Preparation and application of supported catalyst

Abstract

The invention provides a supported catalyst as well as preparation and application thereof. The supported catalyst comprises a main catalytic component and a co-catalytic component which are supported on a carrier, wherein the main catalytic component is selected from potassium fluoride, cesium fluoride or a combination thereof; the co-catalysis component is selected from one or more of the following components: magnesium fluoride, calcium fluoride, aluminum fluoride, nickel fluoride and ferric fluoride (III). The catalyst can be used for catalyzing the catalytic rearrangement reaction of perfluoro-2, 3-epoxy-2-methylpentane with extremely high catalytic activity to prepare perfluoro-2-methyl-3-pentanone, and has the advantages that the reaction yield is improved, the target product selectivity is improved, catalytic reaction conditions are easy to control, the service life of the catalyst is long and the like.

Description

Technical Field

[0001] The invention relates to the field of catalysis, and in particular to a multi-active component supported catalyst, a method for synthesizing the catalyst, and a method for performing a catalytic rearrangement reaction using the catalyst. Background Art

[0002] Perfluoro-2-methyl-3-pentanone is an important fluorine-containing chemical with extremely excellent properties such as low boiling point, low vapor pressure, low toxicity, high safety, non-flammability, easy storage, and easy transportation. In addition, this substance also has excellent environmental protection potential. Specifically, it will not damage the ozone layer (ODP=0), can be naturally decomposed in the atmosphere within 5 days, and has an extremely low global warming potential (GWP=1). It has broad application and market prospects and is widely used as fire extinguishing agents, electronic cleaning agents, electronic thermal fluids, fluorinated solvents, and various chemical process intermediates.

[0003] The methods used in the prior art to synthesize perfluoro-2-methyl-3-pentanone or other perfluoroketone compounds mainly include using various fluoroolefins or fluoroketones as starting materials, using various catalysts to catalyze these materials to undergo epoxidation, isomerization, rearrangement and other reactions to obtain the target product. However, these prior art reaction processes all have serious defects, such as too complicated process steps, very low target product yield, and difficulty in actual industrialization. Complex organic substances must be used in the reaction process (for example, some catalysts used in the prior art contain macromolecular crown ethers, organic impregnation liquid dimethyl sulfoxide, etc.), and industrial wastes are easily generated in the reaction process. In addition, the catalysts used in the prior art often contain toxic components (for example, metallic chromium, etc.), the service life of the catalyst is short, and the catalytic activity is also unsatisfactory, and the raw material conversion rate and target product selectivity are often low (these two indicators of the prior art are usually lower than 90%, and some are even lower than 70%).

[0004] The above-mentioned defects of the prior art and the growing demand for perfluoro-2-methyl-3-pentanone in the field form a huge contradiction, and people are eager to develop a new technology that can solve the above-mentioned problems.

[0005] In response to this urgent problem, the applicant has conducted a lot of in-depth research and unexpectedly found that the use of the specially designed catalyst system of the present invention can achieve excellent catalytic activity and a very long catalyst life. In addition, the catalyst of the present invention can be prepared by an extremely simple process, completely avoiding the use of toxic components, thereby solving safety-related problems.

[0006] It should also be noted that, although several catalysts for rearrangement reactions have been reported in the prior art, all catalysts reported in the prior art are different from the catalysts of the present application, or the rearrangement reactions reported are rearrangement reactions of perfluorinated or fluorinated reaction raw materials that are completely different from those of the present application; it is well known in the art that catalysts and / or process conditions suitable for rearrangement reactions of other specific different reaction raw materials cannot be simply used for the catalytic rearrangement reaction of the reaction raw materials of the present invention. Summary of the invention

[0007] The first aspect of the present invention provides a supported catalyst, wherein the supported catalyst comprises a main catalytic component and a co-catalytic component supported on a carrier.

[0008] The main catalytic component is selected from: potassium fluoride, cesium fluoride, or a combination thereof;

[0009] The co-catalyst component is selected from one or more of the following: magnesium fluoride, calcium fluoride, aluminum fluoride, nickel fluoride, iron (III) fluoride;

[0010] The carrier is selected from one or more of the following: activated carbon, porous metal fluoride, molecular sieve, zeolite, amorphous alumina, silicon oxide, silicon-aluminum composite oxide and porous ceramics.

[0011] According to one embodiment of the first aspect of the present application, the ratio of the sum of the weight of the main catalytic component and the co-catalytic component to the weight of the carrier is: (main catalytic component + co-catalytic component): carrier = 0.01: 1 to 0.6: 1. According to another embodiment of the first aspect of the present application, the weight ratio of the main catalytic component to the co-catalytic component is 1: 0.01 to 1: 0.5.

[0012] According to another embodiment of the first aspect of the present application, the weight ratio of the main catalytic component to the co-catalytic component is 1:0.02 to 1:0.08.

[0013] According to another embodiment of the first aspect of the present application, the ratio of the sum of the weights of the main catalytic component and the auxiliary catalytic component to the weight of the carrier is: (main catalytic component+auxiliary catalytic component):carrier=0.1:1 to 0.5:1.

[0014] According to another embodiment of the first aspect of the present application, the carrier is a porous carrier having a specific surface area of ​​50-1600 m 2 / g, and the specific pore volume is 0.1ml / g-0.85ml / g.

[0015] The second aspect of the present application provides a method for synthesizing the supported catalyst of the present invention, the method comprising:

[0016] Step 1: providing one or more precursor solutions or precursor suspensions containing the main catalytic component and the co-catalytic component;

[0017] Step 2: mixing the precursor solution or the precursor suspension with the carrier to form a mixed material;

[0018] Step 3: heating the mixture to dryness, and then calcining it to obtain the supported catalyst.

[0019] The third aspect of the present application provides a method for preparing perfluoro-2-methyl-3-pentanone from perfluoro-2,3-epoxy-2-methylpentane, the method comprising subjecting the perfluoro-2,3-epoxy-2-methylpentane to a catalytic rearrangement reaction in the presence of the supported catalyst of the present invention to generate perfluoro-2-methyl-3-pentanone.

[0020] According to one embodiment of the third aspect of the present application, the method comprises introducing the perfluoro-2,3-epoxy-2-methylpentane and an inert carrier gas into a reactor containing the supported catalyst, so that the perfluoro-2,3-epoxy-2-methylpentane undergoes a catalytic rearrangement reaction and generates perfluoro-2-methyl-3-pentanone.

[0021] According to another embodiment of the third aspect of the present application, the inert carrier gas is selected from one or more of the following: nitrogen, helium, neon, and argon.

[0022] According to another embodiment of the third aspect of the present application, the molar ratio of perfluoro-2,3-epoxy-2-methylpentane to the inert carrier gas is 1:0.1 to 1:12.

[0023] According to another embodiment of the third aspect of the present application, the total space velocity of the perfluoro-2,3-epoxy-2-methylpentane and the inert carrier gas is 200-3,000 hours -1 .

[0024] According to another embodiment of the third aspect of the present application, the inert carrier is nitrogen; and the molar ratio of the perfluoro-2,3-epoxy-2-methylpentane to the inert carrier gas is 1:0.1 to 1:3.

[0025] According to another embodiment of the third aspect of the present application, the reaction temperature of the catalytic rearrangement reaction is 160-320° C.; the reaction pressure of the catalytic rearrangement reaction is 0.1-1.0 MPa.

[0026] According to another embodiment of the third aspect of the present application, the catalytic rearrangement reaction is carried out in a reactor selected from the following: a tubular reactor, a shell-and-tube reactor, and a microchannel reactor.

[0027] The fourth aspect of the present application provides a perfluoro-2-methyl-3-pentanone product, which is prepared by the method of the third aspect of the present application.

[0028] In the following detailed description section, the process and design of the present application are described in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A schematic diagram showing the mechanism of the rearrangement reaction in the method of the present application is shown;

[0030] Figure 2 A reaction device for performing a catalytic rearrangement reaction according to one embodiment of the present invention is shown;

[0031] Figure 3 The F19-NMR spectrum of the product obtained in the embodiment of the present invention is shown;

[0032] Figure 4 shows a gas chromatogram of a product obtained in an embodiment of the present invention;

[0033] Figure 5 A graph characterizing the life of a catalyst according to one embodiment of the present application is shown. DETAILED DESCRIPTION

[0034] "Range" disclosed herein is in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundary of a particular range. All ranges that can be defined in this way are inclusive of end values ​​and combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0035] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0036] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0037] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0038] In the present invention, if there is no special explanation, the "including" mentioned herein means open or closed. For example, the "including" may mean that other components not listed may also be included, or only the listed components may be included.

[0039] In the present invention, when describing the spatial relationship of a specific component or object relative to other components or objects, the terms "inside", "outside", "above", "below", etc. are used to indicate that the former is located inside, outside, above or below the latter, and the two may be in direct contact, or be separated by a certain distance or separated by a third component or object.

[0040] It should be emphasized that what is shown in the drawings and described below are only some specific embodiments of the present invention, and the protection scope of the present invention is not limited to these specific embodiments. The protection scope of the present invention is defined by the claims of the present invention, and may include any technical solution within the scope of the claims, including but not limited to further improvements and substitutions to these specific embodiments.

[0041] Figure 1 A schematic diagram of the reaction mechanism of the etherification reaction and the cyclization reaction according to an exemplary embodiment of the present application is shown in FIG. Figure 1 As shown, in a reactor loaded with the supported catalyst of the present invention, the raw material perfluoro-2,3-epoxy-2-methylpentane is rearranged under heating conditions to generate perfluoro-2-methyl-3-pentanone.

[0042] According to one embodiment of the present application, the supported catalyst of the present invention comprises a main catalytic component and a co-catalytic component supported on a carrier.

[0043] According to one embodiment of the present application, the main catalytic component is selected from: potassium fluoride, cesium fluoride, or a combination thereof. According to one embodiment of the present application, the co-catalyst component is selected from one or more of the following: magnesium fluoride, calcium fluoride, aluminum fluoride, nickel fluoride, iron (III) fluoride, preferably the co-catalyst is magnesium fluoride, aluminum fluoride or calcium fluoride, more preferably the co-catalyst is magnesium fluoride or calcium fluoride.

[0044] According to one embodiment of the present application, the carrier is selected from one or more of the following: activated carbon, porous metal fluoride, molecular sieve, zeolite, amorphous alumina, silicon oxide, silicon-aluminum composite oxide and porous ceramics, and preferably the carrier is activated carbon.

[0045] According to one embodiment of the present application, in the supported catalyst of the present invention, the ratio of the sum of the weight of the main catalytic component and the co-catalytic component to the weight of the carrier is: (main catalytic component + co-catalytic component): carrier = 0.01: 1 to 0.6: 1, preferably 0.05: 1 to 0.4: 1, more preferably 0.1: 1 to 0.25: 1. According to another embodiment of the present application, the above ratio can be within a range selected from the following: 0.08: 1 to 0.11: 1, 0.1: 1 to 0.12: 1, 0.11: 1 to 0.15: 1, 0.12: 1 to 0.14: 1, 0.20: 1 to 0.28: 1, 0.14: 1 to 0.25: 1.

[0046] According to one embodiment of the present application, in the supported catalyst of the present invention, the weight ratio of the main catalytic component to the co-catalytic component is 1:0.01 to 1:0.5, preferably 1:0.02 to 1:0.1, more preferably 1:0.02 to 1:0.08. According to another embodiment of the present application, the above ratio can be within a range selected from the following: 1:0.01 to 1:0.025, 1:0.025 to 1:0.035, 1:0.04 to 1:0.06, 1:0.07 to 1:0.09.

[0047] According to one embodiment of the present application, the carrier is a porous carrier with a specific surface area of ​​50-1600 m 2 / g, and the specific pore volume is 0.1ml / g-0.85ml / g.

[0048] According to a preferred embodiment of the present application, the main catalyst component is potassium fluoride, and the co-catalyst component is magnesium fluoride. According to another preferred embodiment of the present application, the main catalyst component is potassium fluoride, and the co-catalyst component is calcium fluoride. According to another preferred embodiment of the present application, the co-catalyst component is cesium fluoride, and the co-catalyst component is calcium fluoride. According to another preferred embodiment of the present application, the co-catalyst component is potassium fluoride, and the co-catalyst component is aluminum fluoride.

[0049] According to one embodiment of the present application, the supported catalyst of the present invention can be prepared by a solution impregnation-deposition method comprising the following steps:

[0050] Step 1: providing one or more precursor solutions (for the case where the main catalytic component and / or the co-catalytic component are easily soluble in water) or precursor suspensions (for the case where the main catalytic component and / or the co-catalytic component are slightly soluble in water or insoluble in water) comprising the main catalytic component (selected from potassium fluoride, cesium fluoride, or a combination thereof) and the co-catalytic component (selected from magnesium fluoride, calcium fluoride, aluminum fluoride, nickel fluoride, iron (III) fluoride, or any combination thereof);

[0051] Step 2: mixing the precursor solution or the precursor suspension with the carrier to form a mixed material;

[0052] Step 3: heating the mixture to dryness, and then calcining it to obtain the supported catalyst.

[0053] According to one embodiment of the present application, by carefully selecting and controlling the relative contents of the above-mentioned main catalyst component, co-catalyst component and carrier during the preparation of the supported catalyst of the present invention, the "weight ratio of the main catalyst component to the co-catalyst component" and the "weight ratio of (main catalyst component + co-catalyst component): carrier" in the prepared catalyst are within the above-mentioned ranges.

[0054] According to one embodiment of the present application, the solvent or dispersant used to prepare the precursor solution or the precursor suspension is preferably water. According to another embodiment of the present application, the weight ratio of water used to prepare the precursor solution or the precursor suspension to the carrier can be 1:10 to 10:1, for example, 1:5 to 5:1, or 1:2 to 2:1, or 1:1 to 3:1, or within the numerical range obtained by combining any two of the above end values.

[0055] According to an exemplary embodiment of the present application, the solution impregnation-deposition method is carried out in the following manner: after preparing a precursor solution or suspension according to a pre-designed catalyst ratio, the carrier is added to the precursor solution or precursor suspension according to a pre-designed ratio, and the resulting mixture is fully stirred so that the metal fluoride (i.e., the main catalyst component and the co-catalyst component) in the precursor solution / suspension is dispersed in the carrier, for example, dispersed on the surface of the carrier and within the pore structure of the carrier (for a porous carrier). Then the mixture is continued to be stirred, and while stirring, the mixture is heated, for example, at a temperature of 90-150°C, preferably at a temperature of 110-120°C, to evaporate the water in the mixture. The solid thus obtained is further dried, for example, at 100-150°C for 1-24 hours, for example, at 110-120°C for 10-12 hours. The dried solid is then calcined, for example, at a temperature of 400-600° C., preferably 480-520° C., for 1-12 hours, preferably 3-6 hours, to obtain the supported catalyst of the present invention.

[0056] According to one embodiment of the present application, the heating to dryness, heating to dryness, and calcination can be performed in an inert atmosphere, for example, heating can be performed in nitrogen.

[0057] According to a preferred embodiment of the present application, the catalyst of the present invention does not use organic solvents or auxiliary agents (such as methanol, ethanol, acetone, etc. conventionally used in the prior art), and the catalyst does not contain organic ligands (such as macromolecular crown ethers, etc.). Therefore, the catalyst of the present application will not generate waste materials and related costs (material acquisition costs and waste material disposal costs) related to the above-mentioned organic substances during the synthesis process, and the catalyst finally synthesized is also an "inorganic" catalyst, which will neither cause the catalyst to be deactivated due to the decomposition or dissociation of the organic components in the catalyst during long-term use, nor will the organic ligands, organic auxiliary agents, and organic solvents contained in the catalyst (the organic solvents used in the prior art in the process of preparing the catalyst may be adsorbed and retained in the catalyst) be precipitated to cause the formation of organic pollutants.

[0058] According to one embodiment of the present application, the solid material after the above calcination can then be loaded into a reactor for carrying out the catalytic rearrangement reaction of the present invention.

[0059] According to one embodiment of the present application, Figure 1 The catalytic rearrangement reaction shown is carried out in a reactor selected from a tubular reactor, a shell-and-tube reactor, and a microchannel reactor. Preferably, a tubular reactor is used to carry out the reaction of the present invention. Figure 2 An exemplary tubular reactor is shown.

[0060] According to a specific embodiment of the present application, the amount of catalyst loaded in the catalytic rearrangement reactor depends on the scale of the reaction and the size of the reactor. For example, for a tubular reactor with a diameter of 12 mm and a length of 150 mm, the amount of catalyst filled therein can be 5-20 grams, preferably 10 grams. When the scale of the catalytic reaction equipment is further enlarged, the amount of catalyst loaded can be increased proportionally as needed.

[0061] According to one embodiment of the present application, the catalytic rearrangement reaction of the present invention can be carried out in the following manner: after the catalyst is added to the reactor (for example, loaded into a tubular reactor), an inert gas (the inert gas is selected from nitrogen, argon, neon, argon, preferably nitrogen) is first introduced into the reactor, and the space velocity of the inert gas can be 100-2000 hours. -1 , preferably 500-1500 hours -1 , more preferably 800-1200 hours -1 The reactor is heated while continuously introducing an inert gas, the heating temperature is 100-300°C, preferably 150-220°C, more preferably 180-200°C; the heating time is 1-6 hours, preferably 2-4 hours, and the catalyst is dried by the heating treatment.

[0062] After drying is completed, the reaction raw material (perfluoro-2,3-epoxy-2-methylpentane) is mixed with an inert gas outside the reactor (for example, in a premixer-preheater) to form a raw material mixed gas. According to one embodiment of the present application, the molar ratio of the perfluoro-2,3-epoxy-2-methylpentane to the inert gas in the raw material mixed gas is 1:0.1 to 1:12, preferably 1:0.1 to 1:5, and more preferably 1:0.2 to 1:0.5.

[0063] The raw mixed gas is preheated, for example, to 200-280°C, preferably 230-250°C, and then the preheated raw mixed gas is fed into the reactor filled with the catalyst of the present invention. The mixed gas contacts the catalyst in the reactor and undergoes a catalytic rearrangement reaction to generate perfluoro-2-methyl-3-pentanone. According to one embodiment of the present application, the space velocity of the preheated raw mixed gas fed into the reactor is 100-2000 hours. -1 , preferably 500-1500 hours -1 , more preferably 800-1200 hours -1 , most preferably 1000-1100 hours. According to another embodiment of the present application, the reaction temperature of the catalytic rearrangement reaction is 160-320°C, preferably 200-300°C, and more preferably 250-280°C. According to another embodiment of the present application, in the catalytic rearrangement reaction, the pressure in the reactor is 0.1-1.0MPa, preferably 0.2-0.5MPa.

[0064] According to one embodiment of the present application, the conversion rate of the raw material (perfluoro-2,3-epoxy-2-methylpentane) of the catalytic rearrangement reaction of the present invention can be 95-100°C, preferably higher than 98%, more preferably higher than 99%, and most preferably up to 99.8%. The above conversion rate percentage is a molar percentage calculated based on the molar amount of the perfluoro-2,3-epoxy-2-methylpentane raw material introduced into the reactor.

[0065] According to another embodiment of the present application, the selectivity of the target product (perfluoro-2-methyl-3-pentanone) of the catalytic rearrangement reaction of the present invention can be 90-99.9°C, higher than 97%, preferably higher than 98%, and most preferably higher than 99%. The above selectivity percentage is a molar percentage calculated based on the molar amount of the perfluoro-2,3-epoxy-2-methylpentane raw material participating in the reaction.

[0066] The advantages of the present invention are:

[0067] 1. The catalyst of the present application can be used to efficiently synthesize perfluoro-2-methyl-3-pentanone, and can achieve significantly improved raw material conversion rate and target product selectivity compared with the prior art. Specifically, the raw material conversion rate of the present invention is higher than 98%, preferably higher than 99%, and most preferably up to 99.8%; the target product selectivity is higher than 97%, preferably higher than 98%, and most preferably higher than 99%;

[0068] 2. The process reaction conditions of the present application are controllable and easy for industrial production;

[0069] 3. The catalyst of the present invention is easy to prepare and can maintain catalytic activity for a long time, and the catalyst life exceeds 1000 hours;

[0070] 4. The catalyst of the present invention is an inorganic catalyst that does not contain any organic ligand or organic solvent, nor does it contain highly toxic and highly polluting components such as chromium. It is green and environmentally friendly overall, and produces less three wastes.

[0071] In addition, as mentioned above, the starting material used in the present application is perfluoro-2,3-epoxy-2-methylpentane, and the synthesized target product is perfluoro-2-methyl-3-pentanone. It is known in the art that in the catalytic reforming reaction of fluorinated epoxides, especially fluorinated epoxides with a carbon number greater than 3, the types of raw materials and target products have a very large impact on the selection of process parameters and catalysts. The technical solution suitable for the design of a specific raw material and / or target product is completely of no reference value for the design of another specific raw material and / or target product.

[0072] The method of the present application is specifically described in the following examples, the purpose of which is to provide a better understanding of the content of the present application. It should be understood that these examples are merely illustrative and not restrictive.

[0073] Example

[0074] The water used in the following examples is deionized water. The perfluoro-2,3-epoxy-2-methylpentane raw material used is provided by Changshu San Ai Fu Zhong Hao Chemical New Materials Co., Ltd. with a purity of 99.5%. The other raw materials used are commercially purchased products and are used directly without further purification and treatment. The activated carbon carrier used below is wood activated carbon, with a specific surface area of ​​850m 2 / g, and the specific pore volume is 0.55mL / g.

[0075] In the following examples, a gas chromatograph of model GC7890 produced by Agilent was used.

[0076] Example 1

[0077] In this Example 1, first, a catalyst was synthesized through the following steps.

[0078] 50 grams of potassium fluoride was dissolved in 1000 grams of deionized water, and then 1 gram of magnesium fluoride was added to the aqueous solution, and a small amount of nitric acid was added to promote dissolution, and the mixture was stirred thoroughly to form a uniform mixture. Then 510 grams of activated carbon was added to the mixture, and the obtained mixture containing activated carbon was continuously stirred and heated at a temperature of 110°C while stirring until the water in the mixture was evaporated. The obtained solid was dried at a temperature of 110°C for 10 hours, and then transferred to a muffle furnace and calcined at 520°C for 3 hours. That is, a potassium fluoride-magnesium fluoride / activated carbon catalyst was obtained, which is hereinafter referred to as catalyst 1.

[0079] The composition of Catalyst 1 is listed in Table 1 below.

[0080] Next, a catalytic rearrangement reaction was carried out using Catalyst 1. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, such as Figure 2 As shown, the reactor is provided with a heating jacket. 10 g of catalyst 1 is filled in the tubular reactor. -1 Nitrogen was introduced into the reactor at a space velocity of 1.5 ℃, and the reactor was heated to 200°C for 2 hours to dry the catalyst. After drying, perfluoro-2,3-epoxy-2-methylpentane and nitrogen were mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours. -1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0081] The products of the reaction are 19 - Characterization by NMR (e.g. Figure 3 As shown), it is determined that the obtained product is the target product perfluoro-2-methyl-3-pentanone; the composition is analyzed using gas chromatography, and the gas chromatogram is as shown Figure 4 The results are summarized in Table 2.

[0082] Example 2

[0083] In this Example 2, a catalyst was first synthesized through the following steps.

[0084] 50 grams of potassium fluoride was dissolved in 1000 grams of deionized water, and then 1.5 grams of aluminum fluoride was added to the aqueous solution, a little nitric acid was added to promote dissolution, and the mixture was stirred thoroughly to form a uniform mixture. Then 429 grams of activated carbon was added to the mixture, and the obtained mixture containing activated carbon was continuously stirred and heated at a temperature of 110°C while stirring until the water in the mixture was evaporated. The obtained solid was dried at a temperature of 110°C for 10 hours, and then transferred to a muffle furnace and calcined at 520°C for 3 hours. That is, a potassium fluoride-aluminum fluoride / activated carbon catalyst was obtained, which will be referred to as catalyst 2 below.

[0085] The composition of Catalyst 2 is listed in Table 1 below.

[0086] Next, a catalytic rearrangement reaction was carried out using Catalyst 2. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, and 10 g of Catalyst 2 was filled in the tubular reactor. -1 Nitrogen was introduced into the reactor at a space velocity of 1.5 ℃, and the reactor was heated to 200°C for 2 hours to dry the catalyst. After drying, perfluoro-2,3-epoxy-2-methylpentane and nitrogen were mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours. -1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0087] The products of the reaction are 19 -NMR characterization was performed to determine that the obtained product was the target product, perfluoro-2-methyl-3-pentanone; its composition was analyzed using gas chromatography, and the results are summarized in Table 2.

[0088] Example 3

[0089] In this Example 3, first, a catalyst was synthesized through the following steps.

[0090] 50 grams of potassium fluoride was dissolved in 1000 grams of deionized water, and then 2.5 grams of calcium fluoride was added to the aqueous solution, a small amount of nitric acid was added to promote dissolution, and the mixture was stirred thoroughly to form a uniform mixture. Then 375 grams of activated carbon was added to the mixture, and the obtained mixture containing activated carbon was continuously stirred and heated at a temperature of 110°C while stirring until the water in the mixture was evaporated. The obtained solid was dried at a temperature of 110°C for 10 hours, and then transferred to a muffle furnace and calcined at 520°C for 3 hours. That is, a potassium fluoride-calcium fluoride / activated carbon catalyst was obtained, which is hereinafter referred to as catalyst 3.

[0091] The composition of Catalyst 3 is listed in Table 1 below.

[0092] Next, a catalytic rearrangement reaction was carried out using Catalyst 3. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, and 10 g of Catalyst 3 was filled in the tubular reactor. -1 Nitrogen was introduced into the reactor at a space velocity of 1.5 ℃, and the reactor was heated to 200°C for 2 hours to dry the catalyst. After drying, perfluoro-2,3-epoxy-2-methylpentane and nitrogen were mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours. -1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0093] The products of the reaction are 19 -NMR characterization was performed to determine that the obtained product was the target product, perfluoro-2-methyl-3-pentanone; its composition was analyzed using gas chromatography, and the results are summarized in Table 2.

[0094] Example 4

[0095] In this Example 4, first, a catalyst was synthesized through the following steps.

[0096] 50 grams of cesium fluoride was dissolved in 1000 grams of deionized water, and then 4 grams of calcium fluoride was added to the aqueous solution, a little nitric acid was added to promote dissolution, and the mixture was stirred thoroughly to form a uniform mixture. Then 216 grams of activated carbon was added to the mixture, and the obtained mixture containing activated carbon was continuously stirred and heated at a temperature of 110°C while stirring until the water in the mixture was evaporated. The obtained solid was dried at a temperature of 110°C for 10 hours, and then transferred to a muffle furnace and calcined at 520°C for 3 hours. That is, a cesium fluoride-calcium fluoride / activated carbon catalyst was obtained, which will be referred to as catalyst 4 below.

[0097] The composition of Catalyst 4 is listed in Table 1 below.

[0098] Next, a catalytic rearrangement reaction was carried out using catalyst 4. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, and 10 g of catalyst 3 was filled in the tubular reactor. -1 Nitrogen was introduced into the reactor at a space velocity of 1.5 ℃, and the reactor was heated to 200°C for 2 hours to dry the catalyst. After drying, perfluoro-2,3-epoxy-2-methylpentane and nitrogen were mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours.-1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0099] The products of the reaction are 19 -NMR characterization was performed to determine that the obtained product was the target product, perfluoro-2-methyl-3-pentanone; its composition was analyzed using gas chromatography, and the results are summarized in Table 2.

[0100] Comparative Example 1

[0101] In this Comparative Example 1, first, a catalyst was synthesized by the following steps.

[0102] 50 g of chromium fluoride was added to 1000 g of deionized water, a little nitric acid was added to promote dissolution, and the mixture was stirred thoroughly to form a uniform mixture. Then 250 g of activated carbon was added to the mixture, and the obtained mixture containing activated carbon was continuously stirred and heated at 110°C while stirring until the water in the mixture was evaporated. The obtained solid was dried at 110°C for 10 hours, then transferred to a muffle furnace and calcined at 520°C for 3 hours. The chromium fluoride / activated carbon catalyst was obtained, which is hereinafter referred to as comparative catalyst 1.

[0103] The composition of Comparative Catalyst 1 is listed in Table 1 below.

[0104] Next, a catalytic rearrangement reaction was carried out using Comparative Catalyst 1. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, and 10 g of Comparative Catalyst 1 was filled in the tubular reactor. -1 Nitrogen was introduced into the reactor at a space velocity of 1.5 ℃, and the reactor was heated to 200°C for 2 hours to dry the catalyst. After drying, perfluoro-2,3-epoxy-2-methylpentane and nitrogen were mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours. -1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0105] The composition of the products produced by the reaction was analyzed by gas chromatography, and the results are summarized in Table 2.

[0106] Comparative Example 2

[0107] In this Comparative Example 2, first, a catalyst was synthesized by the following steps.

[0108] Weigh 30g of chromium nitrate and dissolve it in 100ml of water, and weigh 28.0g of ammonium oxalate and add it directly to the above solution. Heat the above mixed solution to 60°C under stirring to promote the complete dissolution of ammonium oxalate. Then cool the solution to 20°C and quickly pour the solution into 750mL of a mixed solvent consisting of 375mL of methanol and 375mL of acetone. The resulting mixture is allowed to stand for aging for 60 minutes at room temperature, then filter out the precipitate, rinse it three times with ethanol, and dry it at 60°C for 24 hours. The obtained solid sample is calcined at 350°C in an air atmosphere in a muffle furnace for 2 hours. The calcined solid is tableted at 30MPa using a tablet press, and then crushed to 14-18 mesh (1.0-1.4mm), and the catalyst obtained is referred to as comparative catalyst 2 below.

[0109] The composition of Comparative Catalyst 2 is listed in Table 1 below.

[0110] Next, a catalytic rearrangement reaction was carried out using comparative catalyst 2. Specifically, a nickel tubular reactor with a diameter of 12 mm and a length of 150 mm was used, and 10 g of comparative catalyst 2 was filled in the tubular reactor. The reaction was first heated to 250°C, and CHClF2 was introduced into it at a flow rate of 50 mL / min to fluorinate comparative catalyst 2 for 2 hours. Perfluoro-2,3-epoxy-2-methylpentane and nitrogen were then mixed in a premixer-preheater at a molar ratio of 10:2 to form a mixed gas, which was preheated to 250°C and then heated for 1000 hours. -1 The reaction was carried out at a temperature of 280°C and a pressure of 0.2 MPa in the reactor.

[0111] The composition of the products produced by the reaction was analyzed by gas chromatography, and the results are summarized in Table 2.

[0112] Table 1: Composition of the catalysts synthesized in Examples 1-4 and Comparative Examples 1-2

[0113]

[0114] The reaction results of the catalytic rearrangement reaction using the catalysts prepared in Examples 1-4 and Comparative Examples 1-2 are shown in Table 2 below. It can be seen that Examples 1-4 of the present invention achieve excellent feedstock conversion rates and target product selectivity. Among them, Example 1 achieves a feedstock conversion rate and target product selectivity far superior to those of other Examples.

[0115] Table 2: Catalytic results achieved using the catalysts of Examples 1-4 and Comparative Examples 1-2

[0116] Catalytic reaction Catalyst used Conversion rate / % Selectivity / % Example 1 Catalyst 1 99.8 99.4 Example 2 Catalyst 1 99.3 98.5 Example 3 Catalyst 2 99.1 97.9 Example 4 Catalyst 3 98.2 99.2 Comparative Example 1 Comparative Catalyst 1 65.6 85.5 Comparative Example 2 Comparative Catalyst 2 47.9 77.6

[0117] Example 5 Characterization of Catalyst Life

[0118] In this example, the catalyst synthesized in Example 1 (catalyst 1) was used to carry out the catalytic reaction according to the steps described in Example 1, and the catalytic reaction was continued for 1200 hours. The curve graph of the measured conversion rate and selectivity over time is shown in Figure 5 .

[0119] For catalyst 1, after 1200 hours of catalytic reaction, the conversion rate was 99.2% and the selectivity of the target product was 99.0%, which still maintained at an excellent level.

Claims

1. A supported catalyst, comprising a main catalytic component and a co-catalytic component supported on a carrier, The main catalytic component is selected from: potassium fluoride, cesium fluoride, or a combination thereof; The co-catalyst component is selected from one or more of the following: magnesium fluoride, calcium fluoride, aluminum fluoride, nickel fluoride, iron (III) fluoride; The carrier is selected from one or more of the following: activated carbon, porous metal fluoride, molecular sieve, zeolite, amorphous alumina, silicon oxide, silicon-aluminum composite oxide and porous ceramics.

2. The supported catalyst according to claim 1, characterized in that The ratio of the sum of the weight of the main catalytic component and the auxiliary catalytic component to the weight of the carrier is: (main catalytic component + auxiliary catalytic component): carrier = 0.01:1 to 0.6:1; The weight ratio of the main catalytic component to the auxiliary catalytic component is 1:0.01 to 1:0.

5.

3. The supported catalyst according to claim 1, wherein The weight ratio of the main catalytic component to the co-catalytic component is 1:0.02 to 1:0.08; The ratio of the sum of the weight of the main catalytic component and the auxiliary catalytic component to the weight of the carrier is: (main catalytic component+auxiliary catalytic component):carrier=0.1:1 to 0.5:

1.

4. The supported catalyst according to claim 1, characterized in that The carrier is a porous carrier with a specific surface area of ​​50-1600m 2 / g, and the specific pore volume is 0.1ml / g-0.85ml / g.

5. A method for synthesizing a supported catalyst, wherein the supported catalyst is the supported catalyst according to any one of claims 1 to 4, the method comprising: Step 1: providing one or more precursor solutions or precursor suspensions containing the main catalytic component and the co-catalytic component; Step 2: mixing the precursor solution or the precursor suspension with the carrier to form a mixed material; Step 3: heating the mixture to dryness, and then calcining it to obtain the supported catalyst.

6. A method for preparing perfluoro-2-methyl-3-pentanone from perfluoro-2,3-epoxy-2-methylpentane, the method comprising subjecting the perfluoro-2,3-epoxy-2-methylpentane to a catalytic rearrangement reaction to generate perfluoro-2-methyl-3-pentanone in the presence of a supported catalyst according to any one of claims 1 to 4.

7. The method according to claim 6, characterized in that The method comprises introducing the perfluoro-2,3-epoxy-2-methylpentane and an inert carrier gas into a reactor containing the supported catalyst, so that the perfluoro-2,3-epoxy-2-methylpentane undergoes a catalytic rearrangement reaction and generates perfluoro-2-methyl-3-pentanone; The inert carrier gas is selected from one or more of the following: nitrogen, helium, neon, and argon; The molar ratio of the perfluoro-2,3-epoxy-2-methylpentane to the inert carrier gas is 1:0.1 to 1:12; and The total space velocity of the perfluoro-2,3-epoxy-2-methylpentane and the inert carrier gas is 200-3,000 hours -1 .

8. The method according to claim 7, characterized in that The inert carrier is nitrogen; the molar ratio of the perfluoro-2,3-epoxy-2-methylpentane to the inert carrier gas is 1:0.1 to 1:

3.

9. The method according to claim 6, characterized in that The reaction temperature of the catalytic rearrangement reaction is 160-320° C.; the reaction pressure of the catalytic rearrangement reaction is 0.1-1.0 MPa; The catalytic rearrangement reaction is carried out in a reactor selected from the following: a tubular reactor, a shell-and-tube reactor, and a microchannel reactor.

10. A perfluoro-2-methyl-3-pentanone product, wherein the product is prepared by the method according to any one of claims 6 to 9.

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