CN114105766B - Preparation method of fluoro acyl fluoride - Google Patents

Preparation method of fluoro acyl fluoride Download PDF

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CN114105766B
CN114105766B CN202011582611.3A CN202011582611A CN114105766B CN 114105766 B CN114105766 B CN 114105766B CN 202011582611 A CN202011582611 A CN 202011582611A CN 114105766 B CN114105766 B CN 114105766B
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fluoride
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methylpyrazole
difluoromethyl
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CN114105766A (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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Kelaibo Jiangsu Technology Co ltd
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Abstract

The invention relates to a preparation method of fluoroacyl fluoride, which comprises the steps of reacting halogenated olefin shown in a formula I, oxygen and hydrogen fluoride under the action of a catalyst to generate the fluoroacyl fluoride shown in 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 sources, simple process, good catalytic activity, safe and reliable reaction and high automation degree, and is suitable for industrial production.

Description

Preparation method of fluoro acyl fluoride
Technical Field
The invention relates to a preparation method of fluoro acyl fluoride, and belongs to the technical field of fine chemical engineering.
Background
Acyl Halide (Acyl Halide) refers to the product of substituting hydroxyl in carboxylic acid with halogen, and is commonly known as Acyl chloride, acyl fluoride and Acyl bromide. Acyl halide does not exist in the nature and can only be prepared by chemical synthesis, and the acyl halide in the chemical field at present is mainly prepared by reacting carboxylic acid with an acylating agent, wherein the reaction equation is as follows:
。
in this reaction scheme: x may be F, cl, br, I or the like; r may be aliphatic hydrocarbon, aliphatic olefin, aromatic hydrocarbon, aromatic olefin, halogenated aliphatic hydrocarbon, halogenated aromatic hydrocarbon, etc.
Common acylating agents are phosphorus halides, sulfoxide halides, oxalyl halides, triphenylphosphine halides, and the like. The disadvantage of these acylating agents for the preparation of acid halides is remarkable: (1) The cost of carboxylic acid is high, such as the tonnage market price of difluoro acetic acid and 3-difluoro methyl-1-methyl pyrazole-4-carboxylic acid is higher than 20 ten thousand yuan; (2) The acylating agent has irritation, and the labor protection requirement of a contact person is high; (3) The preparation process of acyl halide is accompanied by a large amount of waste gas, and the environmental protection and control difficulty is high; (4) The requirement on the corrosion resistance of the production device is high, and the investment of the production device is large.
Since the 90 s of the last century, there have been reports of the preparation of acid halides by oxidation of halogenated olefins with oxygen in the presence of a catalyst, of which the following are typical:
(1) EP623578 reports that trichloroethylene can be oxidized to dichloroacetyl chloride in the presence of the amine catalyst tetramethylpiperidine, which has the obvious disadvantage of the formation of the by-product halogenated propylene oxide and of low atomic utilization.
(2) Chinese patent documents CN1131140 and CN101445445 both report that trichloroethylene reacts with oxygen under the environmental conditions of 0.1 MPa-0.8 MPa and 40-180 ℃ in the presence of catalyst azodiisobutyl ester and initiator triethylamine to obtain dichloroacetyl chloride, the yield is 20-85%, and the reaction stability and the yield of the method are poor.
(3) German patent document DE19620018 reports that trichloroethylene can be oxidized by oxygen to dichloroacetyl chloride at 50-200 ℃, the realization of which requires light with a wavelength of more than 280nm and high temperature and a chromium-based catalyst, although good yields, requires too high production equipment.
(4) In 2007, ou, hsin-Hung et al reported that trichloroethylene can be subjected to an illumination reaction under the catalytic action of platinum-doped carbon dioxide to form dichloroacetyl chloride and phosgene, and that phosgene is extremely toxic, and because of the extremely active chemical characteristics of phosgene, if phosgene cannot be thoroughly separated from dichloroacetyl chloride, the downstream product preparation is unfavorable, so that the industrial production of the technology of the patent is difficult.
