Supported catalyst, preparation method thereof and diisobutyl ketone prepared by catalysis thereof

Abstract

The present application relates to the technical field of organic catalysts, and specifically to a supported catalyst, a preparation method thereof, and diisobutyl ketone prepared by catalysis thereof. The supported catalyst of the present application includes a carrier and an active molecule supported on the carrier; the carrier is alumina modified with metal Ln; the Ln includes metal La; and the active molecule is a complex of metal ions and citric acid, which includes metal Mn and metal La. The present application also relates to a method for preparing a supported catalyst, the steps of preparing the carrier, and the steps of immersing the carrier in a solution containing the active molecule, drying, and repeatedly calcining. The present application also relates to a method for preparing diisobutyl ketone, which has a high yield and the diisobutyl ketone obtained has strong selectivity and high purity.

Description

Technical Field

[0001] The present application relates to the technical field of organic catalysts, and in particular to a supported catalyst, a preparation method thereof, and diisobutyl ketone prepared by catalysis thereof. Background Art

[0002] Diisobutyl ketone (DIBK), also known as 2,6-dimethyl-4-heptanone (2,6-dimethyl-4-heptanone, 2,6-dimethyl-heptan-4-one), isopropylacetone, and is abbreviated as DIBK. It is a colorless, oily liquid with a minty odor at room temperature. Naturally occurring in kangniang wine and grape wine, it is relatively stable, slightly soluble in water, and miscible with most organic solvents. Diisobutyl ketone is primarily used as an organic solvent and can also be used in organic synthesis. It can dissolve cellulose acetate, nitrocellulose, polystyrene, vinyl resins, waxes, varnishes, natural resins, and raw rubber. Due to its high boiling point and slow evaporation rate, it is used as a solvent for nitro-lacquer spray paints, vinyl resin coatings, and other synthetic resin coatings. Diisobutyl ketone is also used as a raw material for the synthesis of diisobutyl carbinol, the hydroanthraquinone solvent used in the anthraquinone process for producing hydrogen peroxide.

[0003] At present, there is no direct production process in the industry that uses diisobutyl ketone as the main product. Countries around the world generally adopt the method of co-producing methyl isobutyl ketone and diisobutyl ketone to produce diisobutyl ketone. That is, when producing methyl isobutyl ketone, diisobutyl ketone is produced as a by-product together with other by-products, and then further distilled to obtain diisobutyl ketone product. This results in a low yield of diisobutyl ketone, which cannot meet market demand. In addition, when obtaining diisobutyl ketone, its isomer 4,6-dimethyl-2-heptanone is also obtained. The boiling points of the two differ by only 2.2°C (diisobutyl ketone boiling point 168.1°C, 4,6-dimethyl-2-heptanone 170.3°C), making it difficult to separate and purify.

[0004] CN111936452A discloses a catalytic method for upgrading a crude and / or refined fusel oil mixture into higher-value renewable chemicals using a fixed-bed continuous reaction via a mixed metal oxide or zeolite catalyst. The method can chemically convert isoamyl alcohol in fusel oil into diisobutyl ketone, but the yield (approximately 40%) still needs to be improved.

[0005] Therefore, it is of great significance to provide a method for preparing diisobutyl ketone with high yield. Summary of the Invention

[0006] Based on this, the purpose of this application includes providing a supported catalyst that can be used to catalyze the preparation of diisobutyl ketone, and the prepared diisobutyl ketone has high yield, high purity and high selectivity.

[0007] The first aspect of the present application is a supported catalyst comprising a carrier and an active molecule supported on the carrier;

[0008] The carrier is alumina modified with metal Ln;

[0009] Ln includes metallic La;

[0010] The active molecule is a complex of metal ions and citric acid, and the complex includes metal Mn and metal La.

[0011] In some embodiments of the present application, in the supported catalyst, the mass ratio of the active molecule to the carrier is (0.2-0.3):1; and / or,

[0012] In the active molecule, the molar ratio of La to Mn is (1-1.2):1; and / or,

[0013] In the carrier, the metal Ln has a mass percentage of 1% to 10% as calculated as its oxide.

[0014] In some embodiments of the present application, in the supported catalyst, the carrier is in powder form, and the particle size of the powder is 100 nm to 200 nm.

[0015] The second aspect of the present application provides a method for preparing a supported catalyst, comprising the following steps: impregnating alumina powder in a Ln salt solution for 3 to 5 hours, drying, and then calcining at 800° C. to 900° C. for 5 to 7 hours to obtain a carrier;

[0016] In the presence of citric acid in a salt solution, the metal ions are complexed to obtain a solution containing active molecules;

[0017] The carrier is immersed in a solution containing active molecules for 1 hour to 3 hours, dried, calcined at 300° C. to 400° C. for 1 hour to 3 hours, and then calcined at 800° C. to 900° C. for 1 hour to 3 hours to obtain the supported catalyst;

[0018] Wherein, the Ln and the active molecule are as defined in any one of claims 1 to 3.

