CN114105766A - Preparation method of fluoro acyl fluoride - Google Patents

Preparation method of fluoro acyl fluoride Download PDF

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CN114105766A
CN114105766A CN202011582611.3A CN202011582611A CN114105766A CN 114105766 A CN114105766 A CN 114105766A CN 202011582611 A CN202011582611 A CN 202011582611A CN 114105766 A CN114105766 A CN 114105766A
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fluoride
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atom
methylpyrazole
difluoromethyl
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CN114105766B (en
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林韦康
王明春
相雪理
朱海
蔡以恒
杨沫
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Suqian Keylab Biochemical Co ltd
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Abstract

The invention relates to a preparation method of fluoro acyl fluoride, which comprises the step of reacting halogenated olefin shown as a formula I, oxygen and hydrogen fluoride under the action of a catalyst to generate fluoro acyl fluoride shown as a formula II, wherein the catalyst is 3-difluoromethyl-1H-methylpyrazole-4-chromium formate. The preparation method of the fluoro acyl fluoride has the advantages of wide raw material source, simple process, good catalytic activity, safe and reliable reaction, high automation degree and suitability for industrial production.

Description

Preparation method of fluoro acyl fluoride
Technical Field
The invention relates to a preparation method of fluoroacyl fluoride, belonging to the technical field of fine chemical engineering.
Background
Acyl Halide (Acyl Halide) refers to a product in which hydroxyl in carboxylic acid is substituted by halogen, and common acid chloride, Acyl fluoride and Acyl bromide are used. Acyl halide does not exist in nature and can only be prepared by chemical synthesis, and the acyl halide in the current chemical field is mainly prepared by reacting carboxylic acid and acylating agent, and the reaction equation is as follows:
Figure 350162DEST_PATH_IMAGE001
。
in this reaction scheme: x can be F, Cl, Br, I, etc.; r can be aliphatic hydrocarbon, aliphatic olefin, aromatic hydrocarbon, aromatic olefin, halogenated aliphatic hydrocarbon, halogenated aromatic hydrocarbon and the like.
Common acylating agents are phosphorus halides, sulfoxide halides, oxalyl halides, triphenylphosphine halides and the like. The disadvantages of these acylating agents for the preparation of acyl halides are significant: (1) the cost of the carboxylic acid is high, such as the tonnage market price of difluoroacetic acid and 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid is higher than 20 ten thousand yuan; (2) the acylating agent is irritant and has high requirement on labor protection of a contactor; (3) the acyl halide preparation process is accompanied by a large amount of waste gas, so that the environmental protection control difficulty is high; (4) the requirement on the corrosion resistance of a production device is high, and the investment of the production device is large.
Since the last 90 s of the century, there have been reports of studies on the preparation of acid halides from halogenated olefins by oxidation with oxygen in the presence of catalysts, among which are more typical:
(1) european patent document EP623578 reports that trichloroethylene can be oxidized to dichloroethylene chloride in the presence of an amine catalyst, tetramethylpiperidine, and has the obvious disadvantages of the formation of a by-product, halogenated propylene oxide, and low atom utilization.
(2) Chinese patent documents CN1131140 and CN101445445 both report that dichloroacetyl chloride can be prepared by reacting trichloroethylene with oxygen under the environmental conditions of 0.1 MPa-0.8 MPa and 40-180 ℃ in the presence of azodiisobutyl catalyst and triethylamine initiator, and the yield is 20-85 percent.
(3) The german patent document DE19620018, whose realization requires light and high temperatures at wavelengths greater than 280nm and a chromium-based catalyst, reports that trichloroethylene can be oxidized by oxygen to dichloroacetyl chloride at temperatures between 50 ℃ and 200 ℃ and that, although the yields are good, the requirements on the production plant are too high.
(4) In 2007, Ou, Hsin-Hung et al reported that trichloroethylene can be irradiated by light to react with dichloroacetyl chloride and phosgene under the catalysis of platinum-doped carbon dioxide, phosgene is extremely toxic, and phosgene is extremely reactive chemical property, so if phosgene cannot be completely separated from dichloroacetyl chloride, preparation of downstream products is not favorable, and industrial production difficulty of the process technology disclosed in the patent is high.