(5) Chinese patent documents CN101195563 and CN107573242A report that trichloroethylene reacts with dry air at 100-110 ℃ under the catalysis of vanadium pentoxide or manganese dioxide, triphenylphosphine and ammonium chloride to obtain dichloroacetyl chloride with the purity of 99%. The catalyst prepared by the patent is complex, a catalyst recovery method is not clarified, and the disposal cost of the heavy metal dead catalyst is high.
(6) Chinese patent document CN102471207B discloses a process for preparing haloacetylfluorides and derivatives thereof. The haloacetyl halide is prepared by photooxidation of a halovinyl compound, and then the haloacetyl halide is reacted with hydrofluoric acid to obtain the haloacetyl fluoride. In the production process, the oxidation reaction and the fluorination reaction are carried out separately, the reactant hydrofluoric acid is liquid, and the separation step is complicated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of fluoroacyl fluoride, which has simple process and is simultaneously oxidized and fluorinated.
The invention provides a technical scheme for solving the technical problems, which is as follows: a preparation method of fluoroacyl fluoride comprises the steps of reacting halogenated olefin shown in a formula I, oxygen and hydrogen fluoride under the action of a catalyst to generate fluoroacyl fluoride shown in a formula II, wherein the reaction formula is as follows:
，
wherein X is 2 Is a hydrogen atom, a chlorine atom or a bromine atom, X 1 And X 3 Is a chlorine atom or a bromine atom, R 1 Is hydrogen atom, chlorine atom, bromine atom, C1-C8 alkyl with chlorine substituent or C1-C8 alkyl with bromine substituent;
when X is 2 X is a hydrogen atom 2 ' is a hydrogen atom; when X is 2 In the case of chlorine or bromine atoms, X 2 ' is a fluorine atom;
when R is 1 R is hydrogen atom 2 Is a hydrogen atom; when R is 1 R is C1-C8 alkyl 2 Is C1-C8 alkyl; when R is 1 When the compound is a chlorine atom or a bromine atom, R 2 Is a fluorine atom; when R is 1 R is C1-C8 alkyl having chlorine substituent or C1-C8 alkyl having bromine substituent 2 C1-C8 alkyl substituted by fluorine substituent for chlorine substituent or bromine substituent;
the catalyst is 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, the catalyst has a structure shown in a formula III,
。
the catalyst is a supported catalyst prepared by taking molecular sieve, silica gel or diatomite as a carrier and preparing the supported catalyst by dipping 3-difluoromethyl-1H-methylpyrazole-4-chromium formate aqueous solution.
The dipping method of the invention takes purified water as a solvent, and the dosage of the purified water is preferably just dissolved and clear 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, and is usually 6 times to 8 times of the weight of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate.
The supported catalyst is a product generated by reacting chromium trichloride hexahydrate and 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in water, the product is dissolved in water, a carrier is added, acetonitrile, methanol, ethanol, isopropanol or n-butanol is used for extraction, the powder solid is prepared by drying, then the solid is granulated into spheres with the sphere diameter of 5-6 mm, and the spheres are activated for 3-8H at the temperature of 105-150 ℃.
Before the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate is prepared into a supported catalyst, chloride ions need to be removed, the removal method is preferably water washing, water recrystallization, water pulping and other methods, and the content of the chloride ions in the catalyst is strictly controlled to be less than 5ppm.
The carrier can be any one of silica gel, ZSM type molecular sieve, Y type molecular sieve and diatomite. Preferably, the carrier is ZSM-5 molecular sieve, and can improve the mechanical strength of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, so that the performances of wear resistance, pressure resistance, impact resistance and the like of the carrier are obviously improved.
The 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 fluoro acyl fluoride is 150-200 ℃, the pressure for synthesizing the fluoro acyl fluoride is-1 MPa-0.1 MPa, and no moisture exists in the reaction for synthesizing the fluoro acyl fluoride.
