CN117718036A - Catalyst for fluorination reaction, preparation method and application thereof, and preparation method of fluoroethylene carbonate - Google Patents
Catalyst for fluorination reaction, preparation method and application thereof, and preparation method of fluoroethylene carbonate Download PDFInfo
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- CN117718036A CN117718036A CN202311419362.XA CN202311419362A CN117718036A CN 117718036 A CN117718036 A CN 117718036A CN 202311419362 A CN202311419362 A CN 202311419362A CN 117718036 A CN117718036 A CN 117718036A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 34
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims description 19
- 238000010537 deprotonation reaction Methods 0.000 claims description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
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- 238000003756 stirring Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 150000003841 chloride salts Chemical class 0.000 claims description 6
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010981 drying operation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 239000002000 Electrolyte additive Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012025 fluorinating agent Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- DDXGMOVCPFHPIV-UHFFFAOYSA-N carbonic acid;chloroethene Chemical compound ClC=C.OC(O)=O DDXGMOVCPFHPIV-UHFFFAOYSA-N 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- MJIULRNAOLSIHL-UHFFFAOYSA-N carbonic acid;fluoroethene Chemical compound FC=C.OC(O)=O MJIULRNAOLSIHL-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 150000002367 halogens Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
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- 230000036632 reaction speed Effects 0.000 description 1
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Abstract
The invention relates to the fields of catalysts and organic chemistry, in particular to a catalyst for a fluorination reaction, a preparation method and application thereof, and a preparation method of fluoroethylene carbonate. Wherein the catalyst comprises a carrier SiO 2 And an active component M element, wherein the general formula of the catalyst is xM@SiO 2 The M element is selected from Sb or Mo; the content x=1 to 20wt% of M element. The catalyst is stable and efficient, can be applied to the preparation of fluoroethylene carbonate from chloroethylene carbonate, can improve the yield of fluorination reaction, is stable in the reaction process and can be recycled. In addition, the process route of the preparation method of fluoroethylene carbonate is simpleThe GC content of the prepared fluoroethylene carbonate is more than 99.95%, and the chromaticity, the acid value and the moisture meet the requirement of serving as high-quality electrolyte additives.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a catalyst for a fluorination reaction, a preparation method and application thereof, and a preparation method of fluoroethylene carbonate.
Background
The electrolyte is one of important materials of the lithium ion battery, is prepared from electrolyte, organic solvent and various additives, and has important influence on the safety and electrochemical performance of the battery. The fluoroethylene carbonate is a main additive of the lithium ion battery electrolyte, has good solid electrolyte interface forming performance, forms a compact structure layer without increasing impedance, can prevent the low-temperature performance of the electrolyte and improves the cycle life of the lithium ion battery. In addition, fluoroethylene carbonate is also an important intermediate for medicines, pesticides, and the like.
At present, the methods for synthesizing fluoroethylene carbonate mainly comprise the following steps: 1) JP2000309583 describes the preparation of fluoroethylene carbonate by direct fluorine substitution of a mixture of fluorine and an inert gas with ethylene carbonate at a temperature. The method can generate partial difluorination products because of the strong activity of fluorine gas, and the fluorination process is difficult to control. The selectivity of the reaction is poor and the yield is low. These drawbacks limit the applicability of the process in industrial production. 2) CN201410538078 is fluoroethylene carbonate prepared by electrolytic fluorination in an electrolytic tank with graphite as anode and nickel as cathode. The carbon-carbon bond is easy to break in the electrochemical fluorination process, so that byproducts are generated, and compared with methods such as halogen exchange, the method has the advantage of no obvious effect. 3) CN103539772A, CN102993160a et al discloses that the substitution reaction of chloroethylene carbonate and fluorinating agent KF in organic solvent produces fluoroethylene carbonate, the reaction time is long, the reaction liquid needs to be subjected to solid-liquid separation, and a large amount of solid waste mixed by potassium chloride and fluorinating agent is generated, and the post-treatment process is complicated. Although the method is adopted by more enterprises to carry out industrial production, the current environmental protection requirement is increasingly enhanced, and the method lacks competitive power due to the defects of three wastes, complex post-treatment and the like. 4) CN103113345B et al patent uses anhydrous hydrogen fluoride as a fluorinating agent to prepare fluoroethylene carbonate. In the absence of a high-efficiency catalyst, the reaction activity is weak, and a high conversion rate is difficult to obtain in actual reaction.
