CN106946706B - Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol - Google Patents
Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol Download PDFInfo
- Publication number
- CN106946706B CN106946706B CN201710147867.3A CN201710147867A CN106946706B CN 106946706 B CN106946706 B CN 106946706B CN 201710147867 A CN201710147867 A CN 201710147867A CN 106946706 B CN106946706 B CN 106946706B
- Authority
- CN
- China
- Prior art keywords
- dimethyl carbonate
- methanol
- ionic liquid
- carbon dioxide
- preparation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing dimethyl carbonate by directly reacting carbon dioxide and methanol. The method takes imidazole bicarbonate ionic liquid as a catalyst and a dehydrating agent, so that carbon dioxide and methanol directly react under mild conditions to generate dimethyl carbonate. Compared with the prior art, the method realizes the functions of catalysis and dehydration by using a single substance, simplifies the production flow of the dimethyl carbonate, and provides a green and economic synthesis method of the dimethyl carbonate. The conversion rate of methanol can reach 54 percent, and the selectivity of generating dimethyl carbonate can reach 99 percent.
Description
Technical Field
The invention relates to ionic liquid catalysis, in particular to a novel method for preparing dimethyl carbonate through direct reaction of carbon dioxide and methanol.
Technical Field
Dimethyl carbonate is an environmentally friendly chemical raw material, and can be used for synthesizing high molecular compounds, serving as battery electrolyte, serving as a reaction solvent, organically synthesizing intermediates and the like.
At present, the synthesis methods of dimethyl carbonate are numerous, including direct reaction of methanol and phosgene to prepare dimethyl carbonate, reaction of methanol and carbonic ester to prepare dimethyl carbonate through ester exchange reaction (CN201410300187.7, CN201210226548.9, CN201110415385.4), reaction of methanol and ethylene carbonate to prepare dimethyl carbonate (CN201410677148.9, CN201410428934.5, CN201410497814.0, CN201410195315.6), reaction of methanol and urea to prepare dimethyl carbonate (cn201410585479.x), reaction of methanol and carbon monoxide/oxygen to prepare dimethyl carbonate (CN201510257233.4, CN201420170787.1, CN201110439725.7) and the like.
Dimethyl carbonate (CN201310103111.0, cn201310101652.x, CN201010292222.7) is directly prepared by the reaction of carbon dioxide and methanol, and attracts more and more attention due to the advantages of safe, cheap and easily available raw material carbon dioxide. However, the direct reaction of carbon dioxide and methanol to prepare dimethyl carbonate produces water, and due to the limitation of thermodynamic equilibrium, numerous experimental results show that the reaction conversion rate is lower than 15% without adding a dehydrating agent (J.Catal.2010,269, 44-52; Catal.Commun.2016,75, 87-91; Ind.Eng.chem.Res.2014,53, 15798-. In order to increase the reaction conversion, the existing methods must introduce additional chemical dehydrating agents into the reaction system, such as: dicyclohexylcarbodiimide, dimethoxypropane, trimethyl orthoformate, benzonitrile, etc. (CN201210565573. X; J.Catal.2014,318, 95-107; ChemSus Chem 2013,6, 1341-1344; J.Mater.Chem.A 2014,2, 18861-18866; appl.Catal.B: environ.2015,168, 353-362; appl.Catal.A: Gen.2015,493, 142-148). However, these methods of adding additional chemical dehydrating agents have an inherent disadvantage in that the dehydrating agent is converted into other organic compounds by reaction with water, such as benzonitrile and water into amide, dimethoxypropane and water into acetone, so that the dehydrating agent loses its dehydrating ability and cannot be regenerated. Therefore, dehydration is costly. In addition, the catalysts and dehydrating agents used in all of the above methods are different substances, making the subsequent separation process cumbersome and tedious.
Finding a dehydration method with low cost, high efficiency and easy regeneration and realizing the integration of the catalyst and the dehydrating agent is the key of the route industrialization of directly preparing the dimethyl carbonate by the carbon dioxide and the methanol.
Disclosure of Invention
The invention aims to overcome the defect of directly preparing dimethyl carbonate by carbon dioxide and methanol, and provides a brand-new catalysis-dehydration integrated method, which takes imidazole bicarbonate ionic liquid as a catalyst and a dehydrating agent, and is beneficial to improving the process efficiency, simplifying the operation steps and reducing the production cost.