The invention provides another technical scheme for solving the technical problems as follows: a catalyst having a structure according to formula iii:
。
the invention provides another technical scheme for solving the technical problems as follows: a method for 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 under 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 in the step B in pure water, adding a carrier 2.5-3.5 times of the weight of the product for soaking, stirring to form paste at the soaking temperature of 25-100 ℃, extracting with acetonitrile, methanol, ethanol, isopropanol or n-butanol, and drying to obtain powdery solid;
D. granulating the powdery solid to obtain a sphere with a sphere diameter of 5-6 mm;
E. and (3) activating the spherical solid for 3-8 hours 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 above step A is 6 to 8 times by weight of 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid. The step B is to recrystallize the wet product with purified water with the weight 1.5-2 times of that 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, has good catalytic activity, takes chlorinated olefin or brominated olefin as a raw material, and when double bonds are positioned at the tail end of a molecular structure and two substituted chlorine atoms or bromine atoms are arranged at the tail end, one substituted atom can be rearranged and migrate to adjacent carbon atoms during oxidation, so that the fluoro acyl fluoride can be prepared through one-step reaction, and the preparation method has the advantages of short process flow, high automation degree, continuity and sealing, wide raw material sources, safe and reliable reaction and suitability for large-scale industrial production at lower temperature and lower pressure.
(2) The preparation method of the fluoro acyl fluoride can use trichloroethylene as a raw material to prepare difluoro acetyl fluoride, and the prepared difluoro acetyl fluoride can be directly used as a raw material for synthesizing 3-difluoro methyl-1H-methylpyrazole-4-carboxylic acid even if hydrogen chloride, hydrogen fluoride and other gases are mixed, and 3-difluoro methyl-1H-methylpyrazole-4-carboxylic acid is a production raw material of a catalyst, so that the production cost can be effectively reduced by recycling.
(3) According to the preparation method of the fluoroacyl fluoride, 3-difluoromethyl-1H-methylpyrazole-4-chromium formate is used as a catalyst, and although the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate has obvious catalytic activity, the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate is difficult to prepare into a high-dispersion state, a proper carrier is required to be selected as a skeleton for depositing the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, and the carrier increases the active surface of the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate according to a proper pore structure, so that the consumption of the expensive 3-difluoromethyl-1H-methylpyrazole-4-chromium formate can be reduced, and the preparation cost of the catalyst is saved.
Drawings
FIG. 1 is a chromatogram of methyl difluoroacetate obtained by reacting the product of example 1, difluoroacetyl fluoride, with methanol.
FIG. 2 is a chromatogram of methyl nonafluorovalerate obtained by reacting the product of example 2, nonafluorovaleryl fluoride, with methanol.
FIG. 3 is a chromatogram of methyl trifluoroacetate obtained by reacting the product of example 3, trifluoroacetyl fluoride, with methanol.
FIG. 4 is a schematic diagram of a reaction apparatus for producing a fluorinated acyl fluoride in example 4.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing 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. Alkyl of C1-C8 refers to alkyl groups having 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 C1 to C8 alkyl group having a substituent 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 outsourcing reagents unless specified, and the concentration is chemically pure.
Example 1
The preparation method of the difluoroacetyl fluoride comprises the following specific steps:
firstly, heating heat conduction oil for a premixer to 110-115 ℃, heating the heat tracing of a reactor filled with a supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst to 180-190 ℃, and purging with nitrogen from a raw material feed inlet or a hydrogen fluoride feed inlet to ensure that no moisture exists in the whole reaction device.
Then starting the pre-mixer to stir, starting to introduce hydrogen fluoride gas (flow rate: 5m, 5 m/h) into the pre-mixer, and after hydrogen fluoride escapes from the product outlet at the top of the reactor, simultaneously introducing trichloroethylene and dry oxygen into the pre-mixer (flow rate: 1.5 m/h, oxygen flow rate: 1.8 m/h), and reacting at 180-190 ℃ under the back pressure of 0.1MPa of the reactor to stably obtain mixed gas of difluoroacetyl fluoride, hydrogen chloride and hydrogen fluoride. The reaction formula is as follows:
。
the preparation method of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst in the implementation comprises the following steps:
purified water (5000.00 kg,277.78 kmol) and 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid (600.00 kg,3.41 kmol) are sequentially added into a 10000L glass lining reaction kettle, the temperature is raised to 80 ℃ to 90 ℃, at this time, the feed liquid is white suspension, a small amount of 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid is still undissolved, centrifugal separation is carried out while the hot, a filter cake is recycled and reused, the filtrate is pumped into another 10000L glass lining reaction kettle, chromium trichloride hexahydrate (880.00 kg,3.30 kmol) is added at the temperature of not lower than 80 ℃, the temperature is reduced to 60 ℃ after continuing stirring for 2 hours, then reduced pressure (-0.095 MPa) is started to concentrate to 1/3 of the original volume, the temperature is reduced to 25 ℃ for centrifugal separation, the filter cake is catalyst 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid chromium, the yellow green granular crystal (the weight of 821.92 kg) is obtained, and the filtrate can be recycled.
