CN102964254A - Method for preparing dimethyl carbonate - Google Patents
Method for preparing dimethyl carbonate Download PDFInfo
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- CN102964254A CN102964254A CN2012104864403A CN201210486440A CN102964254A CN 102964254 A CN102964254 A CN 102964254A CN 2012104864403 A CN2012104864403 A CN 2012104864403A CN 201210486440 A CN201210486440 A CN 201210486440A CN 102964254 A CN102964254 A CN 102964254A
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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 invention relates to a method for preparing dimethyl carbonate, characterized by reacting dimethyl ether with carbon dioxide in a mol ratio of 1: (4-10) in the presence of a magnesium oxide-zinc oxide composite rare earth oxide catalyst, thereby directly synthesizing dimethyl carbonate, wherein the dosage of the catalyst is 0.5-5 wt% of that of dimethyl ether; the reaction temperature is 95-105 DEG C; and the pressure is 7.5-8.5 Mpa. The method provided by the invention has the advantages that as the dimethyl carbonate is directly generated from dimethyl ether and carbon dioxide, the process is simple and industrial production is easy to realize, the preparation process is high in reaction rate, and high in percent conversion and product yield, and the greenhouse gas CO2 is utilized so that environmental pollution is reduced; the reaction process of the method is very advantageous in thermodynamics; only dimethyl carbonate is generated in the reaction and no other byproduct and water are generated, so that the reaction has high industrial application value; and the obtained dimethyl carbonate is nontoxic, biodegradable, excellent in usability and wide in application range.
Description
Technical field
The present invention relates to a kind of preparation method of methylcarbonate, belong to chemical technology field.
Background technology
Methylcarbonate is the environmental protective type chemical product that is subject in recent years domestic and international extensive concern.Owing to contain CH in its molecule
3-, CH
3O-, CH
3O-CO-,-the multiple functional groups such as CO-, thereby has a good reactive behavior, the fine chemicals that can substitute at numerous areas that the severe toxicity such as phosgene, methyl-sulfate, methyl chloride and methyl-chloroformate or carcinogens carry out carbonylation, methylate, the reactions such as esterification and transesterify generates multiple important high added value is in the acquisition widespread use of the fields such as medicine, agricultural chemicals, synthetic materials, dyestuff, lubricating oil additive, food flavoring agent, electronic chemical product.On the other hand, its non-reacted purposes such as solvent, solvent and gasoline dope etc. are also or soon practical.
Methylcarbonate has good solubility property, and not only the intermiscibility with other solvents is good, also has the characteristics such as higher vaporization temperature and velocity of evaporation be fast, can be used as solvent that low poison solvent uses as paint solvent and pharmaceutical industries etc.Oxygen level in the dialkyl carbonate ester molecule also is improved the function of octane value up to 53%, and therefore, methylcarbonate enjoys both at home and abroad as most potential gasoline dope to be gazed at.
Dme is a kind of broad-spectrum product, mainly as the propellent of refrigerant, solvent, extraction agent, aerosol and fuel etc.Dme has the similar vapour pressure of oil liquefied gas, can be used as domestic fuel and uses.Dme n-Hexadecane ester is high, be the desirable fuel substitute of diesel motor, and automobile exhaust pollution thing quantity discharged is low.Dme acts as a fuel and uses is that dme is used potential great market.In addition, the chemical use of dme is also very wide.
Summary of the invention
The purpose of this invention is to provide a kind of with cleaning, nontoxic, environmental protection, cheap dme and carbonic acid gas as raw material, the preparation process speed of reaction is fast, the preparation method of the methylcarbonate that transformation efficiency, selectivity and product yield are high; The methylcarbonate that present method makes is nontoxic, biodegradable, use properties is good, have wide range of applications.
Method of the present invention is as follows:
With dme and carbonic acid gas 1:4-10 in molar ratio, react at magnesium oxide-zinc oxide composite rare-earth oxide catalyzer, catalyst levels is the 0.5-5wt% of dme, and temperature of reaction is 95 ~ 105 ℃, pressure 7.5 ~ 8.5MPa, dme and supercritical liq CO
2Direct Synthesis of Dimethyl Carbonate, its reaction equation is as follows:
Described magnesium oxide-zinc oxide composite rare-earth oxide catalyzer adopts the coprecipitation method preparation, with 1mol/L Mg (NO
3)
2With 1mol/L Zn (NO
3)
2Mixing solutions stirs and is warming up to 45 ℃, slowly adds the Na of 1mol/L
2CO
3Solution, about 30min of period, adjust pH keep 45 ℃ of aging 2h to 8-9, leave standstill, filter, wash, 110 ℃ of dry 12h adopt the method for dipping, and lanthanum nitrate, the cerous nitrate of 1mol/L is immersed on the dried material, flooded 110 ℃ of dry 3h, 500 ℃ of lower roasting 3h 12 hours; Wherein the mol ratio of Mg:Zn is 1-4:1, and the mass percent of rare earth oxide is 0.1-1%.
