A modified inorganic oxide carrier and its preparation method and application

Abstract

The present invention belongs to the field of catalysts, specifically to a modified inorganic oxide support and its preparation method. In this invention, a variable-valence metal is loaded onto the inorganic oxide using ionizing radiation. This allows for a strong interaction between the variable-valence metal and the inorganic oxide support, resulting in uniform dispersion within the support. This avoids the sintering effects associated with the high-temperature calcination and reduction processes of conventional preparation methods. The preparation method provided by this invention is simple, low-cost, environmentally friendly, and easily industrializable.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a modified inorganic oxide carrier and a preparation method and application thereof. Background Art

[0002] Alumina is widely used in the field of industrial catalysis due to its high strength, heat resistance, corrosion resistance, and low cost. Because the properties of pure alumina are relatively simple, different catalytic fields have different requirements for inorganic oxide supports. Therefore, researchers usually add some variable-valence metals to inorganic oxide supports to change their physical and chemical properties. Traditional modification methods generally use high-temperature calcination to treat alumina containing variable-valence metal precursor compounds (such as Chinese patent CN106732692A), and further use gas / liquid phase treatment methods to obtain variable-valence metals with richer valence states. For example, Chinese patent CN106732692A modifies an inorganic oxide support by adding a surfactant to a slurry; Chinese patent CN107511178A hydrothermally treats alumina immersed in an acidic solution containing a vanadium compound to obtain a modified inorganic oxide support; and Chinese patent CN112619632A uses two modifiers to load a Group VIII metal onto alumina, followed by dry / wet sulfidation to obtain a modified inorganic oxide support. However, high-temperature calcination can cause sintering and agglomeration of the variable-valence metal; gas or solution treatment methods have limited effectiveness in regulating the valence state of the variable-valence metal, and gas-phase treatment is generally performed at high temperatures, which further exacerbates the migration and aggregation of the variable-valence metal. Furthermore, liquid-phase treatment often uses a large amount of surfactants such as capping agents, dispersants, and emulsifiers, making the process complex, environmentally unfriendly, and costly. Summary of the Invention

[0003] In response to the shortcomings of the existing technology, the present invention loads variable-valence metals on inorganic oxide carriers through ionizing radiation to obtain modified inorganic oxide carriers. The variable-valence metals are uniformly dispersed in the inorganic oxide carriers, avoiding the sintering effect caused by high temperatures in traditional preparation methods, the adverse effects of surfactants on the environment, and the cumbersome loading process.

[0004] One of the objects of the present invention is to provide a modified inorganic oxide support, comprising an inorganic oxide and a variable-valence metal, wherein the inorganic oxide is selected from at least one of aluminum oxide, silicon dioxide, barium oxide, and calcium oxide, and the valence state of the variable-valence metal includes at least two valence states.

[0005] Preferably,

[0006] The inorganic oxide is selected from alumina; the alumina has a crystal form of at least one of θ-type, α-type, γ-type, η-type, δ-type, and amorphous type, preferably at least one of θ-type, α-type, and γ-type; the alumina may be in the form of powdered alumina or formed alumina, wherein the formed alumina has a shape of flake, strip, sphere, granular, ring, tooth, cloverleaf, cylinder, and ellipsoid; the water absorption rate of the alumina is 30-150%, preferably 50-100%;

[0007] The valence state of the variable-valence metal includes a highest valence state and at least one other valence state. Preferably, the other valence states include at least one of a subvalent state, a subvalent state, and a sub-subvalent state. For the same metal, in the variable-valence metal, the molar ratio of the highest valence metal content to the total amount of the variable-valence metal is (0.01-0.99):1, preferably (0.35-0.85):1; the molar ratio of the total content of the subvalent metal and / or subvalent metal to the total amount of the variable-valence metal is (0.001-0.6):1, preferably (0.05-0.55):1; the molar ratio of the sub-subvalent state content to the total amount of the variable-valence metal is (0-0.2):1, preferably (0-0.15):1;

[0008] The variable valence metal is 0.001 to 30% by weight of the aluminum oxide, preferably 0.01 to 10% by weight, calculated as the weight of the metal element;

[0009] The variable-valence metal is selected from at least one of transition metals, Group IIIA metals, and Group IVA metals, preferably selected from at least one of Ni, Sb, Sn, Ti, Fe, Cu, Co, Mo, W, Sn, Ga, In, La, Ce, Re, and V, and more preferably selected from at least one of Ti, Fe, Ga, In, Ce, and V.