The obtained wet product is recrystallized 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, and the recrystallization mother liquor can be recycled to the catalyst preparation process and cannot be used in the recrystallization process (the chlorine ions are unqualified).
Dissolving the obtained recrystallized product in 3000L glass lining reactor with 6 times of purified water at 60-70 ℃, adding 3 times of ZSM-5 molecular sieve, stirring to form paste, transferring to industrial Soxhlet extractor by using a dispersion pump, and extracting with a proper amount of methanol.
After extraction, transferring the material to a spray dryer by using a dispersing pump, and drying at the normal pressure at the temperature of 105 ℃ to obtain 1792.55g of light green powdery solid dry product which is powdery supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst.
The obtained powdery solid is granulated under certain conditions to prepare the spherical supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst with the spherical diameter of 5 mm-6 mm.
The obtained spherical supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst is activated for 5 hours at 115-125 ℃, and the supported catalyst with fluorination and oxidation catalytic activities is obtained after natural cooling.
。
Since the detection of the difluoroacetyl fluoride is difficult, the difluoroacetyl fluoride prepared by the preparation method of the embodiment reacts with a proper amount of methanol to obtain methyl difluoroacetate, and the purity of the methyl difluoroacetate is 99.48% as determined by gas chromatography, and the chromatogram of the methyl difluoroacetate is shown in figure 1. The chromatographic analysis results of methyl difluoroacetate are shown in Table 1.
TABLE 1 chromatographic analysis results Table
When the difluoroacetyl fluoride purity decreases, the catalyst is replaced by taking into account stopping the reaction.
Example 2
The preparation method of the nonafluorovaleryl fluoride comprises the following specific steps:
firstly, heating the heat conduction oil for the premixer to 160-165 ℃, heating the heat tracing of the reactor filled with the supported complex catalyst to 170-175 ℃, and purging the reactor from a raw material feed inlet or a hydrogen fluoride feed inlet by nitrogen to ensure that no moisture exists in the whole reaction device.
Then starting the pre-mixer to stir, starting to introduce hydrogen fluoride gas (flow: 5 m/h) into the pre-mixer, after hydrogen fluoride escapes from the product outlet at the top of the reactor, simultaneously introducing 1,2,3, 4, 5-dechloropent-1-ene and dry oxygen into the pre-mixer (flow: 1.3 m/h, oxygen flow: 1.8 m/h), and reacting at 170-175 ℃ with the back pressure of 0.2MPa of the reactor to obtain the mixed gas of nonafluorovaleryl fluoride, hydrogen chloride and hydrogen fluoride stably. The reaction formula is as follows:
。
since the detection of the nonafluorovaleryl fluoride is difficult, the nonafluorovaleryl fluoride prepared by the preparation method of the embodiment reacts with a proper amount of methanol to obtain methyl nonafluorovalerate, and the purity of the methyl nonafluorovalerate is 99.98 percent as determined by gas chromatography, and the chromatogram of the methyl nonafluorovalerate is shown in figure 2. The chromatographic analysis results of methyl nonafluorovalerate are shown in Table 2.
TABLE 2 chromatographic analysis results Table
When the purity of the nonafluoropentanoyl fluoride decreases, the catalyst is replaced considering stopping the reaction.
Example 3
The preparation method of the trifluoroacetyl fluoride comprises the following specific steps:
firstly, heating the heat conduction oil for the premixer to 120-125 ℃, heating the heat tracing of the reactor filled with the supported complex catalyst to 150-155 ℃, and purging the reactor from a raw material feed inlet or a hydrogen fluoride feed inlet by nitrogen to ensure that no moisture exists in the whole reaction device.