Therefore, the application develops a catalyst for the fluorination reaction, and a preparation method and application thereof, and the catalyst is applied to the preparation method of fluoroethylene carbonate, and has the advantages of stability, high efficiency, less three-waste emission and suitability for large-scale industrial production.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a catalyst for fluorination reaction, a preparation method and use thereof, and a preparation method of fluoroethylene carbonate, wherein the novel catalyst can improve the yield of fluorination reaction, the preparation of the catalyst is simple and easy to obtain, and the catalyst is stable in the reaction process and can be recycled; the preparation process of fluoroethylene carbonate has simple route and little three-waste discharge, and is suitable for large-scale industrial production.
To achieve the above and other related objects, a first aspect of the present invention provides a catalyst for fluorination reaction, comprising a carrier SiO 2 And an active ingredient M element;
the general formula of the catalyst is xM@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The M is selected from Sb or Mo; the content x=1 to 20wt% of M element.
In a second aspect, the present invention provides a method for preparing the catalyst provided in the first aspect, comprising the following steps:
1) Salt of M element and carrier SiO 2 Mixing and stirring with an organic solvent;
2) Filtering the mixed solution obtained in the step 1) to obtain a catalyst precursor;
3) Drying the catalyst precursor in the step 2) to obtain a catalyst xM@SiO 2 。
In a third aspect the invention provides the use of the catalyst provided in the first aspect in the preparation of fluoroethylene carbonate from chloroethylene carbonate.
According to a fourth aspect of the present invention, there is provided a method for preparing fluoroethylene carbonate, wherein fluoroethylene carbonate and HF are subjected to fluorination in the presence of the catalyst according to the first aspect, and post-treatment is performed to obtain fluoroethylene carbonate, wherein the reaction equation is as follows:
as described above, the present invention has at least the following advantageous effects:
1) The novel catalyst can improve the yield of the fluorination reaction, is stable, and has no obvious influence on the speed and the yield of the fluorination reaction after being applied for 10 times;
2) The catalyst is simple and easy to prepare, stable and efficient;
3) The fluoroethylene carbonate has the advantages of simple preparation process and less three wastes, and is suitable for large-scale industrial production; and the fluoroethylene carbonate obtained by the preparation process has high yield;
4) The fluoroethylene carbonate prepared by the fluoroethylene carbonate preparation method has GC content of more than 99.95%, chromaticity less than 5APHA, acid value less than 5ppm and moisture less than 15ppm, and can be used as a high-quality electrolyte additive.
Drawings
FIG. 1 shows a GC spectrum according to example 5 of the present invention;
Detailed Description
The inventors of the present application have found that, by investigation, conventional Lewis acids MoCl 5 And SbCl 5 In the catalytic process, raw materials of chloroethylene carbonate and fluoroethylene carbonate are prepared in MoCl 5 Or SbCl 5 Is easy to decompose when heated in the presence of the catalyst. The applicant therefore aimed at developing a new catalyst, in hopes of obtaining, as follows, in the first place: the raw materials of chloroethylene carbonate and fluoroethylene carbonate are contacted with a catalystCan be kept stable when in use; second,: it is desirable that the catalyst be capable of multiple reuse and that the repeated use of the catalyst have no significant effect on the rate and yield of fluorination reactions; third,: it is desired to make the fluoroethylene carbonate preparation process simple and less in three wastes, thereby being industrially mass-produced. The present invention has been completed on the basis of this finding.
The first aspect of the present invention provides a catalyst for fluorination reaction, the catalyst comprising a support SiO 2 And an active ingredient M element; the general formula of the catalyst is xM@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The M is selected from Sb or Mo; the content of the M element x=1 to 20wt%, the wt% represents concentration mass percent, and optionally, x=1 to 5wt%, x=5 to 10wt%, x=10 to 15wt% or x=15 to 20wt%, the content of the M element can be selected according to actual catalytic effects, and through the research of the application, in the fluorination reaction of chloroethylene carbonate, the preferable content of the M element is x=10 to 15wt%, and the excellent catalytic effect is achieved.