(5) Chinese patent documents CN101195563 and CN107573242A report that the dichloroacetyl chloride with the purity of 99 percent can be obtained by the reaction of trichloroethylene with dry air at the temperature of 110 ℃ under the catalysis of vanadium pentoxide or manganese dioxide, triphenylphosphine and ammonium chloride. The catalyst prepared by the patent is complex, a catalyst recovery method is not clarified, and the treatment cost of the heavy metal waste catalyst is high.
(6) Chinese patent document CN102471207B discloses a method for preparing halogenated acetyl fluoride and its derivatives. The halogenated acetyl halide is prepared by photo-oxidizing halogenated ethylene compounds, and then the halogenated acetyl halide is reacted with hydrofluoric acid to obtain the halogenated acetyl fluoride. In the production process, the oxidation reaction and the fluorination reaction are separately carried out, the reactant hydrofluoric acid is liquid, and the separation step is complicated.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of fluorinated acyl fluoride, which has simple process and can carry out oxidation and fluorination simultaneously.
The invention provides a technical scheme for solving the technical problems, which comprises the following steps: a preparation method of fluoro acyl fluoride comprises the reaction of halogenated olefin shown as a formula I, oxygen and hydrogen fluoride under the action of a catalyst to generate fluoro acyl fluoride shown as a formula II, wherein the reaction formula is as follows:
Figure 618333DEST_PATH_IMAGE002
，
wherein, X2Is a hydrogen atom, a chlorine atom or a bromine atom, X1And X3Is a chlorine atom or a bromine atom, R1Is hydrogen atom, chlorine atom, bromine atom, C1-C8 alkyl, C1-C8 alkyl with chlorine substituent or C1-C8 alkyl with bromine substituent;
when X is present2When it is a hydrogen atom, X2' is a hydrogen atom; when X is present2When it is a chlorine atom or a bromine atom, X2' is a fluorine atom;
when R is1When it is a hydrogen atom, R2Is a hydrogen atom; when R is1When the alkyl is C1-C8, R2Is C1-C8 alkyl; when R is1When it is a chlorine atom or a bromine atom, R2Is a fluorine atom; when R is1When the alkyl is C1-C8 with chlorine substituent or C1-C8 with bromine substituent, R is2Is C1-C8 alkyl with chlorine substituent or bromine substituent replaced by fluorine substituent;
the catalyst is 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, has a structure shown in a formula III,
Figure 407297DEST_PATH_IMAGE003
。
the catalyst is a supported catalyst prepared by taking a molecular sieve, silica gel or diatomite as a carrier and 3-difluoromethyl-1H-methylpyrazole-4-chromium formate aqueous solution through an impregnation method.
The impregnation method of the invention takes purified water as a solvent, the amount of the purified water is preferably just enough to dissolve the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, and is usually 6-8 times of the weight of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate.
The supported catalyst is prepared by dissolving a product generated by reacting chromium trichloride hexahydrate and 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in an aqueous solution in water, adding a carrier, extracting by acetonitrile, methanol, ethanol, isopropanol or n-butanol, drying to prepare a powdery solid, granulating to prepare a sphere with the sphere diameter of 5-6 mm, and activating for 3-8H at the temperature of 105-150 ℃.
The chromium 3-difluoromethyl-1H-methylpyrazole-4-carboxylate needs to remove chloride ions before being prepared into a supported catalyst, the removal method is preferably a method of washing, water recrystallization, water pulping and the like, and the content of the chloride ions in the catalyst is strictly controlled to be less than 5 ppm.
The carrier can be any one of silica gel, ZSM type molecular sieve, Y type molecular sieve and diatomite. Preferably, the carrier is a ZSM-5 type molecular sieve, and the carrier can improve the mechanical strength of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, so that the properties of wear resistance, pressure resistance, impact strength and the like of the carrier are obviously improved.
The above ZSM-5 type molecular sieve has a silica-alumina molar ratio of 15 to 20.
The hydrogen fluoride is hydrogen fluoride gas, the reaction temperature for synthesizing the fluoroacyl fluoride is 150-200 ℃, the pressure for synthesizing the fluoroacyl fluoride is-1 MPa-0.1 MPa, and no water exists in the reaction for synthesizing the fluoroacyl fluoride.
