CN1298696C - Process for synthesizing methyl carbonate by alcoholysis of urea with aliphatic diol as cyclic agent - Google Patents
Process for synthesizing methyl carbonate by alcoholysis of urea with aliphatic diol as cyclic agent Download PDFInfo
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- CN1298696C CN1298696C CNB2004100191753A CN200410019175A CN1298696C CN 1298696 C CN1298696 C CN 1298696C CN B2004100191753 A CNB2004100191753 A CN B2004100191753A CN 200410019175 A CN200410019175 A CN 200410019175A CN 1298696 C CN1298696 C CN 1298696C
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Abstract
The present invention discloses a method for synthesizing methyl carbonate by alcoholysis of urea by using aliphatic dihydric alcohol as a cyclic agent. The reaction process comprises the following two steps: in a first step, the urea and the aliphatic dihydric alcohol (ethylene glycol or 1, 2-propanediol) react to synthesize ethylene carbonate or propylene carbonate under the reaction conditions that the temperature is from 100 to 200 DEG C and the pressure intensity is from 0 to 0.5MPa, or 0.5 to 5 mL/min of nitrogen is guided into a reaction system; in a second step, the ethylene carbonate or the propylene carbonate and methanol ester are exchanged to synthesize the methyl carbonate under the reaction conditions that the temperature is from 70 to 160 DEG C, and the pressure intensity is from 0 to 2MPa. Two components or more than two components of compound metallic oxides, such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, lead oxide, copper oxide, zinc oxide, titanium oxide, zirconium oxide, molybdenum oxide, iron oxide, cobalt oxide, nickel oxide and lanthanum oxide, are used as catalysts. The present invention has the advantages that the reaction conditions are moderate, reaction is carried out at ordinary pressure, a product which is synthesized by the present invention is easy to recover and regenerate and can be repeatedly used, and the environment can not be polluted.
Description
Technical field
The present invention relates to a kind of method of Synthesis of dimethyl carbonate, specifically a kind of is the method for the urea alcoholysis Synthesis of dimethyl carbonate of circulation agent with the aliphatic dihydroxy alcohol.
Background technology
The urea alcoholysis Synthesis of dimethyl carbonate method that with the aliphatic dihydroxy alcohol is the circulation agent comprised for two steps, the first step is urea and aliphatic dihydroxy alcohol (ethylene glycol or 1, the 2-propylene glycol) reaction synthesizing ethylene carbonate or propylene carbonate, second step was NSC 11801 or propylene carbonate and methyl alcohol transesterify Synthesis of dimethyl carbonate, by product ethylene glycol or 1,2-propylene glycol are circulated in the first step reaction.In addition, NSC 11801 (being called for short EC) and propylene carbonate (being called for short PC) be the high boiling organic solvent and the organic synthesis intermediate of excellent property still, has obtained widespread use in fields such as organic synthesis, chemical fibre industry, gas delivery, electrochemistry and metal extractions.The main synthetic method of EC and PC comprises phosgenation, ester-interchange method and CO
2With oxyethane or propylene oxide synthesis method etc.Current industrialized EC and PC synthetic method mainly adopt phosgenation and CO
2With oxyethane or propylene oxide synthesis method.Problems such as there is the raw material severe toxicity in phosgenation, and product yield is low and of poor quality, and is seriously polluted and meet with to eliminate.With CO
2With oxyethane or propylene oxide be that raw material synthetic carbonic acid alkene ester purity, yield are all higher, cost is also lower, but uses inflammable and explosive oxyethane or propylene oxide, temperature of reaction and pressure are higher, security is relatively poor.Therefore novel process and then the development of new catalyst system of studying carbonate synthesis alkene ester are significant with the production efficiency that improves EC and PC.
