CN115108911A - Method for preparing dimethyl carbonate by directly esterifying alkylene oxide - Google Patents
Method for preparing dimethyl carbonate by directly esterifying alkylene oxide Download PDFInfo
- Publication number
- CN115108911A CN115108911A CN202210585027.6A CN202210585027A CN115108911A CN 115108911 A CN115108911 A CN 115108911A CN 202210585027 A CN202210585027 A CN 202210585027A CN 115108911 A CN115108911 A CN 115108911A
- Authority
- CN
- China
- Prior art keywords
- dimethyl carbonate
- alkylene oxide
- reaction
- reaction kettle
- preparing dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 46
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- 229940102001 zinc bromide Drugs 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 21
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- -1 1,1,3, 3-tetramethyl-2-butyl guanidine imidazole salt Chemical group 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 5
- BGSUDDILQRFOKZ-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C)=C1 BGSUDDILQRFOKZ-UHFFFAOYSA-M 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing dimethyl carbonate by directly esterifying alkylene oxide, which generates dimethyl carbonate by a one-step esterification method, has high conversion rate of alkylene oxide and high selectivity of products, and can greatly reduce production cost. The method for preparing dimethyl carbonate by directly esterifying alkylene oxide comprises the following steps: (1) mixing alkylene oxide, solvent and catalyst to prepare raw material liquid, fully mixing and adding into a reaction kettle; (2) after the reaction kettle is sealed, replacing air in the system with carbon dioxide, and filling CO 2 Pressurizing the reaction kettle; (3) adjusting the temperature of the oil bath pot, opening the stirrer, and putting the reaction kettle into the oil bath pot for reaction; (4) after the reaction is finished, cooling, emptying and taking out a reaction product to obtain the dimethyl carbonate.
Description
Technical Field
The invention relates to a method for preparing dimethyl carbonate, in particular to a method for preparing dimethyl carbonate by directly esterifying alkylene oxide.
Background
With the rapid development of economy, the environmental pollution is becoming more serious, the green chemical production urgently needs low-toxicity or nontoxic raw materials, and dimethyl carbonate (DMC) is an environment-friendly organic chemical raw material meeting the requirements of modern 'clean technology', and because of having low toxicity, high solubility, excellent environment-friendly performance and good reaction performance, the DMC is widely applied to carbonylation and methylation reagents and gasoline additives, can be used as a raw material for synthesizing Polycarbonate (PC), a coating solvent and lithium battery electrolyte, and is also an important organic intermediate. Has wide market prospect and is a popular 'green' chemical product in the field of chemical industry at present.
The current methods for the industrial synthesis of DMC are mainly: phosgene process, transesterification process and carbonyl oxidation process. The HCl gas generated by the virulent reaction of the raw materials of the phosgene method can cause corrosion to equipment, and the method is eliminated. The oxidative carbonylation method has green chemical prospect, but DMC yield is low, and the catalyst is easy to deactivate. Most of the transesterification methods use CO 2 Reacts with propylene oxide to generate propylene carbonate, and then reacts with methanol to prepare dimethyl carbonate. Chinese patent publication No. CN105503607A discloses a method for producing dimethyl carbonate by catalyzing ethylene carbonate and methanol with a strong base type complex imidazolyl resin, wherein the conversion rate of ethylene carbonate obtained is 41.5%, the selectivity of dimethyl carbonate is 99.1%, and the selectivity of ethylene glycol is 98.9% under the conditions that the reaction temperature is 80 ℃, the reaction time is 4 hours, and the molar ratio of methanol to ethylene carbonate is 4; the Chinese patent with the publication number of CN202110550515.9 provides a method for catalyzing propylene carbonate and methanol to generate dimethyl carbonate by using La2O2CO3 nano triangular plate solid base catalyst, wherein the reaction temperature is 150 ℃, the reaction time is 5 hours, and the methanolUnder the condition that the volume ratio of the ethylene carbonate to the ethylene carbonate is 5, the highest conversion rate of the ethylene carbonate can reach 82.3 percent, and the selectivity of dimethyl carbonate can reach 96.1 percent; the publication No. CN113185407A discloses a preparation method and application of a guanidine salt