The invention provides another technical scheme for solving the technical problems, which comprises the following steps: a catalyst having a structure according to formula iii:
Figure 368300DEST_PATH_IMAGE003
。
the invention provides another technical scheme for solving the technical problems, which comprises the following steps: a method of preparing a catalyst comprising the steps of:
A. dissolving 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in pure water, adding chromium trichloride hexahydrate, reacting at 80-90 deg.C for 2-4H while stirring, cooling to below 25 deg.C, centrifuging to obtain wet product,
B. removing chloride ions from the wet product by water washing, water recrystallization or water pulping;
C. dissolving the product obtained in the step B in pure water, adding a carrier with the weight of 2.5-3.5 times that of the product to soak the product at the temperature of 25-100 ℃, stirring the product into paste, extracting the paste by using acetonitrile, methanol, ethanol, isopropanol or n-butanol, and drying the paste to prepare powdery solid;
D. granulating the powdery solid into a ball shape with the ball diameter of 5-6 mm;
E. activating the spherical solid for 3-8H at the temperature of 105-150 ℃ to obtain a finished product of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst.
The amount of pure water used in the step A is 6 to 8 times of the weight of 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid. B, recrystallizing the wet product with purified water which is 1.5-2 times of the weight of the wet product to obtain crystals; the dipping temperature in the step C is 60-70 ℃, the dipping pressure is normal pressure, and the extraction solvent is methanol.
The invention has the positive effects that:
(1) the preparation method of the fluoro acyl fluoride adopts the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst, has the catalytic performance of fluorination reaction and oxidation reaction, and has good catalytic activity, chlorinated olefin or brominated olefin is used as a raw material, when a double bond is positioned at the tail end of a molecular structure, and two substituted chlorine atoms or bromine atoms are arranged at the tail end, and when the double bond is oxidized, one substituted atom can be rearranged and transferred to adjacent carbon atoms, so that the fluoro acyl fluoride can be prepared only through one-step reaction.
(2) The preparation method of the fluoroacyl fluoride can use trichloroethylene as a raw material to prepare difluoroacetyl fluoride, and because reactants and products are gases, the prepared difluoroacetyl fluoride can be directly used as the raw material to synthesize the 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid even if the prepared difluoroacetyl fluoride is mixed with gases such as hydrogen chloride, hydrogen fluoride and the like, and the 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid is the production raw material of the catalyst, so the cyclic utilization can effectively reduce the production cost.
(3) The preparation method of the fluoro acyl fluoride adopts 3-difluoromethyl-1H-methylpyrazole-4-chromium formate as a catalyst, although the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate has obvious catalytic activity, the high dispersion state is difficult to prepare, a proper carrier is selected as a framework for depositing the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, the carrier increases the active surface of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate by a proper pore structure, and the use amount of expensive 3-difluoromethyl-1H-methylpyrazole-4-chromium formate can be reduced, so that the preparation cost of the catalyst is saved.
Drawings
FIG. 1 is a chromatogram of methyl difluoroacetate obtained by reacting the product difluoroacetyl fluoride of example 1 with methanol.
FIG. 2 is a chromatogram of methyl nonafluoropentanoate obtained by reacting the product nonafluoropentanoyl fluoride of example 2 with methanol.
FIG. 3 is a chromatogram of methyl trifluoroacetate obtained by reaction of trifluoroacetyl fluoride and methanol as a product of example 3.
FIG. 4 is a schematic diagram of a reaction apparatus for producing fluoroacyl fluoride according to example 4.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure. 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. Halogen atoms, such as: bromine atom, iodine atom, fluorine atom and chlorine atom. The alkyl of C1-C8 refers to alkyl with a carbon chain length of 1-8, such as: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like. The substituted alkyl group having C1 to C8 means a group in which 1 or more hydrogen atoms of the alkyl group are substituted with a substituent.
The chemical reagents used in the invention are all purchased reagents without special description, and the concentration is chemical purity.
Example 1
The preparation method of difluoroacetic acid fluoride of the embodiment comprises the following specific steps:
firstly, heating a heat conducting oil for a premixer to 110-115 ℃, heating a reactor filled with a supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst to 180-190 ℃ with heat tracing, and purging with nitrogen from a raw material feed port or a hydrogen fluoride feed port to ensure that no moisture exists in the whole reaction device.
