CN115382534A - Method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide - Google Patents
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- CN115382534A CN115382534A CN202211047738.4A CN202211047738A CN115382534A CN 115382534 A CN115382534 A CN 115382534A CN 202211047738 A CN202211047738 A CN 202211047738A CN 115382534 A CN115382534 A CN 115382534A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 53
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- SPFUWSBRIIKPOR-UHFFFAOYSA-N carbonyl dichloride;methanol Chemical compound OC.ClC(Cl)=O SPFUWSBRIIKPOR-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HUFRYSPDNYTSMI-UHFFFAOYSA-N sodium carbonyl dichloride methanolate Chemical compound C(=O)(Cl)Cl.C[O-].[Na+] HUFRYSPDNYTSMI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/83—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 rare earths or actinides
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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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- 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
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide.
Background
Dimethyl carbonate (DMC) is a basic organic chemical starting material known as the green organic chemical for the 21 st century. The method for producing the dimethyl carbonate is more, such as a methanol phosgene method, a sodium methoxide phosgene method, a methanol oxidation hydroxylation method, a methanol and carbon monoxide electrochemical reaction method, a carbon dioxide and methanol supercritical synthesis method, a urea alcoholysis method and an ester exchange method. Some of these methods have been industrialized and some are under development and exploration.
The method for synthesizing dimethyl carbonate by oxidative carbonylation using methanol, carbon monoxide and oxygen as raw materials is divided into a gas phase method and a liquid phase method. The gas phase method is represented by a patent of Ube corporation of Japan, and NO is selected as a catalyst, so that the deactivation of the catalyst is reduced. The liquid phase method has the advantages of easily obtained raw materials, simple process, no three-waste pollution, low cost and the like, and takes the patents (EP 04607352A2, 1991) of Enichem company of Italy as representatives to firstly realize the industrialization of synthesizing DMC by methanol oxidation and carbonylation, the patents consist of a reaction tube and a return tube, and the problems of insufficient contact of gas, liquid and solid, low reaction efficiency, inconvenient amplification and the like caused by large bubbles exist in the reaction process. The patent is improved by Li Guangxing et al (CN 1204644A, 1999) of China university of science and technology, a multi-tube circulation reactor is adopted, the number of reaction tubes is increased, and a distributor is arranged every 1000-5000mm, so that the medium is uniformly distributed, the contact area of reactants is increased, and the conversion rate of methanol is further increased. However, the reaction and separation process is relatively complex, and the DMC content in the crude product obtained by separation after the system is stabilized is only 19.2%. Wang Gong Ying et al (CN 1333086A, 2002) of Chinese academy of sciences institute of organic chemistry adopts CuCl complex catalyst to make methanol oxidative carbonylation reaction in intermittent high-pressure kettle, DMC selectivity is greater than or equal to 99.9, methanol single-pass conversion rate is greater than or equal to 32%, and can greatly raise DMC production capacity. The catalyst produced in batch by the technology is successfully applied to a device for producing 4000t/a dimethyl carbonate by using a CuMP catalyst (Wanggui, research progress of green synthesis technology of carbonate, J fine chemical engineering, 2013, 30 (4)). Cao Yong et al (CN 1376665a, 2002) at university of compound denier, in a batch stirred tank reactor, a liquid phase oxidative carbonylation of methanol is carried out using a heteroatom-polymer complex catalyst, methanol and catalyst are added first, after stirring thoroughly, CO and O2 are introduced, and the reaction conditions are as follows: 90-160 ℃, 1.0-5.0MPa of pressure and 99.5 percent of reaction selectivity. After the batch reaction, the aeration was stopped, the reaction solution was removed and distilled to give a CH3OH-DMC azeotrope. To obtain DMC with higher purity, it is necessary to subject the azeotropic product obtained by distillation to further special distillation, such as pressure distillation, extractive distillation, etc.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provides a method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide.
In order to achieve the above object, the present invention provides a method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide: methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide, so as to obtain the dimethyl carbonate product.
