CN116535296A - Preparation method of perfluoro-2-methyl-3-pentanone - Google Patents

Preparation method of perfluoro-2-methyl-3-pentanone Download PDF

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CN116535296A
CN116535296A CN202310562772.3A CN202310562772A CN116535296A CN 116535296 A CN116535296 A CN 116535296A CN 202310562772 A CN202310562772 A CN 202310562772A CN 116535296 A CN116535296 A CN 116535296A
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catalyst
reaction
perfluoro
methyl
reactor
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薛旭金
李凌云
胡胜伟
邵龙
司腾飞
赵璐
韩拥军
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Duofudo New Material Co ltd
Shanxi Jiafu New Materials Co ltd
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Duofudo New Material Co ltd
Shanxi Jiafu New Materials Co ltd
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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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for preparing perfluoro-2-methyl-3-pentanone by a one-step method, which takes perfluoro-2-methyl-2-pentene as a raw material, oxygen or air and other oxidizing gases as an oxidant, nitrogen as a carrier gas and self-made formed metal fluoride as a catalyst. The raw materials are subjected to gas phase reaction in a fluidized bed reactor to generate perfluoro-2-methyl-3-pentanone in one step. The invention adopts the continuous gas-solid reaction process of the circulating fluidized bed reactor, shortens the traditional multistage reaction process into one-step reaction, improves the efficiency of catalytic reaction, avoids the generation of waste liquid and solves the problem of solvent separation. Therefore, the invention has the characteristics of simple reaction process, low cost, easy regeneration of the catalyst, high conversion rate of raw materials and the like.

Description

Preparation method of perfluoro-2-methyl-3-pentanone
Technical Field
The invention relates to a preparation method of perfluoro-2-methyl-3-pentanone, in particular to a method for generating perfluoro-2-methyl-3-pentanone by one-step reaction of perfluoro-2-methyl-2-pentene vapor in a circulating fluidized bed reactor.
Technical Field
The perfluoro-2-methyl-3-pentanone is one of new generation fire extinguishing agents, has an ozone layer damage ODP value of 0 and a greenhouse effect GWP of 1, has good environmental protection effect, and has the advantages of low toxicity, good safety, low fire extinguishing concentration, high fire extinguishing efficiency, small influence on equipment and materials, no residue, convenient storage and transportation, wide application range and the like, thereby solving the application problem of the past fluorocarbon fire extinguishing agents in the environmental protection aspect while ensuring the fire extinguishing efficiency. Therefore, as a novel clean fire extinguishing agent, the product has high cost performance, is a real-sense halon substitute, and has wide development prospect.
At present, two main production processes of perfluoro-2-methyl-3-pentanone are available, namely oxidation rearrangement of hexafluoropropylene dimer and addition method of perfluoro propionyl fluoride and hexafluoropropylene.
Hexafluoropropylene dimer comprises two isomers, perfluoro-4-methyl-2-pentene and perfluoro-2-methyl-2-pentene, respectively. The process for preparing perfluoro-2-methyl-3-pentanone by oxidative rearrangement of hexafluoropropylene dimer generally comprises preparing corresponding epoxide by oxidizing hexafluoropropylene dimer, and then subjecting the epoxide to catalytic rearrangement to obtain perfluoro-2-methyl-3-pentanone.
In patent CN1056362C, the hexafluoropropylene dimer isomerization process mainly uses a liquid phase method. The synthesis process uses hexafluoropropylene as raw material, fluoride as catalyst, and makes them react in aprotic polar solvent, the solid catalyst is dispersed but not dissolved in organic solvent, the contact probability of hexafluoropropylene dimer and catalyst is low, the reaction time is long, and the solvent consumption is large.
The hexafluoropropylene dimer epoxidation process in patent CN103508983B mainly adopts a liquid phase method to prepare perfluoro-2-methyl-3-pentanone. In the synthesis process, perfluoro-2-methyl-2-pentene is used as a raw material, hydrogen peroxide or sodium hypochlorite is used as an oxidant, acetonitrile is used as a solvent, and [007] perfluoro-2-methyl-2, 3-pentane oxide is prepared. The oxidation efficiency of the oxidant is low, the reaction time is long, and a large amount of waste liquid is generated.
Patent CN105198719B discloses the preparation of perfluoro-2-methyl-2, 3-epoxypentane by reacting in the gas phase with molecular oxygen or air as an oxidant using a tubular reactor under the action of a catalyst. The process has no organic solvent, solves the problem of waste liquid, adopts a tubular reactor, has a reaction temperature of 100-300 ℃, is easy to deactivate catalyst and has low reaction efficiency.
The process for preparing perfluoro-2-methyl-3-pentanone by rearrangement of perfluoro-2-methyl-2, 3-epoxypentane has two methods, namely a liquid phase method and a gas phase method. Patents CN103508868B and CN105439835B disclose that in the liquid phase route, the solid fluoride catalyst is dispersed but insoluble in the organic solvent, the contact probability of the solid catalyst and perfluoro-2-methyl-2, 3-pentane oxide is relatively low, the reaction time is long, the product yield is low, and the solvent usage is large.
Patent CN103787854B discloses a process for rearrangement of perfluoro-2-methyl-2, 3-epoxypentane by gas phase method, which uses carrier fluoride as catalyst and crown ether as cocatalyst, and uses tubular reactor to make reaction at 100-250 deg.c. The process does not use an organic solvent, but uses a tubular reactor, so that the catalyst is easy to deactivate, and the reaction efficiency is low.
The 3M company in the United states discloses a process for preparing perfluoro-2-methyl-3-pentanone by directly reacting hexapropene with perfluoropropionyl fluoride, wherein the process uses diglyme as a solvent, and hexafluoropropylene and perfluoropropionyl fluoride react at 70 ℃ and 1MPa to obtain a product. The process has better yield and selectivity, and the main difficulty is in preparing the perfluoropropionyl fluoride.