And then starting the premixer to stir, starting to introduce hydrogen fluoride gas into the premixer (flow: 5 m/h), after hydrogen fluoride escapes from a product outlet at the top of the reactor, simultaneously introducing trichloroethylene and dry oxygen into the premixer (trichloroethylene flow: 1.5 m/h, oxygen flow 1.8 m/h), and performing reaction at 180-190 ℃ under the reactor backpressure of 0.1MPa, so that the mixed gas of difluoroacetylfluoride, hydrogen chloride and hydrogen fluoride can be stably obtained. The reaction formula is as follows:
Figure 141084DEST_PATH_IMAGE004
。
the preparation method of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst in the implementation comprises the following steps:
sequentially putting purified water (5000.00 kg, 277.78 kmol) and 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid (600.00 kg,3.41 kmol) into a 10000L glass-lined reaction kettle, heating to 80-90 ℃, wherein the feed liquid is white suspension, a small amount of 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid is still undissolved, centrifugally separating while the solution is hot, recycling a filter cake, pumping the filtrate into another 10000L glass-lined reaction kettle, controlling the temperature to be not lower than 80 ℃, adding chromium trichloride hexahydrate (880.00 kg, 3.30 kmol), controlling the temperature to be 80-90 ℃, continuously stirring for 2 hours, reducing the temperature to 60 ℃, concentrating under reduced pressure (-0.095 MPa) to 1/3 of the original volume, cooling to 25 ℃, centrifugally separating, wherein the filter cake is catalyst 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, the filtrate is in yellow green granular crystal (the weight of wet product is 821.92 kg), and can be recycled.
And recrystallizing the obtained wet product in a 3000L glass lining reaction kettle by using 1.5 times of purified water to obtain 560.13kg of light green needle-shaped crystals, wherein the recrystallization mother liquor can be circularly applied to the catalyst preparation process and cannot be applied to the recrystallization process (the unqualified chloride ions can be caused).
Dissolving the obtained recrystallized product in a 3000L glass lining reaction kettle by 6 times of purified water at 60-70 ℃, adding 3 times of ZSM-5 type molecular sieve, stirring into paste, transferring the material to an industrial Soxhlet extractor by a dispersion pump, and extracting by using a proper amount of methanol.
After extraction, the mixture was transferred to a spray dryer by a dispersion pump and dried at 105 ℃ under normal pressure to obtain 1792.55g of a light green powdery solid dry product which is a powdery supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst.
The obtained powdery solid is granulated under certain conditions to prepare the spherical load type 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst with the sphere diameter of 5-6 mm.
Activating the obtained spherical supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst for 5H at the temperature of 115-125 ℃, and naturally cooling to obtain the supported catalyst with fluorination and oxidation catalytic activities.
Figure 744103DEST_PATH_IMAGE005
。
Since difluoroacetyl fluoride is difficult to detect, difluoroacetyl fluoride prepared by the preparation method of the embodiment is reacted with a proper amount of methanol to obtain methyl difluoroacetate, the purity of which is 99.48% by gas chromatography, and the chromatogram of methyl difluoroacetate is shown in fig. 1. The results of the chromatographic analysis of methyl difluoroacetate are shown in Table 1.
TABLE 1 chromatographic analysis results Table
Figure 918733DEST_PATH_IMAGE006
When the purity of difluoroacetyl fluoride is reduced, the reaction is considered to be stopped and the catalyst is replaced.
Example 2
The preparation method of nonafluoropentanoyl fluoride of the embodiment comprises the following specific steps:
firstly, heating a premixer to 160-165 ℃ by using heat conducting oil, heating a reactor filled with a supported complex catalyst to 170-175 ℃ by means of heat tracing, and purging by using nitrogen from a raw material feed port or a hydrogen fluoride feed port to ensure that no moisture exists in the whole reaction device.
And then starting the premixer to stir, starting to introduce hydrogen fluoride gas into the premixer (flow: 5 m/h), after hydrogen fluoride escapes from a product outlet at the top of the reactor, simultaneously introducing 1,1,2,3,3,4,4,5,5, 5-decachloropent-1-ene and dry oxygen into the premixer (flow: 1.3 m/h, oxygen flow: 1.8 m/h), wherein the back pressure of the reactor is 0.2MPa, the reaction is carried out at 170-175 ℃, and the mixed gas of nonafluoropentanoyl fluoride, hydrogen chloride and hydrogen fluoride can be stably obtained. The reaction formula is as follows:
Figure 785058DEST_PATH_IMAGE007
。
since the detection of nonafluoropentanoyl fluoride is difficult, nonafluoropentanoyl fluoride prepared by the preparation method of the embodiment reacts with an appropriate amount of methanol to obtain methyl nonafluoropentanoate, the purity is 99.98% as determined by gas chromatography, and the chromatogram of methyl nonafluoropentanoate is shown in fig. 2. The results of the chromatographic analysis of methyl nonafluoropentanoate are shown in table 2.