[0010] A second object of the present invention is to provide a method for preparing the modified inorganic oxide support, comprising loading the variable-valence metal on an inorganic oxide and irradiating the inorganic oxide to obtain the modified inorganic oxide support. Preferably, the preparation method specifically comprises the following steps:

[0011] Step (1) dissolving a soluble variable-valence metal salt compound in water to prepare a metal salt aqueous solution;

[0012] Step (2) immersing the inorganic oxide in the metal salt aqueous solution prepared in step (1) to obtain an inorganic oxide loaded with a variable-valence metal salt;

[0013] Step (3) irradiates the inorganic oxide loaded with the variable-valence metal salt obtained in step (2) to obtain the modified inorganic oxide carrier.

[0014] Specifically, when the variable-valence metal is a single metal, the modified inorganic oxide support is prepared according to the above steps (1) to (3); when the variable-valence metal is two or more variable-valence metals, the modified inorganic oxide support can be prepared by loading all variable-valence metals with inorganic oxides in one step and then irradiating them, or by loading inorganic oxides in steps according to different variable-valence metals and then irradiating them in steps.

[0015] In the above preparation method,

[0016] The soluble variable-valence metal salt compound is selected from at least one of nitrates, acetates, sulfates, chlorides, and transition metal salts of variable-valence metals, preferably selected from at least one of nitrates, acetates, chlorides, and transition metal salts of variable-valence metals;

[0017] The molar concentration of the metal salt aqueous solution is 0.01 to 5 mol / L, preferably 0.3 to 3 mol / L;

[0018] The impregnation can be carried out by any one or more of the impregnation methods commonly used in the art, such as equal volume impregnation, unsaturated impregnation, excess impregnation, surface spraying, and vacuum impregnation. The impregnated support can also be dried, and the drying conditions and methods can adopt the drying processes commonly used in the art.

[0019] The irradiation can be performed on irradiation equipment commonly used in the art. Preferably, the irradiation source is selected from at least one of electron beam, X-ray, gamma ray and laser. When the irradiation source is electron beam or X-ray, the irradiation dose rate is 0.001-20 kGy / min, preferably 0.5-10 kGy / min. When the irradiation source is gamma ray, the irradiation dose rate is 5-200 kGy / min, preferably 30-100 kGy / min. When the irradiation source is laser, the wavelength of the laser is 200-1000 nm and the power is 0.5-1000 W. Preferably, the wavelength of the laser is 300-700 nm and the power is 1 W-800 W.

[0020] When the radiation source is γ-rays, a free radical scavenger solution needs to be added; the volume percentage concentration of the free radical scavenger solution is 1 to 99%, preferably 10 to 60%; the free radical scavenger is selected from alcohol compounds, preferably at least one selected from methanol, ethanol, ethylene glycol, and isopropanol;

[0021] The irradiation time is 0.1 to 24 hours, preferably 2 to 20 hours;

[0022] The inorganic oxide carrier loaded with variable-valence metal salt obtained in step (2) further needs to be dried. The drying conditions and methods can adopt the drying processes commonly used in the art, for example, the drying temperature is 60-150°C, preferably 80-120°C.

[0023] A third object of the present invention is to provide the modified inorganic oxide support or the modified inorganic oxide support obtained by the above preparation method for use in preparing catalyst products.

[0024] The present invention, based on in-depth research on inorganic oxide support materials, discovered that ionizing radiation not only partially reduces the variable-valent metal to obtain the desired modified inorganic oxide support, but also enables a strong interaction between the variable-valent metal and the inorganic oxide support, resulting in a uniform dispersion within the inorganic oxide support, thus avoiding the sintering effects associated with the high-temperature calcination and reduction processes of traditional preparation methods. Furthermore, by varying the type of variable-valent metal precursor, irradiation source, irradiation time, and irradiation dose rate, the ratio of each valence state in the variable-valent metal can be precisely controlled, thereby fully improving and regulating the properties of the modified inorganic oxide support.