In order to achieve the above object, the present invention is characterized by using an imidazole bicarbonate ionic liquid as a recoverable catalyst and a dehydrating agent (see fig. 1).
The technical scheme of the invention is as follows:
a method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol, which comprises the steps of placing methanol, N-dialkyl imidazole bicarbonate ionic liquid and carbon dioxide into a high-pressure kettle, wherein the pressure of the carbon dioxide is 0.1-5 MPa, and under the temperature of room temperature to 100 ℃, the N, N-dialkyl imidazole bicarbonate ionic liquid is used as a catalyst and a dehydrating agent, and the dimethyl carbonate is prepared by direct reaction under continuous stirring; after the reaction is finished, the dimethyl carbonate and the methanol are removed by distillation, the obtained residue (containing the ionic liquid and the cesium carbonate) is dried in vacuum for 24 hours at the temperature of 40-80 ℃, and the imidazole bicarbonate ionic liquid with the catalytic and dehydration capabilities can be regenerated.
In the method for preparing dimethyl carbonate, in the N, N-dialkyl imidazole bicarbonate ionic liquid, alkyl is straight chain or branched chain alkyl with the carbon atom number of 1-6, and the structure is as follows:
in the method for preparing the dimethyl carbonate, the mass ratio of the dialkyl imidazole bicarbonate ionic liquid to the methanol is 1:10-2: 1.
In the above method for preparing dimethyl carbonate, the reaction temperature is preferably between room temperature and 50 DEG C
In the method for preparing dimethyl carbonate, dibromomethane or dichloromethane can be added into the methanol and the N, N-dialkyl imidazole bicarbonate ionic liquid as a solvent. The volume ratio of the added solvent to the methanol is 100:1-10: 1.
In the above method for preparing dimethyl carbonate, alkali can be added into the reaction mixture, and the alkali can be Na2CO3、NaHCO3、K2CO3、KHCO3、Cs2CO31, 8-diazabicycloundecen-7-ene, 1, 4-diazabicyclo [2.2.2]Octane or 2,2,6, 6-tetramethylpiperidine.
In the method for preparing the dimethyl carbonate, the mass ratio of the added alkali to the methanol is 1:3-3: 1.
The invention was realized based on the findings shown in fig. 2 by the inventors: presence of bicarbonate Ionic liquids (IL-HCO) in imidazole bicarbonate Ionic liquids3) And azabicyclo carbene-carbon dioxide adduct (NHC-CO)2) Balancing of (1). IL-HCO3Under the heating condition, NHC-CO is generated2，NHC-CO2Reacting with water to generate IL-HCO3. So that the imidazole bicarbonate ionic liquid can be used as a catalyst and a dehydrating agent in the synthesis of the dimethyl carbonate. By NHC-CO2The dehydration action of the catalyst greatly improves the conversion rate of methanol during the synthesis of dimethyl carbonate. Meanwhile, NHC-CO can be heated after the reaction is finished2Is regenerated.
It is noted that although there are some examples of using ionic liquid as catalyst to catalyze the reaction of carbon dioxide and methanol to prepare dimethyl carbonate (ind. eng. chem. res.2011,50, 1981-. The conversion rate of methanol can reach 54 percent, and the selectivity of generating dimethyl carbonate can reach 99 percent.
Drawings
FIG. 1 shows the catalytic and dehydration of imidazole bicarbonate ionic liquid.
FIG. 2 IL-HCO in Imidazolium bicarbonate Ionic liquids3And NHC-CO2Balancing of (1).
Detailed Description
The following examples will more fully describe the invention.
Example 1
Adding into a 100ml stainless steel high-pressure reaction kettle5mmol of methanol, 10ml of dibromomethane, and 5mmol of 1-methyl-3-butylimidazolium bicarbonate ionic liquid [ C1C4Im][HCO3]5mmol of cesium carbonate, carbon dioxide at a pressure of 1 MPa. After stirring and reacting for 24 hours at room temperature, the conversion rate of methanol was 45% and the selectivity of dimethyl carbonate was 99% by gas chromatography.