Patent US5684193, CN103145544, CN105541606 discloses a preparation method of perfluoropropionyl fluoride, the process adopts a gas phase or liquid phase route, hexafluoropropylene oxide is used as raw material, liquid hydrogen fluoride amine complex, organic base and fluoride complex or supported fluoride are used as catalyst, reaction is carried out at the reaction temperature of 0-200 ℃ and under the pressure of 0-1MPa, and the yield of perfluoropropionyl fluoride is 85-95%. However, the liquid phase method has harsh reaction conditions, complex reactor design, and other impurities contained in the product, and industrial production is not utilized. The gas phase method adopts a tubular reactor, so that the catalyst is easy to deactivate and the reaction efficiency is low.
Patent CN105198719B discloses a process for preparing perfluoro-2-methyl-3-pentanone starting from perfluoro-methyl-2-pentene, however in this process a fixed bed is used, in which the catalyst is fixedly arranged in a straight tube, which needs to be taken out for replacement when the catalyst is exhausted.
Therefore, the gas phase method usually adopts a tubular reactor, and the tubular reactor has the problems of easy deactivation of the catalyst and low reaction efficiency; the liquid phase rule has the problems of harsh reaction conditions, complex reactor design, more product impurities and no utilization of industrialized mass production; the contact probability of the solid fluoride catalyst and the raw materials is small, so that the problems of low reaction efficiency, long duration, low product yield and large solvent consumption are caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for realizing continuous reaction by timely activation after the deactivation of a catalyst.
The invention provides a method for preparing perfluoro-2-methyl-3-pentanone by taking perfluoro-2-methyl-2-pentene as a raw material. The method comprises the steps of reacting oxidizing gas with perfluoro-2-methyl-2-pentene vapor in a circulating fluidized bed reactor under the action of a catalyst to generate perfluoro-2-methyl-3-pentanone in one step, wherein the model of a circulating fluidized bed used in a main reactor and a regeneration reactor is YC-LHC.
The chemical process of the reaction is as follows:
the first invention provides a preparation method of perfluoro-2-methyl-3-pentanone.
Further, the method comprises the step of reacting oxidizing gas with perfluoro-2-methyl-2-pentene vapor in the presence of a catalyst in a circulating fluidized bed reactor to obtain perfluoro-2-methyl-3-pentanone by a one-step method.
Further, the one-step reaction process comprises:
s1, respectively filling the catalyst of the invention into a main reactor and a regeneration reactor, respectively introducing oxidizing gas and carrier gas with an oxidation function into the main reactor and the regeneration reactor, and using the carrier gas to realize fluidization of the catalyst;
s2, respectively raising the temperature of the main reactor and the regeneration reactor to 150-250 ℃, and introducing a supply pipeline of the preheated gasified perfluoro-2-methyl-2-pentene vapor into a loop where the main reactor is positioned to start the reaction. Wherein the reaction space velocity of perfluoro-2-methyl-2-pentene is 10-500h -1 ；
S3, after the reaction in the main reactor is carried out for 0.5-1.5 hours, switching the raw material supply pipeline to a loop where the regeneration reactor is located, so that perfluoro-2-methyl-2-pentene vapor generates the same reaction in the regeneration reactor, and simultaneously activating the catalyst in the main reactor, specifically, quickly raising the temperature of the main reactor to 300-450 ℃ to restore the catalyst activity, and then lowering the temperature to 150-250 ℃ to wait for the subsequent reaction; the purpose of the rapid temperature rise is to save time and shorten the time of the catalyst regeneration section.
S4, after the reaction in the regeneration reactor is carried out for 0.5-1.5 hours, switching the raw material supply pipeline to a loop where the main reactor is located, and activating the catalyst in the regeneration reactor, wherein the activation process is to quickly raise the temperature of the regeneration reactor to 300-450 ℃ and then lower the temperature to 150-250 ℃ for subsequent reaction.
S5, the process of S3-S4 is circularly carried out until the reaction is finished.
In the step S1, the gas speed of the oxidizing gas is 0.1L-5L/min, specifically 0.1L/min, 0.5L/min, 1L/min, 2L/min, 3L/min, 4L/min or 5L/min;
the gas speed of the carrier gas is 0.5L-5L/min, specifically 0.5L/min, 1L/min, 2L/min, 3L/min, 4L/min or 5L/min;
the reaction space velocity of the perfluoro-2-methyl-2-pentene is 10-500h -1 Specifically, it can be 10h -1 、50h -1 、100h -1 、150h -1 、200h -1 、250h -1 、300h -1 、350h -1 、400h -1 、、450h -1 Or 500h -1 Preferably 200h -1 。
The oxidizing gas with the oxidizing function comprises oxygen, air or any other combustible gas.
The carrier gas comprises N 2 、He、Ar、H 2 O、CO 2 One or a mixture of any two or more thereof.
The volume ratio of the perfluoro-2-methyl-2-pentene vapor, the oxidizing gas and the carrier gas is (1-13): (1-12.5): 5, and may specifically be 1:1:5, 1:5:5, 1:12.5:5, 5:1:5, 5:12.5:5, 13:1:5, 13:5:5 or 13:12.5:5.
In step S2, the temperatures of the main reactor and the regeneration reactor are raised to 150 to 250 ℃, respectively, and specifically, the temperatures of each of the main reactor and the regeneration reactor may be raised to 150 ℃, 200 ℃, or 250 ℃.
And (3) dedusting the product obtained in the step (S1) by a bag-type dust remover, and then carrying out dehydration treatment at 120-150 ℃ to obtain perfluoro-2-methyl-3-pentanone, specifically, carrying out heat preservation at 120 ℃, 130 ℃, 140 ℃ or 150 ℃ and then carrying out dehydration treatment to obtain perfluoro-2-methyl-3-pentanone.
