CN111635313B - Method for preparing electrolyte solvent dimethyl carbonate by oxidizing methyl acetate under catalysis of selenium - Google Patents
Method for preparing electrolyte solvent dimethyl carbonate by oxidizing methyl acetate under catalysis of selenium Download PDFInfo
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- CN111635313B CN111635313B CN202010507325.4A CN202010507325A CN111635313B CN 111635313 B CN111635313 B CN 111635313B CN 202010507325 A CN202010507325 A CN 202010507325A CN 111635313 B CN111635313 B CN 111635313B
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- ammonium bromide
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 33
- 239000011669 selenium Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 28
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 title claims abstract description 11
- 239000003792 electrolyte Substances 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- 230000001590 oxidative effect Effects 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- ZLNXOZTXXWOOCD-UHFFFAOYSA-M diethyl-di(propan-2-yl)azanium bromide Chemical compound [Br-].C(C)[N+](C(C)C)(C(C)C)CC ZLNXOZTXXWOOCD-UHFFFAOYSA-M 0.000 claims description 2
- AATGHKSFEUVOPF-UHFFFAOYSA-N diethylazanium;bromide Chemical compound [Br-].CC[NH2+]CC AATGHKSFEUVOPF-UHFFFAOYSA-N 0.000 claims description 2
- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 claims description 2
- VVNBOKHXEBSBQJ-UHFFFAOYSA-M dodecyl(triethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](CC)(CC)CC VVNBOKHXEBSBQJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- KIJXMUOJNZXYHU-UHFFFAOYSA-N n-propan-2-ylpropan-2-amine;hydrobromide Chemical compound [Br-].CC(C)[NH2+]C(C)C KIJXMUOJNZXYHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing electrolyte solvent dimethyl carbonate by oxidizing methyl acetate under the catalysis of selenium, which comprises the following steps: mixing a selenium catalyst, ferric trifluoride and methyl acetate according to a mass ratio of 0.001-0.005: 0.0002 to 0.0006:1, under the oxygen pressure of 0.5-1.0 MPa, 100-140 o Heating for 4-8 hours, and distilling to obtain dimethyl carbonate product. The method for synthesizing the dimethyl carbonate has the advantages of cheap and safe reaction raw materials and clean overall route, and is a brand new synthesis process for synthesizing the dimethyl carbonate.
Description
Technical Field
The invention relates to a method for preparing electrolyte solvent dimethyl carbonate by oxidizing methyl acetate under the catalysis of selenium, belonging to the technical field of chemical synthesis.
Background
Dimethyl carbonate (namely DMC) is an important chemical solvent with low toxicity, environmental protection and safety. It can be used as a solvent in battery electrolytes. With the rise of the lithium battery industry, the market demand of DMC is increasingly expanding, and the DMC has good development prospect. The conventional production route for DMC is the phosgene process, but this route is being phased out due to the high toxicity and corrosiveness of phosgene and environmental problems caused by sodium chloride emissions. Currently, there are three synthetic routes commonly used: copper chloride or nitric oxide is used as a catalyst for oxidative carbonylation, propylene carbonate and methanol ester exchange reaction and urea methanolysis reaction. However, the above three methods still have problems such as the use of nitrogen oxides which destroy the ozone layer, the high toxicity of allyl alcohol which is a by-product, and the production of odorous ammonia gas by alcoholysis of urea. The problems are overcome, a new green and clean production route is developed, and the method has good application value.
Disclosure of Invention
The invention aims to provide a method for preparing dimethyl carbonate serving as an electrolyte solvent by catalyzing methyl acetate oxidation through selenium, wherein cheap and easily-obtained methyl acetate is used as a raw material, and the dimethyl carbonate is prepared by catalyzing oxygen oxidation through nano selenium-ferric trifluoride.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing electrolyte solvent dimethyl carbonate by oxidizing methyl acetate under the catalysis of selenium comprises the following steps: mixing a selenium catalyst, ferric trifluoride and methyl acetate according to a mass ratio of 0.001-0.005: 0.0002 to 0.0006:1, heating for 4-8 hours at 100-140 ℃ under the oxygen pressure of 0.5-1.0 MPa, and obtaining the dimethyl carbonate product through distillation and separation.
In the invention, the selenium catalyst is prepared by the following steps: : stirring and mixing an ethanol solution of sodium borohydride and selenium powder at the temperature of 0 +/-1 ℃, and then adding a mixture consisting of sugar, dodecyl ammonium bromide, triethyl ammonium bromide and diethyl ammonium bromide, diisopropyl ammonium bromide to obtain a mixed system; heating the mixed system to 20-60 ℃ under the stirring condition for reaction, obtaining precipitate after the reaction is finished, and calcining at the temperature of 450-550 ℃ after suction filtration to obtain the nano selenium material; the molar ratio of selenium powder, sugar, dodecyl triethyl ammonium bromide, diethyl diisopropyl ammonium bromide and sodium borohydride in the ethanol solution of sodium borohydride is 100: 1000: 8.20: 2.60: 100.