In a preferred embodiment, M is Mo and the catalyst has the general formula xMo@SiO 2 The content of Mo element is preferably x=10 to 15wt%.
In a preferred embodiment, the catalyst is a heterogeneous catalyst, the heterogeneous catalyst determines that the catalyst is easy to recover and apply, and experiments prove that the application time is at least 10 times, and the application can be performed 10 to 50 times, for example 10 to 20 times, 20 to 30 times or 30 to 50 times, and the specific application mode is that after the reaction is finished, the catalyst is recovered by filtration and can be directly applied as the catalyst of the fluorination reaction without other treatment.
In a preferred embodiment, the M element is derived from a chloride salt of M element or a nitrate salt of M element, preferably a chloride salt of M element, such as MoCl 5 Or SbCl 5 。
In a preferred embodiment, the carrier SiO 2 The particle diameter of the catalyst is 40-100 mu m, the carrier can be directly selected from the commercial products, and the research proves that the carrier SiO 2 The particle size of the particles is 40-70 mu m, and the effect is better.
In a specific embodiment, theCarrier SiO 2 For deprotonated SiO 2 Specific means of deprotonation are known to those skilled in the art, and in this application the deprotonation is preferably carried out using an alkaline reagent, preferably selected from potassium tert-butoxide or LiCH 2 SiMe 3 At least one of them.
In a preferred embodiment, the fluorination reaction is a fluorination reaction of vinyl chloride carbonate, preferably, the catalyst is applicable at least 10 times, preferably 10 to 30 times, and has industrial value of application at 10 to 30 times, more preferably, 10 to 20 times, without significantly affecting the reaction rate of the fluorination reaction of vinyl chloride carbonate and the yield of vinyl fluoride carbonate.
A second aspect of the present application provides a method for preparing the catalyst according to any one of the above embodiments, including the steps of:
1) Salt of M element and carrier SiO 2 Mixing and stirring with an organic solvent;
preferably, the M element is selected from Sb or Mo, and the salt of the M element is selected from chloride salt of the M element or nitrate of the M element. More preferably the chloride salt of element M, e.g. MoCl 5 Or SbCl 5 。
Specifically, the content of the M element x=1 to 20wt%, alternatively, x=1 to 5wt%, x=5 to 10wt%, x=10 to 15wt% or x=15 to 20wt%, and in the fluorination reaction of chloroethylene carbonate, the preferred content of the M element x=10 to 15wt%, has a good catalytic effect, and the determination of the salt amount of the M element in the preparation method is performed according to the specific content of the M element. Optionally, the salt of M element and carrier SiO 2 The mass ratio of the catalyst to the organic solvent is (0.5-1) (40-100), the mass ratio of the catalyst to the organic solvent is (0.5-3) (40-100), the catalyst prepared according to the reagent can be adjusted according to the catalytic effect and the application effect of the catalyst, for example (0.5-0.8) (1.5-3) (40-100), (0.8-1) (1.5-3) (40-100), (0.5-1) (1.5-2) (40-100), (0.5-1) (2-100), (0.5-1) (1.5-3) (40-60), (0.5-1) (1.5-3) (60-100), (0.5-0.8) (40-60), (0.5-3) (0.8-1)) (1.5-3) and (60-100). In the preparation method of fluoroethylene carbonate, the salt of M element and a carrier SiO 2 And the mass ratio of the organic solvent is preferably (0.6-0.8): 1.5-3): 40-60.
Still more specifically, the carrier SiO 2 The particle size of the carrier is 40-60 mu m, and the carrier can be selected from 40-50 mu m or 50-60 mu m and can be directly sold in the market, and the research proves that the particle size effect of the carrier is better.