[0019] In some embodiments of the present application, in the preparation method, the mass ratio of the Ln salt solution to the alumina powder is (0.3-0.6):1;

[0020] The molar concentration of element Ln in the Ln salt solution is 0.1 mol / L to 0.5 mol / L;

[0021] The molar ratio of the citric acid to the metal ion is (1-1.5):1.

[0022] In some embodiments of the present application, in the preparation method, the particle size of the aluminum oxide powder is 80 nm to 200 nm; and / or,

[0023] The mass ratio of the solution containing the active molecule to the carrier is (0.2-0.3):1.

[0024] The third aspect of the present application provides a method for preparing diisobutyl ketone, comprising the following steps: vaporizing 3-methylbutanol, passing the vaporized 3-methylbutanol into a gas-solid phase reactor filled with a catalyst, and producing the diisobutyl ketone through a gas-solid phase reaction;

[0025] The catalyst is the supported catalyst described in the first aspect of the present application.

[0026] In some embodiments of the present application, in the preparation method, the vaporization temperature of the 3-methylbutanol is 135° C. to 150° C.; and / or,

[0027] The reaction temperature of the gas-solid phase reaction is 360° C. to 430° C., and the reaction pressure is 0.1 to 0.5 MPa; and / or,

[0028] The mass space velocity based on the catalyst is 0.01~1.0h -1 .

[0029] In some embodiments of the present application, the preparation method further includes the following purification step: condensing the reactants obtained after the gas-solid phase reaction, obtaining a liquid phase through gas-liquid separation, performing oil-water separation on the liquid phase to obtain an oil phase, and purifying the oil phase through distillation to obtain diisobutyl ketone.

[0030] The fourth aspect of the present application provides diisobutyl ketone prepared by the preparation method provided in the third aspect of the present application, wherein the selectivity of the diisobutyl ketone is 65-95%.

[0031] Currently, the industrial preparation methods for diisobutyl ketone include the acetone method and the isopropanol method. Acetone and isopropanol are used as raw materials, respectively, and diisobutyl ketone and methyl isobutyl ketone are produced through condensation, dehydration, and selective hydrogenation. The yield of diisobutyl ketone as a by-product is relatively low. The isopropanol method is also prone to producing the difficult-to-separate by-product 4,6-dimethyl-2-heptanone. The preparation method of the present application has a high reaction yield, the diisobutyl ketone produced is highly selective, 4,6-dimethyl-2-heptanone is not produced, and the product is easy to purify. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0033] Figure 1 This is a flow chart of the preparation process of an embodiment of the present application, wherein 1A is the process from feeding reaction to treatment in a dealdehyde tower, and 1B is the process from discharging from the dealdehyde tower to refining to obtain the product. DETAILED DESCRIPTION

[0034] The present application will be further described below in conjunction with the embodiments, examples and accompanying drawings. It should be understood that these examples are intended only to illustrate the present application and are not intended to limit the scope of the present application. In addition, it should be understood that after reading the content taught in this application, those skilled in the art may make various changes or modifications to the present application, and these equivalent forms also fall within the scope of protection of the claims appended hereto.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0036] the term

[0037] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0038] The terms "and / or", "or / and", and "and / or" used herein include any one of two or more related listed items, and also include any and all combinations of the related listed items, wherein the any and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND" and technical solutions connected by "logical OR". For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution of all being connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solution of all being connected by "logical AND").

[0039] Herein, "preferred", "better", "better", etc. are only used to describe implementation methods or examples with better effects. It should be understood that they do not constitute limitations on the scope of protection of this application.

[0040] In this application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0041] In this application, the terms "first," "second," "third," "fourth," etc. in "the first aspect," "the second aspect," "the third aspect," "the fourth aspect," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0042] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0043] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the above numerical interval is considered continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0044] Unless otherwise specified, the temperature parameters in this application allow for both constant temperature treatment and temperature fluctuations within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the accuracy range of instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0045] In this application, unless otherwise specified, the size, particle size, and diameter generally refer to the average value.

[0046] The first aspect of the present application

[0047] In a first aspect of the present application, a supported catalyst is provided, which can be used to catalyze the preparation of diisobutyl ketone, and the prepared diisobutyl ketone has high yield, high purity and high selectivity.

[0048] In some embodiments, the supported catalyst includes a support and an active molecule supported on the support;

[0049] The support is alumina modified with metallic Ln;

[0050] Ln includes metallic La;

[0051] The active molecule is a complex of metal ions and citric acid, and further, the complex includes metal Mn and metal La.

[0052] In some embodiments of the present application, the mass percentage of the active molecule and the carrier is (0.2-0.3):1.

[0053] In some embodiments of the present application, in the active molecule, the molar ratio of the element La to the element Mn is (1-1.2):1.

[0054] In some embodiments of the present application, based on the mass percentage content of the carrier being 100%, the mass percentage content of the metal Ln calculated as oxide is 1% to 10%.

[0055] In some embodiments of the present application, the carrier is in powder form, and the particle size of the powder is 100 nm to 200 nm.

[0056] The second aspect of this application

[0057] The second aspect of the present application provides a method for preparing a supported catalyst, which can be used to prepare the supported catalyst provided in the first aspect of the present application.

[0058] In some embodiments of the present application, the method for preparing a supported catalyst comprises the following steps:

[0059] S100: impregnating alumina powder in a Ln salt solution, drying, and calcining to obtain a carrier;

[0060] S200: impregnating the support in a solution containing active molecules, drying, and calcining to obtain a supported catalyst;

[0061] Preferably, Ln and the active molecule are defined according to the first aspect of the present application.

[0062] S100: Prepare the carrier

[0063] In some embodiments of the present application, alumina powder is impregnated in a Ln salt solution, dried, and calcined to prepare a support.

[0064] In some embodiments of the present application, the particle size of the aluminum oxide powder is 100 nm to 200 nm, and can further be 120 nm to 180 nm.

[0065] In some embodiments of the present application, the mass ratio of the Ln salt solution to the aluminum oxide powder is (0.3-0.6):1, and may further be (0.4-0.5):1.

[0066] In some embodiments of the present application, the molar concentration of element Ln in the Ln salt solution is 0.1 mol / L to 0.5 mol / L, and can further be 0.2 mol / L to 0.4 mol / L.

[0067] In some embodiments of the present application, the aluminum oxide powder is immersed in the Ln salt solution for 3 hours to 5 hours, and further for 4 hours to 5 hours.

[0068] In some embodiments of the present application, the aluminum oxide powder is impregnated in the Ln salt solution and then dried at room temperature.

[0069] In some embodiments of the present application, alumina powder is impregnated in a Ln salt solution, dried, and then calcined at 800° C. to 900° C., and further, the calcination temperature can be 820° C. to 880° C. In some embodiments, the calcination time is 5 to 7 hours, and further, can be 6 to 7 hours.

[0070] In some embodiments of the present application, alumina is impregnated in a lanthanum nitrate (La) solution, wherein the weight of metallic La accounts for 5% of the total weight. After impregnation for 4 hours, it is dried at room temperature and then calcined at 850°C for 5 to 7 hours to obtain a powdered carrier.

[0071] S200: Preparation of supported catalysts

[0072] In some embodiments of the present application, metal ions are complexed in a salt solution in the presence of citric acid to obtain a solution containing active molecules.

[0073] In some embodiments of the present application, the molar ratio of citric acid to metal ions is (1-1.5):1.

[0074] In some embodiments of the present application, the molar concentration of La in the solution containing the active molecule is 0.1 to 0.5 mol / L, and the molar concentration of Mn is 0.1 to 0.5 mol / L. Furthermore, the molar ratio of La to Mn is (1 to 1.2):1, preferably 1:1.

[0075] In some embodiments of the present application, the solution containing the active molecule is an aqueous solution of nitrate.

[0076] In some embodiments of the present application, the carrier is impregnated in a solution containing active molecules, dried, and calcined to prepare a supported catalyst.

[0077] In some embodiments of the present application, the mass ratio of the solution containing the active molecule to the carrier is (0.3-0.6):1.

[0078] In some embodiments of the present application, the carrier is immersed in a solution containing active molecules for 1 to 3 hours, dried, calcined at 300 to 400°C for 1 to 3 hours, and then calcined at 800 to 900°C for 1 to 3 hours to prepare the supported catalyst.

[0079] In some embodiments of the present application, a nitrate solution with a molar ratio of La:Mn (manganese) = 1:1 is dissolved to obtain an aqueous solution. The metal ions are then complexed by adding 1.2 mol of citric acid per mol of metal to the solution. A powdered La-Al2O3 support is suspended in a solution containing a citric acid perovskite precursor. The mixture is evaporated and extruded into strips. The strips are then calcined at 350°C for 2 hours and finally at 850°C for 2 hours.

[0080] The third aspect of this application

[0081] The third aspect of the present application provides a method for preparing diisobutyl ketone. The preparation method of the present application has a high reaction yield, the prepared diisobutyl ketone is highly selective, does not produce 4,6-dimethyl-2-heptanone, and the product is easy to purify.

[0082] In some embodiments of the present application, the preparation method of diisobutyl ketone comprises the following steps: vaporizing 3-methylbutanol and passing it into a gas-solid phase reactor filled with a catalyst to perform a dehydrogenation coupling reaction; further,

[0083] The catalyst is the supported catalyst provided in the first aspect of the present application.

[0084] In some embodiments of the present application, the vaporization temperature for vaporizing 3-methylbutanol is 135°C to 150°C.

[0085] In some embodiments of the present application, the reaction temperature of the gas-solid phase reaction is 360° C. to 430° C., and the reaction pressure is 0.1 MPa to 0.5 MPa.

[0086] In some embodiments of the present application, the mass space velocity based on the catalyst is 0.01h -1 ~1.0h -1 .

[0087] In some embodiments of the present application, the preparation method further includes the following purification step: condensing the reactants obtained after the gas-solid phase reaction, obtaining a liquid phase through gas-liquid separation, performing oil-water separation on the liquid phase to obtain an oil phase, and purifying the oil phase through a distillation system to obtain diisobutyl ketone.

[0088] In some embodiments of the present application, the distillation system includes an aldehyde removal tower, a lightness removal tower, and a refining tower.

[0089] In some embodiments, the parameters of the distillation system purification are as follows:

[0090]

[0091]

[0092] The fourth aspect of this application

[0093] The fourth aspect of the present application provides diisobutyl ketone prepared by the preparation method provided in the third aspect of the present application, and further, the selectivity of the diisobutyl ketone is 65-95%.

[0094] The following are some specific examples.

[0095] For experimental parameters not specified in the following specific examples, reference is made to the guidance given in this application document, and reference may also be made to experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.

[0096] The raw materials and reagents involved in the following specific examples can be obtained commercially, or can be prepared by those skilled in the art according to known methods.

[0097] Example 1

[0098] 1. After 3-methylbutanol (isoamyl alcohol) is vaporized at 140°C, it is reacted in a fixed bed at a temperature of 360°C and a mass space velocity of 0.01h -1 , reaction pressure 0.15MPa; after gas-liquid separation and oil-water separation, the oil phase is distilled and separated, wherein the operating parameters of each distillation tower are as follows:

[0099]

[0100] Finally, the diisobutyl ketone product with a purity of 99.2% was obtained, of which the conversion rate of 3-methylbutanol was 71% and the selectivity of diisobutyl ketone product was 93.1%.

[0101] 2. After 3-methylbutanol (isoamyl alcohol) is vaporized at 136°C, it is reacted in a fixed bed at a temperature of 400°C and a mass space velocity of 0.06 h -1 , reaction pressure 0.20MPa; after gas-liquid separation and oil-water separation, the oil phase is distilled and separated, wherein the operating parameters of each distillation tower are as follows:

[0102]

[0103]

[0104] Finally, a diisobutyl ketone product with a purity of 99.4% was obtained, wherein the conversion rate of 3-methylbutanol was 95.0%, and the selectivity of the diisobutyl ketone product was 82.4%.

[0105] 3. After 3-methylbutanol (isoamyl alcohol) is vaporized at 150°C, it is reacted in a fixed bed at a temperature of 400°C and a mass space velocity of 0.06h -1 , reaction pressure 0.20MPa; after gas-liquid separation and oil-water separation, the oil phase is distilled and separated, wherein the operating parameters of each distillation tower are as follows:

[0106]

[0107] Finally, a diisobutyl ketone product with a purity of 99.4% is obtained, wherein the conversion rate of 3-methylbutanol is 98.7%, and the selectivity of the diisobutyl ketone product is 88.6%.

[0108] 4. After 3-methylbutanol (isoamyl alcohol) is vaporized at 140°C, it is reacted in a fixed bed at a temperature of 425°C and a mass space velocity of 0.10 h -1 , reaction pressure 0.50MPa; after gas-liquid separation and oil-water separation, the oil phase is distilled and separated, wherein the operating parameters of each distillation tower are as follows:

[0109]

[0110] Finally, a diisobutyl ketone product with a purity of 99.3% is obtained, wherein the conversion rate of 3-methylbutanol is 85%, and the selectivity of the diisobutyl ketone product is 94.0%.

[0111] 5. After 3-methylbutanol (isoamyl alcohol) is vaporized at 140°C, it is reacted in a fixed bed at a temperature of 410°C and a mass space velocity of 0.01h -1 , reaction pressure 0.25MPa; after gas-liquid separation and oil-water separation, the oil phase is distilled and separated, wherein the operating parameters of each distillation tower are as follows:

[0112]

[0113]

[0114] Finally, a diisobutyl ketone product with a purity of 99.2% is obtained, wherein the conversion rate of 3-methylbutanol is 100%, and the selectivity of the diisobutyl ketone product is 73.5%.

[0115] In the preparation of organic compounds, the key factors affecting the yield are selectivity and conversion rate. In actual production, the reaction process conditions determine the conversion rate and selectivity. For example, increasing the vaporization temperature can increase the conversion rate and selectivity, and increasing the reaction temperature can increase the conversion rate of the reaction, but excessive increase will lead to reduced selectivity. The distillation process also has a certain auxiliary effect on improving the yield. Therefore, the key factors in the preparation process need to be matched with each other to obtain high selectivity and conversion rate.

[0116] The preparation method of the present application fully considers the mutual influence between parameters such as catalyst, reaction temperature, pressure, feed space velocity, etc., and greatly improves the selectivity and conversion rate by limiting the above parameters to an appropriate range.

[0117] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited in their entirety and for all purposes. When cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be adaptively amended according to the description in this application.

[0118] The various technical features of the above-mentioned implementation modes and examples can be combined in any appropriate manner. In order to make the description concise, not all possible combinations of the various technical features in the above-mentioned implementation modes and examples are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of the description in this specification.

[0119] The embodiments described above only express several implementation methods of the present application, but they should not be understood as limiting the scope of the patent application. It should be pointed out that, for those of ordinary skill in the art, without departing from the concept of the present application, several variations and improvements can be made, which all fall within the scope of protection of the present application. In addition, it should be understood that after reading the above-mentioned teaching content of the present application, those skilled in the art can make various changes or modifications to the present application, and the equivalent forms obtained also fall within the scope of protection of the present application. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent in this application shall be based on the attached claims, and the description and drawings may be used to explain the contents of the claims.

Claims

1. A method for preparing diisobutyl ketone, characterized in that: The method comprises the following steps: vaporizing 3-methylbutanol and introducing the vaporized 3-methylbutanol into a gas-solid phase reactor filled with a catalyst to obtain the diisobutyl ketone through a gas-solid phase reaction; The catalyst is a supported catalyst; The preparation method of the supported catalyst comprises the following steps: The alumina powder is immersed in a Ln salt solution for 3 hours to 5 hours, dried, and then calcined at 800° C. to 900° C. for 5 hours to 7 hours to prepare a carrier; the Ln includes metallic La; In a salt solution containing citric acid, metal ions are complexed to obtain a solution containing active molecules; the active molecules are complexes of metal ions and citric acid, and the metal ions are metal Mn and metal La; The carrier is immersed in the solution containing active molecules for 1 to 3 hours, dried, calcined at 300 to 400° C. for 1 to 3 hours, and then calcined at 800 to 900° C. for 1 to 3 hours to obtain the supported catalyst.

2. The preparation method according to claim 1, characterized in that The mass ratio of the active molecule to the carrier is (0.2-0.3):1; and / or, In the active molecule, the molar ratio of La to Mn is (1-1.2):1; and / or, In the carrier, the Ln content, calculated as its oxide, is 1% to 10% by mass.

3. The preparation method according to claim 2, characterized in that The carrier is in powder form, and the particle size of the powder is 100nm to 200nm.

4. The preparation method according to claim 1, characterized in that The vaporization temperature of the 3-methylbutanol is 135° C. to 150° C.; and / or, The reaction temperature of the gas-solid phase reaction is 360° C. to 430° C., and the reaction pressure is 0.1 to 0.5 MPa; and / or, The mass space velocity based on the catalyst is 0.01~1.0h -1 .

5. The preparation method according to claim 1, characterized in that The method further includes the following purification step: condensing the reactants obtained after the gas-solid phase reaction, performing gas-liquid separation to obtain a liquid phase, performing oil-water separation on the liquid phase to obtain an oil phase, and purifying the oil phase by distillation to obtain diisobutyl ketone.

6. The preparation method according to claim 1, characterized in that The mass ratio of the Ln salt solution to the alumina powder is (0.3-0.6):1; The molar concentration of element Ln in the Ln salt solution is 0.1 mol / L to 0.5 mol / L; The molar ratio of the citric acid to the metal ion is (1-1.5):

1.

7. The preparation method according to claim 1, characterized in that The particle size of the aluminum oxide powder is 80 nm to 200 nm.

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