ionic liquid, which comprises the steps of catalyzing propylene carbonate and methanol to perform ester exchange to generate dimethyl carbonate, wherein the conversion rate of the propylene carbonate is 76.2 percent and the yield of the dimethyl carbonate is 76.2 percent under the conditions that a catalyst is 1,1,3, 3-tetramethyl-2-butyl guanidine imidazole salt, the reaction temperature is 80 ℃ and the reaction time is 2.5 hours; the Chinese patent with the publication number of CN103980124B discloses a method for synthesizing dimethyl carbonate by catalyzing propylene carbonate with ionic liquid, wherein the method takes quaternary ammonium salt ionic liquid as a catalyst, methanol, propylene carbonate and the ionic liquid catalyst react and are separated in a reaction rectifying tower, and the separation and purification of propylene glycol in tower bottom materials consists of three rectifying towers, namely a light component removal tower, a propylene glycol product tower and a methanol recovery tower; the separated catalyst is returned to the reaction rectification system for reuse. From the above studies, it was found that the two-step process for synthesizing dimethyl carbonate by transesterification has the advantages of mild reaction conditions and easily controlled process; but has the main problems of complex catalyst, large methanol-carbonate feeding ratio, long reaction time, low DMC yield and the like, and simultaneously has the problems of high energy consumption, high cost, complex byproduct treatment and the like due to long process production flow and more equipment. The Chinese patent with publication number CN1204110C discloses that dimethyl carbonate is synthesized by taking potassium halide as a catalyst and propylene oxide, methanol and carbon dioxide as raw materials through a direct esterification method, and the selectivity of DMC is 69% and lower at high temperature of 150 ℃ and high pressure of 15 MPa. In addition, Wanxiang et al (petrochemical, 2010,39(10): 1089-. 2015 Dingxianha et al (college chemical engineering report 2015,29(01):164- 2 CO 3 (NaHCO 3 )/γ-Al 2 O 3 The catalytic reaction performance of directly synthesizing dimethyl carbonate by using epoxy chloropropane, methanol and carbon dioxide is studied, and the yield of the dimethyl carbonate is 25.2%.
The prior art shows that the two-step ester exchange method for preparing the dimethyl carbonate has the problems of long reaction process, high energy consumption, high cost, complex reaction separation treatment and the like. The one-step method for synthesizing the dimethyl carbonate avoids the separation process in the two-step production of cycloaddition and ester exchange, simplifies the technical process, is simple to operate, greatly reduces the production cost if the yield and the selectivity of a target product can be improved and coproduces the alkanediol and the alkene carbonate, meets the requirements of green energy-saving chemical industry, and is considered to be the method with the greatest development prospect for producing the dimethyl carbonate.
Disclosure of Invention
Aiming at the problems and the defects of the prior art, the invention provides a method for preparing dimethyl carbonate by directly esterifying alkylene oxide, which generates the dimethyl carbonate by a one-step esterification method, has high conversion rate of the alkylene oxide and high selectivity of products, and can greatly reduce the production cost.
The invention is realized by the following technical scheme:
the method for preparing dimethyl carbonate by directly esterifying alkylene oxide comprises the following steps:
(1) mixing alkylene oxide, solvent and catalyst to prepare raw material liquid, fully mixing and adding into a reaction kettle;
(2) after the reaction kettle is sealed, the air in the system is replaced by carbon dioxide, and CO is filled 2 Pressurizing the reaction kettle;
(3) adjusting the temperature of the oil bath pot, opening the stirrer, and putting the reaction kettle into the oil bath pot for reaction;
(4) after the reaction is finished, cooling, emptying and taking out a reaction product to obtain the dimethyl carbonate.
The method for preparing the dimethyl carbonate by directly esterifying the alkylene oxide has the further technical scheme that the solvent is methanol, the molar ratio of the methanol to the alkylene oxide is 0.5:1-5:1, the mass percent of the catalyst in a raw material liquid is 0.5-3.5%, the catalyst consists of 1-alkyl-3-methylimidazole bromide salt and zinc bromide, and the mass ratio of the 1-alkyl-3-methylimidazole bromide salt to the zinc bromide is 2:1-4: 1. The further technical proposal is that the alkyl in the 1-alkyl-3-methylimidazolium bromide is ethyl or hexyl.
