CN113769770B - Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application - Google Patents
Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims abstract description 12
- 239000001354 calcium citrate Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 235000013337 tricalcium citrate Nutrition 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- 239000002638 heterogeneous catalyst Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/942—Calcium carbide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a catalyst for synthesizing dimethyl carbonate by transesterification, a catalyst and application thereof. The method comprises the following steps: and carbonizing the calcium citrate to obtain the catalyst. The carbonization temperature is 500-900 ℃; the carbonization time is 1-3 hours. The catalyst of the invention can reduce the dosage of the catalyst while maintaining higher conversion rate, greatly shortens the reaction time and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of solid base catalysts, in particular to a heterogeneous catalyst, a preparation method of a catalyst for synthesizing dimethyl carbonate by transesterification, the catalyst and application of the catalyst in synthesizing dimethyl carbonate by transesterification.
Background
Dimethyl carbonate (Dimethyl carbonate, DMC) is an important environment-friendly chemical intermediate, has the advantages of higher dielectric constant, oxygen content (53%), octane number (105), lower toxicity, quick biodegradability and the like, and is widely applied to the fields of polycarbonate raw materials, electrolyte solvents, additives of fuel oil and the like; in recent years, research on DMC and its derivatives has become one of the world's chemical research hotspots. The synthesis of DMC mainly comprises a phosgene route, a carbonylation route and a transesterification route; compared with other routes, the transesterification route has mild reaction conditions, the raw materials are environment-friendly, the method not only accords with the current green synthesis process, but also has extremely high industrial value in co-production of the product glycol; therefore, the synthesis of DMC has become a mainstream route.
Catalysts currently used in transesterification to synthesize DMC are largely divided into two broad categories, homogeneous and heterogeneous. Homogeneous catalysts include triethylamine, sodium methoxide, metal acetates, alkali metal salts, and the like; but has great disadvantages in the later separation use. The heterogeneous catalyst has the greatest advantage that the separation of the product from the catalyst can be achieved in a simple manner (e.g. centrifugation, filtration, etc.) at a later stage; patent 200310109693 discloses a method for preparing a composite catalyst of zirconia and calcium fluoride; when the reaction temperature is 120 ℃ and the reaction time is 48 hours, the yield of the dimethyl carbonate can reach 97 percent. Patent 201510700289.2 discloses a preparation method of a graphene oxide-based magnesium oxide supported catalyst; the method has high preparation cost, and is unfavorable for the industrial mass production in the later period, wherein the selectivity and the yield of the dimethyl carbonate are respectively 99.3 percent and 87.1 percent. Patent 201610988571.X discloses a method for synthesizing dimethyl carbonate by using ethylene carbonate and methanol as raw materials and active carbon as a catalyst, wherein the method is carried out in a high-pressure reaction kettle, when the dosage of the active carbon is 20% (compared with the mass fraction of the ethylene carbonate), the pressure is 0.3MPa, the reaction temperature is 160 ℃, and the reaction time is 8 hours, the conversion rate and the selectivity of the ethylene carbonate are as high as 97% and 99%; however, the reaction needs to be carried out under high pressure and high temperature conditions, and the reaction time is long.
In summary, heterogeneous catalysts currently used for synthesizing DMC by transesterification generally have the problems of large catalyst reaction amount, high reaction temperature, long reaction time and the like. In view of the above, it is important to design and develop a heterogeneous catalyst with low preparation cost, good catalytic performance and short reaction period.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a catalyst for synthesizing dimethyl carbonate by transesterification, a catalyst and application thereof. The catalyst disclosed by the invention is a heterogeneous catalyst, has the advantages of lower preparation cost and better catalytic performance, can obviously shorten the reaction time, reduce the reaction temperature, and is suitable for large-scale production.
The invention aims at providing a preparation method of a catalyst for synthesizing dimethyl carbonate by transesterification.
The method comprises the following steps:
and carbonizing the calcium citrate to obtain the catalyst.
In a preferred embodiment of the present invention,
the carbonization temperature is 500-900 ℃;
the carbonization time is 1-3 hours.
In a further preferred embodiment of the invention,
the carbonization temperature is 700-800 ℃.
In a further preferred embodiment of the invention,
and during carbonization, heating to the carbonization temperature at a heating rate of 3-5 ℃/min.
In a more preferred embodiment of the present invention,
the CaC-based catalyst is prepared by using calcium citrate as a raw material and adjusting carbonization temperature to promote the calcium citrate to be cracked.
Typical methods of catalyst preparation are as follows, but are not limited to such methods: weighing a certain mass of calcium citrate in a clean quartz ark, placing the calcium citrate in a tube furnace which can be programmed to heat under the protection of nitrogen, heating to 500-900 ℃ according to the heating rate of 3-5 ℃/min, preserving heat for 1-3h, taking out the calcium citrate after cooling to room temperature, and grinding the calcium citrate to obtain heterogeneous catalysts with different carbonization temperatures.