Preferably, the cerium-based oxide has a general formula of MCeOX, wherein M may be In, fe, co, cu, ni, and Zr.
Preferably, the cerium-based oxide is prepared by a liquid phase precipitation method, and comprises the following steps: m (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O are prepared into 0.1mol/L mixed solution according to the mol ratio of 1:9, 1mol/L ammonia water is added into the solution after the first heating, the PH value of a precipitation system is controlled, the solution is stirred for 2 hours, the solution is stood and aged for 3 hours, the solution is washed, filtered, heated and dried for 12 hours for the second time, and then the solution is roasted for 4 hours at the temperature of 260-340 ℃ to prepare the cerium-based oxide.
Preferably, the pH is 8 to 10, preferably 9.
Preferably, the temperature of the first heating is 80-100 ℃, preferably 90 ℃; the temperature of the second heating is 80-100 ℃, and preferably 90 ℃.
Preferably, the mass ratio of the cerium-based oxide to the methanol is 0.002 to 0.004:1, preferably 0.003.
Preferably, the reaction is carried out under a carbon dioxide pressure of 1.3 to 1.80MPa, preferably under an oxygen pressure of 1.5 MPa.
Preferably, the reaction is carried out at a temperature of from 120 ℃ to 160 ℃, preferably at a temperature of 140 ℃.
Preferably, the reaction is heated at 140 ℃ for 4 hours.
Preferably, after the reaction is finished, the dimethyl carbonate product is obtained by distillation separation.
The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide has the beneficial effects that:
1. the invention has cheap reaction raw materials, environment-friendly and mild reaction process, no waste, and safer and more reliable synthesis process because no toxic and harmful reactants and solvents are used;
2. the invention introduces cerium-based oxide as a catalyst, and improves the conversion rate and purity of dimethyl carbonate by adjusting the temperature, pressure and PH value during synthesis.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide, which comprises the following steps: methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide, so as to obtain the dimethyl carbonate product.
Further, the general formula of the cerium-based oxide is MCeOX, wherein M can be In, fe, co, cu, ni and Zr.
Further, the cerium-based oxide is prepared by a liquid phase precipitation method and comprises the following steps: m (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O are prepared into 0.1mol/L mixed solution according to the mol ratio of 1:9, 1mol/L ammonia water is added into the solution after the first heating, the PH value of a precipitation system is controlled, the solution is stirred for 2 hours, the solution is stood and aged for 3 hours, the solution is washed, filtered, heated and dried for 12 hours for the second time, and then the solution is roasted for 4 hours at the temperature of 260-340 ℃ to prepare the cerium-based oxide.
Further, the pH is 8 to 10, preferably 9.
Further, the temperature of the first heating is 80-100 ℃, preferably 90 ℃; the temperature of the second heating is 80-100 ℃, and preferably 90 ℃.
Further, the mass ratio of the cerium-based oxide to the methanol is 0.002-0.004: 1, preferably 0.003.
Further, the reaction is carried out under a carbon dioxide pressure of 1.3 to 1.80MPa, preferably under an oxygen pressure of 1.5 MPa.
Further, the reaction is carried out at a temperature of 120 ℃ to 160 ℃, preferably at a temperature of 140 ℃.
Further, the reaction was heated at 140 ℃ for 4 hours.
Further, after the reaction is finished, the dimethyl carbonate product is obtained by distillation separation.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates a method for preparing dimethyl carbonate from methanol catalyzed by cerium-based oxide according to the present invention.
Preparing 0.1mol/L mixed solution of In (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O according to the molar ratio of 1:9, adding 1mol/L ammonia water into the solution after first heating, controlling the PH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
Example 2
This example illustrates a method for preparing dimethyl carbonate from methanol catalyzed by cerium-based oxide according to the present invention.
Preparing 0.1mol/L mixed solution of Fe (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O according to the molar ratio of 1:9, adding 1mol/L ammonia water into the solution after first heating, controlling the PH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
Example 3
This example illustrates a method for preparing dimethyl carbonate from methanol catalyzed by cerium-based oxide according to the present invention.
