CN1128131C - Process for directly synthesizing dimethyl carbonate from Co2 and methanol - Google Patents

Process for directly synthesizing dimethyl carbonate from Co2 and methanol Download PDF

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CN1128131C
CN1128131C CN01102306A CN01102306A CN1128131C CN 1128131 C CN1128131 C CN 1128131C CN 01102306 A CN01102306 A CN 01102306A CN 01102306 A CN01102306 A CN 01102306A CN 1128131 C CN1128131 C CN 1128131C
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reaction
methanol
gram
dmc
temperature
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CN1368495A (en
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侯振山
韩布兴
刘志敏
杨冠英
何俊
张小岗
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention discloses a synthesis method for di-methyl carbonate (DMC). The method comprises that a dehydrating agent of a four-star type molecular sieve is added under the existence of K2CO3 as a major catalyst and CH3I as a cocatalyst, and carbon dioxide and methanol are directly synthesized into the di-methyl carbonate. In the present invention, reaction systems are controlled near a critical point by the control of the conditions of the proportions of raw materials for reaction, temperature, apparent density, time, etc., and the conversion rate of the methanol can reach more than 13% by that the reaction balance moves because of the specific molecular aggregation in the system near the critical point. Finally, the present invention has the advantages of improved production efficiency and reduced production cost.

