops the cooling back and goes out volatile component with air distillation, steams the productive rate (is standard substance with urea) that thing calculates DMC with gas chromatographic analysis, and analytical results is listed in table 1.
Embodiment 6:
Take by weighing urea 7.5 grams, measure 30 milliliters of methyl alcohol, the methyl alcohol urea mol ratio is about 6: 1, takes by weighing C again
4H
9Li, ph
3Each 4 gram of P, the autoclave magneton of putting into 75 milliliters stirs, and is heated rapidly to 215 ℃ from room temperature, keeps 9 hours.Reaction stops the cooling back and goes out volatile component with air distillation, steams thing with gas chromatographic analysis and calculates DMC (is standard substance with urea), and analytical results is listed in table 1.
Table 1
Embodiment cold zone low temperature time high-temperature zone high-temperature time DMC productive rate
(℃) (h) (℃) (h) (％)
1 140 3 190 9 3.96
2 150 4 215 6 13.46
3 140 2 210 8 2.24
4 - - 220 10 20.46
5 - - 235 15 24.42
6 - - 215 9 17.82
Annotate: conversion rate of urea is about 80%, and intermediate product Urethylane and methylcarbonate selectivity are more than 95%.
Claims (1)
1. method with urea and methyl alcohol Synthesis of dimethyl carbonate, it is characterized in that described synthetic method is: urea and methyl alcohol are put into reactor, add Primary Catalysts or Primary Catalysts and promotor, be warmed up to 120-190 ℃, reacted 1-4 hour, be warming up to 190-250 ℃ again, reacted 4-18 hour, or once be warmed up to 190-250 ℃, reacted 4-18 hour, temperature of reaction is reduced to room temperature, separates to make product;
Wherein the ratio of each component is: urea and methyl alcohol mol ratio are urea: methyl alcohol=1: 2-10
The weight ratio of Primary Catalysts, promotor and urea is a Primary Catalysts: promotor: urea=1: 0-5: 1-20;
Described Primary Catalysts is organometallic compound C
4H
9Li, R
2SnX
2, R
2SnO; Wherein X represents Cl, R ' O, R ' COO, and it is the alkyl of 2-12 that R, R ' represent carbon number;
Described promotor is Lewis Acids and Bases ph
3P, BF
3Or 4-dimethylamino pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130478 CN1204109C (en) | 2001-11-23 | 2001-11-23 | Method for synthesizing methyl carbonate by using urea and carbinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130478 CN1204109C (en) | 2001-11-23 | 2001-11-23 | Method for synthesizing methyl carbonate by using urea and carbinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1431190A CN1431190A (en) | 2003-07-23 |
| CN1204109C true CN1204109C (en) | 2005-06-01 |
Family
ID=4669922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01130478 Expired - Lifetime CN1204109C (en) | 2001-11-23 | 2001-11-23 | Method for synthesizing methyl carbonate by using urea and carbinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204109C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009065352A1 (en) * | 2007-11-16 | 2009-05-28 | Accelergy Shanghai R & D Center Co., Ltd. | Integrated coal-to-liquids process |
| CN103623802A (en) * | 2012-08-27 | 2014-03-12 | 亚申科技研发中心（上海）有限公司 | Method for simultaneously producing dimethyl carbonate and dimethyl ether through urea alcoholysis process, catalyst used thereby, and preparation method of catalyst |
| BR112016005683B1 (en) * | 2013-09-26 | 2021-06-22 | Asahi Kasei Kabushiki Kaisha | ALKYL TIN COMPOUND, COMPOSITION, CATALYST, AND METHOD FOR PRODUCING A CARBON ACID ESTER |
| CN106478421B (en) | 2015-08-31 | 2019-09-13 | 亚申科技(浙江)有限公司 | DMC Processes |
| CN108358786B (en) * | 2018-02-01 | 2021-07-13 | 雷永诚 | Method for preparing dialkyl carbonate by urea alcoholysis |
-
2001
- 2001-11-23 CN CN 01130478 patent/CN1204109C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1431190A (en) | 2003-07-23 |
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| C14 | Grant of patent or utility model | ||
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Owner name: CHINA PETROLEUM CO., LTD.; SHANXI INST. OF COAL C Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20080919 |
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| TR01 | Transfer of patent right |
Effective date of registration: 20080919 Address after: Postal code of intercontinental 16, Andry Road, Dongcheng District, Beijing: 100011 Co-patentee after: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: PetroChina Company Limited Address before: 165 mailbox, Taiyuan City, Shanxi Province: 030001 Patentee before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
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Granted publication date: 20050601 |