Examples 2 to 10
The results obtained by operating under different conditions, analogously to example 1, are shown in the following table:
remarking: DBU represents 1, 8-diazabicycloundec-7-ene; BABCO stands for 1, 4-diazabicyclo [2.2.2]Octane; HTMP represents 2,2,6, 6-tetramethylpiperidine. C4Is n-butyl, C6Is n-hexyl.
Example 18
The imidazole bicarbonate ionic liquid with catalytic and dehydration capabilities can be regenerated by the following method: after the reaction shown in example 1, dimethyl carbonate, methanol and dibromomethane are removed by distillation, and the obtained residue (containing ionic liquid and cesium carbonate) is dried in vacuum at 50 ℃ for 24 hours, so that the imidazole bicarbonate ionic liquid with catalytic and dehydration capabilities can be regenerated. To the regenerated ionic liquid and cesium carbonate mixture, 5mmol of methanol, 10ml of dibromomethane, and carbon dioxide under a pressure of 1MPa were added. After the reaction was stirred at room temperature for 24 hours, the conversion of methanol was 43% and the selectivity of dimethyl carbonate was 97% by gas chromatography.
Claims (7)
1. A method for preparing dimethyl carbonate by directly reacting carbon dioxide and methanol is characterized in that: putting methanol, N-dialkyl imidazole bicarbonate ionic liquid and carbon dioxide into a high-pressure kettle, wherein the pressure of the carbon dioxide is 0.1 to 5MPa, and the dimethyl carbonate is prepared by taking the N, N-dialkyl imidazole bicarbonate ionic liquid as a catalyst and a dehydrating agent at the temperature of between room temperature and 100 ℃ and directly reacting the mixture by continuous stirring; after the reaction is finished, removing the dimethyl carbonate and the methanol by distillation, and drying the obtained residue for 24 hours in vacuum at the temperature of 40-80 ℃ to regenerate the imidazole bicarbonate ionic liquid with the catalytic and dehydration capabilities.
2. The process for the preparation of dimethyl carbonate according to claim 1, characterized in that: in the N, N-dialkyl imidazole bicarbonate ionic liquid, alkyl is straight chain or branched chain alkyl with the carbon atom number of 1-6.
3. The process for the preparation of dimethyl carbonate according to claim 1, characterized in that: the mass ratio of the dialkyl imidazole bicarbonate ionic liquid to the methanol is 1:10-2: 1.
4. The process for the preparation of dimethyl carbonate according to claim 1, characterized in that: the reaction temperature is from room temperature to 50 ℃.
5. The process for the preparation of dimethyl carbonate according to claim 1, characterized in that: dibromomethane or dichloromethane is added into the methanol and the N, N-dialkyl imidazole bicarbonate ionic liquid as a solvent, and the volume ratio of the added solvent to the methanol is 100:1-10: 1.
6. The process for the preparation of dimethyl carbonate according to claim 1, characterized in that: adding alkali into the reaction mixture, wherein the alkali is Na2CO3、NaHCO3、K2CO3、KHCO3、Cs2CO31, 8-diazabicycloundecen-7-ene, 1, 4-diazabicyclo [2.2.2]OctaneOr2,2,6, 6-tetramethylpiperidine.
