CN110563585A - Preparation method of dimethyl carbonate - Google Patents
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- CN110563585A CN110563585A CN201910962576.9A CN201910962576A CN110563585A CN 110563585 A CN110563585 A CN 110563585A CN 201910962576 A CN201910962576 A CN 201910962576A CN 110563585 A CN110563585 A CN 110563585A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- 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
Abstract
The invention discloses a preparation method of dimethyl carbonate, which takes carbon dioxide and methanol as raw materials, adds a catalyst into a fixed bed reactor, and introduces CO2Purging, continuously introducing CO2Heating to 120-140 deg.C, maintaining constant temperature, adding methanol under 0.5-0.8MPa, and reacting to obtain dimethyl carbonate; the catalyst is a supported catalyst and comprises an active center and a carrier; the active center is transition metal, and the carrier comprises silicon dioxide, aluminum oxide andOne of an alkali metal or an alkaline earth metal. The invention adopts the combined action of the bimetallic active centers, improves the activity of the catalyst, and simultaneously improves the reaction conversion rate and the selectivity of a target product.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of dimethyl carbonate.
Background
Dimethyl Carbonate (DMC), chemical structure formula is CH3O-CO-CH3O is an important environment-friendly green organic chemical raw material, and because the structure of the O has methyl, carbonyl, methoxy and other groups, the O can replace phosgene to be used as a carbonylation agent, dimethyl sulfate to be used as a methylation agent and methyl tert-butyl ether to be used as an environment-friendly gasoline additive. On the other hand, the dimethyl carbonate is taken as a raw material, can be developed and prepared into various fine special chemicals with high added values, and has wide application in the fields of medicines, pesticides, synthetic materials, dyes, lubricating oil additives, food flavoring agents, electronic chemicals and the like.
Currently, the industrial synthesis of dimethyl carbonate mainly comprises a phosgene method, a methanol oxidative carbonylation method, an ester exchange method, a methanol urea method and the like. The direct synthesis of DMC from carbon dioxide and methanol is a hot point studied in recent years, and the reaction method is considered to be the most economical and safe synthesis method without any solvent and pollution discharge, but because of the stability of carbon dioxide, the reaction for directly synthesizing DMC from carbon dioxide and methanol as raw materials is difficult to perform thermodynamically, so that the development of a high-activity catalyst to promote the activation of carbon dioxide and the improvement of the reaction conversion rate are key points of the whole process.
Catalysts that have been disclosed in the prior art include supported metal catalysts, solid base catalysts, oxide catalysts, heteropolyacid catalysts, and the like. Chinese patent publication No. CN103521266B discloses a composite catalyst for synthesizing dimethyl carbonate, which takes an oxide with an ordered nanotube, wire and rod array structure as a substrate, and a supported catalyst is prepared by loading catalytic active components on the nano array oxide substrate by a sol-gel method, so that the utilization efficiency of the catalyst can be effectively improved, but the catalyst is used for catalytically synthesizing the dimethyl carbonate, the reaction pressure is high, the temperature is high, the conditions are harsh, and the yield of DMC is limited; chinese patent publication No. CN1222357C discloses a catalyst for gas-phase synthesis of dimethyl carbonate, the active component of which is represented by the general formula CuX2·H2O orCuX2The catalyst has high selectivity of catalyzing and synthesizing dimethyl carbonate, but has low repeated utilization rate and contains harmful components such as halogen.
disclosure of Invention
In order to make up the defects of the prior art, the invention provides the preparation method of the dimethyl carbonate, and the preparation method has good catalytic effect of directly preparing the dimethyl carbonate by taking methanol and carbon dioxide as raw materials.
The invention is realized by the following technical scheme:
The preparation method of the dimethyl carbonate is characterized in that: carbon dioxide and methanol are taken as raw materials, a catalyst is added into a fixed bed reactor, and CO is introduced2Purging, continuously introducing CO2Heating to 120-140 deg.C, maintaining constant temperature, adding methanol under 0.5-0.8MPa, and reacting to obtain dimethyl carbonate; the catalyst is a supported catalyst and comprises an active center and a carrier; the active center is a transition metal, and the carrier comprises silicon dioxide, aluminum oxide and one of alkali metal or alkaline earth metal.