Description

A kind of method by carbonic acid gas and the direct Synthesis of dimethyl carbonate of methyl alcohol
The present invention relates to the synthetic method of a kind of methylcarbonate (DMC), relate in particular to a kind of method by carbonic acid gas and the direct Synthesis of dimethyl carbonate of methyl alcohol.
Methylcarbonate is a kind of important chemical material, as organic synthesis intermediate commonly used, at polycarbonate, isocyanic ester, carbamate, in Chemicals such as malonic ester synthetic extensive use is arranged, and alternative severe toxicity or carcinogenic methyl-sulfate photoreactive gas be as methylating and the reagent of carbonylation, its application in the organic chemical industry is paid attention to by people day by day.
Methylcarbonate (DMC) synthetic route mainly contains following four kinds so far: one, phosgenation; This method is a synthetic DMC method early, earlier by CO and CI 2Effect generates phosgene (COCI 2), then by phosgene and methyl alcohol or sodium methylate generation DMC.Though the DMC productive rate of these methods is higher, because raw material phosgene severe toxicity, and cost is higher, is restricted so use.Two, ester-interchange method; Generate DMC by ethylene carbonate (EC) or Texacar PC (PC) and methyl alcohol by transesterification reaction.But this method production cost height, the product separation difficulty.Three, oxidative carbonylation of methanol method; This method is with methyl alcohol, CO, O 2Be the synthetic DMC of raw material, the seventies, middle and late was very active to the research of this method abroad.Propose technology and have two kinds: liquid phase method and vapor phase process.Employed catalyzer has copper system, palladium system, and selenium system and compound system, basic metal in addition, alkaline-earth metal or other transistion metal compound, the interpolation of promotors such as organic compounds containing nitrogen can improve the yield of DMC.This method advantage is that raw material is simple, and cost is low, and the DMC yield is also higher.Shortcoming is that CO is poisonous hazardous gas, and catalyzer easy inactivation when reaction.Four, with methyl alcohol, CO 2Synthetic DMC is a technology newly developed in recent years for raw material, and the entire reaction route is the reaction of atom economy type, and raw material is easy to get, and is pollution-free, and product separates easily, has very big industrial value.
In above four kinds of synthesis techniques, with methyl alcohol, CO 2Be the tool development potentiality of the processing method of the synthetic DMC of raw material, but open source literature is reported in the reaction of using this technology Synthesis of dimethyl carbonate at present, although adopted multiple concrete reaction scheme, comprise conditions such as reaction raw materials ratio, temperature, pressure, time are optimized combination, but methanol conversion is still lower, basically can only reach the transform level about 8%, cause production cost to increase thus, influence the practical application of this technology.
The object of the present invention is to provide a kind of concrete synthetic method with methylcarbonate (DMC) of higher methanol conversion.
The synthetic method of a kind of methylcarbonate (DMC) is included in Primary Catalysts K 2CO 3With promotor CH 3Under the existence of I, add dewatering agent 4 molecular sieves, by carbonic acid gas and the direct Synthesis of dimethyl carbonate of methyl alcohol, the reaction times is 6～12 hours.Temperature of reaction is 345～365K, and the reactant apparent density is 0.55～0.65g/ml; CO wherein 2And CH 3The mol ratio of OH is 3: 1～8: 1, and preferred molar ratio is 4: 1; CH 3OH and CH 3The mol ratio of I is 5: 1～10: 1; CH 3OH and K 2CO 3Mol ratio is 30: 1～100: 1, CH 3OH: CH 3I: K 2CO 3Preferred molar ratio be 64: 8: 1.CH 3The mass ratio of OH and 4 molecular sieves is 10: 1～30: 1, and the preferred mass ratio is 20: 1.Described apparent density is the ratio of the quality and the reaction vessel volume of all raw materials.
In the synthetic method of methylcarbonate of the present invention (DMC), by control to conditions such as reaction raw materials ratio, temperature, apparent density, times, reaction system is near the stagnation point, utilizing near the stagnation point in the system specific molecule to assemble moves molecular balance, make the methanol conversion can be up to more than 13%, improve production efficiency, reduced production cost.
The present invention is further illustrated below in conjunction with embodiment and Comparative Examples.
Embodiment 1
At volume is to add 0.17 gram K in 24.3 milliliters the reactor 2CO 3, 1.40 gram CH 3I and 2.52 gram CH 3OH and 10.4 gram CO 2, adding 0.15 gram dewatering agent, 4 molecular sieves, its temperature of reaction is 355K, apparent density is 0.59g/ml, sealed reaction 10 hours.Measuring methanol conversion is 12.5%.
Embodiment 2
Add 0.14 gram K in the reactor of volume 24.3ml 2CO3,1.15 gram CH 3I and 2.07 gram CH 3OH and 11.36 gram CO 2, adding 0.12 gram dewatering agent, 4 molecular sieves, its temperature of reaction is 353K, apparent density is 0.60g/ml, sealed reaction 10 hours.Measuring methanol conversion is 13.5%.
Embodiment 3
At volume is to add 0.11 gram K in 24.3 milliliters the reactor 2CO 3, 0.88 gram CH 3I and 1.58 gram CH 3OH and 12.35 gram CO 2, adding 0.08 gram dewatering agent, 4 molecular sieves, its temperature of reaction is 347K, apparent density is 0.61g/ml, sealed reaction 10 hours.Measuring methanol conversion is 12.3%.Comparative Examples 1
Add 0.11 gram K in the reactor of volume 24.3ml 2CO 3, 1.00 gram CH 3I and 1.40 gram CH 3OH and 7.57 gram CO 2, adding 0.10 gram dewatering agent, 4 molecular sieves, its temperature of reaction is 353K, apparent density is 0.41g/ml, sealed reaction 10 hours.Measuring methanol conversion is 8.5%.
Comparative Examples 2
At volume is to add 0.206 gram K in 24.3 milliliters the reactor 2CO 3, 1.69 gram CH 3I and 3.05 gram CH 3OH and 9.78 gram CO 2, adding 0.165 gram dewatering agent, 4 molecular sieves, its temperature of reaction is 400K, apparent density is 0.60g/ml, sealed reaction 10 hours.Measuring methanol conversion is 8.34%.
Comparative Examples 3
Be selected from Collect.Czech.Chem.Commun. (Vol.58) (1993), the experiment content of 1399-1402 document.
Use the stainless steel cauldron of 250ml, add 150ml methyl alcohol earlier, add the 10mmol tin compound then, add the 5mmol additive again, add 44g dry ice (CO at last as catalysts 2), closed reactor begins to be warming up to temperature of reaction, reaction 6-12h, and after reaction finished, frozen water cooling reactor took out the reaction product analysis.Table 1 has been listed some typical reaction results.
The reaction result of table 1 carbonic acid gas and methyl alcohol system DMC
Catalyst additive DMC productive rate (%) a
Bu 2Sn(OBu) 2 - 80(0.43％)
Bu 2Sn(OBu) 2 CH 3I 88(0.47％)
Bu 2Sn(OBu) 2 I 2 118(0.62％)
Bu 2Sn(OBu) 2 I 2 122(0.65％) b
Bu 2Sn (OBu) 2I 2145 (0.77%) cA:150 ℃, total pressure: 6.6MPa, 6.0h, b:200 ℃, 6.0hc:200 ℃, 6.0h, sodium sulfate is as dewatering agent.Annotate: percentage ratio is represented methanol conversion in the bracket.Calculate by raw data.
Comparative Examples 4
Be selected from the experiment content of T.zhao et al./Fuel Processing Technologu 62 (2000) 187-194 documents
Utilize the 80ml autoclave, add the 4mmol catalyzer earlier, the 2mmol additive, 100mmol methyl alcohol, and then add carbonic acid gas to reaction pressure, and after reaction for some time, taking out product and analyze with GC, the result is as shown in table 2.
The reaction result of table 2 carbonic acid gas and methyl alcohol system DMC
Methanol conversion (%) a
Catalyst additive
Ni(CH 3COO) 2·4H 2O - 6.41％
Ni (CH 3COO) 24H 2O K 2CO 37.07%a: reaction conditions, 305K, reaction pressure: 10.3MPa, the reaction times is 8h.Annotate: methanol conversion is calculated by raw data.
Comparative Examples 5
Be selected from the experiment content of " East China University of Science's journal " Vol.24 No.1 1998.2 P7-10 documents
Utilize the autoclave of certain volume, take by weighing 10 gram magnesium powder and 200ml methanol mixed, sealing back stirring reaction under temperature of reaction generates magnesium methylate, behind the frozen water cooling reactor, pump into carbonic acid gas and make reaction pressure, under 180 ℃ of conditions of temperature, react 5h to 3.0MPa, frozen water cooling reactor, the abstraction reaction mixture is analyzed, and calculates reaction result according to this, and is as shown in table 3.
The reaction result of table 3 carbonic acid gas and methyl alcohol system DMC
Catalyst additive (5mmol) methanol conversion (%)
Magnesium methylate-6.21%
Magnesium methylate-6.44% is annotated: methanol conversion is calculated by raw data.
Comparative Examples 6
Be selected from J.Org.Chem.1999,64, the experiment content of 4506-4508 document
The disadvantageous effect that reaction is caused for fear of product water, can earlier methyl alcohol be become the form of acetal (ketone), generate DMC with carbon dioxide reaction then, concrete scheme is as follows: methyl alcohol 8.1ml, acetal (ketone) 10mmol, metal composite catalyzer 0.17mmol, additive 0.17mmol adds CO at last under temperature of reaction 2To reaction pressure, after temperature reaction for some time, the cooling reactor.Product is with gas chromatographic analysis.The result is as shown in table 4
Acetal methanol conversion (%) Bu that the reaction result catalyzer of table 4 carbonic acid gas and methyl alcohol system DMC uses 2Sn (OMe) 2(OCH 3) 2C (CH 3) 25.59% aBu 2Sn (OMe) 2(OCH 3) 2C (CH 2CH 3) 25.69% bBu 2Sn (OMe) 2(OCH 3) 2C (CH 3) 28.12% cReaction conditions: a: 180 ℃ of temperature, reaction pressure, 30MPa, 96h.
B: 180 ℃ of temperature, reaction pressure, 30MPa, 72h.
C: 180 ℃ of temperature, reaction pressure, 200MPa, 24h.
From the contrast of above embodiment and Comparative Examples as can be known, mainly be selection by the height of methanol conversion in carbonic acid gas and the direct Synthesis of dimethyl carbonate of methyl alcohol synthetic to conditions such as various raw materials and proportioning thereof, temperature, apparent densities, from above Comparative Examples result as can be known, although adopt multiple concrete synthetic schemes, but methanol conversion is still only about 8%, and under the determined reaction conditions of the present invention, methanol conversion can be up to about 13%.In addition, can also see that from Comparative Examples 1 and 2 depart from Reaction conditions range of the present invention, methanol conversion will drop sharply to about 8%.