Advantage of the present invention is: utilize dme and CO
2Direct Formed dimethyl phthalate, technique is simple, easily realizes industrialization production; The preparation process speed of reaction is fast, transformation efficiency, product yield height; Utilized greenhouse gases CO
2, reduced environmental pollution; Reaction process of the present invention is very favourable on thermodynamics, and a reaction Formed dimethyl phthalate does not have other by products and water to generate, and is the reaction that industrial application value is extremely arranged; The methylcarbonate that makes is nontoxic, biodegradable, use properties is good, have wide range of applications.
Embodiment
The present invention is take dme and supercritical co liquid as raw material, on magnesium oxide-zinc oxide composite rare-earth oxide catalyzer, and Direct Synthesis of Dimethyl Carbonate under certain temperature of reaction, reaction pressure.
Embodiment 1
1, the preparation of catalyzer
Magnesium oxide-zinc oxide composite rare-earth oxide (preferential oxidation lanthanum, cerium oxide) catalyzer:
The preparation of employing coprecipitation method is with 1mol/L Mg (NO
3)
2With 1mol/L Zn (NO
3)
2Mixing solutions stirs and is warming up to 45 ℃, slowly adds the Na of 1mol/L
2CO
3Solution, about 30min of period, adjust pH keep 45 ℃ of aging 2h to 8-9, leave standstill, filter, wash, 110 ℃ of dry 12h.Adopt the method for dipping, lanthanum nitrate, the cerous nitrate of 1mol/L is immersed on the dried catalyzer, flooded 110 ℃ of dry 3h, 500 ℃ of lower roasting 3h 12 hours.Wherein the mol ratio of Mg:Zn is 2:1.The mass percent of rare earth oxide is 0.5%.
2, the preparation of methylcarbonate:
Dme and carbonic acid gas mol ratio are 1:6, and on magnesium oxide-zinc oxide composite rare-earth oxide catalyzer (catalyst levels is dme 1wt%), temperature of reaction is 100 ~ 105 ℃, under relative pressure 10.0 ~ 10.5MPa condition, and dme and supercritical liq CO
2Direct Synthesis of Dimethyl Carbonate, dimethyl ether conversion rate are 98%, and the methylcarbonate yield is 85%.
Embodiment 2
1, the preparation of catalyzer
Magnesium oxide-zinc oxide composite rare-earth oxide (preferential oxidation lanthanum, cerium oxide) catalyzer:
The preparation of employing coprecipitation method is with 1mol/L Mg (NO
3)
2With 1mol/L Zn (NO
3)
2Mixing solutions stirs and is warming up to 50 ℃, slowly adds the Na of 1mol/L
2CO
3Solution, about 30min of period, adjust pH keep 50 ℃ of aging 2h to 8-9, leave standstill, filter, wash, 110 ℃ of dry 12h.Adopt the method for dipping, lanthanum nitrate, the cerous nitrate of 1mol/L is immersed on the dried catalyzer, flooded 110 ℃ of dry 3h, 550 ℃ of lower roasting 3h 12 hours.Wherein the mol ratio of Mg:Zn is 2:1.The mass percent of rare earth oxide is 0.5%.
2, the preparation of methylcarbonate:
Dme and carbonic acid gas mol ratio are 1:6, and on magnesium oxide-zinc oxide composite rare-earth oxide catalyzer (catalyst levels is dme 1wt%), temperature of reaction is 100 ~ 105 ℃, under relative pressure 7.5 ~ 8MPa condition, and dme and supercritical liq CO
2Direct Synthesis of Dimethyl Carbonate, dimethyl ether conversion rate are 90%, and the methylcarbonate yield is 75%.
Embodiment 3
1, the preparation of catalyzer
Magnesium oxide-zinc oxide composite rare-earth oxide (preferential oxidation lanthanum, cerium oxide) catalyzer:
The preparation of employing coprecipitation method is with 1mol/L Mg (NO
3)
2With 1mol/L Zn (NO
3)
2Mixing solutions stirs and is warming up to 65 ℃, slowly adds the Na of 1mol/L
2CO
3Solution, about 30min of period transfers pH value to 7-8, keeps 65 ℃ of aging 2h, leaves standstill, filters, washs, 110 ℃ of dry 12h.Adopt the method for dipping, lanthanum nitrate, the cerous nitrate of 1mol/L is immersed on the dried catalyzer, flooded 110 ℃ of dry 3h, 600 ℃ of lower roasting 3h 12 hours.Wherein the mol ratio of Mg:Zn is 2:1.The mass percent of rare earth oxide is 0.5%.