In step S3, samples are taken at the time of 0.5 hour, 1 hour and 1.5 hours, respectively, and the perfluoro-2-methyl-3-pentanone content in the obtained product is tested, and when the perfluoro-2-methyl-3-pentanone content in the obtained product is lower than 90%, the above-mentioned one-step reaction is circulated, and when the perfluoro-2-methyl-3-pentanone content in the obtained product is higher than 90%, preferably 95%, the material collection is started.
In the step S4, after the main reactor reacts for 0.5 to 1.5 hours, the catalyst in the main reactor is partially deactivated, and the raw material supply pipeline is switched to a loop where the regeneration reactor is positioned to continue the reaction, specifically, the reaction can be carried out for 0.5 hour, 1 hour or 1.5 hours;
in step S5, the temperature of the main reactor is rapidly raised to 300-450 ℃, specifically 300 ℃, 350 ℃, 400 ℃ or 450 ℃, for 0.5-1 hour, specifically 0.5 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1 hour; then the temperature of the main reactor is rapidly reduced to 150-250 ℃, specifically 150 ℃, 200 ℃ or 250 ℃; after the reaction is carried out in the regeneration reactor for 0.5 to 1.5 hours, specifically for 0.5 hour, 1 hour or 1.5 hours, the feed pipe is switched to the loop where the main reactor is positioned to continue the reaction.
Compared with the prior art, the invention has the following advantages:
the second invention is to provide a preparation process of the catalyst.
The preparation process of the catalyst comprises the following steps:
s1, mixing and dissolving a catalyst active component and a catalyst auxiliary agent in water, and stirring to obtain a feed liquid a;
s2, mixing and dissolving the catalyst carrier, the template agent and the binder in water, and stirring to obtain a feed liquid b;
and S3, slowly adding the feed liquid a into the feed liquid b, stirring, and then pouring the mixed liquid into a beater for carrying out abrasive treatment.
S4, spraying the mixture obtained in the step S3 to obtain a molded catalyst;
and S5, roasting the formed catalyst obtained in the step S4 at the temperature of 400-600 ℃ to obtain a final catalyst product.
In step S1, the catalyst active component is one or a mixture of any two or more of NaF, KF, csF and RbF; the catalyst auxiliary agent is one or a mixture of any two or more of Ru, rh, pd and Pt;
in the step S2, the catalyst carrier is one or a mixture of any two or more of active carbon, kaolin and halloysite; the template agent is one or a mixture of any two or more of anionic, cationic, zwitterionic and nonionic surfactants; the binder is one or a mixture of any two or more of nitric acid, hydrochloric acid and acetic acid.
The mass fractions of the components are respectively as follows: 1-20 parts of a catalyst active component, 0.1-5 parts of a catalyst auxiliary, 15-20 parts of a catalyst carrier, 1-5 parts of a template agent, and a trace amount of a binder, wherein the meaning of "trace" is a bonding effective amount, e.g., 0-1 part.
In step S4, the shaped catalyst particle size is 50-100 microns, and may specifically be 50 microns, 60 microns, 70 microns, 80 microns, 90 microns or 100 microns.
In step S5, the preliminarily molded catalyst obtained in S3 is calcined at 400 to 500 ℃ for 4 to 12 hours, and the specific calcination temperature may be 400 ℃, 450 ℃ or 500 ℃, and the calcination time may be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.
The invention prepares perfluoro-2-methyl-3-pentanone by taking perfluoro-2-methyl-2-pentene as a raw material, adopts oxidizing gas with oxidizing function and perfluoro-2-methyl-2-pentene steam to carry out gas phase reaction in a circulating fluidized bed reactor under the action of self-made catalyst, and prepares perfluoro-2-methyl-3-pentanone by adopting a one-step method.
Compared with the prior art, the invention has the following technical effects:
(1) The existing fixed bed or tubular catalyst has low mechanical strength, low activity and short reaction life. The invention adopts the continuous gas-solid reaction process of the circulating fluidized bed reactor, and shortens the traditional multistage reaction process into one-step reaction. The main reactor and the regeneration reactor are matched for recycling, so that the continuous reaction and the continuous regeneration of the catalyst can be realized, and the reaction efficiency is improved.
(2) Meanwhile, the strength, the reactivity and the reaction life of the catalyst are improved through the self-made catalyst, and the conversion rate of raw materials and the selectivity of the perfluorinated hexanone are improved. Specifically, when the content of perfluoro-2-methyl-3-pentanone in the reaction product is lower than 90%, the reaction is circularly carried out, so that the recycling of the catalyst and the solvent system can be realized, and the continuous synthesis efficiency is further improved. The raw materials of perfluoro-2-methyl-2-pentene and oxidizing gas undergo the cyclic re-reaction process in a circulating fluidized bed reactor, so that the rapid conversion of the raw materials is finally realized, the conversion rate of the raw materials is more than 98%, and the yield of the product perfluoro-2-methyl-3-pentanone reaches more than 95%.
(3) In the manufacturing process, a catalyst regeneration system is used, and fluoride and an auxiliary agent are prepared into a spherical catalyst through a spray forming technology. The catalyst has the properties of high specific surface area, large contact area with raw materials, large content of active components and high mechanical strength. When the catalyst is exhausted, the spherical container floats out in a circulating mode, so that the catalyst can be rapidly filled to realize continuous reaction, and meanwhile, the on-line regeneration of the deactivated catalyst is realized, so that the efficiency of the catalyst is greatly improved. The manufacturing process has the characteristics of simple process, low cost, easy regeneration of the catalyst, high conversion rate of raw materials and the like.