Still more specifically, the carrier SiO 2 Is anhydrous SiO 2 Can obtain a porous catalyst with higher quality and a carrier SiO 2 Vacuum drying at 100-130 deg.c to obtain the anhydrous SiO 2 。
Still more specifically, the carrier SiO 2 For deprotonated SiO 2 Preferably, the carrier SiO 2 Deprotonation reaction is carried out by adopting alkali reagent to obtain the deprotonated SiO 2 . More preferably, the alkaline reagent is selected from potassium tert-butoxide or LiCH 2 SiMe 3 . The deprotonation reaction further comprises a deprotonation reaction solvent, preferably the deprotonation reaction solvent is selected from ether solvents, more preferably the deprotonation reaction solvent is selected from THF or diethyl ether. More preferably, the reaction temperature of the deprotonation reaction is 20-35 ℃, and the reaction time of the deprotonation reaction is 8-24 hours, wherein the reaction temperature is generally room temperature, and the reaction time is 8-12 hours or 12-24 hours. Experiments prove that the carrier SiO obtained under the deprotonation reaction conditions 2 The catalyst can be applied to the preparation of the catalyst, and the catalyst with higher catalytic quality can be obtained.
Still more specifically, the carrier SiO 2 The mass ratio of the alkali agent to the alkali agent is 1 (1-5), and the alkali agent is 1 (1-3) or 1 (3-5). The carrier SiO 2 The mass ratio of the deprotonating solvent to the deprotonating solvent is 1 (4-20), optionally 1 (4-8), 1 (8-10), 1 (10-15) or 1 (15-20).
Still more specifically, the organic solvent is a polar organic solvent, preferably, the organic solvent is at least one selected from 1, 2-dimethoxyethane, DMAC (N, N-dimethylacetamide), DMF (N, N-dimethylformamide), NMP (N-methylpyrrolidone), DMSO (dimethylsulfoxide), or acetonitrile.
2) Filtering the mixed solution obtained in the step 1) to obtain a catalyst precursor, wherein in the step 2), the filtering is preferably performed under the protection of nitrogen; more preferably, the filtration is followed by rinsing with a solvent to remove excess alkaline reagent and other impurities.
3) Drying the catalyst precursor obtained in the step 2) to obtain a catalyst xM@SiO 2 Preferably, the drying operation of step 3) is carried out at a temperature of-30 to 10 ℃, and the drying operation of step 3) is carried out under vacuum. The catalyst xM@SiO obtained 2 Is a heterogeneous catalyst.
A third aspect of the present application provides the use of a catalyst according to any one of the embodiments described above for the preparation of fluoroethylene carbonate from chloroethylene carbonate. It is worth noting that the novel catalyst is a newly developed catalyst, and the development process is aimed at being applied to fluorination reaction, because in the current preparation process of fluoroethylene carbonate, chloroethylene carbonate and fluoroethylene carbonate are prepared in MoCl 5 Or SbCl 5 The Applicant has therefore aimed at improving the catalysts used in this process and to develop the xM@SiOs of the present application, which are susceptible to decomposition by heating in the presence of 2 The catalyst is applied to the preparation process of fluoroethylene carbonate, has high yield of fluorination reaction, and has no obvious influence on the speed and yield of the fluorination reaction after being applied for at least 10 times.
According to a fourth aspect of the present invention, there is provided a method for preparing fluoroethylene carbonate, wherein fluoroethylene carbonate and HF are subjected to fluorination in the presence of the catalyst according to the first aspect, and post-treatment is performed to obtain fluoroethylene carbonate, wherein the reaction equation is as follows:
in a preferred embodiment, the mass ratio of the chloroethylene carbonate to the catalyst is 1 (0.01% -0.10%), the catalyst dosage can be adjusted according to the reagent requirement, and experiments prove that the catalytic effect is better when the mass ratio of the chloroethylene carbonate to the catalyst is 1 (0.01% -0.05%) or 1 (0.01% -0.04%).