TABLE 2 chromatographic analysis results Table
Figure 45138DEST_PATH_IMAGE008
When the purity of nonafluorovaleryl fluoride is reduced, the reaction is considered to be stopped and the catalyst is replaced.
Example 3
The preparation method of trifluoroacetyl fluoride of this embodiment comprises the following specific steps:
firstly, heating a premixer to 120-125 ℃ by using heat conducting oil, heating a reactor filled with a supported complex catalyst to 150-155 ℃ by means of heat tracing, and purging the reactor by using nitrogen from a raw material feed port or a hydrogen fluoride feed port to ensure that no moisture exists in the whole reaction device.
And then starting the premixer to stir, starting to introduce hydrogen fluoride gas into the premixer (flow: 5 m/h), introducing tetrachloroethylene and dry oxygen into the premixer simultaneously after hydrogen fluoride escapes from a product outlet at the top of the reactor (tetrachloroethylene: 1.7m for cultivation/h, oxygen flow 1.7m for cultivation/h), and reacting at 150-155 ℃ under the backpressure of the reactor of 0.1MPa, so that the mixed gas of trifluoroacetyl fluoride, hydrogen chloride and hydrogen fluoride can be obtained stably. The reaction formula is as follows:
Figure 655111DEST_PATH_IMAGE009
。
because the detection of trifluoroacetyl fluoride is difficult, trifluoroacetyl fluoride prepared by the preparation method of the embodiment reacts with a proper amount of methanol to obtain methyl trifluoroacetate, the purity is 99.89% by gas chromatography, and the chromatogram of methyl trifluoroacetate is shown in fig. 3. The results of the chromatographic analysis of methyl nonafluoropentanoate are shown in table 3.
TABLE 3 chromatographic analysis results Table
Figure 687176DEST_PATH_IMAGE010
When the trifluoroacetyl fluoride purity decreases, the reaction is considered to be stopped and the catalyst is replaced.
Example 4
Referring to FIG. 4, the apparatus for producing fluoroacyl fluoride according to the present invention is a dedicated apparatus suitable for use in the method for producing fluoroacyl fluoride according to the present invention, and includes a premixer 1 and a packed column 2. Install rabbling mechanism 3 and heating element on the premixer 1, the bottom of premixer 1 is linked together through conveying pipeline 11 and the bottom of packed tower 2, the top of packed tower 2 is equipped with discharging pipe 21, the middle section of packed tower 2 is equipped with catalyst filling layer 24, rabbling mechanism 3 is including extending to the (mixing) shaft 31 of premixer 1 bottom and the stirring vane 32 of fixed connection in (mixing) shaft 31 bottom, stirring vane 32 is located the bottom in premixer 1, be equipped with intake pipe 12 and the inlet pipe 13 that the bottom extended to premixer 1 bottom on the premixer 1, the bottom of intake pipe 12 is close to the periphery department of stirring vane 32, the bottom of intake pipe 12 is close to the bottom of (mixing) shaft 31. The top of the premixer 1 is provided with a feed inlet 17. The gas inlet pipe 12 and the feed pipe 13 extend into the premixer 1 from the feed port 17 and are hermetically fixed at the feed port 17. The stirring blade 32 includes a base 321 extending horizontally outward from the stirring shaft 31, a plurality of uprights 322 extending vertically upward from the base 321, and a diagonal brace 323 connecting the adjacent uprights 322 and the stirring shaft 31, the uprights 322 being uniformly distributed and the uprights 322 located at the outer edge of the base 321 being disposed adjacent to the inner wall of the premixer 1. The top of the premixer 1 is also provided with a gas-liquid separator 14. The gas-liquid separator 14 is vertically arranged, the bottom of the gas-liquid separator 14 is connected with the top of the premixer 1, and the top of the gas-liquid separator 14 is provided with an emergency discharge port 141. The heating component is a heat conducting oil jacket 15 arranged at the middle lower part of the outer wall of the premixer 1, and a heat conducting oil inlet 161 and a heat conducting oil outlet 162 are respectively arranged at two sides of the top of the heat conducting oil jacket 16. A kettle bottom valve 15 is arranged at the joint of the material conveying pipe 11 and the bottom of the premixer 1, and the kettle bottom valve 15 is a downward-expanding kettle bottom valve. The catalyst filling layer 24 has at least two layers, each layer of catalyst filling layer 24 is arranged along the up-down direction of the packed tower 2 at intervals, cavities 241 are arranged above each layer of catalyst filling layer 24, and the outer wall of the packed tower 2 is provided with manholes 242 corresponding to the positions of the cavities 241. The top of packed tower 2 is equipped with the filter layer 27 that the level set up, be equipped with on the packed tower 2 and stretch into the first gas sampling tube 23 between filter layer 27 and the topmost catalyst filling layer 24, still be equipped with the second gas sampling tube 25 that stretches into the packed tower 2 bottom on the packed tower 2, the terminal downwarping that first gas sampling tube 23 stretched into packed tower 2 extends to and is close to corresponding catalyst filling layer 24, the terminal that second gas sampling tube 25 stretched into packed tower 2 is equipped with the decurrent opening of slant.