In the invention, the mass ratio of the selenium catalyst to the methyl acetate is 0.001-0.005: 1. among them, 0.003;
in the present invention, iron trifluoride is used as a co-catalyst. The mass ratio of the methyl acetate to the methyl acetate is 0.0002-0.0006: 1, wherein preferably 0.0004:1. under the condition, the conversion rate of the raw materials can be improved, and the reduction of selectivity caused by side reaction due to the use of excessive cocatalyst can be avoided.
In the present invention, the reaction is carried out in an oxygen gas of 0.5 to 1.0MPa, preferably 0.8MPa. Oxygen at this pressure can promote the full conversion of the raw material and avoid the reduction of product selectivity caused by transitional oxidation
In the invention, the reaction temperature is 100-140 ℃, wherein the reaction temperature is preferably 120 ℃, the temperature can ensure that the raw materials are fully converted, and the product selectivity is high.
In the present invention, the reaction time is 4 to 8 hours, and preferably 6 hours. Sufficient conversion of the starting materials is ensured at this reaction time.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing electrolyte solvent dimethyl carbonate by catalyzing methyl acetate to oxidize by selenium. The reaction raw materials are cheap, the reaction process is environment-friendly and mild, and no waste is generated. And because toxic and harmful reactants and solvents are not used, the synthesis process is safer and more reliable.
Detailed Description
In the invention, a selenium catalyst developed by the inventor (see patent No. ZL 201610899676.8) is used, a proper amount of ferric trifluoride cocatalyst is used, cheap and easily-obtained methyl acetate is used as a raw material under a certain pressure, and the dimethyl carbonate is prepared by catalyzing oxygen oxidation by selenium-ferric trifluoride, wherein the method is simple, the raw material is easily obtained, the reaction process is clean, the selectivity is high, and the method is a brand new synthesis process for synthesizing dimethyl carbonate and has a good application prospect.
The following examples illustrate the invention in more detail, but do not limit the invention further.
Example 1
First, a selenium catalyst was prepared according to the method of example 1 in the invention patent "a method for synthesizing nano-selenium material" (patent No. ZL 201610899676.8). Then, 100 g of methyl acetate, 0.3 g of the above selenium catalyst and 0.04 g (i.e., 40 mg) of iron trifluoride were charged into a high-pressure reactor, stirred, oxygenated, and reacted at 120 ℃ under 0.8MPa for 6 hours. After cooling, dimethyl carbonate (atmospheric boiling point 89.1-90.2 ℃) can be obtained by a distillation method, and the yield is 96%.
Example 2
The effect of using different amounts of selenium catalyst was tested as in example 1 under the other conditions and the results are shown in table 1.
TABLE 1 comparison of the effectiveness of the use of different amounts of selenium catalyst
From the above results, it was found that the mass ratio of the selenium catalyst to methyl acetate reached 0.001:1, dimethyl carbonate can be obtained in a higher yield. When the mass ratio of the selenium catalyst to the methyl acetate reaches 0.003. Therefore, from the viewpoint of efficiency, the use of a selenium catalyst in a mass ratio of 0.003 to methyl acetate is most effective (example 1). Meanwhile, the key of the reaction is that a selenium catalyst is needed, and the reaction does not occur without the selenium catalyst.
Example 3
The effect of the various cocatalysts was examined under otherwise the same conditions as in example 1, and the results are shown in Table 2.
TABLE 2 comparison of the effectiveness of different cocatalysts
From the above results, it is clear that the cocatalyst is essential in the reaction. No cocatalyst is added, and only selenium catalyst is used for catalysis, so that the product yield is only 53%, and the industrial production requirement cannot be met. The oxidation of methyl acetate is essentially a Baeyer-Villiger oxidation. According to our preliminary experience in the field of selenium-catalyzed reactions, the attack of the selenium peroxygen species on the carbonyl carbon positive center will first occur (adv. Synth. Cat. 2015,357, 955-960). Thus, the addition of a lewis acid catalyst facilitates the enhancement of the electropositivity of the carbon positive centers, thereby facilitating the reaction to occur. Iron trifluoride, as a metal salt with strongly electron-withdrawing groups, achieves this effect. According to the past experience, a series of Lewis acid catalysts are screened, and the Lewis acid catalysts have more or less effects. However, it is surprising that some of the common more Lewis acidic metal salts, such as ferric chloride, aluminum fluoride, yttrium triflate, etc., are far less effective than the common, inexpensive, but less frequently used ferric trifluoride. This experimental phenomenon illustrates that the effect of iron trifluoride is not limited to the expected lewis acids, where iron and fluorine, both of which play a key role in the activation of the catalyst. The fluorine salt without metal, such as ammonium fluoride, can also play a certain promoting effect. This further confirms the effect of the fluoride ion. By analysis, we believe that it is possible that fluoride ions, as small volume ions, readily penetrate the catalyst material, thereby activating the catalyst. In addition, the positive center of selenium in fluorine impregnated catalysts can be enhanced, thereby improving its oxidation and facilitating catalytic oxidation (appl. On the other hand, copper salts which, like iron, likewise have a variable valence, such as copper fluoride, also have a very good effect as cocatalysts. This suggests that the oxygen-carrying properties of variable valence iron also play a critical role in this reaction system, consistent with our topic group lead work results (adv. Synth. Call.2019, 361, 603-610). In summary, in this system, ferric trifluoride improves selenium catalyst activity through three pathways: (1) a lewis acid; (2) fluoride ion penetration; and (3) oxygen carrying effect of variable valence iron.