At present, considerably less to the technical study of urea and aliphatic dihydroxy alcohol carbonate synthesis alkene ester, employed catalyzer mainly is homogeneous catalyst and powder catalyst.Su in 1991, people such as Wei-Yang have proposed urea and aliphatic dihydroxy alcohol under normal pressure (or high pressure) in patent EP 0 443 758 A1, use the operational path of stanniferous homogeneous catalyst carbonate synthesis alkene ester, carbonic acid alkene ester to the selectivity of dibasic alcohol up to 84~99%, but the urea transformation rate is less than 66%, and carbonic acid alkene ester also only has 63% to the selectivity of urea, and most of urea has decomposed in reaction process.People such as Masaharu Daya were to Su in 1993, the reaction of people's carbonate synthesis alkene esters such as wei-yang improves, and in patent EP 0 581 131 A2, propose under reduced pressure, metal-powder or compound with zinc, magnesium, lead, calcium are catalyzer carbonate synthesis alkene ester, making the yield of carbonic acid alkene ester that significant raising arranged, is between 80~92% with the yield of the carbonic acid alkene ester of ureometer.But in the reaction process, decompression operation is consumes energy not only, and wayward, and what be unfavorable for reacting normally carries out.Two technology common shortcomings are that homogeneous phase separates with product and the recycling difficulty with powder catalyst.
About NSC 11801 or propylene carbonate and the reaction of methyl alcohol transesterify Synthesis of dimethyl carbonate, it is the transesterification reaction Synthesis of dimethyl carbonate that catalyzer carries out EC and methyl alcohol that US4661609 adopts oxide compound, salt or the complex compound of zirconium, titanium and tin.Under 20 ℃~200 ℃ condition, in the methylcarbonate selectivity of EC up to 98%.CN1380140 adopts the catalyzer of being made up of metal oxide, gac, alkali earth metal phosphate or the carbonate of alkali metal hydroxide, carbonate, nitrate or the alkine earth metal nitrate and 60~90% (wt) of 10~40% (wt), under 50 ℃~130 ℃, 0~1MPa, carry out the transesterification reaction Synthesis of dimethyl carbonate of EC or PC and methyl alcohol.
Summary of the invention
The objective of the invention is, on the synthesis under normal pressure device, utilize high catalytic activity, recycle easily and eco-friendly O composite metallic oxide catalyst carries out urea and reacts with aliphatic dihydroxy alcohol carbonate synthesis alkene ester.Adopt identical catalyzer to carry out EC or PC and methyl alcohol transesterification reaction Synthesis of dimethyl carbonate.
Implementation procedure of the present invention is as follows:
This method comprises two steps, and the first step is urea and ethylene glycol or 1,2-propylene glycol reaction synthesizing ethylene carbonate or propylene carbonate, and reaction conditions is: 100~200 ℃, 0~0.5MPa or introduce the nitrogen of 0.5~5mL/min to reaction system; Second step was NSC 11801 or propylene carbonate and methyl alcohol transesterify Synthesis of dimethyl carbonate, and by product ethylene glycol or 1,2-propylene glycol are circulated in the first step reaction, and reaction conditions is 70~160 ℃, 0~2Mpa; Employed catalyzer is a complex metal oxides, it is characterized in that it is to be made of two or more metal oxide component in magnesium oxide, calcium oxide, aluminum oxide, plumbous oxide, cupric oxide, zinc oxide, zirconium white, molybdenum oxide, ferric oxide, cobalt oxide, nickel oxide, the lanthanum trioxide, the catalyst levels weight percent is 0.5~10% of a reaction system.
Beneficial effect of the present invention
Compared with prior art, the advantage that has of the first step of the present invention is: A. reaction conditions gentleness.React under the normal pressure.B. catalyzer easily separates with reaction solution.There are problems such as product separation, recycling difficulty in homogeneous catalyst and powder catalyst, and quality product is affected.Catalyzer of the present invention can load on the carrier of certain particle size, easy and product separation.C. reclaiming easily is reusable, free from environmental pollution.Composite oxide catalysts of the present invention can re-use after simple drying treatment.
Embodiment
Embodiment 1
Get Mg (CH
3COO)
24H
2O is dissolved in and is made into C in the distilled water
Mg 2+=0.8mol/L solution is got Zn (CH again
3COO)
22H
2O adds above-mentioned solution, is made into C
Zn 2+=0.1mol/L solution; Get the ammoniacal liquor of a certain amount of 25% (wt%), its dilution is the ammoniacal liquor of 1.33mol/L; The pH value remains on about 10, stirs 1h after titration finishes, and then aging 24h filters, and the gained precipitation is 600 ℃ of roasting 4h in retort furnace after drying, make the O composite metallic oxide catalyst of Mg and Zn, and is standby.