The method for preparing dimethyl carbonate by directly esterifying the alkylene oxide can be further characterized in that the alkylene oxide is ethylene oxide, propylene oxide or butylene oxide.
The method for preparing dimethyl carbonate by directly esterifying alkylene oxide can be further characterized in that the air in the system is replaced by carbon dioxide for 2-3 times; said CO charge 2 The pressure in the reaction kettle is increased to 1.5-4 MPa.
The method for preparing dimethyl carbonate by directly esterifying alkylene oxide can be further characterized in that the reaction temperature in the step (3) is 80-150 ℃, the reaction time is 0.5-3.5h, and the rotating speed of a stirrer is 800 r/min.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the dimethyl carbonate by directly esterifying the alkylene oxide has high yield and selectivity of a target product, the total selectivity of the carbonic ester reaches over 95 percent, and the production cost is greatly reduced; the conversion rate of the alkylene oxide is close to 100 percent, and simultaneously, the alkylene glycol and the alkylene carbonate can be co-produced in the preparation process, which are very raw materials with economic value and can further improve the economic benefit.
The method of the invention is different from the two-step method for synthesizing the dimethyl carbonate, the reaction for synthesizing the alkene carbonate in the first step generally needs a solvent, and the methanol in the invention not only is a reaction raw material, but also can be used as a solvent, thereby greatly saving the process production cost; the invention is also a green process method for fixing carbon dioxide to generate organic compounds, has simple process flow and can change waste into valuable.
Detailed Description
Example 1
Weighing 4.4g of ethylene oxide, 16g of methanol and 0.30g of catalyst (0.2 g of 1-hexyl-3-methylimidazolium bromide salt and 0.1g of zinc bromide), adding the mixture into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 4.0MPa, the temperature of the oil bath is adjusted to 150 ℃, the stirrer is opened, and the reaction kettle is placed in the oil bath for reaction. After reacting for 3.5h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The products produced were ethylene carbonate, ethylene glycol, dimethyl carbonate, the conversion of ethylene oxide was 99.22%, the total selectivity of ethylene carbonate and dimethyl carbonate reached 96.54%, with the yield of dimethyl carbonate being 1.45 g.
Example 2
Weighing 5.8g of propylene oxide, 16g of methanol and 0.44g of catalyst (0.33 g of 1-hexyl-3-methylimidazolium bromide salt and 0.11g of zinc bromide), adding the materials into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 3.5MPa, the temperature of the oil bath is adjusted to 140 ℃, the stirrer is opened, and the reaction kettle is placed in the oil bath for reaction. After reacting for 3.5h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The products produced comprise propylene carbonate, propylene glycol and dimethyl carbonate, the conversion rate of the propylene oxide is 98.32 percent, the total selectivity of the propylene carbonate and the dimethyl carbonate reaches 97.04 percent, and the yield of the dimethyl carbonate is 1.92 g.
Example 3
Weighing 5.8g of propylene oxide, 16g of methanol and 0.64g of catalyst (0.48 g of 1-hexyl-3-methylimidazolium bromide and 0.16g of zinc bromide), adding the materials into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 3.5MPa, the temperature of the oil bath is adjusted to 130 ℃, the stirrer is opened, and the reaction kettle is placed in the oil bath for reaction. After reacting for 3.5h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The product produced contains propylene carbonateThe conversion rate of ester, propylene glycol and dimethyl carbonate to propylene oxide is 98.56%, the total selectivity of propylene carbonate and dimethyl carbonate reaches 98.04%, and the yield of dimethyl carbonate is 1.88 g.