Preparing Co (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O into 0.1mol/L mixed solution according to the mol ratio of 1:9, adding 1mol/L ammonia water into the solution after first heating, controlling the PH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
Example 4
This example illustrates a method for preparing dimethyl carbonate from methanol catalyzed by cerium-based oxide according to the present invention.
Preparing a 0.1mol/L mixed solution of Cu (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O according to a molar ratio of 1:9, adding 1mol/L ammonia water into the solution after first heating, controlling the pH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
Example 5
This example illustrates a method for preparing dimethyl carbonate from methanol catalyzed by cerium-based oxide according to the present invention.
Preparing 0.1mol/L mixed solution of Ni (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O according to the mol ratio of 1:9, adding 1mol/L ammonia water into the solution after the first heating, controlling the PH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
Example 6
This example illustrates the preparation of dimethyl carbonate by the catalysis of methanol with cerium-based oxide.
Preparing Zr (NO 3) X.yH 20 and (NH 3) 2Ce (NO 3) 4.6H 2O into 0.1mol/L mixed solution according to the molar ratio of 1:9, adding 1mol/L ammonia water into the solution after the first heating, controlling the PH value of a precipitation system, stirring for 2H, standing and aging for 3H, washing and filtering, heating and drying for 12H for the second time, then roasting for 4H at 300 ℃ to prepare cerium-based oxide,
methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product
The invention introduces cerium-based oxide as a catalyst, and improves the conversion rate and purity of dimethyl carbonate by adjusting the temperature, pressure and PH value during synthesis.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide is characterized by comprising the following steps: methanol is adopted as a raw material, cerium-based oxide is adopted as a catalyst, and the reaction is carried out for a period of time in the atmosphere of carbon dioxide to obtain a dimethyl carbonate product.
2. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 2, wherein the cerium-based oxide has a general formula of MCeO X Wherein M can be In, fe, co, cu, ni and Zr.
3. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 1, wherein: the cerium-based oxide is prepared by adopting a liquid phase precipitation method and comprises the following steps: mixing M (NO) 3 ) X ·yH 2 0 and (NH) 3 ) 2 Ce(NO 3 ) 4 ·6H 2 O is prepared into 0.1mol/L mixed solution according to the molar ratio of 1:9, 1mol/L ammonia water is added into the solution after the first heating, the PH value of a precipitation system is controlled, the solution is stirred for 2 hours, the solution is kept stand and aged for 3 hours, the solution is heated and dried for 12 hours after being washed and filtered, and then the solution is roasted for 4 hours at the temperature of 260-340 ℃ to prepare the cerium-based oxide.
4. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 3, wherein: the pH value is 8 to 10, preferably 9.
5. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 3, wherein: the temperature of the first heating is 80-100 ℃, and the optimal temperature is 90 ℃; the temperature of the second heating is 80-100 ℃, and preferably 90 ℃.
6. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 1, wherein: the mass ratio of the cerium-based oxide to the methanol is 0.002-0.004: 1, preferably 0.003.
7. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 1, wherein: the reaction is carried out under a carbon dioxide pressure of 1.3 to 1.80MPa, preferably under an oxygen pressure of 1.5 MPa.
8. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 1, wherein: the reaction is carried out at a temperature of 120 ℃ to 160 ℃, preferably at a temperature of 140 ℃.
9. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claim 8, wherein: the reaction was heated at 140 ℃ for 4 hours.
10. The method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide as claimed in claims 1 to 9, wherein: after the reaction is finished, the dimethyl carbonate product is obtained by distillation separation.
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| CN116459839A (en) * | 2022-12-09 | 2023-07-21 | 中国科学院大连化学物理研究所 | Nanometer powder oxide catalyst and preparation method and application thereof |
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| CN111905752A (en) * | 2020-08-12 | 2020-11-10 | 陕西科技大学 | Method for synthesizing dimethyl carbonate by using superfine cobalt-cerium bimetallic nano catalyst as catalyst |
| CN112823879A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol |
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