CN115925670B - Method for synthesizing fluoroethylene carbonate by gas phase method - Google Patents
Method for synthesizing fluoroethylene carbonate by gas phase method Download PDFInfo
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- ethylene carbonate
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 124
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 51
- 239000011737 fluorine Substances 0.000 claims abstract description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012692 Fe precursor Substances 0.000 description 2
- 239000012696 Pd precursors Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing fluoroethylene carbonate by a gas phase method, which comprises the following steps: 1) Preheating ethylene carbonate and fluorine gas, continuously feeding the preheated ethylene carbonate and fluorine gas into a rectifying tower filled with a supported catalyst, carrying out reactive rectification, and obtaining a gas phase A containing fluoroethylene carbonate at the top of the tower; 2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at the temperature of 30-50 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively; 3) Pressurizing the gas phase B by a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of-40 ℃ to-20 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1). The invention can continuously produce fluoroethylene carbonate with high efficiency by a gas phase method, and has high single pass conversion rate and high selectivity.
Description
Technical Field
The invention relates to an organic synthesis method, in particular to a method for synthesizing fluoroethylene carbonate by a gas phase method.
Background
Fluoroethylene carbonate (FEC) is one of the lithium ion battery electrolyte additives with the largest current dosage, and the SEI film formed by the fluoroethylene carbonate (FEC) has good performance, can form a compact structure layer without increasing impedance, can prevent the electrolyte from being further decomposed, improves the low-temperature performance of the electrolyte and prolongs the cycle life of a lithium battery. Under the pulling of new energy automobiles and energy storage, the FEC demand is growing at a high speed.
The fluoroethylene carbonate is prepared by directly reacting ethylene carbonate serving as a raw material with fluorine gas, is the scheme with the shortest reaction flow, and meets the requirement of economic production. However, the prior method for preparing fluoroethylene carbonate generally has the problems of low single pass yield, harsh reaction conditions and the like; meanwhile, a scheme suitable for continuously preparing fluoroethylene carbonate in the production flow is not found at present, and the industrial scale production amplification is not facilitated.
Patent CN108329293A, CN109336859A, CN110041299a discloses a method for preparing fluoroethylene carbonate, which can realize gas phase continuous production, but uses chloroethylene carbonate as raw material, and in hydrogen fluoride atmosphere, gas phase fluorine-chlorine exchange reaction is carried out to generate fluoroethylene carbonate, the reaction tail gas contains excessive hydrogen fluoride, and alkali liquor absorption treatment is needed for generating a large amount of hydrogen chloride, so that the problem of large three-waste production exists; in addition, the reaction temperatures in the above patents are 100-160 ℃, 250-350 ℃ and 135-185 ℃ respectively, and the problems of high reaction temperature, high energy consumption and great process control difficulty generally exist.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for synthesizing fluoroethylene carbonate by a gas phase method. The invention can efficiently and continuously produce fluoroethylene carbonate by utilizing the reactive distillation through a gas phase method, has the advantages of high single-pass conversion rate and high selectivity, and the use of the palladium/iron@graphene catalyst reduces the reaction temperature; in addition, the method can realize simple separation and cyclic application of materials according to the boiling point difference of raw materials and products under different pressures, and has great economic application value.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing fluoroethylene carbonate by a gas phase method, which comprises the following steps:
1) Preheating ethylene carbonate and fluorine gas, continuously feeding the preheated ethylene carbonate and fluorine gas into a rectifying tower filled with a supported catalyst, carrying out reactive rectification, and obtaining a gas phase A containing fluoroethylene carbonate at the top of the tower;
2) Allowing the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 30-50 ℃, preferably 35-40 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B by a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of-40 ℃ to-20 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
As a preferred embodiment, the supported catalyst is a graphene catalyst supporting metallic palladium and iron;
preferably, the load of metal palladium in the supported catalyst is 1-2%, and the load of metal iron is 4-6%, calculated by mass of metal elements;
preferably, the specific surface area of the graphene carrier is 1300-1500m 2 /g。
The preparation method of the supported catalyst can be any known impregnation method, precipitation method, absorption method, deposition method and the like. The following preparation process is only provided as a viable catalyst preparation scheme and is not meant as any limitation of the present invention.