Example 4
Weighing 5.8g of propylene oxide, 16g of methanol and 0.33g of catalyst (0.22 g of 1-hexyl-3-methylimidazolium bromide and 0.11g of zinc bromide), adding the materials into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 2.0MPa, the temperature of the oil bath is adjusted to 120 ℃, the stirrer is opened, and the reaction kettle is placed in the oil bath for reaction. After reacting for 3.5h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The products produced comprise propylene carbonate, propylene glycol and dimethyl carbonate, the conversion rate of the propylene oxide is 63.5 percent, the total selectivity of the propylene carbonate and the dimethyl carbonate reaches 98.04 percent, and the yield of the dimethyl carbonate is 1.10 g.
Example 5
Weighing 5.8g of propylene oxide, 16g of methanol and 0.22g of catalyst (0.16 g of 1-ethyl-3-methylimidazolium bromide and 0.06g of zinc bromide), adding the materials into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 2.5MPa, the temperature of the oil bath is adjusted to 80 ℃, the stirrer is opened, and the reaction kettle is placed in the oil bath for reaction. After reacting for 2h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The products produced comprise propylene carbonate, propylene glycol and dimethyl carbonate, the conversion rate of the propylene oxide is 50.32 percent, the total selectivity of the propylene carbonate and the dimethyl carbonate reaches 97.04 percent, and the yield of the dimethyl carbonate is 1.06 g.
Example 6
Weighing 5.8g of propylene oxide, 8g of methanol and 0.22g of catalyst (0.16 g of 1-ethyl-3-methylimidazolium bromide and 0.06g of zinc bromide), adding the materials into a reaction kettle, adding a rotor, fully stirring and mixing, sealing the reaction kettle, replacing air in a system with carbon dioxide for 2-3 times, and filling CO 2 The pressure in the kettle reaches 2.5MPand a, adjusting the temperature of the oil bath to be 100 ℃, opening the stirrer, and putting the reaction kettle into the oil bath for reaction. After reacting for 1h, cooling, emptying, taking out a reaction product, and carrying out chromatographic analysis and calculation on the reaction product. The products produced comprise propylene carbonate, propylene glycol and dimethyl carbonate, the conversion rate of the propylene oxide is 42.37 percent, the total selectivity of the propylene carbonate and the dimethyl carbonate reaches 98.14 percent, and the yield of the dimethyl carbonate is 0.85 g.
Claims (6)
1. A method for preparing dimethyl carbonate by directly esterifying alkylene oxide is characterized by comprising the following steps:
(1) mixing alkylene oxide, solvent and catalyst to prepare raw material liquid, fully mixing and adding into a reaction kettle;
(2) after the reaction kettle is sealed, replacing air in the system with carbon dioxide, and filling CO 2 Pressurizing the reaction kettle;
(3) adjusting the temperature of the oil bath pot, opening the stirrer, and putting the reaction kettle into the oil bath pot for reaction;
(4) after the reaction is finished, cooling, emptying and taking out a reaction product to obtain the dimethyl carbonate.
2. The method for preparing dimethyl carbonate through direct esterification of alkylene oxide according to claim 1, wherein the solvent is methanol, the molar ratio of methanol to alkylene oxide is 0.5:1-5:1, the mass percentage of the catalyst in the raw material liquid is 0.5-3.5%, the catalyst is composed of 1-alkyl-3-methylimidazole bromide salt and zinc bromide, and the mass ratio of 1-alkyl-3-methylimidazole bromide salt to zinc bromide is 2:1-4: 1.
3. The method for preparing dimethyl carbonate by directly esterifying alkylene oxide according to claim 1 or 2, wherein the alkylene oxide is ethylene oxide, propylene oxide or butylene oxide.
4. The method for preparing dimethyl carbonate through direct esterification of alkylene oxide according to claim 2, wherein the alkyl group in the 1-alkyl-3-methylimidazolium bromide salt is ethyl or hexyl.
5. The method for preparing dimethyl carbonate through direct esterification of alkylene oxide according to claim 1, wherein the number of times of replacing air in the system with carbon dioxide is 2-3 times; said charging of CO 2 The pressure in the reaction kettle is increased to 1.5-4 MPa.