(4) The method does not use an organic solvent or an oxidant such as sodium hypochlorite in the process, and the catalyst and the solvent adopted in the reaction can be separated in the product purification and separation process, so that the method can be directly reused, the waste liquid is avoided, the problem of solvent separation is solved, the raw material cost is reduced, and the method has obvious environmental protection effect.
Drawings
FIG. 1 is a schematic diagram showing the preparation procedure of perfluoro-2-methyl-3-pentanone provided in example 1.
Detailed Description
The term "activation" may be a process conventionally recognized by those skilled in the art as increasing the catalytically active sites in a catalyst.
The term "space velocity" refers to the ratio of the amount of feed entering the reactor per hour to the volume of catalyst in the reactor, calculated as space velocity = standard volumetric flow of feed to the reactor (m 3 Volume of catalyst in reactor (m) 3 )。
The term "active component of a catalyst" refers to a substance that is capable of reacting with a reactant to alter the rate at which a chemical reaction tends to equilibrate (but does not alter the equilibrium location of the chemical reaction) without itself being present in the product;
the term "catalyst promoter" refers to an element or component of the catalyst that serves as a minor influence on the catalytic and selective properties of the catalyst, and in particular, a small amount of a substance added to the catalyst is an adjunct component of the catalyst that is either inactive or of low activity. However, when it is added to the catalyst, the chemical composition, chemical structure, ionic valence state, acidity and alkalinity, lattice structure, surface structure, pore structure, dispersion state, continuous strength, etc. of the catalyst can be changed, so that the activity, selectivity, stability and service life of the catalyst are improved. In addition, the catalyst promoter may also enhance the properties of the support, such as enhancing the thermal stability of the support.
The term "binder" is a substance that enhances the mechanical strength of the catalyst, has a strong resistance to metal contamination and a high coke selectivity, and at the same time, can transfer reactive active substances to provide the catalyst with medium and large pores to enhance the diffusion properties.
The term "templating agent" is a structure directing agent that is used in an amount and in a purity that affects the performance of the catalyst. The template agent has the function of self-assembly in the process of preparing the catalyst, so that the inorganic matters of the catalyst grow around the template agent in the process of precipitation, and the catalyst particles have the characteristic of a certain micropore or mesopore, thereby improving the specific surface area of the catalyst.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and the terms used in the specification of this application are for the purpose of describing particular embodiments only and are not intended to be limiting of this application. Reagents and instruments used herein are commercially available, and reference to characterization means is made to the relevant description of the prior art and will not be repeated herein.
The "several" of the present invention includes two, more or all cases, and will not be described in detail below.
In the present invention, the conditions and methods of the reaction may be those conventional in the art.
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail below. It should be understood that the description is intended to be illustrative of the application and is not intended to limit the scope of the application.
Example 1
This example provides a process for preparing perfluoro-2-methyl-3-pentanone by a one-step reaction method and a process for preparing the catalyst used therein.
FIG. 1 is a schematic diagram showing the steps for preparing perfluoro-2-methyl-3-pentanone according to the present example. The method comprises the following steps:
in a first aspect, a method for preparing perfluoro-2-methyl-3-pentanone by a one-step reaction process comprises:
1. the self-made catalyst is respectively filled into a main reactor and a regeneration reactor, and oxidizing gas and carrier gas with an oxidation function are introduced into the main reactor and the regeneration reactor.
The oxidizing gas with the oxidizing function has the function of supporting combustion, and can be specifically air, oxygen or any gas with the supporting combustion; the carrier gas serves to achieve a circulating flow of the catalyst, i.e. fluidization of the catalyst. The conventional fluidizing gas can perform fluidization, abrasion and classification functions, such as air, nitrogen, steam, helium, etc., and can be one of conventional fluidizing gas, or a mixture of concentrated gas, preferably N 2 、He、Ar、H 2 O、CO 2 One or a mixture of more than one of them. The use of carrier gas improves the fluency of fluidization, circulation and regeneration processes of the reactor, improves the running stability, and has important guiding significance for long-period cyclic utilization of the reactor. Meanwhile, the process has the characteristics of simplicity in operation, good grading effect and strong operation continuity.
In some embodiments, the oxidizing gas has a gas velocity of 0.1-5L/min, specifically 0.1L/min, 0.5L/min, 1L/min, 2L/min, 3L/min, 4L/min, or 5L/min.
In some embodiments, the carrier gas has a gas velocity of 0.5-5L/min, specifically 0.5L/min, 1L/min, 2L/min, 3L/min, 4L/min, or 5L/min.
In some embodiments, the volume ratio of oxidizing gas to carrier gas is (0.2-2.5): 1, which may specifically be 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, or 2.5:1.
2. Primary reaction:
the temperature of the main reactor and the regeneration reactor are respectively increased to 150-250 ℃, and the temperature range is the optimal range of the perfluoro-2-methyl-2-pentene gas-phase reaction determined after repeated practice of the invention.