In the catalyst of the present invention, the carbonization temperature is 500-900 ℃, preferably 700-800 ℃, and when the carbonization temperature is below 500 ℃, calcium carbonate is embedded in the carbonaceous substrate, but the activity is low enough to effectively catalyze the transesterification reaction. When the carbonization temperature is higher than 500 ℃ but lower than 700 ℃, the mixture of calcium carbonate and calcium oxide is embedded in the carbonaceous matrix, and the activity of the catalyst is greatly improved due to the generation of the calcium oxide. When the carbonization temperature is higher than 800 ℃ but lower than 900 ℃, the catalyst is easy to sinter in the carbonization process, so that the catalytic performance is reduced, and the transesterification reaction can be effectively catalyzed. More preferably, the carbonization temperature is 800 ℃, the carbonization time is 2 hours, and the content of the obtained active component is the largest in the carbonization process, at this time, the catalytic performance of the catalyst is the best.
It is a further object of the present invention to provide a catalyst prepared by the process according to one of the objects of the present invention.
The invention also aims to provide an application of the catalyst in synthesizing dimethyl carbonate by transesterification.
In a preferred embodiment of the present invention,
methanol and ethylene carbonate are used as raw materials, the catalytic synthesis of dimethyl carbonate is adopted, the reaction temperature is 70-120 ℃, and the reaction time is 5-30min;
the catalyst dosage is 0.5-2.5% of the mass of the ethylene carbonate;
the molar ratio of the methanol to the ethylene carbonate is 4-12:1.
In a further preferred embodiment of the invention,
the reaction temperature is 90-110 ℃; the reaction time is 15-25min;
the catalyst is used in an amount of 1.0 to 2.0wt% based on the mass of the ethylene carbonate.
The reaction of ethylene carbonate with methanol to prepare dimethyl carbonate belongs to the field of transesterification, kabashima et al [3] As a result of the study, methoxy groups (available for methanolysis) have a high catalytic activity in transesterification, and the transesterification starts to occur in the presence of methoxy groups. Next, for the transesterification catalyst, what is needed is to promote the decomposition of methanol to methoxy (CH) 3 OH＝CH 3 O - +H + ). CaC-based catalysts with appropriate base amount and basicity can make H in methanol + Adsorption in catalyst for oxidationThe calcium is grown on lattice oxygen to form a large amount of methoxy groups, which in turn promotes the reaction.
[3]Kabashima H,Tsuji H,Hattori H.Michael addition of methyl crotonate over solid base catalysts[J].Applied Catalysis A General,1997,165(1-2):319-325.
The invention provides a preparation method of a supported catalyst; the carrier is composed of two parts of active species and a carrier, wherein the general expression method is A/B, wherein A represents the active species, and B represents the carrier; whereas conventional preparation methods are generally divided into two steps, the first step is to load the active species onto a carrier and the second step is to perform activation.
However, we have found that calcium citrate, due to its specific structure, readily cleaves to form active species and gaseous small molecules at high temperatures under inert gas protection, while also retaining a large amount of carbon species that can act as carriers for these active species; that is, only one step (carbonization) is required to obtain a supported carbon-based catalyst; compared with the traditional preparation method of the catalyst, the preparation method has breakthrough progress and greatly reduces the preparation cost.
The beneficial effects of the invention are as follows:
(1) The catalyst has low preparation cost and simple method, and heterogeneous catalysts can be obtained in batches rapidly through carbonization treatment.
(2) The catalyst of the invention is applied to the synthesis of the dimethyl carbonate, the transesterification reaction condition is mild, and the reaction time is short and the reaction rate is fast on the basis of keeping higher conversion rate of reactant ethylene carbonate and selectivity of product dimethyl carbonate.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1:
and (3) preparing the catalyst, namely placing the calcium citrate with a certain mass in a clean quartz ark, placing the calcium citrate in a tube furnace under the protection of nitrogen, heating to 800 ℃ at a heating rate of 4 ℃/min, preserving heat for 2 hours, cooling to room temperature, and grinding to obtain the CaC-based catalyst.
Catalytic reaction, adding 0.088g of CaC-based catalyst, 8.8g of ethylene carbonate and 25.6g of methanol into a 150ml round bottom flask, stirring at 100 ℃ for 30min, and taking products in the flask for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 78.5%, and the selectivity and the yield of the dimethyl carbonate are 99.0% and 77.7%, respectively.
Example 2:
according to the preparation method of the catalyst in the example 1, the temperature is raised to 700 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, then the catalyst is cooled to room temperature, and the CaC-based catalyst is obtained after grinding.