And dissolving a palladium precursor and an iron precursor in a proper amount of solvent, slowly adding graphene, stirring and reacting for 0.5-5h, filtering out the obtained solid, and then roasting in an inert atmosphere at 700-900 ℃ for 3-8h to obtain the graphene catalyst loaded with metal palladium and iron.
Wherein the palladium precursor is selected from divalent palladium salts, preferably palladium acetate; the iron precursor is selected from ferrous salts, preferably ferrous sulfate.
As a preferred embodiment, in step 1), the molar ratio of ethylene carbonate to fluorine is 1:1-4, preferably 1:1.5-2.
As a preferred embodiment, in step 1), the ethylene carbonate has a mass space velocity of from 100 to 300h -1 。
Preferably, the preheating temperature of the raw material ethylene carbonate and fluorine gas may be 10-15 ℃.
As a preferred embodiment, the reaction temperature around the catalyst packing in the rectification column is 80-85 ℃ and the reaction pressure is 1-3kPaA; the temperature of the reboiler at the bottom of the rectifying tower is 94-96 ℃.
As a preferred embodiment, the reflux ratio in the rectification column is 8-10:1.
As a preferred embodiment, the rectifying tower is divided into a rectifying section, a reaction section and a stripping section from top to bottom in sequence; wherein the catalyst packing is filled in the reaction section.
As a preferred embodiment, the rectifying section and the stripping section are filled with nonmetallic fillers, preferably polytetrafluoroethylene fillers.
As a preferred embodiment, the theoretical plate number of the rectifying section is 5 to 8; the theoretical plate number of the stripping section is 20-25.
As a preferred embodiment, the feeding position of the fluorine gas is the middle part of the stripping section; the feeding position of the ethylene carbonate is the middle part of the rectifying section.
The invention has the beneficial effects that:
1. the fluoroethylene carbonate is synthesized by a gas phase method, and has the advantages of short production flow and continuous production;
2. in the reaction process, fluoroethylene carbonate products can be generated with high efficiency and high selectivity under the lower temperature condition under the action of palladium/iron@graphene catalyst, so that the generation of excessive byproducts is avoided;
3. the fluoroethylene carbonate product, the byproduct hydrogen fluoride and excessive fluorine gas flow generated by the reaction can realize simple separation and cyclic application of materials under different temperature and pressure conditions, and three wastes are hardly generated in the reaction process, so that the environmental protection performance is good.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
1. The main raw materials used in the embodiment of the invention are as follows:
ethylene carbonate with purity >99%, innochem;
fluorine gas with purity of 99.99%, liquefied air group in France;
palladium acetate with purity >98%, aladine;
ferrous sulfate with purity >98%, aladine;
sodium hydroxide, 99%, aletin;
graphene with purity >98%, aletin;
2. gas Chromatography (GC) analysis conditions:
chromatographic column: hp-5ms 30 x 0.25
Column oven temperature: 60 DEG C
Sample introduction temperature: 250 DEG C
Sample injection mode: split flow
Flow control mode: linear velocity
Pressure: 57.4kPa
Total flow rate: 14.0ml/min
Column flow rate: 1.00ml/min
Linear velocity: 36.5cm/sec
Purge flow rate: 3.0ml/min
Split ratio: 10.0
Column incubator temperature procedure:
taking 60 ℃ as an initial temperature, preserving heat for 2min, heating to 120 ℃ at a heating rate of 30 ℃/min, preserving heat for 5min, heating to 240 ℃ at a heating rate of 60 ℃/min, and preserving heat for 2min.
[ preparation example 1 ]
Palladium acetate 2.1g and ferrous sulfate heptahydrate 14.9g were dissolved in 50mL ethanol, and 50g graphene (specific surface area 1500 m) was slowly added 2 And/g), stirring and reacting for 2 hours, filtering out the obtained solid, then roasting in an inert atmosphere, and roasting at 800 ℃ for 2 hours to obtain the graphene catalyst A loaded with metal palladium and iron.