Since perfluoro-2-methyl-2-pentene is liquid at ordinary temperature, it must be preheated and vaporized before it is fed into the reactor. After the perfluoro-2-methyl-2-pentene is preheated to 150-250 ℃, the generated perfluoro-2-methyl-2-pentene vapor is introduced into a main reactor to carry out gas phase reaction, and the chemical formula of the gas phase reaction is as follows:
the main reactor and the regeneration reactor used in the invention are both fluidized bed reactors, as shown in figure 1. Wherein the outlet of the left main reactor is connected with a pipeline, and the pipeline conveys the product obtained by the reaction to obtain perfluoro-2-methyl-3-pentanone (shown by an arrow in the figure) after the procedures of dust removal, heat preservation, dehydration and drying. The inlet of the main reactor is connected with a supply pipeline of perfluoro-2-methyl-2-pentene. Similarly, the outlet of the right-hand regeneration reactor is also connected to a line for transporting the reaction product, and the inlet is connected to a supply line for perfluoro-2-methyl-2-pentene. Thus, left and right loops (i.e., two closed loops) as shown are formed, and the above reaction is alternately performed in the two loops. The process is as follows:
introducing a supply pipeline of the preheated raw material perfluoro-2-methyl-2-pentene vapor into a loop where a main reactor is located, and starting the reaction, wherein the reaction space velocity of the perfluoro-2-methyl-2-pentene vapor is (10-500) h -1 Specifically, it can be 10h -1 、50h -1 、100h -1 、200h -1 、300h -1 、400h -1 Or 500h -1 . The space velocity here is the ratio of the amount of feed fed to the reactor per hour to the volume of catalyst in the reactor, and the specific formula is space velocity = standard volumetric flow of feed fed to the reactor (m 3 Volume of catalyst in reactor (m) 3 ). Thus, the volume ratio of perfluoro-2-methyl-2-pentene to catalyst in the reactor is (10-500): 1, which may be in particular 10:1, 50:1, 100:1, 150:1, 200:1, 300:1, 400:1 or 500:1.
The catalyst dosage in the invention has influence on the reaction, and the reaction yield is improved along with the increase of the catalyst dosage; but the yield is not obviously improved when the catalyst reaches a certain dosage. Thus, the space velocity of perfluoro-2-methyl-2-pentene was selected to be (10-500) h after the reaction yield and the cost were taken into consideration -1 When the method is used, the yield of the reaction is highest, and the cost is not obviously increased.
The volume ratio of the perfluoro-2-methyl-2-pentene vapor to the carrier gas is (1-13): (1-12.5): 5, and specifically may be 1:1:5, 1:5:5, 1:12.5:5, 5:1:5, 5:12.5:5, 13:1:5, 13:5:5, 13:12.5:5, or any value within the above ratio ranges.
The reaction temperature has influence on the reaction conversion rate, and the perfluoro-2-methyl-2-pentene conversion rate is smaller when the temperature is too low; the conversion rate is not obviously improved after the temperature reaches a certain temperature, and the conversion rate and the energy consumption are comprehensively considered, wherein the reaction temperature is 150-250 ℃, specifically can be 150 ℃, 200 ℃ or 250 ℃, and is preferably 200 ℃.
Similarly, the reaction time in the invention also has an influence on the reaction conversion rate, and after multiple times of practice, the reaction time is selected to be 0.5-1.5 hours, preferably 1 hour, so that the reaction conversion rate and the reaction efficiency reach a better balance.
The reaction product is subjected to conventional dust removal through a dust removal bag to remove dust mixed in the product, and then the reaction product is subjected to heat preservation at 120-150 ℃, wherein the temperature can be 120 ℃, 130 ℃, 140 ℃ or 150 ℃; and then dehydrating to obtain perfluoro-2-methyl-3-pentanone.
3. And (3) cyclic reaction:
after the above reaction was carried out for 0.5 to 1.5 hours, the content of perfluoro-2-methyl-3-pentanone in the product was measured. When the perfluoro-2-methyl-3-pentanone content in the obtained product is lower than the expected value, for example, 90%, the raw material supply line is switched to the loop where the regeneration reactor is located, so that the perfluoro-2-methyl-2-pentene vapor reacts in the regeneration reactor in the same way, and the catalyst in the main reactor is activated.
In some embodiments, when the reaction is carried out in one of the main reactor and the regeneration reactor for 0.5 to 1.5 hours, for example 0.5 hour, 1 hour or 1.5 hours, at which time the catalyst in the reactor line is deactivated or partially deactivated, in order to restore its activity, to achieve maximum reaction efficiency, the feed line is switched to the circuit in which the other of the two reactors is located, and the reaction is continued; at the same time, the temperature of the catalyst deactivated reactor is rapidly raised to 300-450 ℃, for example 300 ℃, 350 ℃, 400 ℃ or 450 ℃, to regenerate and activate the catalyst at this high temperature. The purpose of the rapid temperature rise is to save time and shorten the time of the catalyst regeneration section. This regeneration activation process is maintained for 0.5 to 1 hour, specifically 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1 hour, until the catalyst in the reactor has been regenerated activated.
The deactivation of the catalyst in the process mainly comprises the reduction and blockage of the surface area of the catalyst caused by carbon deposition and coking, the reduction of the surface area and the reduction of the catalytic activity caused by noble metal pollution, and the reduction of the active site of the catalyst caused by poison adsorption. The regeneration and activation of the catalyst are mainly fluidized bed charcoal-burning method, the catalyst is burned back and forth in the natural air of the fluidized bed for 3-4 times, the temperature is from low to high, the highest temperature is not more than 450 ℃, and the cokes are removed.
After the catalyst is activated, the temperature of the reactor in which it is located is reduced to the original reaction temperature, i.e. between 150 and 250 ℃, in particular 150 ℃, 200 ℃ or 250 ℃, in order to be ready for further reaction.
The above reactions take place alternately in the main reactor and the regeneration reactor, achieving the continuity of the reaction until the recovery is started when the perfluoro-2-methyl-3-pentanone content in the product is higher than the desired value, for example 90% -100%, preferably 95%. In the actual production process, the product with higher content can be obtained by adopting the conventional rectification operation in the field according to the market demand.
In a second aspect, the method for preparing the catalyst in the above process includes the following steps:
1. mixing the catalyst active component, the catalyst auxiliary agent, the catalyst carrier, the template agent, the binder and water to obtain a mixture;
in some embodiments, the catalyst active component, the catalyst auxiliary agent, the catalyst carrier, the template agent, a proper amount of binder and water are mixed to obtain a mixture, wherein the mass fractions of the components are as follows: 1-20 parts of a catalyst active component, 0.1-5 parts of a catalyst auxiliary, 15-20 parts of a catalyst carrier, 1-5 parts of a template agent, and a trace amount of a binder, wherein the meaning of "trace" is a bonding effective amount, e.g., 0-1 part.