In the 250mL four-hole bottle, add 9g urea, 46g1, the 2-propylene glycol, the aforementioned made catalyzer of 5g is opened agitator, is heated to 170 ℃, and reaction times 3h is equipped with thermometer on the four-hole bottle, reflux exchanger, agitator and nitrogen inlet.Thermal conductivity detector is adopted in the gas chromatographic analysis of product composition, determines each components contents in the sample with external standard method, and recording the PC yield is 92%.
Embodiment 2
Get Co (NO
3)
22H
2O 1.12g, Zn (CH
3COO)
22H
2O 6.72g mixes the back and grinds evenly, at 450 ℃~550 ℃ following roasting 4h, makes the O composite metallic oxide catalyst of Co and Zn, and is standby.
In the 250mL four-hole bottle, add 9g urea, 46g1, the 2-propylene glycol, the aforementioned made catalyzer of 5g is opened agitator, is heated to 170 ℃, and reaction times 3h is equipped with thermometer on the four-hole bottle, reflux exchanger, agitator and nitrogen inlet.Thermal conductivity detector is adopted in the gas chromatographic analysis of product composition, determines each components contents in the sample with external standard method, and recording the PC yield is 90%.
Embodiment 3
Incipient impregnation makes the composite oxides of Fe and Mg.Fe (the NO of preparation 0.12mol/L
3)
3The aqueous solution slowly is added drop-wise in the MgO carrier, and makes catalyzer in 450 ℃ of following roasting 4h, and is standby.
In the 250mL four-hole bottle, add 9g urea, 46g1, the 2-propylene glycol, the aforementioned made catalyzer of 5g is opened agitator, is heated to 180 ℃, and reaction times 3h is equipped with thermometer on the four-hole bottle, reflux exchanger, agitator and nitrogen inlet.Thermal conductivity detector is adopted in the gas chromatographic analysis of product composition, determines each components contents in the sample with external standard method, and recording the PC yield is 93%.
Embodiment 4
In batch autoclave, carry out the transesterification reaction of PC and methyl alcohol Synthesis of dimethyl carbonate under the condition of 140 ℃, methyl alcohol and PC mol ratio 8: 1, reaction times 2h, the reaction result on the different composite metal oxide catalyst is as shown in the table.
Catalyzer | Productive rate % | Transformation efficiency % | Selectivity % |
CaO-MgO CaO-ZrO 2 MgO-Al 2O 3 MgO-CuO MgO-Fe 2O 3 ZnO-Fe 2O 3 ZnO-PbO ZnO-La 2O 3 ZnO-CoO ZnO-MoO 3 | 40.1 39.1 25.0 24.1 21.9 20.5 19.9 15.8 4.9 3.2 | 47.5 68.3 38.1 33.6 29.4 22.4 28.7 23.5 10.9 3.2 | 84.4 57.2 65.6 71.7 74.5 91.5 70.4 67.2 45.0 100 |
Embodiment 5
In batch reactor, adopt Al
2O
3-MgO catalyzer carries out the transesterification reaction of EC and methyl alcohol Synthesis of dimethyl carbonate under the condition of 100 ℃, methyl alcohol and EC mol ratio 4: 1, reaction times 2h, analyze to such an extent that the EC transformation efficiency is 50%, the selectivity 98% of methylcarbonate.
Claims (1)
1. one kind is the urea alcoholysis Synthesis of dimethyl carbonate method of circulation agent with the aliphatic dihydroxy alcohol, comprise two steps, the first step is urea and ethylene glycol or 1,2-propylene glycol reaction synthesizing ethylene carbonate or propylene carbonate, reaction conditions is: 100~200 ℃, and 0~0.5MPa or introduce the nitrogen of 0.5~5mL/min to reaction system; Second step was NSC 11801 or propylene carbonate and methyl alcohol transesterify Synthesis of dimethyl carbonate, reaction conditions is 70~160 ℃, 0~2MPa, the employed catalyzer of two-step reaction is complex metal oxides, it is characterized in that it is to be made of two or more metal oxide component in magnesium oxide, calcium oxide, aluminum oxide, plumbous oxide, cupric oxide, zinc oxide, zirconium white, molybdenum oxide, ferric oxide, cobalt oxide, nickel oxide, the lanthanum trioxide, the catalyst levels weight percent is 0.5~10% of a reaction system.