In a preferred embodiment, the amount of HF relative to the amount of chloroethylene carbonate is generally equal or in excess in terms of molar amount, in this embodiment the molar ratio of chloroethylene carbonate to HF is from 1:1 to 3; preferably, in the fluorination reaction, the HF is introduced into the reaction system at a rate of 0.05 to 0.15g/min, and the HF is introduced into the reaction system at a rate of 0.05 to 0.10g/min or 0.10 to 0.15g/min. Preferably, anhydrous HF gas is used as HF. The reaction temperature of the fluorination reaction is 20-130 ℃, preferably, the reaction temperature can be specifically selected according to a reaction process section, generally, the reaction substrate and the heterogeneous catalyst are kept in a good contact state in a mixing section of chloroethylene carbonate and the catalyst, wherein the temperature is 20-35 ℃, namely, the room temperature is generally room temperature, and the stirring is carried out for 20-60 min; the HF section is introduced at 35-130 deg.c, which may be 35-50 deg.c, 50-60 deg.c, 50-70 deg.c, 70-100 deg.c or 70-130 deg.c, and the reaction time of the section is 3-8 hr, preferably 5-6 hr.
In a preferred embodiment, the post-treatment comprises filtration to obtain a spent catalyst and filtrate; preferably, the catalyst is applied at least 10 times, preferably 10 to 30 times, and has industrial value of application at 10 to 30 times, more preferably 10 to 20 times, and has no obvious influence on the reaction speed of the fluorination reaction of the chloroethylene carbonate and the yield of the fluoroethylene carbonate.
The method for obtaining fluoroethylene carbonate by post-treatment it is possible for the person skilled in the art to select a suitable post-treatment method for the product obtained by each reaction, such as distillation, filtration, drying or recrystallization. Specifically, in the application, the filtrate is subjected to rectification treatment to obtain fluoroethylene carbonate; more preferably, the rectification treatment is carried out under reduced pressure under the condition of 1-2 mmHg, and fractions with the temperature of 56-60 ℃ are collected to obtain fluoroethylene carbonate, wherein the GC content of the obtained fluoroethylene carbonate is more than 99.95 percent, the chromaticity is less than 5APHA, the acid value is less than 5ppm, and the moisture is less than 15ppm.
In the fluorination reaction, the reaction time can be appropriately adjusted by those skilled in the art according to the reaction progress, and the method for detecting the progress of the reaction should be known to those skilled in the art, and may be an analytical method such as chromatography. In general, the end point of the reaction may be the substantial disappearance of the starting substrate.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
Example 1.2 wt% Mo@SiO 2 Is prepared from
Silica gel (4.32 g, silica model: silica 60M, particle size 40-63 μm, merck, germany), potassium tert-butoxide (7.27 g,0.0648 mol), THF (26 g) were added to the reaction flask, and stirred for 12 hours. The deprotonated silica gel was washed 3 times with THF. 1, 2-Dimethoxyethane (100 g) and MoCl were added 5 (2.73 g,0.01 mol) was stirred at room temperature for 12 hours. Filtering under the protection of nitrogen, rinsing with 1, 2-dimethoxyethane, and vacuum drying at-30 to-10 ℃ to obtain the high-efficiency metal porous catalyst Mo@SiO 2 (6.3 g). ICP gave a Mo content of 13.2wt%. The yield was 87.3% calculated from the Mo content.
Example 2.5wt% Mo@SiO 2 Is prepared from
Silica gel (4.32 g, silica 60M, particle size 40-63 μm, germany Merck), liCH are added into a reaction flask 2 SiMe 3 (1.0M pentane solution, 64.8mL,0.0648 mol), THF (26 g), and stirring for 12h. The deprotonated silica gel was washed 3 times with THF. 1, 2-Dimethoxyethane (100 g) and MoCl were added 5 (2.73 g,0.01 mol) was stirred at room temperature for 12 hours. Filtering under the protection of nitrogen, rinsing with 1, 2-dimethoxyethane, and vacuum drying at-30 to-10 ℃ to obtain the high-efficiency metal porous catalyst Mo@SiO 2 (5.8 g). ICP gave a Mo content of 12.5wt%. The yield was 75.5% calculated from the Mo content.
Example 3.4wt% Mo@SiO 2 Is prepared from
The solvent was changed from 1, 2-dimethoxyethane to DMAC as in example 1. ICP gave a Mo content of 13.4wt%. The yield thereof was found to be 80.1%.
Example 4.6 wt% Mo@SiO 2 Is prepared from
As in example 1, the solvent was changed from DMAC to acetonitrile. ICP gave a Mo content of 12.6wt%. The yield thereof was found to be 77.6%.