The catalyst active component can be a component commonly used in the catalyst field, preferably one or a mixture of any two or more of NaF, KF, csF and RbF; for example, a mixture of NaF, KF, csF, rbF, naF and KF, a mixture of CsF and RbF, and the like. When the active component is a mixture of two or more, the mass ratio between the components has no fixed range, and can be changed according to the reaction conditions; the raw material providing the active component may be a metal monomer of the above elements, or a nitrate thereof.
The catalyst auxiliary agent can be an auxiliary agent which is used for improving the catalytic activity or selectivity of the catalyst and is commonly used in the catalyst field, and is preferably one or a mixture of any two or more of Ru, R hours, pd and Pt;
the catalyst carrier may be a conventionally used carrier, preferably one or a mixture of any two or more of activated carbon, kaolin and halloysite; the wall thickness of the catalyst support may be conventional in the art, preferably from 0.1 to 0.2mm, more preferably from 0.15 to 0.18mm. The shape of the catalyst support may be conventional in the art, preferably one or more of powder, granules, rods and honeycombs, more preferably honeycombs;
the binder is one or a mixture of any two or more of nitric acid, hydrochloric acid and acetic acid;
the template agent is one or a mixture of any two or more of anionic, cationic, zwitterionic and nonionic surfactants; the template agent has the function of self-assembly in the process of preparing the catalyst, so that the inorganic matters of the catalyst grow around the template agent in the process of precipitation, thereby ensuring that the catalyst particles have the characteristics of a certain micropore or mesopore and improving the specific surface area of the catalyst.
The catalyst active component and the catalyst auxiliary agent are loaded on the catalyst carrier in various modes, such as the active component is in the inner layer of the carrier and the auxiliary agent is in the outer layer of the carrier, or the active component is in the outer layer of the carrier and the auxiliary agent is in the inner layer of the carrier, or the active component and the auxiliary agent are uniformly distributed in each part of the carrier.
2. Grinding and pulping:
and (2) preparing spray-formed slurry from the mixture obtained in the step (1) through grinding and pulping, and preparing the formed catalyst with the particle size of 50-100 microns by spray-forming the raw material liquid through a spray-forming device.
In some embodiments, the mixture is poured into an abrasive machine to be polished for 15-30min to prepare spray forming slurry, and the polishing can be 15min, 20min, 25min or 30min.
In some embodiments, the shaped catalyst has a particle size of 50-100 microns, specifically 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, or 100 microns;
3. roasting to obtain a finished product:
the shaped catalyst obtained in step 2 is calcined at 400-500 c for 4-12 hours, the specific calcination temperature may be 400 c, 450 c or 500 c and the calcination time may be any value from 4-12 hours, for example 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, to obtain the final catalyst.
Example 2
The embodiment provides a specific preparation process of the catalyst.
S1, 114g of potassium fluoride, 0.64g of chloroplatinic acid and 1.1g of cetyltrimethylammonium bromide are dissolved in 1.2L of water, and stirred to obtain a feed liquid a.
S2, 358g of kaolin and 12g of nitric acid are dissolved in 1.2L of water, and the mixture is stirred to obtain a feed liquid b.
S3, slowly adding the feed liquid a into the feed liquid b, stirring for 0.5 hour, and then pouring the mixed liquid into a beater for grinding for 0.5 hour.
S4, setting the inlet temperature of the spray tower to 150 ℃, setting the rotation speed of a spray wheel to 10000 revolutions per minute, and introducing the ground raw materials into the spray tower, wherein the feeding speed is 0.8L/min.
And S5, roasting the prepared catalyst in a muffle furnace at 500 ℃ for 4 hours to obtain the catalyst.
Example 4
The embodiment provides a specific preparation process of the catalyst.
S1, 137g of cesium fluoride, 0.84g of palladium chloride and 2.4g of P123 are dissolved in 1.5L of water, and stirred to obtain a feed liquid a.
S2, 364g of halloysite and 15.4g of hydrochloric acid are dissolved in 1.5L of water, and the mixture is stirred to obtain a feed liquid b.
S3, slowly adding the feed liquid a into the feed liquid b, stirring for 0.5 hour, and then pouring the mixed liquid into a beater for grinding for 0.5 hour.
S4, setting the inlet temperature of the spray tower to 200 ℃, setting the rotation speed of a spray wheel to 9000 revolutions per minute, and introducing the ground raw materials into the spray tower, wherein the feeding speed is 1L/min.
And S5, roasting the prepared catalyst in a muffle furnace at 400 ℃ for 12 hours to obtain the catalyst.
Example 5
The embodiment provides a specific preparation process of the catalyst.
S1, 184g of sodium fluoride, 1.17g of rhodium chloride and 1.89g of sodium dodecyl benzene sulfonate are dissolved in 1.9L of water, and the mixture is stirred to obtain a feed liquid a.
S2, 364g of pseudo-boehmite and 20.1g of acetic acid are dissolved in 1.9L of water and stirred to obtain a feed liquid b.
S3, slowly adding the feed liquid a into the feed liquid b, stirring for 0.5 hour, and then pouring the mixed liquid into a beater for grinding for 0.5 hour.
S4, setting the inlet temperature of the spray tower to 200 ℃, setting the rotation speed of a spray wheel to 10000 revolutions per minute, and introducing the ground raw materials into the spray tower, wherein the feeding speed is 0.6L/min.
And S5, roasting the prepared catalyst in a muffle furnace at 400 ℃ for 5 hours to obtain the catalyst.
Example 6
The embodiment provides a specific method for preparing perfluoro-2-methyl-3-pentanone by adopting a one-step reaction process.