6. The method for preparing dimethyl carbonate through direct esterification of alkylene oxide according to claim 1, wherein the reaction temperature in the step (3) is 80-150 ℃, the reaction time is 0.5-3.5h, and the rotating speed of the stirrer is 800 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210585027.6A CN115108911A (en) | 2022-05-26 | 2022-05-26 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210585027.6A CN115108911A (en) | 2022-05-26 | 2022-05-26 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115108911A true CN115108911A (en) | 2022-09-27 |
Family
ID=83326365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210585027.6A Pending CN115108911A (en) | 2022-05-26 | 2022-05-26 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115108911A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302950A (en) * | 2011-06-02 | 2012-01-04 | 南京工业大学 | Catalyst system for synthesizing hydroxyacid ester with oxidative carbonyl and using method of catalyst system |
| WO2014005417A1 (en) * | 2012-07-03 | 2014-01-09 | 深圳市绿微康生物工程有限公司 | Method for preparing dimethyl carbonate |
| WO2015114474A1 (en) * | 2014-01-30 | 2015-08-06 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| CN111423326A (en) * | 2020-05-12 | 2020-07-17 | 中国石油大学(华东) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method |
| CN113563189A (en) * | 2021-07-07 | 2021-10-29 | 沈阳化工大学 | One-step method for efficiently catalyzing CO2Method for converting dimethyl carbonate catalyst |
-
2022
- 2022-05-26 CN CN202210585027.6A patent/CN115108911A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302950A (en) * | 2011-06-02 | 2012-01-04 | 南京工业大学 | Catalyst system for synthesizing hydroxyacid ester with oxidative carbonyl and using method of catalyst system |
| WO2014005417A1 (en) * | 2012-07-03 | 2014-01-09 | 深圳市绿微康生物工程有限公司 | Method for preparing dimethyl carbonate |
| WO2015114474A1 (en) * | 2014-01-30 | 2015-08-06 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| CN111423326A (en) * | 2020-05-12 | 2020-07-17 | 中国石油大学(华东) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method |
| CN113563189A (en) * | 2021-07-07 | 2021-10-29 | 沈阳化工大学 | One-step method for efficiently catalyzing CO2Method for converting dimethyl carbonate catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111423326B (en) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method | |
| CN108610324B (en) | Preparation method of vinyl sulfate | |
| EP3950660A1 (en) | Method for preparing dimethyl carbonate | |
| CN104447312B (en) | A kind of method of Synthesis of dimethyl carbonate | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN105344341A (en) | Preparation method of solid catalyst used for synthesizing dimethyl carbonate | |
| CN112409190B (en) | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst | |
| CN111909094A (en) | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid | |
| CN114163333B (en) | Method for synthesizing methyl ethyl carbonate in one step | |
| CN100427477C (en) | Process of synthesizing cyclic carbonate by epoxy compound with carbon dioxide reaction | |
| CN113563191A (en) | Method for continuously producing dimethyl carbonate by catalysis of composite alkaline ionic liquid | |
| CN106588657B (en) | Method for synthesizing dimethyl carbonate | |
| CN105085282A (en) | Preparation method for alkyl alcohol amine | |
| CN115108911A (en) | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide | |
| CN113548957B (en) | Production method of tertiary carbonic acid | |
| CN109364959A (en) | The solid base catalyst and preparation method of a kind of ester-interchange method synthesis of dialkyl carbonates and application | |
| CN113385225B (en) | Supermolecule ionic liquid catalyst and preparation method and application thereof | |
| CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
| CN101210007B (en) | Method for preparing ethylene sulfite | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| CN103252239B (en) | Catalyst for synthesizing glycerol carbonic, preparation method for catalyst and application of catalyst | |
| CN113999170B (en) | Preparation of pyridyl ionic liquid and method for catalytically synthesizing cyclic carbonate by using pyridyl ionic liquid | |
| CN1318384C (en) | Polyphosphoric acid catalyzed dimethyl carbonate synthesizing process | |
| CN115784889B (en) | Method for preparing methyl ethyl carbonate and diethyl carbonate by taking dimethyl oxalate as raw material | |
| CN103524476B (en) | The method of multicomponent reaction system synthesis of glycerol carbonate coproduction short carbon chain carbonic ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220927 |