Preferably, the catalyst active center comprises at least two of Co, Cu, Mn, Ni and Mo.
Preferably, the catalyst carrier contains SiO2Is 45-90% by mass, A12O3the mass percentage is 5-30%.
Further, the alkali metal or alkaline earth metal in the catalyst carrier is one of Rb, Cs, Mg and Sr.
Furthermore, the mass fraction of the alkali metal and the alkaline earth metal in the catalyst carrier is 5-20%.
Preferably, the reaction temperature is 140 ℃ and the reaction pressure is 0.6 MPa.
Preferably, the catalyst carrier is prepared by adopting the following method: under the condition of stirring, uniformly mixing an alkali metal or alkaline earth metal precursor with a silicon dioxide and alumina precursor aqueous solution at the temperature of 20-85 ℃, adding acid to adjust the pH value to 0.5-5.5, continuously stirring, carrying out spray drying and forming on the mixture to obtain spherical particles with the particle size of 50-100 mu m, and roasting in an air atmosphere to obtain the carrier.
The invention has the beneficial effects that: the invention adopts the combined action of the bimetallic active centers, improves the activity of the catalyst, improves the reaction conversion rate and the selectivity of a target product, and under the reaction condition of the invention, the selectivity of the dimethyl carbonate is close to 100 percent, the catalyst can obviously reduce the reaction pressure, and the selectivity and the total carbon conversion rate of the dimethyl carbonate are high, thereby being hopeful to realize industrialized expanded production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof to assist those skilled in the art in providing a more complete, accurate and thorough understanding of the inventive concept and aspects thereof, and the scope of the present invention includes, but is not limited to, the following examples, and any modifications in the details and form of the technical aspects thereof that fall within the spirit and scope of the present application are intended to be included therein.
Example 1
(1) Preparing a carrier: weighing 10kg of silica sol (30 wt%) under stirring, adding 2kg of aluminum nitrate during stirring, adding 1kg of magnesium nitrate after dissolution, uniformly mixing at normal temperature, adding concentrated nitric acid to adjust the pH value, continuously stirring at 50 ℃ for 24h, cooling to room temperature, and spray drying to obtain spherical SiO with particle size of about 50 mu m2-Al2O3MgO powder, which is then roasted for 5 hours at 650 ℃ in an air atmosphere and cooled to room temperature for later use;
(2) Preparing a catalyst: uniformly dispersing 5kg of carrier dry particles into a solvent, sequentially adding 180g of cobalt nitrate and 195g of copper nitrate, introducing inert gas shielding gas, heating and refluxing at 70 ℃, evaporating the solvent to dryness, and continuously roasting in air at 300 ℃ for 24 hours to obtain a catalyst Co-Cu/SiO2-Al2O3-MgO。
Example 2
The carrier preparation was the same as in example 1, step (1); catalysisPreparation of the catalyst Co-Mn/SiO was carried out in the same manner as in (2) in example 1, except that copper nitrate was replaced with manganese nitrate2-Al2O3-MgO。
Example 3
The carrier preparation was the same as in example 1, step (1); the catalyst preparation was the same as in example 1, step (2), and copper nitrate was replaced with nickel nitrate to obtain Co-Ni/SiO2-Al2O3-MgO。
Example 4
The carrier preparation was the same as in example 1, step (1); catalyst preparation As in example 1, step (2), the copper nitrate was replaced with molybdenum nitrate to obtain Co-Mo/SiO2-Al2O3-MgO。
Example 5
The carrier preparation was the same as in example 1, step (1); the catalyst preparation was the same as in example 1, step (2), and cobalt nitrate was replaced with manganese nitrate to obtain a catalyst Mn-Cu/SiO2-Al2O3-MgO。
Example 6