The fluoro acyl fluoride reaction unit also comprises a condenser 22, the condenser 22 is vertically arranged and is fixedly connected to one side of the top of the packed tower 2 through a triangular bracket 221, a bottom air inlet of the condenser 22 extends into the packed tower 2 through a return pipe 222 and extends to a position between the filter layer 27 and the uppermost catalyst filling layer 24, and a top air outlet of the condenser 22 is connected with a discharge pipe 21 through an air outlet pipe 211. The bottom of the packed tower 2 is provided with an arc-shaped bottom plate 28, the central position of the arc-shaped bottom plate 28 is provided with an air blowing pipe 26 extending out of the packed tower 2, and the feed delivery pipe 11 extends into the bottom of the packed tower 2, and the tail end of the feed delivery pipe extending into the packed tower 2 is inclined downwards and extends to a position close to the arc-shaped bottom plate 28. The stirring mechanism 3 further comprises a variable frequency speed regulating motor 33 fixedly connected above the top of the premixer 1, and a power output shaft of the variable frequency speed regulating motor 33 is vertically arranged downwards and is connected with the top end of the stirring shaft 31 through a coupler. The outer wall of the packed tower 2 is wound with a heat tracing band.
It should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And such obvious variations or modifications which fall within the spirit of the invention are intended to be covered by the scope of the present invention.

Claims (10)

1. A method for producing a fluoroacyl fluoride, characterized by: halogenated olefin shown as a formula I, oxygen and hydrogen fluoride react under the action of a catalyst to generate fluorinated acyl fluoride shown as a formula II, wherein the reaction formula is as follows:
Figure DEST_PATH_IMAGE001
，
wherein, X2Is a hydrogen atom, a chlorine atom or a bromine atom, X1And X3Is a chlorine atom or a bromine atom, R1Is hydrogen atom, chlorine atom, bromine atom, C1-C8 alkyl, C1-C8 alkyl with chlorine substituent or C1-C8 alkyl with bromine substituent;
when X is present2When it is a hydrogen atom, X2' is a hydrogen atom; when X is present2When it is a chlorine atom or a bromine atom, X2' is a fluorine atom;
when R is1When it is a hydrogen atom, R2Is a hydrogen atom; when R is1When the alkyl is C1-C8, R2Is C1-C8 alkyl; when R is1When it is a chlorine atom or a bromine atom, R2Is a fluorine atom; when R is1When the alkyl is C1-C8 with chlorine substituent or C1-C8 with bromine substituent, R is2Is C1-C8 alkyl with chlorine substituent or bromine substituent replaced by fluorine substituent;
the catalyst is 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, has a structure shown in a formula III,
Figure 65284DEST_PATH_IMAGE002
。
2. the method for producing a fluoroacyl fluoride according to claim 1, wherein: the catalyst is a supported catalyst prepared by taking a molecular sieve, silica gel or diatomite as a carrier and 3-difluoromethyl-1H-methylpyrazole-4-chromium formate aqueous solution through an impregnation method.
3. A method of producing a fluoroacyl fluoride according to claim 2, wherein: the supported catalyst is a product generated by reacting chromium trichloride hexahydrate and 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in an aqueous solution, is dissolved in water, added with a carrier, extracted by acetonitrile, methanol, ethanol, isopropanol or n-butanol, dried to form a powdery solid, then granulated to form a sphere with the sphere diameter of 5-6 mm, and activated for 3-8H at the temperature of 105-150 ℃.