0.088g of the catalyst, 8.8g of ethylene carbonate and 25.6g of methanol are added into a 150ml round bottom flask, the mixture is stirred at 100 ℃ for reaction for 30min, and products in the flask are taken for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 73.7%, and the selectivity and the yield of the dimethyl carbonate are 97.7% and 72.0%, respectively.
Example 3:
according to the preparation method of the catalyst in the example 1, the temperature is raised to 900 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 2 hours, then the catalyst is cooled to room temperature, and the CaC-based catalyst is obtained after grinding.
0.088g of the catalyst, 8.8g of ethylene carbonate and 25.6g of methanol are added into a 150ml round bottom flask, the mixture is stirred at 100 ℃ for reaction for 30min, and products in the flask are taken for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 77.8%, and the selectivity and the yield of the dimethyl carbonate are 98.6% and 76.7%, respectively.
Example 4:
the catalyst prepared in example 1 was used.
0.132g of the catalyst, 8.8g of ethylene carbonate and 25.6g of methanol are added into a 150ml round bottom flask, the mixture is stirred at 100 ℃ for reaction for 20min, and products in the flask are taken for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 81.2%, and the selectivity and the yield of the dimethyl carbonate are 99.3% and 80.6%, respectively.
Comparative example 1:
0.088g of sodium methoxide, 8.8g of ethylene carbonate and 25.6g of methanol are added into a 150ml round bottom flask, the mixture is stirred at 100 ℃ for reaction for 20min, and products in the flask are taken for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 69.6%, and the selectivity and the yield of the dimethyl carbonate are 99.3% and 69.1%, respectively.
Comparative example 2:
0.132g of sodium methoxide, 8.8g of ethylene carbonate and 25.6g of methanol are added into a 150ml round bottom flask, the mixture is stirred at 100 ℃ for reaction for 20min, and products in the flask are taken for detection and analysis, wherein the analysis result shows that the conversion rate of the ethylene carbonate is 74.9%, and the selectivity and the yield of the dimethyl carbonate are 99.1% and 74.2%, respectively.
Sodium methoxide is the only homogeneous catalyst produced industrially in China at present, and as can be seen from the data of examples and comparative examples, the catalyst has higher conversion rate under the same conditions compared with sodium methoxide, and is easy to separate from products and can be reused.
Table 1 shows some data of heterogeneous catalysts in some documents disclosed in the prior art, and it can be seen from the data of table 1 that the catalyst of the present application has a reduced catalyst usage and a greatly reduced reaction time while maintaining a high yield.
TABLE 1
Note that: the last column is the catalyst prepared in example 4.
The above-described embodiments are provided to illustrate the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. An application of catalyst in synthesizing dimethyl carbonate by transesterification,
the method is characterized in that:
the preparation method of the catalyst comprises the following steps:
carbonizing calcium citrate under the protection of nitrogen, cooling to room temperature and grinding to obtain the catalyst;
the carbonization temperature is 700-900 ℃; carbonizing for 1-3 hours;
during carbonization, heating to the carbonization temperature at a heating rate of 3-5 ℃/min;
methanol and ethylene carbonate are used as raw materials, and the catalyst is adopted to synthesize dimethyl carbonate;
the molar ratio of the methanol to the ethylene carbonate is 4-12:1; and/or the number of the groups of groups,
the catalyst is used in an amount of 0.5-2.5% of the mass of the ethylene carbonate.
2. The use according to claim 1, wherein:
the carbonization temperature is 700-800 ℃.
3. The use according to claim 1, wherein:
the reaction temperature is 70-120 ℃ and the reaction time is 5-30min.
4. The use according to claim 1, wherein:
the catalyst is used in an amount of 1.0 to 2.0wt% based on the mass of the ethylene carbonate.
5. A use according to claim 3, wherein:
the reaction temperature is 90-110 ℃; the reaction time is 15-25min.
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| "Synthesis of dimethyl carbonate by transesterification over CaO/carbon composites";Tong Wei et al.;《Green Chemistry》;第5卷;实验部分 * |
| "多孔碳及氧化物/多孔碳锂离子电池负极材料的制备与性能";高阳;《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》(第3期);第22-23页 * |
| "钙基高温二氧化碳吸附材料的制备及其吸附性能";张明明;《中国优秀博硕士学位论文全文数据库（博士）工程科技Ⅰ辑》(第9期);第41-42页 * |
| 张明明."钙基高温二氧化碳吸附材料的制备及其吸附性能".《中国优秀博硕士学位论文全文数据库（博士）工程科技Ⅰ辑》.2014,(第9期),第41-42页. * |
| 高阳."多孔碳及氧化物/多孔碳锂离子电池负极材料的制备与性能".《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》.2018,(第3期),第22-23页. * |
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