[ preparation example 2 ]
Palladium acetate 1.1g and ferrous sulfate heptahydrate 10.0g were dissolved in 50mL ethanol, and 50g graphene (specific surface area 1300 m) was slowly added 2 And/g), stirring and reacting for 3 hours, filtering out the obtained solid, then roasting in an inert atmosphere, and roasting at 750 ℃ for 3 hours to obtain the graphene catalyst B loaded with metal palladium and iron.
[ preparation example 3 ]
1.6g of palladium acetate and 12.4g of ferrous sulfate heptahydrate are taken and dissolved in 50mL of ethanol, and 50g of graphene (with a specific surface area of 1400 m) is slowly added 2 And/g), stirring and reacting for 4 hours, filtering out the obtained solid, then roasting in an inert atmosphere, and roasting at 850 ℃ for 5 hours to obtain the graphene catalyst C loaded with metal palladium and iron.
[ preparation for comparative example 1 ]
Supported catalyst D was prepared in substantially the same manner as in preparation example 1, except that palladium acetate was not added.
[ preparation for comparative example 2 ]
Supported catalyst E was prepared in substantially the same manner as in preparation example 1, except that ferrous sulfate heptahydrate was not added.
[ preparation for comparative example 3 ]
A supported catalyst F was prepared in substantially the same manner as in preparation example 1, except that graphene was replaced with activated carbon.
[ example 1 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:1.5 to 15 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst A for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 100h -1 The pressure in the tower is 2kPaA, the temperature of a reboiler at the bottom of the tower is 94 ℃, the reaction temperature around the catalyst filler is 80 ℃, and the reflux ratio is 8:1; in addition, the theoretical plate number of the rectifying section is 5, the stripping section is 20, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is fed from the top to the bottom of the 3 rd column plate of the rectifying section, and the fluorine gas is fed from the top to the bottom of the 16 th column plate of the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 30 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing the gas phase B at the temperature of minus 25 ℃ and separating the gas phase B to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 76.5%, and the selectivity of the fluoroethylene carbonate is 97.85%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 74.86%.
[ example 2 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:1.5 to 12 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst A for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 200h -1 The pressure in the tower is 2kPaA, the temperature of a reboiler at the bottom of the tower is 94 ℃, the reaction temperature around the catalyst filler is 82 ℃, and the reflux ratio is 10:1; in addition, the theoretical plate number of the rectifying section is 8, the stripping section is 25, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is from top to bottom in the rectifying section4 trays were fed with fluorine gas from top to bottom in the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 50 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing the gas phase B at the temperature of minus 35 ℃ and separating the gas phase B to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 71.7%, and the selectivity of the fluoroethylene carbonate is 97.95%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 70.23%.
[ example 3 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:2 to 15 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst B for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 100h -1 The pressure in the tower is 2kPaA, the temperature of a reboiler at the bottom of the tower is 95 ℃, the reaction temperature around the catalyst filler is 81 ℃, and the reflux ratio is 10:1; in addition, the theoretical plate number of the rectifying section is 5, the stripping section is 20, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is fed from the top to the bottom of the 3 rd column plate of the rectifying section, and the fluorine gas is fed from the top to the bottom of the 16 th column plate of the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 35 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of minus 40 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 77.5%, and the selectivity of the fluoroethylene carbonate is 95.8%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 74.25%.
[ example 4 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:1.5 to 10 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst B for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 100h -1 The pressure in the tower is 2kPaA, the temperature of a reboiler at the bottom of the tower is 96 ℃, the reaction temperature around the catalyst filler is 78 ℃, and the reflux ratio is 8:1; in addition, the theoretical plate number of the rectifying section is 5, the stripping section is 20, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is fed from the top to the bottom of the 3 rd column plate of the rectifying section, and the fluorine gas is fed from the top to the bottom of the 16 th column plate of the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 45 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing the gas phase B at the temperature of minus 30 ℃ and separating the gas phase B to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 72.13%, and the selectivity of the fluoroethylene carbonate is 95.14%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 68.62%.