108g of the catalyst prepared in example 3 was charged into a circulating fluidized bed main regeneration reactor having a volume of 500ml, and oxygen was introduced at a rate of 0.7L/min; introducing carrier gas N 2 The speed was 2.4L/min.
The temperature of the main reactor and the regeneration reactor were respectively raised to 150 ℃.
The perfluoro-2-methyl-2-pentene is introduced into the main reactor, and the reaction space velocity is 50h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed was subsequently switched to the regeneration reactor, the reaction was run for 0.5 hours, 1 hour and 1.5 hours before sampling analysis of the product.
After switching the reactors, the temperature of the main reactor was rapidly raised to 300℃at the same time, and after 1 hour of incubation, the temperature was rapidly lowered to 150 ℃.
The feed supply line was switched from the loop in which the regeneration reactor was located to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour, and 1.5 hours of reaction, respectively.
TABLE 1 conversion of feedstock to Main regeneration reactor and yield of product
Example 7
This example provides a method for preparing perfluoro-2-methyl-3-pentanone using a one-step reaction process.
134g of catalyst A was charged into each of the circulating fluidized bed main regeneration reactors having a volume of 500ml, and air was introduced at a rate of 2.3L/min and water vapor was introduced at a rate of 3.7L/min.
The temperature of the main reactor and the regeneration reactor was raised to 200 ℃.
The raw material supply pipeline of perfluoro-2-methyl-2-pentene is switched to the loop where the main reactor is located, and the reaction space velocity is 200h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed supply line was then switched to the loop in which the regeneration reactor was located, the reaction was sampled after 0.5 hours, 1 hour and 1.5 hours.
After switching, the temperature of the main reactor is rapidly increased to 500 ℃ at the same time, and the temperature is rapidly reduced to 200 ℃ after heat preservation for 1 hour.
The feed supply line was switched from the loop in which the regeneration reactor was located to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 2 conversion of feedstock to Main regeneration reactor and yield of product
Example 8
This example provides a method for preparing perfluoro-2-methyl-3-pentanone using a one-step reaction process.
In a volume of 500ml of recycle stream129g of catalyst B is filled in each of the main regeneration reactors of the fluidized bed, and oxygen is introduced at the speed of 4.4L/min; introducing N 2 The speed was 2.8L/min.
The temperature of the main reactor and the regeneration reactor was raised to 300 ℃. The raw material supply pipeline of perfluoro-2-methyl-2-pentene is switched to the loop where the main reactor is located, and the reaction space velocity is 480h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
The feed supply line was then switched to the line in which the regeneration reactor was located and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After switching, the temperature of the main reactor is rapidly increased to 400 ℃ at the same time, and the temperature is rapidly reduced to 300 ℃ after heat preservation for 1 hour.
The feed supply line was switched from the regeneration reactor to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 3 conversion of feedstock to Main regeneration reactor and yield of product
Example 9
This example provides a method for preparing perfluoro-2-methyl-3-pentanone using a one-step reaction process.
210g of catalyst C is filled in a circulating fluidized bed main regeneration reactor with the volume of 500ml, and air is introduced at the speed of 3.7L/min; he was introduced at a rate of 1.3L/min.
The temperature of the main reactor and the regeneration reactor was raised to 250 ℃.
The raw material supply line of perfluoro-2-methyl-2-pentene was switched to the loop where the main reactor was located, and the reaction space velocity was 310h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed supply line was then switched to the loop in which the regeneration reactor was located, the reaction was sampled after 0.5 hours, 1 hour and 1.5 hours.
After switching, the temperature of the main reactor is quickly raised to 400 ℃ at the same time, and after heat preservation for 1 hour, the temperature is quickly lowered to 250 ℃. The feed supply line was switched to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 4 conversion of feedstock to Main regeneration reactor and yield of product
Comparative example 1
This comparative example provides a method for preparing perfluoro-2-methyl-3-pentanone by a one-step reaction process.
210g of catalyst C is filled in a circulating fluidized bed main regeneration reactor with the volume of 500ml, and air is introduced at the speed of 3.7L/min; he gas was introduced at a rate of 1.3L/min.
Raising the temperature of the main reactor and the regeneration reactor to 120 ℃ to prepare for reaction;
the raw material supply line of perfluoro-2-methyl-2-pentene was switched to the loop where the main reactor was located, and the reaction space velocity was 310h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed supply line was then switched to the loop in which the regeneration reactor was located, the reaction was sampled after 0.5 hours, 1 hour and 1.5 hours.
After switching, the temperature of the main reactor is quickly raised to 400 ℃ at the same time, and after heat preservation for 1 hour, the temperature is quickly lowered to 250 ℃. The feed supply line was switched to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 5 conversion of feedstock to Main regeneration reactor and yield of product
The reaction temperature of the one-step reaction in the process is 120 ℃, and the temperature is 150-250 ℃ below the optimal temperature range. The results show that the conversion rate of the raw materials is lower, and the yield of the product is also reduced, which indicates that the lower reaction temperature is unfavorable for the reaction.
Comparative example 2
This comparative example provides a method for preparing perfluoro-2-methyl-3-pentanone by a one-step reaction process.
210g of catalyst C is filled in a circulating fluidized bed main regeneration reactor with the volume of 500ml, and air is introduced at the speed of 3.7L/min; he was introduced at a rate of 1.3L/min.
Raising the temperature of the main reactor and the regeneration reactor to 280 ℃ to prepare for reaction;
the raw material supply line of perfluoro-2-methyl-2-pentene was switched to the loop where the main reactor was located, and the reaction space velocity was 310h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed supply line was then switched to the loop in which the regeneration reactor was located, the reaction was sampled after 0.5 hours, 1 hour and 1.5 hours.
After switching, the temperature of the main reactor is quickly raised to 400 ℃ at the same time, and after heat preservation for 1 hour, the temperature is quickly lowered to 250 ℃. The feed supply line was switched to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 6 conversion of feedstock to Main regeneration reactor and yield of product
The reaction temperature of the one-step reaction in the process is 280 ℃, and the temperature is 150-250 ℃ higher than the optimal temperature range. The results show that the conversion rate of the raw materials is increased, but the yield of the product is obviously reduced, and the conversion rate of the raw materials can be effectively improved after the reaction temperature exceeds the optimal range, but the product is decomposed due to the excessively high reaction temperature, so that the yield is reduced.
Comparative example 3
This comparative example provides a method for preparing perfluoro-2-methyl-3-pentanone by a one-step reaction process.
210g of catalyst C is filled in a circulating fluidized bed main regeneration reactor with the volume of 500ml, and air is introduced at the speed of 3.7L/min; he was introduced at a rate of 1.3L/min.
Raising the temperature of the main reactor and the regeneration reactor to 250 ℃ to prepare for reaction;
the raw material supply line of perfluoro-2-methyl-2-pentene was switched to the loop where the main reactor was located, and the reaction space velocity was 310h -1 Sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
After the feed supply line was then switched to the loop in which the regeneration reactor was located, the reaction was sampled after 0.5 hours, 1 hour and 1.5 hours.
After switching, the temperature of the main reactor was rapidly raised to 480 ℃ simultaneously to restore the catalyst activity, and after 1 hour of incubation, the temperature was rapidly lowered to 250 ℃. The feed supply line was switched to the loop in which the main reactor was located, and sampling analysis was performed after 0.5 hours, 1 hour and 1.5 hours of reaction.
TABLE 7 conversion of feedstock to Main regeneration reactor and yield of product
The temperature is quickly raised to 480 ℃ in the process to restore the activity of the catalyst, and the optimal regeneration and activation temperature range of the catalyst is 300-450 ℃. After the catalyst exceeds the optimal regeneration activation temperature, the mechanical strength of the catalyst is reduced, and the catalyst surface active components are lost in the catalyst regeneration process, so that the performance of the catalyst is reduced.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, or alternatives falling within the spirit and principles of the present application.

Claims (10)

1. The preparation method of perfluoro-2-methyl-3-pentanone is characterized by comprising the step of reacting raw material perfluoro-2-methyl-2-pentene under the action of a catalyst to obtain perfluoro-2-methyl-3-pentanone.
2. The method of claim 1, wherein the one-step reaction comprises:
s1: the method comprises the steps of respectively introducing a catalyst, oxidizing gas with an oxidizing function and carrier gas into a main reactor and a regeneration reactor;
s2: raising the temperature of the main reactor and the regeneration reactor to 150-250 ℃, and introducing a supply pipeline of raw material perfluoro-2-methyl-2-pentene into the main reactor for reaction;
s3: after the reaction is carried out in the main reactor for 0.5 to 1.5 hours, the supply pipeline of the raw materials is switched to a regeneration reactor, so that perfluoro-2-methyl-2-pentene vapor is subjected to the same reaction in the regeneration reactor; simultaneously activating the catalyst in the main reactor;
s4: after the reaction is carried out in the regeneration reactor for 0.5 to 1.5 hours, switching the raw material supply line to the main reactor again while activating the catalyst in the regeneration reactor;
s5: the process of S3-S4 is cycled until the reaction is completed.
3. The method of claim 2, wherein activating the catalyst in the main reactor/regeneration reactor comprises raising the temperature of the main reactor/regeneration reactor to 300-450 ℃ and then lowering the temperature to 150-250 ℃.
4. The process according to claim 2, wherein the reaction space velocity of the perfluoro-2-methyl-2-pentene in the main reactor and the regeneration reactor is 10 to 500 hours -1 。
5. The method according to claim 2, wherein in step S1, the oxidizing gas comprises oxygen, air or any other combustible gas; the carrier gas is N 2 、He、Ar、H 2 O and CO 2 One or a mixture of any of the above.
6. The method according to claim 2, wherein the perfluoro-2-methyl-2-pentene is vaporized to vapor by preheating before the reaction, and the volume ratio of the perfluoro-2-methyl-2-pentene vapor, the oxidizing gas and the carrier gas is (1-13): (1-12.5): 5.
7. The preparation method according to claim 2, wherein the preparation method of the catalyst in step S1 comprises:
s1, mixing and dissolving a catalyst active component and a catalyst auxiliary agent in water, and stirring to obtain a feed liquid a;
s2, mixing and dissolving the catalyst carrier, the template agent and the binder in water, and stirring to obtain a feed liquid b;
s3, adding the feed liquid a into the feed liquid b to obtain mixed liquid, and carrying out abrasive treatment on the mixed liquid;
s4, spraying the product obtained in the step S3 to obtain a formed catalyst;
and S5, roasting the formed catalyst obtained in the step S4 at 400-600 ℃ to obtain the final catalyst.
8. The preparation method according to claim 7, wherein the catalyst active component is one or a mixture of any of NaF, KF, csF and RbF; the catalyst auxiliary agent is one or a mixture of more of Ru, rh, pd and Pt.
9. The preparation method according to claim 7, wherein the catalyst carrier is one or a mixture of any of activated carbon, kaolin and halloysite; the template agent is one or a mixture of any of anionic, cationic, amphoteric and nonionic surfactants; the binder is one or a mixture of any of nitric acid, hydrochloric acid and acetic acid.
10. The preparation method of claim 7, wherein the catalyst comprises the following components in parts by mass: 1-20 parts of catalyst active component, 0.1-5 parts of catalyst auxiliary agent, 15-20 parts of catalyst carrier, 1-5 parts of template agent and a trace amount of binder.
CN202310562772.3A 2023-05-18 2023-05-18 Preparation method of perfluoro-2-methyl-3-pentanone Pending CN116535296A (en)

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