2, the preparation of methylcarbonate:
Dme and carbonic acid gas mol ratio are 1:6, and on magnesium oxide-zinc oxide composite rare-earth oxide catalyzer (catalyst levels is dme 1wt%), temperature of reaction is 100 ~ 105 ℃, under relative pressure 12 ~ 12.5MPa condition, and dme and supercritical liq CO
2Direct Synthesis of Dimethyl Carbonate, dimethyl ether conversion rate are 100%, and the methylcarbonate yield is 83%.
Claims (2)
1. the preparation method of a methylcarbonate, it is characterized in that: with dme and carbonic acid gas 1:4-10 in molar ratio, react at magnesium oxide-zinc oxide composite rare-earth oxide catalyzer, Direct Synthesis of Dimethyl Carbonate, catalyst levels is the 0.5-5wt% of dme, temperature of reaction is 95 ~ 105 ℃, pressure 7.5 ~ 8.5Mpa.
2. the preparation method of methylcarbonate according to claim 1 is characterized in that: described magnesium oxide-zinc oxide composite rare-earth oxide catalyzer adopts the coprecipitation method preparation, with 1mol/L Mg (NO
3)
2With 1mol/L Zn (NO
3)
2Mixing solutions stirs and is warming up to 45 ℃, slowly adds the Na of 1mol/L
2CO
3Solution, about 30min of period, adjust pH keep 45 ℃ of aging 2h to 8-9, leave standstill, filter, wash, 110 ℃ of dry 12h adopt the method for dipping, and lanthanum nitrate, the cerous nitrate of 1mol/L is immersed on the dried material, flooded 110 ℃ of dry 3h, 500 ℃ of lower roasting 3h 12 hours; Wherein the mol ratio of Mg:Zn is 1-4:1, and the mass percent of rare earth oxide is 0.1-1%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486440.3A CN102964254B (en) | 2012-11-26 | 2012-11-26 | Method for preparing dimethyl carbonate |
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|---|---|---|---|
| CN201210486440.3A CN102964254B (en) | 2012-11-26 | 2012-11-26 | Method for preparing dimethyl carbonate |
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| CN102964254A true CN102964254A (en) | 2013-03-13 |
| CN102964254B CN102964254B (en) | 2014-07-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243345A (en) * | 2017-07-05 | 2017-10-13 | 陕西煤业化工技术研究院有限责任公司 | A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction |
| CN107694555A (en) * | 2017-09-12 | 2018-02-16 | 安徽大学 | A kind of indium cerium mixed oxide catalyst and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1180096A (en) * | 1997-09-10 | 1999-03-23 | Nkk Corp | Production of dimethyl carbonate |
-
2012
- 2012-11-26 CN CN201210486440.3A patent/CN102964254B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1180096A (en) * | 1997-09-10 | 1999-03-23 | Nkk Corp | Production of dimethyl carbonate |
Non-Patent Citations (3)
| Title |
|---|
| MICHAEL A ET AL: "Review of Dimethyl Carbonate(DMC) Manufacture and Its Characteristics as a Fuel Additive", 《ENERGY & FUELS》, vol. 11, 30 December 1997 (1997-12-30), pages 2 - 29 * |
| TOSHIYASU SAKAKURA ET AL.: "Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis", 《J.ORG.CHEM》, 30 December 1998 (1998-12-30), pages 7095 - 7096 * |
| 仇鹏等: "羰基合成碳酸二甲酯的研究进展", 《化工进展》, vol. 29, no. 6, 5 June 2010 (2010-06-05), pages 1027 - 1033 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243345A (en) * | 2017-07-05 | 2017-10-13 | 陕西煤业化工技术研究院有限责任公司 | A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction |
| CN107694555A (en) * | 2017-09-12 | 2018-02-16 | 安徽大学 | A kind of indium cerium mixed oxide catalyst and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN102964254B (en) | 2014-07-23 |
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Address after: 014060 Wanshuiquan, Rare Earth High-tech Zone, Baotou City, Inner Mongolia Autonomous Region Patentee after: Pretty Oriental Bio Fuel Group Limited Address before: 014030 Jinjiao Industrial Park, Binhe New Area, Baotou Rare Earth High-tech Zone, Inner Mongolia Autonomous Region Patentee before: Jinjiao Special New Materials (Group) Co., Ltd. |
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