[ example 5 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:1.75 to 12 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst C for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 150h -1 The pressure in the tower is 2kPaA, and the bottom of the tower is reboiledThe reactor temperature is 96 ℃, the reaction temperature around the catalyst filler is 80 ℃, and the reflux ratio is 9:1; in addition, the theoretical plate number of the rectifying section is 7, the stripping section is 22, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is fed from the top to the bottom of the 3 rd column plate of the rectifying section, and the fluorine gas is fed from the top to the bottom of the 18 th column plate of the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 40 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of minus 20 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 80.07%, and the selectivity of the fluoroethylene carbonate is 97.93%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 78.41%.
[ example 6 ]
1) Preheating ethylene carbonate and fluorine gas with the molar ratio of 1:3 to 15 ℃, and then sending the ethylene carbonate and the fluorine gas into a rectifying tower filled with a catalyst C for reactive rectification, wherein the mass space velocity of the ethylene carbonate is 300h -1 The pressure in the tower is 2kPaA, the temperature of a reboiler at the bottom of the tower is 94 ℃, the reaction temperature around the catalyst filler is 82 ℃, and the reflux ratio is 9:1; in addition, the theoretical plate number of the rectifying section is 7, the stripping section is 22, and polytetrafluoroethylene fillers are filled in the rectifying section and the stripping section. The raw material ethylene carbonate is fed from the top to the bottom of the 3 rd column plate of the rectifying section, and the fluorine gas is fed from the top to the bottom of the 18 th column plate of the stripping section. After the rectification column parameters were run for 48h, a gas phase A containing fluoroethylene carbonate was obtained at the top of the column.
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at 35 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B to normal pressure through a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of minus 40 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1).
In the embodiment, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 71.07%, and the selectivity of the fluoroethylene carbonate is 94.93%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 67.67%.
Comparative example 1
Fluoroethylene carbonate was synthesized in substantially the same manner as in example 1 except that the catalyst A packed in the rectifying column was replaced with the catalyst D.
In the comparative example, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, and the single pass conversion rate of the ethylene carbonate is 30.11 percent, and the selectivity of the fluoroethylene carbonate is 71.89 percent; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 24.65%.
Comparative example 2
Fluoroethylene carbonate was synthesized in substantially the same manner as in example 1 except that the catalyst A packed in the rectifying column was replaced with the catalyst E.
In the comparative example, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, and the single pass conversion rate of the ethylene carbonate is 60.26 percent, and the selectivity of the fluoroethylene carbonate is 96.85 percent; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 58.36%.
[ comparative example 3 ]
Fluoroethylene carbonate was synthesized in substantially the same manner as in example 1 except that the catalyst A packed in the rectifying column was replaced with the catalyst F.
In the comparative example, the components in the gas phase A and the tower bottom liquid obtained in the step 1) are detected and analyzed, so that the single pass conversion rate of the ethylene carbonate is 54.3%, and the selectivity of the fluoroethylene carbonate is 97.41%; the single pass reaction yield of fluoroethylene carbonate based on ethylene carbonate was 52.89%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (13)
1. A method for synthesizing fluoroethylene carbonate by a gas phase method, which is characterized by comprising the following steps:
1) Preheating ethylene carbonate and fluorine gas, continuously feeding the preheated ethylene carbonate and fluorine gas into a rectifying tower filled with a supported catalyst, carrying out reactive rectification, and obtaining a gas phase A containing fluoroethylene carbonate at the top of the tower;
2) Enabling the gas phase A to enter a first-stage condenser arranged at the top of a rectifying tower, and condensing at the temperature of 30-50 ℃ to obtain liquefied products fluoroethylene carbonate and gas phase B respectively;
3) Pressurizing the gas phase B by a compressor, then, introducing the gas phase B into a secondary condenser, condensing at the temperature of-40 ℃ to-20 ℃ and separating to obtain fluorine gas and liquefied hydrogen fluoride, wherein the fluorine gas is recycled in the step 1);
the supported catalyst is a graphene catalyst supporting metal palladium and iron;
the load of metal palladium in the supported catalyst is 1-2%, and the load of metal iron is 4-6%, based on the mass of metal elements.
2. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein in the step 2), the condensation is performed at 35 to 40 ℃.
3. The method for synthesizing fluoroethylene carbonate by gas phase method according to claim 1, wherein the specific surface area of the graphene carrier is 1300-1500m 2 /g。
4. The method for synthesizing fluoroethylene carbonate according to claim 1, wherein in the step 1), the molar ratio of ethylene carbonate to fluorine gas is 1:1-4.
5. The method for synthesizing fluoroethylene carbonate according to claim 4, wherein in the step 1), the molar ratio of ethylene carbonate to fluorine gas is 1:1.5-2.
6. The method for synthesizing fluoroethylene carbonate according to any one of claims 1 to 5, wherein in step 1), the mass space velocity of the ethylene carbonate is 100 to 300h -1 。
7. The method for synthesizing fluoroethylene carbonate according to any one of claims 1 to 5, wherein the reaction temperature around the catalyst packing in the rectifying column is 80 to 85 ℃ and the reaction pressure is 1 to 3kPaA; the temperature of the reboiler at the bottom of the rectifying tower is 94-96 ℃.
8. The method for synthesizing fluoroethylene carbonate according to claim 7, wherein the reflux ratio in the rectifying column is 8-10:1.
9. The method for synthesizing fluoroethylene carbonate by a gas phase method according to claim 1, wherein the rectifying tower is divided into a rectifying section, a reaction section and a stripping section from top to bottom in sequence; wherein the catalyst packing is filled in the reaction section.
10. The method for synthesizing fluoroethylene carbonate according to claim 9, wherein the rectifying section and the stripping section are filled with a nonmetallic filler.
11. The method for synthesizing fluoroethylene carbonate according to claim 10, wherein the rectifying section and the stripping section are filled with polytetrafluoroethylene filler.
12. The method for synthesizing fluoroethylene carbonate according to claim 9, wherein the theoretical plate number of the rectifying section is 5 to 8; the theoretical plate number of the stripping section is 20-25.
13. The method for synthesizing fluoroethylene carbonate according to any one of claims 9 to 12, wherein the feeding position of the fluorine gas is the middle part of the stripping section; the feeding position of the ethylene carbonate is the middle part of the rectifying section.
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| WO2018113628A1 (en) * | 2016-12-19 | 2018-06-28 | 上海惠和化德生物科技有限公司 | Rapid continuous-flow synthesis process for fluoroethylene carbonate. |
| CN111349018A (en) * | 2019-08-22 | 2020-06-30 | 福建永晶科技股份有限公司 | Process for fluorinating inorganic or organic compounds by direct fluorination |
| CN112321558A (en) * | 2020-11-10 | 2021-02-05 | 湖北省宏源药业科技股份有限公司 | Preparation method of fluoroethylene carbonate |
| CN113121491A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院宁波材料技术与工程研究所 | Method for producing fluoroethylene carbonate through micro-channel |
| CN113135888A (en) * | 2021-03-29 | 2021-07-20 | 珠海理文新材料有限公司 | Preparation method of fluoroethylene carbonate |
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| WO2018113628A1 (en) * | 2016-12-19 | 2018-06-28 | 上海惠和化德生物科技有限公司 | Rapid continuous-flow synthesis process for fluoroethylene carbonate. |
| CN111349018A (en) * | 2019-08-22 | 2020-06-30 | 福建永晶科技股份有限公司 | Process for fluorinating inorganic or organic compounds by direct fluorination |
| CN113121491A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院宁波材料技术与工程研究所 | Method for producing fluoroethylene carbonate through micro-channel |
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