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CN1298696C true CN1298696C (en) | 2007-02-07 |
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CN101121659B (en) * | 2007-09-29 | 2010-06-02 | 中国科学院山西煤炭化学研究所 | Technique for producing organic carbonic acid ester by urea alcoholysis method and fixed bed reactor |
CN101518729B (en) * | 2008-02-26 | 2013-04-24 | 拜耳材料科技(中国)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
CN101328125B (en) * | 2008-07-22 | 2011-04-06 | 西安交通大学 | Method for preparing diethyl carbonate by two-step coupling reaction |
CN101781202B (en) * | 2009-01-16 | 2014-04-23 | 亚申科技研发中心(上海)有限公司 | Reaction process and system for preparing organic carbonic ester by catalytic alcoholysis of urea |
CN102464587A (en) * | 2010-11-16 | 2012-05-23 | 中国科学院兰州化学物理研究所 | Method for preparing small molecular carbonated dialkyl ester through ester exchange |
CN102229597A (en) * | 2011-05-11 | 2011-11-02 | 武汉工程大学 | Method for synthesizing cyclic carbonate through urea alcoholysis |
CN102794189A (en) * | 2011-05-23 | 2012-11-28 | 华中科技大学 | Catalyst for synthesizing glycerol carbonate by urea method |
CN102659747A (en) * | 2012-04-11 | 2012-09-12 | 巨化集团技术中心 | Method for synthesizing 4-trifluoro methyl ethylene carbonate |
CN104961720A (en) * | 2015-08-02 | 2015-10-07 | 何肖凤 | Preparation method of propylene carbonate |
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CN106083585B (en) * | 2016-06-21 | 2019-08-23 | 太仓市东明化工有限公司 | A kind of method that indirect alcoholysis prepares dimethyl carbonate |
CN106345446A (en) * | 2016-08-26 | 2017-01-25 | 安徽金邦医药化工有限公司 | Solid catalyst used for synthesizing dimethyl carbonate |
CN107353207A (en) * | 2017-08-21 | 2017-11-17 | 中石化上海工程有限公司 | A kind of method and its system of urea two-step method production dimethyl carbonate |
CN108586243B (en) * | 2018-03-30 | 2021-07-16 | 昆明理工大学 | Method for indirectly synthesizing organic carbonate from carbon dioxide and organic amine |
CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
CN115518628B (en) * | 2021-06-25 | 2023-11-28 | 中国科学院成都有机化学有限公司 | Preparation method of carbon-based metal oxide catalyst for synthesizing cyclic carbonate through urea alcoholysis, catalyst and application |
CN113522260B (en) * | 2021-07-27 | 2022-09-20 | 西南化工研究设计院有限公司 | Y molecular sieve coated magnesium oxide-titanium dioxide catalyst and application thereof in ester exchange reaction |
CN113797914A (en) * | 2021-09-28 | 2021-12-17 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethylene carbonate, preparation method and application thereof |
CN114653359B (en) * | 2022-05-23 | 2022-08-16 | 山东海科新源材料科技股份有限公司 | Catalyst for synthesizing ammonia and preparation method and application thereof |
CN115448903A (en) * | 2022-08-29 | 2022-12-09 | 山东海科新源材料科技股份有限公司 | Method for purifying ethylene carbonate |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
US5349077A (en) * | 1992-07-31 | 1994-09-20 | Mitsubishi Gas Chemical Company, Inc. | Process for producing alkylene carbonates |
CN1421431A (en) * | 2002-12-16 | 2003-06-04 | 中国科学院山西煤炭化学研究所 | Synthesis process of propylene carbonate or vinyl carbonate |
-
2004
- 2004-05-08 CN CNB2004100191753A patent/CN1298696C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
US5349077A (en) * | 1992-07-31 | 1994-09-20 | Mitsubishi Gas Chemical Company, Inc. | Process for producing alkylene carbonates |
CN1421431A (en) * | 2002-12-16 | 2003-06-04 | 中国科学院山西煤炭化学研究所 | Synthesis process of propylene carbonate or vinyl carbonate |
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