Claims (4)

1. the synthetic method of a methylcarbonate is included in Primary Catalysts K 2CO 3With promotor CH 3Under the existence of I, add dewatering agent 4 molecular sieves, by carbonic acid gas and the direct Synthesis of dimethyl carbonate of methyl alcohol; Its reaction times is 6～12 hours, and temperature of reaction is 345～365K, and the reactant apparent density is 0.55～0.65g/ml, wherein CO 2And CH 3The mol ratio of OH is 3: 1～8: 1, CH 3OH and CH 3The mol ratio of I is 5: 1～10: 1, CH 3OH and K 2CO 3Mol ratio is 30: 1～100: 1, CH 3The mass ratio of OH and 4 molecular sieves is 10: 1～30: 1.
2. according to the synthetic method of claim 1, it is characterized in that wherein CO 2And CH 3The mol ratio of OH 4: 1.
3. according to the synthetic method of claim 1, it is characterized in that CH 3OH: CH 3I: K 2CO 3Mol ratio be 64: 8: 1.
4. according to the synthetic method of claim 1, it is characterized in that CH 3The mass ratio of OH and 4 molecular sieves is 20: 1.
CN01102306A 2001-02-01 2001-02-01 Process for directly synthesizing dimethyl carbonate from Co2 and methanol Expired - Fee Related CN1128131C (en)

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CN100343222C (en) * 2004-12-10 2007-10-17 中国科学院兰州化学物理研究所 Preparation method of carbonate
CN101747203B (en) * 2010-01-19 2013-12-18 昆明理工大学 Method for directly preparing methyl-carbonate and preparing liquid fuel carbinol as byproduct through biogas
CN102949968B (en) * 2012-11-05 2014-06-25 大连理工大学 Reactor with functions of reaction product separation and disturbance increase
CN103524476B (en) * 2013-10-16 2016-03-09 广西科学院 The method of multicomponent reaction system synthesis of glycerol carbonate coproduction short carbon chain carbonic ether
EP3204350B1 (en) 2015-12-02 2018-03-21 AIT Austrian Institute of Technology GmbH Method and device for the continuous production of organic carbonates from co2
CN108689850A (en) * 2018-07-01 2018-10-23 北京化工大学 A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate
CN110563585B (en) * 2019-10-11 2021-02-09 山东德普化工科技有限公司 Preparation method of dimethyl carbonate
CN115382583B (en) * 2022-09-28 2024-05-03 长春工业大学 Preparation and application of efficient catalytic water absorbing material

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