4. A method of producing a fluoroacyl fluoride according to claim 3, wherein: the chloride ion content in the catalyst is less than 5 ppm.
5. A method of producing a fluoroacyl fluoride according to any one of claims 2 to 4, wherein: the carrier is ZSM-5 type molecular sieve.
6. The method of claim 5, wherein the fluorinated acyl fluoride comprises: the ZSM-5 type molecular sieve has a silica to alumina molar ratio of 15 to 20.
7. A method for producing a fluoroacyl fluoride according to any one of claims 1 to 4, wherein: the hydrogen fluoride is hydrogen fluoride gas, the reaction temperature for synthesizing the fluoroacyl fluoride is 150-200 ℃, the pressure for synthesizing the fluoroacyl fluoride is-1 MPa-0.1 MPa, and no water exists in the reaction for synthesizing the fluoroacyl fluoride.
8. A catalyst, characterized by: has a structure shown in formula III:
Figure 547081DEST_PATH_IMAGE002
。
9. a method of preparing the catalyst of claim 8, comprising the steps of:
A. dissolving 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in pure water, adding chromium trichloride hexahydrate, reacting at 80-90 deg.C for 2-4H while stirring, cooling to below 25 deg.C, centrifuging to obtain wet product,
B. removing chloride ions from the wet product by water washing, water recrystallization or water pulping;
C. dissolving the product obtained in the step B in pure water, adding a carrier with the weight of 2.5-3.5 times that of the product to soak the product at the temperature of 25-100 ℃, stirring the product into paste, extracting the paste by using acetonitrile, methanol, ethanol, isopropanol or n-butanol, and drying the paste to prepare powdery solid;
D. granulating the powdery solid into a ball shape with the ball diameter of 5-6 mm;
E. activating the spherical solid for 3-8H at the temperature of 105-150 ℃ to obtain a finished product of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst.
10. The method for preparing a catalyst according to claim 9, characterized in that: the using amount of the pure water in the step A is 6-8 times of the weight of the 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid; b, recrystallizing the wet product with purified water which is 1.5-2 times of the weight of the wet product to obtain crystals; the dipping temperature in the step C is 60-70 ℃, the dipping pressure is normal pressure, and the extraction solvent is methanol.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614129A (en) * 1943-08-10 1952-10-14 Purdue Research Foundation Perfluorination
US2712554A (en) * 1953-12-11 1955-07-05 William T Miller Oxidation of halogenated olefinic compounds
JP2002003410A (en) * 2000-06-27 2002-01-09 Fuji Photo Film Co Ltd Method for producing aromatic halogen compound
CN102471207A (en) * 2009-07-21 2012-05-23 罗地亚经营管理公司 Method for preparing a halogenocetyl fluoride and the derivatives thereof
CN104812700A (en) * 2013-11-28 2015-07-29 阿克马法国公司 Hydrochloric acid purification process
CN109071453A (en) * 2016-05-10 2018-12-21 索尔维公司 Composition comprising 3- (alkylhalide group or formoxyl) -1H- pyrazoles -4- formic acid or ester, manufacture and its purposes for being used to prepare formamide
CN111995516A (en) * 2020-09-03 2020-11-27 宿迁市科莱博生物化学有限公司 Synthesis method of difluoroacetyl fluoride

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614129A (en) * 1943-08-10 1952-10-14 Purdue Research Foundation Perfluorination
US2712554A (en) * 1953-12-11 1955-07-05 William T Miller Oxidation of halogenated olefinic compounds
JP2002003410A (en) * 2000-06-27 2002-01-09 Fuji Photo Film Co Ltd Method for producing aromatic halogen compound
CN102471207A (en) * 2009-07-21 2012-05-23 罗地亚经营管理公司 Method for preparing a halogenocetyl fluoride and the derivatives thereof
CN104812700A (en) * 2013-11-28 2015-07-29 阿克马法国公司 Hydrochloric acid purification process
CN109071453A (en) * 2016-05-10 2018-12-21 索尔维公司 Composition comprising 3- (alkylhalide group or formoxyl) -1H- pyrazoles -4- formic acid or ester, manufacture and its purposes for being used to prepare formamide
CN111995516A (en) * 2020-09-03 2020-11-27 宿迁市科莱博生物化学有限公司 Synthesis method of difluoroacetyl fluoride

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