The carrier preparation was the same as in example 1, step (1); the catalyst was prepared in the same manner as in the step (2) of example 1 by replacing cobalt nitrate with nickel nitrate to obtain a Ni-Cu/SiO catalyst2-Al2O3-MgO。
example 7
The carrier preparation was the same as in example 1, step (1); the catalyst preparation was the same as in example 1, step (2), and the catalyst Mo-Cu/SiO was prepared by replacing the cobalt nitrate with molybdenum nitrate2-Al2O3-MgO。
Example 8
The carrier preparation was the same as in example 5, step (1); catalyst preparation As in example 5 step (2), the copper nitrate was replaced with nickel nitrate to obtain a catalyst Mn-Ni/SiO2-Al2O3-MgO。
Example 8
The carrier preparation was the same as in example 5, step (1); catalyst preparation As in example 5 step (2), the copper nitrate was replaced with molybdenum nitrate to obtain a catalyst Mn-Mo/SiO2-Al2O3-MgO。
Example 10
The carrier preparation was the same as in example 6, step (1); catalyst preparation As in example 6 step (2), the copper nitrate was replaced with molybdenum nitrate to obtain Ni-Mo/SiO2-Al2O3-MgO。
Example 11
1g of the catalyst obtained in examples 1 to 5 was charged into a fixed bed reactor, and CO was introduced thereinto2Purging for 10min, and continuously introducing CO2Heating to 140 ℃, keeping constant temperature, adding 1mol of methanol under the pressure of 0.6MPa, fully reacting, condensing the product, analyzing the product by using gas chromatography, using n-decane as an internal standard substance, calculating the conversion rate of the methanol and the selectivity of the dimethyl carbonate, detecting the temperature at 100 ℃, and sampling the sample at 200 ℃, wherein the results are as follows:
Claims (7)
1. A preparation method of dimethyl carbonate is characterized by comprising the following steps: carbon dioxide and methanol are taken as raw materials, a catalyst is added into a fixed bed reactor, and CO is introduced2Purging, continuously introducing CO2Heating to 120-140 deg.C, maintaining constant temperature, adding methanol under 0.5-0.8MPa, and reacting to obtain dimethyl carbonate; the catalyst is a supported catalyst and comprises an active center and a carrier; the active center is a transition metal, and the carrier comprises silicon dioxide, aluminum oxide and one of alkali metal or alkaline earth metal.
2. The method for preparing dimethyl carbonate according to claim 1, wherein: the active center of the catalyst comprises at least two of Co, Cu, Mn, Ni and Mo.
3. The method for preparing dimethyl carbonate according to claim 1, wherein: the catalyst carrier contains SiO2Is 45-90% by mass, A12O3The mass percentage is 5-30%.
4. the method for preparing dimethyl carbonate according to claim 1, wherein: the alkali metal or alkaline earth metal in the carrier is one of Rb, Cs, Mg and Sr.
5. The method for preparing dimethyl carbonate according to claim 4, wherein: the mass fraction of alkali metal and alkaline earth metal in the carrier is 5-20%.
6. The method for preparing dimethyl carbonate according to claim 1, wherein: the reaction temperature is 140 ℃ and the reaction pressure is 0.6 MPa.
7. The method for preparing dimethyl carbonate according to claim 1, wherein: the catalyst carrier is prepared by the following method: under the condition of stirring, uniformly mixing an alkali metal or alkaline earth metal precursor with a silicon dioxide and alumina precursor aqueous solution at the temperature of 20-85 ℃, adding acid to adjust the pH value to 0.5-5.5, continuously stirring, carrying out spray drying and forming on the mixture to obtain spherical particles with the particle size of 50-100 mu m, and roasting in an air atmosphere to obtain the carrier.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112574036A (en) * | 2020-12-28 | 2021-03-30 | 山东德普化工科技有限公司 | Preparation method and application of dimethyl carbonate |
| CN112679351A (en) * | 2020-12-29 | 2021-04-20 | 山东德普化工科技有限公司 | Production process of dimethyl carbonate |
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