Example 4
The other conditions were the same as in example 1, and the effects of different mass ratios of iron trifluoride co-catalyst to methyl acetate were examined. The results of the experiment are shown in table 3.
TABLE 3 comparison of the effects of different mass ratios of iron trifluoride co-catalyst to methyl acetate
From the above results, it was found that the mass ratio of the iron trifluoride co-catalyst to the methyl acetate was 0.0004: the best effect (example 1). The amount of the cocatalyst is required to be such that the best effect can be achieved, but the amount is further increased, which is not beneficial to improving the effect of the catalyst, and the yield is slightly reduced.
Example 5
The effect of different reaction oxygen pressures was examined under the same conditions as in example 1, and the results are shown in Table 4.
TABLE 4 comparison of different oxygen pressure effects
From the above results, it was found that the reaction hardly occurred under normal pressure. A leap in yield occurs by increasing the pressure gradually to 0.5MPa, and the effect is best at a pressure of 0.8MPa (example 1). Further increasing the pressure does not significantly improve the reaction effect.
Example 6
The effect of the different reaction temperatures was examined under the same conditions as in example 1, and the results are shown in Table 5.
TABLE 5 comparison of the effects of different reaction temperatures
From the above results, the reaction was most effective at 120 ℃. Either too low or too high a temperature leads to a decrease in product yield.
Example 7
The effect of the different reaction times was examined under the same conditions as in example 1, and the results of the experiment are shown in Table 6.
TABLE 6 comparison of the effects of different reaction times
From the above results, it was found that the reaction reached an end point after 6 hours (example 1). Further extension of the time does not improve the product yield.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing electrolyte solvent dimethyl carbonate by catalyzing methyl acetate oxidation by selenium is characterized by comprising the following steps: methyl acetate is taken as a raw material, a selenium catalyst and ferric trifluoride are taken as a catalytic system, and the reaction is carried out for a period of time in an oxygen atmosphere to obtain a dimethyl carbonate product;
wherein, the preparation steps of the selenium catalyst are as follows: stirring and mixing an ethanol solution of sodium borohydride and selenium powder at the temperature of 0 +/-1 ℃, and then adding a mixture consisting of sugar, dodecyl ammonium bromide, triethyl ammonium bromide and diethyl ammonium bromide, diisopropyl ammonium bromide to obtain a mixed system; heating the mixed system to 20-60 ℃ under the stirring condition for reaction, obtaining precipitate after the reaction is finished, and calcining at the temperature of 450-550 ℃ after suction filtration to obtain the nano selenium material; the molar ratio of selenium powder, sugar, dodecyl triethyl ammonium bromide, diethyl diisopropyl ammonium bromide and sodium borohydride in the ethanol solution of sodium borohydride is 100: 1000: 8.20: 2.60: 100.
2. The method of claim 1, wherein: the mass ratio of the selenium catalyst to the methyl acetate is 0.001-0.005: 1.
3. the method of claim 1, wherein: the mass ratio of the selenium catalyst to the methyl acetate is 0.003: 1.
4. The method of claim 1, wherein: the mass ratio of ferric trifluoride to methyl acetate is 0.0002-0.0006: 1.
5. the method of claim 1, wherein: the mass ratio of ferric trifluoride to methyl acetate is 0.0004:1.
6. The method of claim 1, wherein: reacting under the oxygen pressure of 0.5-1.0 MPa.
7. The method of claim 1, wherein: the reaction was carried out under an oxygen pressure of 0.8MPa.
8. The method of claim 1, wherein: heating and reacting for 4-8 hours at 100-140 ℃.
9. The method of claim 1, wherein: the reaction was heated at 120 ℃ for 6 hours.
10. The method of claim 1, wherein: after the reaction is finished, the dimethyl carbonate product is obtained by distillation separation.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5235087A (en) * | 1990-06-30 | 1993-08-10 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl carbonates |
| CN1185757A (en) * | 1996-02-07 | 1998-06-24 | 大赛璐化学工业株式会社 | Oxidation catalyst system and process for oxidation with the same |
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| TW201121938A (en) * | 2009-09-28 | 2011-07-01 | Solvay Fluor Gmbh | Manufacture of difluoroethylene carbonate, trifluoroethylene carbonate and tetrafluoroethylene carbonate |
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