EXAMPLE 5 preparation of fluoroethylene carbonate
Into the reaction flask was charged chloroethylene carbonate (122.5 g), moCl x @SiO 2 (0.0245 g,0.02wt% of the catalyst prepared in example 1) was stirred at room temperature for 30 minutes. Heating to 90 ℃, continuously introducing anhydrous hydrogen fluoride (28 g) at the speed of 0.09g/min, and stirring and reacting for 5 hours at the temperature of 90-110 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum stripping to remove residual hydrogen fluoride and hydrogen chloride gas in the system at 30-40 ℃. Filtering to recover catalyst, and rectifying the filtrate under the condition of pressure of 1-2 mmHg and top temperature collecting temperature of 56-60 ℃. The final product fluoroethylene carbonate (101 g) was obtained. The gas phase (GC) content was 99.98%, the color number was 3APHA, the acid value was 3ppm and the moisture content was 12ppm. The yield thereof was found to be 95.3%.
EXAMPLE 6 preparation of fluoroethylene carbonate
Into the reaction flask was charged chloroethylene carbonate (122.5 g), moCl x @SiO 2 (0.012 g,0.01wt% of the catalyst prepared in example 2) was stirred at room temperature for 30 minutes. Heating to 100deg.C, and continuously introducing anhydrous water at a rate of 0.09g/minHydrogen fluoride (32 g), and stirring and reacting for 6 hours at the temperature of 100-120 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum stripping to remove residual hydrogen fluoride and hydrogen chloride gas in the system at 30-40 ℃. Filtering to recover catalyst, and rectifying the filtrate under the condition of pressure of 1-2 mmHg and top temperature collecting temperature of 56-60 ℃. The final product fluoroethylene carbonate (98.1 g) was obtained. The gas phase (GC) content was 99.97%, the color number was 4APHA, the acid value was 4ppm and the moisture content was 10ppm. The yield thereof was found to be 92.5%.
EXAMPLE 7 preparation of fluoroethylene carbonate
Into the reaction flask was charged chloroethylene carbonate (122.5 g), moCl x @SiO 2 (0.049 g,0.04wt% of the catalyst prepared in example 2) was stirred at room temperature for 30 minutes. Heating to 50 ℃, continuously introducing anhydrous hydrogen fluoride (32 g) at the speed of 0.09g/min, and stirring and reacting for 6 hours at the temperature of 50-70 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum stripping to remove residual hydrogen fluoride and hydrogen chloride gas in the system at 30-40 ℃. Filtering to recover catalyst, and rectifying the filtrate under the condition of pressure of 1-2 mmHg and top temperature collecting temperature of 56-60 ℃. The final product fluoroethylene carbonate (98.9 g) was obtained. The gas phase (GC) content was 99.98%, the color number was 4APHA, the acid value was 5ppm and the moisture content was 11ppm. The yield thereof was found to be 93.3%.
Example 8A mechanically examined catalyst recovered by filtration of example 7
Into a reaction flask was charged chloroethylene carbonate (122.5 g), mo@SiO 2 (catalyst recovered by filtration in example 7, about 0.05 g), and stirred at room temperature for 30 minutes. Heating to 50 ℃, continuously introducing anhydrous hydrogen fluoride (32 g) at the speed of 0.09g/min, and stirring and reacting for 6 hours at the temperature of 50-70 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum stripping to remove residual hydrogen fluoride and hydrogen chloride gas in the system at 30-40 ℃. Filtering to recover catalyst, and rectifying the filtrate under the condition of pressure of 1-2 mmHg and top temperature collecting temperature of 56-60 ℃. The final product fluoroethylene carbonate (97.8 g) was obtained. The gas phase content was 99.98%, the color number was 3APHA, the acid value was 5ppm, and the moisture content was 10ppm. The yield thereof was found to be 92.2%.
Note that: the catalyst can be continuously used for 10 times, the reaction conditions of the verification reaction of the application times are the same as those of the example 8, and experiments prove that the application of the catalyst for 10 times has no obvious influence on the speed and the yield of the fluorination reaction, and specific data are shown in the following table 1.