7. The process for the preparation of dimethyl carbonate according to claim 6, characterized in that: the ratio of the amount of the base to the amount of the methanol added is 1:3 to 3: 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016112419960 | 2016-12-29 | ||
| CN201611241996 | 2016-12-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106946706A CN106946706A (en) | 2017-07-14 |
| CN106946706B true CN106946706B (en) | 2019-12-31 |
Family
ID=59468329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710147867.3A Active CN106946706B (en) | 2016-12-29 | 2017-03-14 | Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106946706B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUE064513T2 (en) * | 2019-08-30 | 2024-03-28 | Shell Int Research | Organic carbonate production process |
| CN110878020B (en) * | 2019-12-04 | 2021-11-30 | 大连理工大学 | Method for directly preparing dimethyl carbonate under low pressure |
| CN111362800B (en) * | 2020-04-02 | 2023-01-17 | 华东理工大学 | Method for preparing organic carbonate at normal temperature and pressure |
| CN113563189B (en) * | 2021-07-07 | 2023-08-18 | 沈阳化工大学 | One-step method for efficiently catalyzing CO 2 Method for converting dimethyl carbonate catalyst |
| CN115124655B (en) * | 2022-06-27 | 2023-05-05 | 福州大学 | Preparation and application of imidazolyl-containing organic polymer material |
| CN115322097B (en) * | 2022-09-21 | 2023-06-23 | 胜华新材料集团股份有限公司 | Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol |
| CN115382583B (en) * | 2022-09-28 | 2024-05-03 | 长春工业大学 | Preparation and application of efficient catalytic water absorbing material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671253A (en) * | 2009-09-21 | 2010-03-17 | 重庆大学 | Catalytic synthesis method of dimethyl carbonate |
-
2017
- 2017-03-14 CN CN201710147867.3A patent/CN106946706B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671253A (en) * | 2009-09-21 | 2010-03-17 | 重庆大学 | Catalytic synthesis method of dimethyl carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106946706A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106946706B (en) | Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol | |
| Wu et al. | Chemical fixation of CO 2 into cyclic carbonates catalyzed by bimetal mixed MOFs: the role of the interaction between Co and Zn | |
| Zhao et al. | Task-specific ionic liquid and CO 2-cocatalysed efficient hydration of propargylic alcohols to α-hydroxy ketones | |
| SadegháLaeini | Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper (II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature | |
| Yu et al. | Pd/C-catalyzed direct formylation of aromatic iodides to aryl aldehydes using carbon dioxide as a C1 resource | |
| Qiao et al. | Polyoxometalate-based protic alkylimidazolium salts as reaction-induced phase-separation catalysts for olefin epoxidation | |
| Yang et al. | Fluoro-functionalized polymeric ionic liquids: highly efficient catalysts for CO 2 cycloaddition to cyclic carbonates under mild conditions | |
| Toyao et al. | Application of an amino-functionalised metal–organic framework: an approach to a one-pot acid–base reaction | |
| Liu et al. | Protonated triethanolamine as multi-hydrogen bond donors catalyst for efficient cycloaddition of CO2 to epoxides under mild and cocatalyst-free conditions | |
| CN108636450B (en) | Polyion liquid composite material and preparation method and application thereof | |
| Liu et al. | Melamine–ZnI 2 as heterogeneous catalysts for efficient chemical fixation of carbon dioxide to cyclic carbonates | |
| CN112778533B (en) | Porphyrin-based porous organic polymer, preparation method thereof and synthesis method of cyclic carbonate | |
| CN108299375B (en) | Method for preparing cyclic carbonate by combined catalysis of succinimide and halide | |
| Zhou et al. | Catalytic effect and recyclability of imidazolium-tagged bis (oxazoline) based catalysts in asymmetric Henry reactions | |
| Kim et al. | CO2 cycloaddition to epichlorohydrin over an aluminum fumarate metal-organic framework synthesized by a sonochemical route | |
| Song et al. | Dual-linker metal-organic frameworks as efficient carbon dioxide conversion catalysts | |
| Chen et al. | From ‘Gift’to gift: Producing organic solvents from CO 2 | |
| KR101301696B1 (en) | Novel metal catalyst suppored on activated carbon aerogel bearing acid site, preparation method thereof and decomposition of lignin compound using said catalyst | |
| CN104072377B (en) | A kind of method of cyclic carbonate and alcohol transesterification reaction synthetic linear carbonic ether | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| Xing et al. | An organic polymer-grafted ionic liquid as a catalyst for the cycloaddition of CO 2 to epoxides | |
| CN109746042B (en) | Catalyst for synthesizing 3-methoxy methyl acrylate and solid-supported and using method | |
| CN114437364A (en) | Metal coupled triazine porous organic framework, construction method thereof and CO catalysis2Application of coupling with epoxide to prepare cyclic carbonate | |
| Liu et al. | One-pot CuI/DBU-catalyzed carboxylative cyclization toward oxazolidinones using recyclable molecular sieves as efficient promoters for fixation of CO2 in water medium | |
| CN106916108B (en) | A kind of pyrazolium ion liquid and the method using its catalytically synthesizing cyclic carbonate ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |