CN114591158B - Method and device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene - Google Patents

Method and device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene Download PDF

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CN114591158B
CN114591158B CN202011408028.0A CN202011408028A CN114591158B CN 114591158 B CN114591158 B CN 114591158B CN 202011408028 A CN202011408028 A CN 202011408028A CN 114591158 B CN114591158 B CN 114591158B
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hexafluoroacetone
condenser
storage tank
methyl
perfluoro
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CN114591158A (en
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周济苍
喻强
廖敏
周遇吉
喻鼎辉
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Jiuding Fluorin Chemicals Co ltd Zhangping Fujian
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Jiuding Fluorin Chemicals Co ltd Zhangping Fujian
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/783—Separation; Purification; Stabilisation; Use of additives by gas-liquid treatment, e.g. by gas-liquid absorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/64—Separation; Purification; Stabilisation; Use of additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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Abstract

The invention discloses a method and a device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene, wherein the method comprises the following steps: (1) Adding perfluoro-2-methyl-2-pentene into a dry reaction kettle, then introducing oxygen and ozone mixed gas, and performing ozone cracking to obtain coarse products of pentafluoropropionyl fluoride and hexafluoroacetone; (2) And discharging the crude products of the pentafluoropropionyl fluoride and the hexafluoroacetone from the reaction kettle, and separating and collecting the crude products by utilizing a selective absorbent to obtain the pentafluoropropionyl fluoride and the hexafluoroacetone respectively. The method has the advantages of easy acquisition and low price of raw material perfluoro-2-methyl-2-pentene, mild reaction conditions, low equipment requirements, simple process operation, good reaction selectivity, almost no byproducts and low production cost; the hexafluoroacetone in the product is absorbed by adding the selective absorbent, so that the separation and collection of the two products are realized, and the post-treatment operation is simple.

Description

Method and device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method and a device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene.
Background
Fluorine-containing intermediates such as pentafluoropropionyl fluoride and hexafluoroacetone have important applications in a variety of fields. For example, the pentafluoropropionyl fluoride is an important intermediate for preparing the perfluoro-hexanone, and the perfluoro-hexanone replaces halons and has the advantages of good environmental protection performance, low fire extinguishing concentration, high efficiency, good safety and the like; pentafluoropropionyl fluoride is also an important raw material for the synthesis of perfluoropropyl vinyl ether (PPVE) and perfluoropropionyl peroxide. Hexafluoroacetone has important application in the fields of medicines, pesticides, synthetic materials and the like, and is an important raw material for synthesizing hexafluoroisopropanol, and the hexafluoroacetone is a raw material for synthesizing an anesthetic sevoflurane; meanwhile, hexafluoroacetone is also an important raw material for synthesizing the fluororubber vulcanizing agent bisphenol AF.
However, the above-mentioned fluorine-containing intermediates, particularly hexafluoroacetone, are not readily available. The existing hexafluoroacetone production process adopts hexafluoropropylene oxide (HFPO) isomerization process under the action of Lewis acid; or a fluorination process of hexachloroacetone with anhydrous Hydrogen Fluoride (HF). The technical route or the technical process is complex, the raw materials are high in price and not easy to obtain, and the production cost is high; or more byproducts are produced in the production process, the emission is serious, and potential safety hazards exist in the production process. Thus, research and development of new production technologies for these intermediates remains of practical interest.
Disclosure of Invention
The invention mainly aims to provide a method and a device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene, wherein the method has the advantages of simple process, few byproducts, easy separation of products, high yield and low production cost.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene, comprising the steps of:
(1) Adding perfluoro-2-methyl-2-pentene into a dry reaction kettle, then introducing oxygen and ozone mixed gas, and performing ozone cracking to obtain coarse products of pentafluoropropionyl fluoride and hexafluoroacetone;
(2) And discharging the crude products of the pentafluoropropionyl fluoride and the hexafluoroacetone from the reaction kettle, and separating and collecting the crude products by utilizing a selective absorbent to obtain the pentafluoropropionyl fluoride and the hexafluoroacetone respectively.
The invention prepares the pentafluoropropionyl fluoride and hexafluoroacetone by the perfluoro-2-methyl-2-pentene through the ozone cracking reaction, and the raw material perfluoro-2-methyl-2-pentene is easy to obtain and has low price. Meanwhile, the reaction condition is mild, the requirement on equipment is low, the process operation is simple, the selectivity of the reaction is good, few byproducts are produced, the production cost is low, and the continuous cracking process can be adopted, so that the production efficiency is improved, and the product quality is stable. According to the invention, hexafluoroacetone in the product is selectively absorbed by a method of adding the selective absorbent, so that separation and collection of the pentafluoropropionyl fluoride and hexafluoroacetone with close boiling points are realized, and the post-treatment operation is simple.
Further, in step (2), the separation and collection of the crude product by means of a selective absorbent means specifically: the mixture of the pentafluoropropionyl fluoride and the hexafluoroacetone is introduced into a storage tank containing a selective absorbent to absorb the hexafluoroacetone in the mixture, and then the pentafluoropropionyl fluoride is separated and collected. Since the boiling points of the pentafluoropropionyl fluoride and the hexafluoroacetone are very close (at-26.5 ℃ and-28 ℃ respectively) and are difficult to separate by a rectification method, the mixture of the pentafluoropropionyl fluoride and the hexafluoroacetone obtained by the reaction is introduced into a storage tank with a selective absorbent, and the hexafluoroacetone in the mixture is absorbed by the selective absorbent, so that the pentafluoropropionyl fluoride and the hexafluoroacetone can be conveniently separated.
Further, in the step (2), the selective absorber is hydrogen fluoride, alcohol or water. The hexafluoroacetone and the anhydrous hydrogen fluoride can form a compound, after the hydrogen fluoride is added to selectively absorb the hexafluoroacetone, the pentafluoropropionyl fluoride can be distilled out, so that the separation of the pentafluoropropionyl fluoride and the hexafluoroacetone is realized, and the hexafluoroacetone can be obtained by further separation of the compound of the hydrogen fluoride and the hexafluoroacetone. Hexafluoroacetone forms unstable ketals and/or hemiketals with alcohols, while pentafluoropropionyl fluoride reacts with alcohols to form esters, which can then be separated by distillation. The alcohol may be anhydrous methanol, anhydrous ethanol, anhydrous isopropanol, and the like, with methanol being preferred. Hexafluoroacetone can also form a water complex with water, while pentafluoropropionyl fluoride forms pentafluoropropionic acid with water, which can then be separated by distillation. The present invention preferably employs anhydrous hydrogen fluoride as a selective absorber to separate pentafluoropropionyl fluoride from hexafluoroacetone.
Further, in the step (1), the molar ratio of perfluoro-2-methyl-2-pentene to ozone is 1: (2-8); preferably, the molar ratio of perfluoro-2-methyl-2-pentene to ozone is 1: (3-5).
Further, in the step (1), the temperature of the ozone cracking reaction is-100 ℃; preferably, the temperature of the ozone cracking reaction is-60 ℃; more preferably, the temperature of the ozone cracking reaction is from-40℃to 40 ℃.
Further, in the step (1), the pressure in the reaction kettle is 1-10 kg; preferably, the pressure in the reaction kettle is 1-8 kg; more preferably, the pressure in the reaction vessel is 1 to 6 kg.
Further, in the step (1), the concentration of ozone in the oxygen-ozone mixed gas is 1% -50%. The concentration of ozone in the ozone mixed gas produced by the commercial ozone generator is generally not more than 20%, and the concentration of ozone in the mixed gas can be improved by a simple concentration method so as to improve the ozone cracking reaction speed.
Further, in the ozone cracking reaction, the raw material perfluoro-2-methyl-2-pentene may be diluted by adding a solvent or other components as needed, or perfluoro-2-methyl-2-pentene may be directly cracked. The solvent used is preferably a fluorocarbon solvent such as CFC-113, hydrofluoroether, perfluoropolyether, etc.; preferably, the ozone cleavage reaction is preferably carried out in a perfluoropolyether. The mass ratio of the fluorocarbon solvent to the perfluoro-2-methyl-2-pentene is (0:100) - (80:20).
According to another aspect of the present invention, there is provided an apparatus for use in the above-described process for producing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene, the apparatus comprising a reaction vessel R-101, an ozone generator G-101, a rectification column T-101, a first condenser E-101, a recovery raw material tank V-101, a first product tank V-102, a second condenser E-102, a second product tank V-103, a third condenser E-103 and a tail gas treatment vessel R-102; the ozone generator G-101 is communicated with an ozone adding port of the reaction kettle R-101, the rectification column T-101 is communicated with a product outlet of the reaction kettle R-101, the first condenser E-101 is communicated with the rectification column T-101, the other end of the first condenser E-101 is communicated with the recovery raw material storage tank V-101, a bottom outlet of the recovery raw material storage tank V-101 is communicated with a raw material recovery port of the reaction kettle R-101, a top outlet of the recovery raw material storage tank V-101 is communicated with an inlet of the first product storage tank V-102, a top outlet of the first product storage tank V-102 is communicated with the second condenser E-102, the other end of the second condenser E-102 is communicated with an inlet of the second product storage tank V-103, a top outlet of the second product storage tank V-103 is communicated with the third condenser E-103, and the third condenser E-103 is communicated with the tail gas treatment kettle R-102.
During production, heating a reaction system, vacuumizing to remove water, then filling nitrogen (inert gas), maintaining pressure and cooling to room temperature, starting a refrigerator, adjusting cooling process parameters of a rectifying column T-101, a first condenser E-101, a second condenser E-102, a third condenser E-103, a recovery raw material storage tank V-101, a first product storage tank V-102, a second product storage tank V-103 and a tail gas treatment kettle R-102 according to process requirements, quickly adding perfluoro-2-methyl-2-pentene into the reaction kettle R-101 under the protection of nitrogen after reaching target values, adding a selective absorbent into the first product storage tank V-102, and closing nitrogen; introducing oxygen and ozone mixed gas to perform ozone cracking reaction to obtain pentafluoropropionyl fluoride and hexafluoroacetone; the reaction products of pentafluoropropionyl fluoride, hexafluoroacetone, oxygen and a small amount of unreacted ozone enter a rectifying column T-101 together, and a small amount of raw material perfluoro-2-methyl-2-pentene carried in the air flow is cooled down to flow back to a reaction kettle R-101; the residual perfluoro-2-methyl-2-pentene is further cooled in a first condenser E-101 and collected in a reclaimed raw material storage tank V-101, and can be reentered into a reaction kettle R-101 for cracking reaction; the gas product enters a subsequent separation and storage system along with the oxygen and ozone mixed gas for separation and storage.
Further, the selective absorber is added to the first product tank V-102 before the ozone cracking reaction proceeds. The gas product enters a first product storage tank V-102 after passing through a recovery raw material storage tank V-101, hexafluoroacetone in the gas product is absorbed by a selective absorbent which is added in advance in the first product storage tank V-102 and then remains in the first product storage tank V-102, and pentafluoropropionyl fluoride enters a second product storage tank V-103; the complex formed by hexafluoroacetone and the absorbent carried in the gas stream as it passes through the second condenser E-102 is condensed back into the first product tank V-102; condensing the pentafluoropropionyl fluoride through a third condenser E-103 to store the pentafluoropropionyl fluoride in a second product tank V-103; the rest tail gas enters a tail gas treatment kettle R-102.
Further, the temperature of the rectifying column T-101 is-50-0 ℃; preferably, the temperature of the rectification column T-101 is-30 to 0 ℃.
Further, the temperature of the first condenser E-101 is-50-0 ℃; preferably, the temperature of the first condenser E-101 is-30℃to 0 ℃.
Further, the temperature of the recycled raw material storage tank V-101 is-50 ℃; preferably, the temperature of the recycled raw material storage tank V-101 is-20 ℃; more preferably, the temperature of the recovered raw material tank V-101 is about-0deg.C.
Further, the temperature of the first product storage tank V-102 is-50 ℃ to 20 ℃; preferably, the temperature of the first product tank V-102 is-40 ℃ to 10 ℃; more preferably, the temperature of the first product tank V-102 is from-30℃to 0 ℃.
Further, the temperature of the second condenser E-102 is-50 ℃ to 20 ℃; preferably, the temperature of the second condenser E-102 is-40 ℃ to 10 ℃; more preferably, the temperature of the second condenser E-102 is-30℃to 0 ℃.
Further, the temperature of the second product storage tank V-103 is-100 ℃ to 0 ℃; preferably, the temperature of the first product storage tank V-102 is-80 ℃ to-20 ℃; more preferably, the temperature of the first product tank V-102 is from-60℃to-40 ℃.
Further, the temperature of the third condenser E-103 is minus 100 ℃ to minus 0 ℃; preferably, the temperature of the third condenser E-103 is-80 ℃ to-20 ℃; more preferably, the temperature of the third condenser E-103 is-60℃to-40 ℃.
Further, the temperature of the tail gas treatment kettle R-102 is-20 ℃ to 20 ℃; preferably, the temperature of the tail gas treatment kettle R-102 is-10 ℃; preferably, the temperature of the tail gas treatment kettle R-102 is about 0 ℃.
The hexafluoroacetone-absorbent complex and the crude pentafluoropropionyl fluoride obtained by the separation can be obtained by the above-described method. The latter can be separated and purified by techniques known to the skilled person to obtain a qualified product.
The reaction kettle R-101 is provided with the gas feed inlet, and the bottom of the gas feed inlet adopts a gas dispersion disc design, so that the gas and the liquid are fully mixed, and the utilization rate of ozone in the reaction process is improved; the bottom of the reaction kettle R-101 is provided with a discharge pipe, and the reaction kettle R-101 is provided with an inner cooling coil pipe, an outer cooling coil pipe and a temperature control system. The gas phase is moved inside the rectifying column T-101, and the gas phase is cooled by the cooling medium introduced into the outer jacket; the rectification column T-101 can be filled with filler according to the requirement; the temperature of the rectification column T-101 is controlled by a cooling medium. The first condenser E-101, the second condenser E-102 and the third condenser E-103 are designed to be internally provided with gas phase, the external jacket is strongly condensed, the heat exchange area of the condenser is large, the material residence time is long, the cooled components are completely liquefied, and the gas-liquid separation is realized. The recovery raw material storage tank V-101, the first product storage tank V-102 and the second product storage tank V-103 are respectively provided with a jacket, the temperature can be controlled, a cooling coil is arranged in the tank to strengthen the cooling effect, and a stirring device can be arranged to strengthen the heat transfer process; the tank top is provided with an air inlet pipe, and the bottom of the air inlet pipe adopts spiral air inlet to reduce the exhaust speed; the tank top is provided with an exhaust pipe which is directly connected with the condenser; the bottom of the tank is provided with a discharge valve.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the pentafluoropropionyl fluoride and hexafluoroacetone by the perfluoro-2-methyl-2-pentene through the ozone cracking reaction, and the raw material perfluoro-2-methyl-2-pentene is easy to obtain and has low price; meanwhile, the reaction condition is mild, the requirement on equipment is low, the process operation is simple, the selectivity of the reaction is good, few byproducts are generated, the reaction yield is high, the production cost is low, and the continuous cracking process can be adopted, so that the production efficiency is improved, and the product quality is stable. According to the invention, hexafluoroacetone in the product is selectively absorbed by a method of adding the selective absorbent, so that separation and collection of the pentafluoropropionyl fluoride and hexafluoroacetone with close boiling points are realized, and the post-treatment operation is simple.
Drawings
Fig. 1 is a schematic view of the structure of the device of the present invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the specific embodiments described below.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
referring to FIG. 1, an apparatus for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to an embodiment of the present invention includes a reaction vessel R-101, an ozone generator G-101, a rectification column T-101, a first condenser E-101, a recovery raw material storage tank V-101, a first product storage tank V-102, a second condenser E-102, a second product storage tank V-103, a third condenser E-103, and a tail gas treatment vessel R-102. Wherein, ozone generator G-101 communicates with the ozone inlet of reaction kettle R-101, rectifying column T-101 communicates with the product outlet of reaction kettle R-101, first condenser E-101 communicates with rectifying column T-101, the other end of first condenser E-101 communicates with recovery raw materials storage tank V-101, the bottom outlet of recovery raw materials storage tank V-101 communicates with the raw materials recovery inlet of reaction kettle R-101, the top outlet of recovery raw materials storage tank V-101 communicates with the inlet of first product storage tank V-102, the top outlet of first product storage tank V-102 communicates with second condenser E-102, the other end of second condenser E-102 communicates with the inlet of second product storage tank V-103, the top outlet of second product storage tank V-103 communicates with third condenser E-103, third condenser E-103 communicates with tail gas treatment kettle R-102. Wherein, the reaction kettle R-101 is a 316L stainless steel reaction kettle with the volume of 1000 ml.
The device is adopted to prepare the pentafluoropropionyl fluoride and the hexafluoroacetone by taking perfluoro-2-methyl-2-pentene as raw materials, and the preparation method specifically comprises the following steps:
heating, vacuumizing and dewatering a reaction system, then filling nitrogen (inert gas), maintaining pressure and cooling to room temperature, starting a refrigerator, adjusting cooling process parameters of a rectifying column T-101, a first condenser E-101, a second condenser E-102, a third condenser E-103, a recovered raw material storage tank V-101, a first product storage tank V-102, a second product storage tank V-103 and a tail gas treatment kettle R-102 according to process requirements, quickly adding 300g of perfluoro-2-methyl-2-pentene into the reaction kettle R-101 under the protection of nitrogen after reaching target values, adding 100g of anhydrous hydrogen fluoride into the first product storage tank V-102, and closing nitrogen.
Introducing oxygen (flow rate is 100 sccm) into the reaction kettle R-101, starting an ozone generator G-101, introducing ozone mixed gas into the reaction kettle R-101, enabling the concentration of ozone in the oxygen ozone mixed gas to be 9%, performing ozone cracking reaction, controlling the pressure in the reaction kettle R-101 to be below 2 kg, and continuously performing ozone cracking for 96 hours at 30 ℃ to prepare the pentafluoropropionyl fluoride and hexafluoroacetone.
The reaction products of pentafluoropropionyl fluoride, hexafluoroacetone, oxygen and a small amount of unreacted ozone enter a rectifying column T-101 (the temperature of the rectifying column T-101 is controlled at minus 20 ℃), and a small amount of raw material perfluoro-2-methyl-2-pentene carried in the air flow is mostly cooled down to flow back to a reaction kettle R-101; the residual perfluoro-2-methyl-2-pentene is further cooled in a first condenser E-101 (the temperature of the first condenser E-101 is controlled at-20 ℃) and is collected in a recovery raw material storage tank V-101 (the temperature of the recovery raw material storage tank V-101 is controlled at 0 ℃), and then the recovery raw material storage tank V-101 is re-introduced into a reaction kettle R-101 for carrying out the cracking reaction.
The gas product enters a first product storage tank V-102 after passing through a reclaimed raw material storage tank V-101 (the temperature of the first product storage tank V-102 is minus 25 ℃), hexafluoroacetone in the product is compounded with anhydrous hydrogen fluoride (selective absorbent) which is added in advance in the first product storage tank V-102 to form a compound, the compound is reserved in the first product storage tank V-102, and pentafluoropropionyl fluoride enters a second product storage tank V-103 after passing through a second condenser E-102 (the temperature of the second condenser E-102 is minus 25 ℃) (the temperature of the second product storage tank V-103 is minus 50 ℃); the compound carried in the air flow is condensed and then flows back to the first product storage tank V-102 when the air flow passes through the second condenser E-102, and hexafluoroacetone-anhydrous hydrogen fluoride compound in the first product storage tank V-102 is further treated to obtain hexafluoroacetone; condensing the pentafluoropropionyl fluoride through the second product tank V-103 and a third condenser E-103 (the temperature of the third condenser E-103 is controlled to-50 ℃), so that the pentafluoropropionyl fluoride is stored in the second product tank V-103; the remaining tail gas was fed into a tail gas treatment vessel R-102 (the temperature of the tail gas treatment vessel R-102 was controlled at (0 ℃ C.) and finally, about 157.7g of pentafluoropropionyl fluoride was collected, the yield was about 95%, the hexafluoroacetone-anhydrous hydrogen fluoride complex was about 242.8g, and the yield was about 86% as calculated from hexafluoroacetone.
The hexafluoroacetone-anhydrous hydrogen fluoride complex can be easily separated from the anhydrous hydrogen fluoride by a rectification method (boiling point of hexafluoroacetone-28 ℃, boiling point of anhydrous hydrogen fluoride 19 ℃ C.) as needed. The crude pentafluoropropionyl fluoride may be purified by a low temperature rectification method (boiling point of pentafluoropropionyl fluoride-26.5 ℃).
Example 2:
the reaction apparatus was identical to example 1, but the specific equipment was used and the process parameters were slightly different. The device is adopted to prepare the pentafluoropropionyl fluoride and hexafluoroacetone by taking perfluoro-2-methyl-2-pentene as raw materials, and the preparation method specifically comprises the following steps:
heating, vacuumizing and dewatering a reaction system, then filling nitrogen (inert gas), maintaining pressure and cooling to room temperature, starting a refrigerator, adjusting cooling process parameters of a rectifying column T-101, a first condenser E-101, a second condenser E-102, a third condenser E-103, a recovered raw material storage tank V-101, a product storage tank 102, a product storage tank 103 and a tail gas treatment kettle R-102 according to process requirements, quickly adding 300g of perfluoro-2-methyl-2-pentene into the reaction kettle R-101 under the protection of nitrogen after reaching target values, adding 100g of anhydrous hydrogen fluoride into the first product storage tank V-102, and closing the nitrogen.
Introducing oxygen (flow rate is 100 sccm) into the reaction kettle R-101, starting an ozone generator G-101, introducing ozone gas into the reaction kettle R-101, enabling the concentration of ozone in the oxygen-ozone mixed gas to be 15%, performing ozone cracking reaction, controlling the pressure in the reaction kettle R-101 to be 1 kg, and continuously performing ozone cracking for 96 hours at 30 ℃ to prepare the pentafluoropropionyl fluoride and hexafluoroacetone.
The reaction products of pentafluoropropionyl fluoride, hexafluoroacetone, oxygen and a small amount of unreacted ozone enter a rectifying column T-101 (the temperature of the rectifying column T-101 is controlled at minus 25 ℃), and a small amount of raw material perfluoro-2-methyl-2-pentene carried in the air flow is mostly cooled down to flow back to a reaction kettle R-101; the residual perfluoro-2-methyl-2-pentene is further cooled in a first condenser E-101 (the temperature of the first condenser E-101 is controlled at-25 ℃) and is collected in a recovery raw material storage tank V-101 (the temperature of the recovery raw material storage tank V-101 is controlled at 0 ℃), and then the recovery raw material storage tank V-101 is re-introduced into a reaction kettle R-101 for carrying out the cracking reaction.
After passing through the recovery raw material storage tank V-101, the gas product enters the first product storage tank V-102 (the temperature of the first product storage tank V-102 is minus 25 ℃), hexafluoroacetone in the gas product is compounded with anhydrous hydrogen fluoride (selective absorbent) which is added in advance in the first product storage tank V-102 to form a compound, the compound is reserved in the first product storage tank V-102, and pentafluoropropionyl fluoride enters the second product storage tank V-103 through the second condenser E-102 (the temperature of the second condenser E-102 is minus 25 ℃) (the temperature of the second product storage tank V-103 is minus 50 ℃); when the air flow passes through the second condenser E-102, the compound carried in the air flow can be condensed and returned to the first product storage tank V-102, and then hexafluoroacetone compound in the first product storage tank V-102 is further processed to obtain hexafluoroacetone; condensing the pentafluoropropionyl fluoride through the second product tank V-103 and a third condenser E-103 (the temperature of the third condenser E-103 is controlled to-50 ℃), so that the pentafluoropropionyl fluoride is stored in the second product tank V-103; the rest tail gas enters a tail gas treatment kettle R-102 (the temperature of the tail gas treatment kettle R-102 is controlled at 0 ℃). Finally, about 162.7g of pentafluoropropionyl fluoride was collected in a yield of about 98%, and about 249.4g of a hexafluoroacetone-hydrogen fluoride mixture was obtained in a yield of about 90% as hexafluoroacetone.
The hexafluoroacetone-anhydrous hydrogen fluoride complex can be easily separated from the anhydrous hydrogen fluoride by a rectification method (boiling point of hexafluoroacetone-28 ℃, boiling point of anhydrous hydrogen fluoride 19 ℃ C.) as needed. The crude pentafluoropropionyl fluoride may be purified by a low temperature rectification method (boiling point of pentafluoropropionyl fluoride-26.5 ℃).
Example 3:
the reaction apparatus was identical to example 1, but the specific equipment was used and the process parameters were slightly different.
In the apparatus, perfluoro-2-methyl-2-pentene was used as a raw material to prepare pentafluoropropionyl fluoride and hexafluoroacetone, unlike example 2, methanol was used as an absorbent. The preparation method comprises the following steps:
heating the reaction system, vacuumizing to remove water, then filling nitrogen (inert gas), maintaining pressure and cooling to room temperature, starting a refrigerator, adjusting cooling process parameters of a rectifying column T-101, a first condenser E-101, a second condenser E-102, a third condenser E-103, a recovered raw material storage tank V-101, a first product storage tank V-102, a second product storage tank V-103 and a tail gas treatment kettle R-102 according to process requirements, quickly adding 300g of perfluoro-2-methyl-2-pentene into the reaction kettle R-101 under the protection of nitrogen after reaching target values, adding 100g of anhydrous methanol into the first product storage tank V-102, and closing the nitrogen.
Introducing oxygen (flow rate is 100 sccm) into the reaction kettle R-101, starting an ozone generator G-101, introducing ozone gas into the reaction kettle R-101, enabling the concentration of ozone in the oxygen-ozone mixed gas to be 15%, performing ozone cracking reaction, controlling the pressure in the reaction kettle R-101 to be 1 kg, and continuously performing ozone cracking for 96 hours at 30 ℃ to prepare the pentafluoropropionyl fluoride and hexafluoroacetone.
The reaction products of pentafluoropropionyl fluoride, hexafluoroacetone, oxygen and a small amount of unreacted ozone enter a rectifying column T-101 (the temperature of the rectifying column T-101 is controlled at minus 25 ℃), and a small amount of raw material perfluoro-2-methyl-2-pentene carried in the air flow is mostly cooled down to flow back to a reaction kettle R-101; the residual perfluoro-2-methyl-2-pentene is further cooled in a first condenser E-101 (the temperature of the first condenser E-101 is controlled at-25 ℃) and is collected in a recovery raw material storage tank V-101 (the temperature of the recovery raw material storage tank V-101 is controlled at 0 ℃), and then the recovery raw material storage tank V-101 is re-introduced into a reaction kettle R-101 for carrying out the cracking reaction.
The gas product passes through a recovered raw material storage tank V-101 and then enters a first product storage tank V-102 (the temperature of the first product storage tank V-102 is minus 25 ℃), hexafluoroacetone in the gas product reacts with methanol (a selective absorbent) which is added in advance in the first product storage tank V-102 to form ketal, meanwhile, partial pentafluoropropionyl fluoride reacts with the methanol to form methyl pentafluoropropionate, the two are reserved in the first product storage tank V-102, and a part of the pentafluoropropionyl fluoride enters a second product storage tank V-103 through a second condenser E-102 (the temperature of the second condenser E-102 is minus 25 ℃) (the temperature of the second product storage tank V-103 is minus 50 ℃); when the air flow passes through the second condenser E-102, hexafluoroacetone ketal and methyl pentafluoropropionate carried in the air flow can be condensed and then flow back to the first product storage tank V-102, and subsequently, the mixture of hexafluoroacetone ketal and methyl pentafluoropropionate in the first product storage tank V-102 is further processed to obtain hexafluoroacetone and methyl pentafluoropropionate; condensing the pentafluoropropionyl fluoride through the second product tank V-103 and a third condenser E-103 (the temperature of the third condenser E-103 is controlled to-50 ℃), so that the pentafluoropropionyl fluoride is stored in the second product tank V-103; the rest tail gas enters a tail gas treatment kettle R-102 (the temperature of the tail gas treatment kettle R-102 is controlled at 0 ℃). Finally, about 41.5g of pentafluoropropionyl fluoride is obtained, the yield is about 25%, and about 354.5g of a mixture of hexafluoroacetone ketal, methanol and methyl pentafluoropropionate is obtained. 120g of hexafluoroacetone is obtained after rectification and decomposition of the mixture of hexafluoroacetone ketal, methanol and methyl pentafluoropropionate, and the yield is about 72%; 115.7g of methyl pentafluoropropionate. The method has low yield of the pentafluoropropionyl fluoride and high difficulty in the post-treatment process of the hexafluoroacetone. In the operation process, methanol can be added into the reaction kettle R-101 for ozone cracking.
Example 4:
the reaction apparatus was identical to example 1, but the specific equipment was used and the process parameters were slightly different.
In the apparatus, perfluoro-2-methyl-2-pentene was used as a raw material to prepare pentafluoropropionyl fluoride and hexafluoroacetone, and water was used as an absorbent unlike example 2. The preparation method comprises the following steps:
heating the reaction system, vacuumizing to remove water, then filling nitrogen (inert gas), maintaining pressure and cooling to room temperature, starting a refrigerator, adjusting cooling process parameters of a rectifying column T-101, a first condenser E-101, a second condenser E-102, a third condenser E-103, a recovered raw material storage tank V-101, a first product storage tank V-102, a second product storage tank V-103 and a tail gas treatment kettle R-102 according to process requirements, quickly adding 300g of perfluoro-2-methyl-2-pentene into the reaction kettle R-101 under the protection of nitrogen after reaching target values, adding 100g of deionized water into the first product storage tank V-102, and closing the nitrogen.
Introducing oxygen (flow rate is 100 sccm) into the reaction kettle R-101, starting an ozone generator G-101, introducing ozone gas into the reaction kettle R-101, enabling the concentration of ozone in the oxygen-ozone mixed gas to be 15%, performing ozone cracking reaction, controlling the pressure in the reaction kettle R-101 to be 1 kg, and continuously performing ozone cracking for 96 hours at 30 ℃ to prepare the pentafluoropropionyl fluoride and hexafluoroacetone.
The reaction products of pentafluoropropionyl fluoride, hexafluoroacetone, oxygen and a small amount of unreacted ozone enter a rectifying column T-101 (the temperature of the rectifying column T-101 is controlled at minus 25 ℃), and a small amount of raw material perfluoro-2-methyl-2-pentene carried in the air flow is mostly cooled down to flow back to a reaction kettle R-101; the residual perfluoro-2-methyl-2-pentene is further cooled in a first condenser E-101 (the temperature of the first condenser E-101 is controlled at-25 ℃) and is collected in a recovery raw material storage tank V-101 (the temperature of the recovery raw material storage tank V-101 is controlled at 0 ℃), and then the recovery raw material storage tank V-101 is re-introduced into a reaction kettle R-101 for carrying out the cracking reaction.
After passing through the recovery raw material storage tank V-101, the gas product enters the first product storage tank V-102 (the temperature of the first product storage tank V-102 is about 0 ℃), hexafluoroacetone in the gas product reacts with deionized water (a selective absorbent) which is added in advance in the first product storage tank V-102 to form hexafluoroacetone hydrate, meanwhile, part of pentafluoropropionyl fluoride reacts with the deionized water to form pentafluoropropionic acid, both of which are reserved in the first product storage tank V-102, and a very small part of pentafluoropropionyl fluoride enters the second product storage tank V-103 (the temperature of the second product storage tank V-103 is-50 ℃) through the second condenser E-102 (the temperature of the second condenser E-102 is controlled at about 0 ℃); when the air flow passes through the second condenser E-102, the compound carried in the air flow can be condensed and reflowed into the first product storage tank V-102, and then hexafluoroacetone hydrate and ketal and pentafluoropropionic acid mixture in the first product storage tank V-102 are further processed to obtain hexafluoroacetone and pentafluoropropionic acid; condensing the pentafluoropropionyl fluoride through the second product tank V-103 and a third condenser E-103 (the temperature of the third condenser E-103 is controlled to-50 ℃), so that the pentafluoropropionyl fluoride is stored in the second product tank V-103; the rest tail gas enters a tail gas treatment kettle R-102 (the temperature of the tail gas treatment kettle R-102 is controlled at 0 ℃). Finally, about 13.3g of pentafluoropropionyl fluoride was collected, and about 381.1g of hexafluoroacetone hydrate, pentafluoropropionic acid and the like were obtained in a yield of about 8%. The hexafluoroacetone hydrate and the pentafluoropropionic acid mixture solution can be separated into hexafluoroacetone trihydrate (boiling point 105-106 ℃) and pentafluoropropionic acid (boiling point 96-97 ℃) by a rectification method, and 159.8g of hexafluoroacetone trihydrate is finally obtained, and the yield is about 78.3%; 124.3g of pentafluoropropionic acid. The method has low yield of the pentafluoropropionyl fluoride and great difficulty in the post-treatment process of the hexafluoroacetone.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A process for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene, comprising the steps of:
(1) Adding perfluoro-2-methyl-2-pentene into a dry reaction kettle, then introducing oxygen and ozone mixed gas, and performing ozone cracking to obtain coarse products of pentafluoropropionyl fluoride and hexafluoroacetone;
(2) Discharging the crude products of the pentafluoropropionyl fluoride and the hexafluoroacetone from the reaction kettle, and separating and collecting the crude products by utilizing a selective absorbent to obtain the pentafluoropropionyl fluoride and the hexafluoroacetone respectively; the selective absorber is hydrogen fluoride, alcohol or water.
2. The process for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to claim 1, wherein in step (2), said separation and collection of the crude product with a selective absorber is specifically: the mixture of the pentafluoropropionyl fluoride and the hexafluoroacetone is introduced into a storage tank containing a selective absorbent to absorb the hexafluoroacetone in the mixture, and then the pentafluoropropionyl fluoride is separated and collected.
3. The process for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to claim 1, wherein in step (1), the molar ratio of perfluoro-2-methyl-2-pentene to ozone is 1: (2-8).
4. The method for producing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to claim 1, wherein in step (1), the temperature of the ozone cracking reaction is-100 ℃ to 100 ℃ and the pressure in the reaction vessel is 1 to 10 kg.
5. The method for producing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to claim 1, wherein the concentration of ozone in the oxygen-ozone mixed gas in step (1) is 1 to 50%.
6. The apparatus used in the method for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene according to any one of claims 1 to 5, comprising a reaction vessel R-101, an ozone generator G-101, a rectification column T-101, a first condenser E-101, a recovered raw material storage tank V-101, a first product storage tank V-102, a second condenser E-102, a second product storage tank V-103, a third condenser E-103 and a tail gas treatment vessel R-102, wherein the ozone generator G-101 is in communication with an ozone addition inlet of the reaction vessel R-101, the rectification column T-101 is in communication with a product outlet of the reaction vessel R-101, the other end of the first condenser E-101 is in communication with the recovered raw material storage tank V-101, a bottom outlet of the recovered raw material storage tank V-102 is in communication with a raw material recovery port of the reaction vessel R-101, the first condenser E-101 is in communication with a raw material recovery port of the reaction vessel V-103, the first condenser E-101 is in communication with a product recovery port of the second condenser V-103, and the top product is in communication with a product recovery port of the third condenser E-102; the selective absorber is added to the first product tank V-102 before the ozone cracking reaction proceeds.
7. The apparatus according to claim 6, wherein the temperature of the rectification column T-101 is from-50 ℃ to 0 ℃; the temperature of the first condenser E-101 is-50-0 ℃; the temperature of the recycled raw material storage tank V-101 is-50 ℃.
8. The apparatus of claim 6, wherein the first product tank V-102 has a temperature of-50 ℃ to 20 ℃; the temperature of the second condenser E-102 is-50-20 ℃; the temperature of the second product storage tank V-103 is-100-0 ℃; the temperature of the third condenser E-103 is-100-0 ℃; the temperature of the tail gas treatment kettle R-102 is-20 ℃ to 20 ℃.
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