TABLE 1
| Sequence number | Total reaction time | Product yield | GC content | Number of times of application |
| 1 (example 7) | 6.5h | 93.3％ | 99.98％ | First time |
| 2 (example 8) | 6.5h | 92.2％ | 99.98％ | Is applied mechanically for 1 time |
| 3 | 6.5h | 92.6％ | 99.97％ | Is applied mechanically for 2 times |
| 4 | 6.5h | 92.1％ | 99.98％ | Is applied mechanically for 3 times |
| 5 | 6.5h | 91.2％ | 99.98％ | Is applied for 4 times |
| 6 | 6.5h | 91.6％ | 99.97％ | Is applied mechanically for 5 times |
| 7 | 6.5h | 91.8％ | 99.97％ | Is applied mechanically for 6 times |
| 8 | 6.5h | 91.1％ | 99.98％ | Is applied mechanically for 7 times |
| 9 | 6.5h | 90.6％ | 99.98％ | 8 times of application |
| 10 | 6.5h | 90.2％ | 99.98％ | 9 times of application |
| 11 | 6.5h | 90.3％ | 99.98％ | Is applied for 10 times |
Comparative example 1
Into the reaction flask was charged chloroethylene carbonate (122.5 g), moCl 5 (0.0123 g,0.01 wt%). Heating to 100 ℃, continuously introducing anhydrous hydrogen fluoride (32 g) at the speed of 0.09g/min, and stirring and reacting for 6 hours at the temperature of 100-120 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum removal of residual hydrogen fluoride and hydrogen chloride gas in the system in 30-40. Rectifying under the condition of the pressure of 1-2 mmHg and the top temperature of 56-60 ℃. The final product fluoroethylene carbonate (37.1 g) was obtained in a yield of 35%.
Comparative example 2
Into the reaction flask was charged chloroethylene carbonate (122.5 g), sbCl 5 (0.03g，0.025wt％)，MoCl 5 (0.092 g,0.075 wt%) was stirred at room temperature for 30 minutes. Heating to 100 ℃, continuously introducing anhydrous hydrogen fluoride (32 g) at the speed of 0.09g/min, and stirring and reacting for 6 hours at the temperature of 100-120 ℃. After the GC central control reaction is finished, the reaction liquid is subjected to vacuum stripping to remove residual hydrogen fluoride and hydrogen chloride gas in the system at 30-40 ℃. Rectifying under the condition of the pressure of 1-2 mmHg and the top temperature of 56-60 ℃. The final product fluoroethylene carbonate (35.0 g) was obtained in 33% yield.
As can be seen from examples 5 to 8 and comparative examples 1 to 2, sbCl was used 5 、MoCl 5 The catalyst can be used alone or in a mixture of a certain proportion to obtain the final fluorinated product, but the yield is low, which is only about 30%. The reason is that the raw material chloroethylene carbonate and fluorinated product fluoroethylene carbonate are prepared in MoCl 5 Or SbCl 5 Is easy to decompose when heated in the presence of the catalyst. Resulting in a decrease in the yield of the fluorination reaction. And raw material chloroethylene carbonate and fluorinated product fluoroethylene carbonate and efficient metal porous catalyst xM@SiO 2 Can keep stable in contact, so xM@SiO 2 Higher yields of fluorination than other catalysts reported to date can be achieved. And the method can be used for recycling through a simple filtering method, has a simple process route, and is suitable for large-scale industrial production.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (11)
1. A catalyst for fluorination reaction, characterized in that the catalyst comprises a carrier SiO 2 And an active ingredient M element;
the general formula of the catalyst is xM@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The M element is selected from Sb or Mo; the content x=1 to 20wt% of M element.
2. The catalyst of claim 1, wherein the catalyst is a heterogeneous catalyst;
and/or, the M element is derived from chloride salt of the M element or nitrate of the M element.
3. The catalyst according to claim 1 or 2, characterized in that the support SiO 2 The grain diameter of the particles is 40-100 mu m;
and/or the carrier SiO 2 Is anhydrous SiO 2 ；
And/or the carrier SiO 2 For deprotonated SiO 2 ；
And/or, the fluorination reaction is a fluorination reaction of chloroethylene carbonate; preferably, the catalyst is applicable at least 10 times in the fluorination of chloroethylene carbonate.