Then starting the pre-mixer to stir, starting to introduce hydrogen fluoride gas (flow: 5m, 5 m/h) into the pre-mixer, allowing the tetrachloroethylene and dry oxygen to simultaneously flow into the pre-mixer (tetrachloroethylene: 1.7 m/h, oxygen flow: 1.7 m/h) after hydrogen fluoride escapes from the product outlet at the top of the reactor, and reacting at 150-155 ℃ under the back pressure of 0.1MPa of the reactor to stably obtain mixed gas of trifluoroacetyl fluoride, hydrogen chloride and hydrogen fluoride. The reaction formula is as follows:
。
since the detection of trifluoroacetyl fluoride is difficult, the trifluoroacetyl fluoride prepared by the preparation method of the embodiment reacts with a proper amount of methanol to obtain methyl trifluoroacetate, the purity of which is 99.89% as determined by gas chromatography, and the chromatogram of the methyl trifluoroacetate is shown in figure 3. The chromatographic analysis results of methyl nonafluorovalerate are shown in Table 3.
TABLE 3 chromatographic analysis results Table
When the trifluoroacetyl fluoride purity decreases, it is considered to stop the reaction and replace the catalyst.
Example 4
Referring to fig. 4, the reaction apparatus for fluoroacyl fluoride of the present embodiment is a special apparatus suitable for the preparation method of fluoroacyl fluoride of the present invention, and comprises a premixer 1 and a packed tower 2. Install rabbling mechanism 3 and heating element on the blender 1, the bottom of blender 1 is linked together with the bottom of packing tower 2 through conveying pipeline 11, the top of packing tower 2 is equipped with discharging pipe 21, the middle section of packing tower 2 is equipped with catalyst dress packing layer 24, rabbling mechanism 3 is including stretching to the (mixing) shaft 31 of blender 1 bottom and fixed connection stirring vane 32 in (mixing) shaft 31 bottom, stirring vane 32 is located the bottom in the blender 1, be equipped with intake pipe 12 and inlet pipe 13 that the bottom extends to the blender 1 bottom on the blender 1, the bottom of intake pipe 12 is close to the outer fringe 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 air inlet pipe 12 and the feeding pipe 13 extend into the premixer 1 from the feeding hole 17 and are fixed at the feeding hole 17 in a sealing way. The stirring vane 32 comprises a base 321 extending outwards from the stirring shaft 31 horizontally, a plurality of vertical rods 322 extending upwards from the base 321 vertically and inclined struts 323 connecting the adjacent vertical rods 322 and the stirring shaft 31, wherein the vertical rods 322 are uniformly distributed and the vertical rods 322 positioned at the outer edge of the base 321 are arranged close 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 pre-mixer 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. The joint of the material conveying pipe 11 and the bottom of the premixer 1 is provided with a kettle bottom valve 15, and the kettle bottom valve 15 is a lower-expansion type kettle bottom valve. The catalyst filling layer 24 has at least two layers, each layer of catalyst filling layer 24 is arranged at intervals along the up-down direction of the packed tower 2, the upper part of each layer of catalyst filling layer 24 is provided with a cavity 241, and the outer wall of the packed tower 2 is provided with a manhole 242 corresponding to the position of each cavity 241. The top of the packed tower 2 is provided with a filter layer 27 which is horizontally arranged, the packed tower 2 is provided with a first gas sampling pipe 23 which extends into the space between the filter layer 27 and the uppermost catalyst filling layer 24, the packed tower 2 is also provided with a second gas sampling pipe 25 which extends into the bottom of the packed tower 2, the tail end of the first gas sampling pipe 23 which extends into the packed tower 2 is downwards bent and extends to be close to the corresponding catalyst filling layer 24, and the tail end of the second gas sampling pipe 25 which extends into the packed tower 2 is provided with an opening which is downwards inclined.
