CN1569810A - 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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- CN1569810A CN1569810A CN 200410019175 CN200410019175A CN1569810A CN 1569810 A CN1569810 A CN 1569810A CN 200410019175 CN200410019175 CN 200410019175 CN 200410019175 A CN200410019175 A CN 200410019175A CN 1569810 A CN1569810 A CN 1569810A
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Abstract
The invention discloses a process for synthesizing methyl carbonate by alcoholysis of urea with aliphatic diol as cyclic agent consisting two steps, (1) reacting urea with aliphatic diatomic alcohol (ethylene glycol or 1,2-methyl ethylene glycol) to synthesize ethylene carbonate ester or propylene carbonate ester, (2) subjecting ethylene carbonate ester or propylene carbonate ester with methanol ester to synthesize methylcarbonate.
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 EP0 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 EP0 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, and the catalyst levels weight percent is 0.5～10% of a reaction system.
Complex metal oxides is to be made of two or more 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.
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
2O1.12g, Zn (CH
3COO)
22H
2O6.72g 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, 46g1,2-ethylene 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.
Catalyst production % transformation efficiency % selectivity %
CaO-MgO 40.1 47.5 84.4
CaO-ZrO
2 39.1 68.3 57.2
MgO-Al
2O
3 25.0 38.1 65.6
MgO-CuO 24.1 33.6 71.7
MgO-Fe
2O
3 21.9 29.4 74.5
ZnO-Fe
2O
3 20.5 22.4 91.5
ZnO-PbO 19.9 28.7 70.4
ZnO-La
2O
3 15.8 23.5 67.2
ZnO-CoO 4.9 10.9 45.0
ZnO-MoO
3 3.2 3.2 100
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 (2)
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, and 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, and the catalyst levels weight percent is 0.5～10% of a reaction system.
2. according to claim 1 a kind of be the urea alcoholysis Synthesis of dimethyl carbonate method of circulation agent with the aliphatic dihydroxy alcohol, it is characterized in that: complex metal oxides is to be made of two or more 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.
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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 |
| CN101781202A (en) * | 2009-01-16 | 2010-07-21 | 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 |
| CN101328125B (en) * | 2008-07-22 | 2011-04-06 | 西安交通大学 | Method for preparing diethyl carbonate by two-step coupling reaction |
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| CN104961720A (en) * | 2015-08-02 | 2015-10-07 | 何肖凤 | Preparation method of propylene carbonate |
| CN105664953A (en) * | 2016-03-04 | 2016-06-15 | 陕西煤业化工技术研究院有限责任公司 | Composite catalyst for synthesizing ethylene carbonate by urea alcoholysis and preparation process and application thereof |
| CN106083585A (en) * | 2016-06-21 | 2016-11-09 | 太仓市东明化工有限公司 | A kind of method that dimethyl carbonate is prepared in indirect alcoholysis |
| 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 |
| EP3135662A1 (en) * | 2015-08-31 | 2017-03-01 | Yashentech Corporation | Process for producing 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 |
| CN108586243A (en) * | 2018-03-30 | 2018-09-28 | 昆明理工大学 | A kind of method of carbon dioxide and organic amine indirect synthesis organic carbonate |
| CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
| CN111841574A (en) * | 2020-08-28 | 2020-10-30 | 华东理工大学 | Catalyst regeneration method for preparing propylene (or ethylene) carbonate by urea alcoholysis method |
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| CN115518628A (en) * | 2021-06-25 | 2022-12-27 | 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 |
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| CA2051488A1 (en) * | 1990-09-20 | 1992-03-21 | Stephen W. King | Processes for the preparation of carboxylated compounds |
| DE69328056T2 (en) * | 1992-07-31 | 2000-10-05 | Mitsubishi Gas Chemical Co | Process for the production of 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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2004
- 2004-05-08 CN CNB2004100191753A patent/CN1298696C/en not_active Expired - Fee Related
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| 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 |
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| 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 |
| CN113522260A (en) * | 2021-07-27 | 2021-10-22 | 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 |
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