4. A method for preparing a catalyst according to any one of claims 1 to 3, comprising the steps of:
1) Salt of M element and carrier SiO 2 Mixing and stirring with an organic solvent;
2) Filtering the mixed solution obtained in the step 1) to obtain a catalyst precursor;
3) Drying the catalyst precursor obtained in the step 2) to obtain a catalyst xM@SiO 2 。
5. The method for preparing a catalyst according to claim 4, characterized by comprising at least one of the following technical features:
1a) The salt of the M element is selected from chloride salt of the M element or nitrate of the M element, and the M element is selected from Sb or Mo;
1b) The carrier SiO 2 The grain diameter of the particles is 40-100 mu m;
1c) The carrier SiO 2 Is anhydrous SiO 2 ；
1d) The carrier SiO 2 For deprotonated SiO 2 ；
1g) The organic solvent is a polar organic solvent;
1h) The salt of M element and a carrier SiO 2 And the mass ratio of the organic solvent is (0.5-1): 1.5-3): 40-100;
2a) In the step 2), the filtration is carried out under the protection of nitrogen;
3a) The temperature of the drying operation of the step 3) is-30 to-10 ℃, and the drying operation of the step 3) is carried out under vacuum condition;
3b) The catalyst is a heterogeneous catalyst.
6. The method for preparing the catalyst according to claim 5, characterized by comprising at least one of the following technical features:
1c1) Carrier SiO 2 Vacuum drying at 100-130 deg.c to obtain the said no-matterSiO with water 2 ；
1d1) Carrier SiO 2 Deprotonation reaction is carried out by adopting alkali reagent to obtain the deprotonated SiO 2 ；
1g1) The organic solvent is at least one selected from 1, 2-dimethoxyethane, DMAC, DMF, NMP, DMSO or acetonitrile;
1h1) The salt of M element and a carrier SiO 2 And the mass ratio of the organic solvent is (0.6-0.8): 1.5-3): 40-60.
7. The method for preparing a catalyst according to claim 6, wherein the alkaline reagent is selected from the group consisting of potassium tert-butoxide and LiCH in technical feature 1d 1) 2 SiMe 3 At least one of (a) and (b);
and/or the carrier SiO 2 The mass ratio of the alkali agent to the alkali agent is 1 (1-5);
and/or the deprotonation reaction further comprises a deprotonation reaction solvent; preferably, the deprotonation reaction solvent is selected from ether solvents, the carrier SiO 2 The mass ratio of the catalyst to the deprotonation reaction solvent is 1 (4-20); more preferably, the deprotonation reaction solvent is selected from THF or diethyl ether;
and/or the reaction temperature of the deprotonation reaction is 20-35 ℃;
and/or the reaction time of the deprotonation reaction is 8-24 h.
8. Use of a catalyst according to any one of claims 1 to 3 for the preparation of fluoroethylene carbonate from chloroethylene carbonate.
9. Use according to claim 8, characterized in that fluoroethylene carbonate and HF are prepared in the presence of said catalyst.
10. A process for producing fluoroethylene carbonate, comprising subjecting chloroethylene carbonate and HF to a fluorination reaction in the presence of the catalyst according to any one of claims 1 to 3, and post-treating to obtain fluoroethylene carbonate, wherein the reaction equation is as follows:
11. the method for producing fluoroethylene carbonate according to claim 10, characterized by comprising at least one of the following technical features:
1) The mass ratio of the chloroethylene carbonate to the catalyst is 1 (0.01% -0.10%);
2) The mol ratio of the chloroethylene carbonate to the HF is 1:1-3;
3) In the fluorination reaction, the speed of introducing HF into a reaction system is 0.05-0.15 g/min;
4) The reaction temperature of the fluorination reaction is 20-130 ℃;
5) The post-treatment comprises the steps of filtering to obtain a catalyst and filtrate; preferably, the catalyst is applied at least 10 times; preferably, the filtrate is subjected to rectification treatment to obtain fluoroethylene carbonate; more preferably, the rectification treatment is carried out under reduced pressure under the condition of 1-2 mmHg, and the fraction at 56-60 ℃ is collected to obtain fluoroethylene carbonate.
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