The fluoro acyl fluoride reaction device further comprises a condenser 22, wherein the condenser 22 is vertically arranged and 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 between the filter layer 27 and the uppermost catalyst filling layer 24, and a top air outlet of the condenser 22 is connected with the discharging pipe 21 through an air outlet pipe 211. The bottom of the packed tower 2 is provided with an arc-shaped bottom plate 28, a gas blowing pipe 26 extending out of the packed tower 2 is arranged at the central position of the arc-shaped bottom plate 28, the material conveying pipe 11 extends into the bottom of the packed tower 2, and the tail end extending into the packed tower 2 is arranged in a downward inclined manner 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 pre-mixer 1, and a power output shaft of the variable frequency speed regulating motor 33 is vertically downwards arranged and 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 belt.
It is apparent that the above examples are merely illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While remaining within the scope of the invention, obvious variations or modifications are incorporated by reference herein.

Claims (6)

1. A preparation method of fluoroacyl fluoride is characterized in that: the halogenated olefin shown in the formula I, oxygen and hydrogen fluoride react under the action of a catalyst to generate the fluorinated acyl fluoride shown in the formula II, wherein the reaction formula is as follows:
，
wherein X is 2 Is a hydrogen atom, a chlorine atom or a bromine atom, X 1 And X 3 Is a chlorine atom or a bromine atom, R 1 Is hydrogen atom, chlorine atom, bromine atom, C1-C8 alkyl with chlorine substituent or C1-C8 alkyl with bromine substituent;
when X is 2 X is a hydrogen atom 2 ' is a hydrogen atom; when X is 2 In the case of chlorine or bromine atoms, X 2 ' is a fluorine atom;
when R is 1 R is hydrogen atom 2 Is a hydrogen atom; when R is 1 R is C1-C8 alkyl 2 Is C1-C8 alkyl; when R is 1 When the compound is a chlorine atom or a bromine atom, R 2 Is a fluorine atom; when R is 1 R is C1-C8 alkyl having chlorine substituent or C1-C8 alkyl having bromine substituent 2 C1-C8 alkyl substituted by fluorine substituent for chlorine substituent or bromine substituent;
the catalyst is supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate, the 3-difluoromethyl-1H-methylpyrazole-4-chromium formate has a structure shown in a formula III,
；
the preparation method of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate comprises the following steps:
A. dissolving 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid in pure water, adding chromium trichloride hexahydrate, reacting at 80-90 ℃ for 2-4H under stirring, cooling to below 25 ℃, and centrifuging to obtain a wet product;
B. removing chloride ions from the wet product by water washing, water recrystallization or water pulping;
C. dissolving the product in the step B in pure water, adding a carrier 2.5-3.5 times of the weight of the product for soaking, stirring to form paste at the soaking temperature of 25-100 ℃, extracting with acetonitrile, methanol, ethanol, isopropanol or n-butanol, and drying to obtain powdery solid;
D. granulating the powdery solid to obtain a sphere with a sphere diameter of 5-6 mm;
E. and (3) activating the spherical solid for 3-8 hours at the temperature of 105-150 ℃ to obtain a finished product of the supported 3-difluoromethyl-1H-methylpyrazole-4-chromium formate catalyst.
2. The method for preparing the fluoro acyl fluoride according to claim 1, which is characterized in that: the chloride ion content in the catalyst is less than 5ppm.
3. The method for preparing the fluoro acyl fluoride according to claim 1, which is characterized in that: the carrier is ZSM-5 type molecular sieve.
4. A process for preparing a fluoroacyl fluoride according to claim 3, characterized in that: the ZSM-5 type molecular sieve has a silicon to aluminum molar ratio of 15 to 20.
5. The method for preparing the fluoro acyl fluoride according to claim 1, which is characterized in that: the hydrogen fluoride is hydrogen fluoride gas, the reaction temperature for synthesizing the fluoro acyl fluoride is 150-200 ℃, the pressure for synthesizing the fluoro acyl fluoride is-1 MPa-0.1 MPa, and no moisture exists in the reaction for synthesizing the fluoro acyl fluoride.
6. The method for preparing the fluoro acyl fluoride according to claim 1, which is characterized in that: the consumption of the pure water in the step A is 6-8 times of the weight of the 3-difluoromethyl-1H-methylpyrazole-4-carboxylic acid; the step B is to recrystallize the wet product with purified water with the weight 1.5-2 times of that 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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