[0025] Compared with the prior art, the present invention has the following advantages and benefits:

[0026] 1. The present invention eliminates the conventional methods of calcination and calcination-gas / liquid phase reduction used when modifying alumina with variable valence metals through irradiation treatment, and significantly improves the dispersibility of the variable valence metals on the surface of the inorganic oxide support;

[0027] 2. In the preparation method provided by the present invention, the ratio of variable-valence metals of different valence states can be more accurately and significantly controlled by varying conditions such as the irradiation dose rate and irradiation time, thereby better adjusting the properties of the inorganic oxide support and providing a good foundation for subsequent improvement of catalyst performance.

[0028] 3. The method provided by the present invention is simple in process, easy to operate, low in cost, environmentally friendly and easy to industrialize, and has good application prospects. DETAILED DESCRIPTION

[0029] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0030] Example 1-8 Preparation of modified inorganic oxide supports A1 to A8

[0031] Example 1

[0032] Take 200 g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120 ml of a 1 mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry at 110°C for 3 hours. Irradiate the resulting solid with an electron beam at a dose rate of 1 kGy / min for 3 hours to obtain modified inorganic oxide support A1.

[0033] Example 2

[0034] Take 200 g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120 ml of a 1 mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate solution into the inorganic oxide support, then dry at 110°C for 16 hours. Irradiate the resulting solid with an electron beam at a dose rate of 1 kGy / min for 6 hours to obtain a modified inorganic oxide support A2.

[0035] Example 3

[0036] Take 200 g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120 ml of a 1 mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry at 110°C for 3 hours. Irradiate the resulting solid with an electron beam at a dose rate of 1.5 kGy / min for 3 hours to obtain a modified inorganic oxide support A3.

[0037] Example 4

[0038] 200 g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60% was prepared. 120 ml of a mixed aqueous solution of potassium titanium oxalate (1 mol / L) and potassium tungstate (0.2 mol / L) was added. An equal volume of this mixed aqueous solution was impregnated into the inorganic oxide support, followed by drying at 110°C for 3 hours. The resulting solid was irradiated with an electron beam at a dose rate of 1.5 kGy / min for 6 hours to obtain modified inorganic oxide support A4.

[0039] Example 5

[0040] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of an aqueous solution of potassium titanium oxalate (at a concentration of 1mol / L). Impregnate an equal volume of the aqueous solution of potassium titanium oxalate into the inorganic oxide support, and then dry it at 110°C for 3h. Irradiate the solid obtained above for 2h using an electron beam at a dose rate of 1.5kGy / min. Prepare another 120ml of an aqueous solution of potassium tungstate (at a concentration of 0.2mol / L), and impregnate an equal volume of the aqueous solution of potassium tungstate into the solid sample obtained above. Irradiate the solid obtained above for 4h using an electron beam at a dose rate of 1.5kGy / min to obtain a modified inorganic oxide support A5.

[0041] Example 6

[0042] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of potassium titanium oxalate aqueous solution (concentration of 1mol / L). Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, and then dry it at 110°C for 3h. Irradiate the above-obtained solid for 4h using an electron beam at a dose rate of 3kGy / min. Prepare another 120ml of potassium tungstate aqueous solution (concentration of 0.2mol / L), and impregnate an equal volume of the potassium tungstate aqueous solution into the solid sample obtained above. Irradiate the above-obtained solid for 4h using an electron beam at a dose rate of 3kGy / min to obtain a modified inorganic oxide support A6.

[0043] Example 7

[0044] Take 200g of spherical α-phase inorganic oxide support with a water absorption rate of 70%. Prepare 160ml of sodium metavanadate (concentration is 1mol / L) aqueous solution. Excessively impregnate the inorganic oxide support with the mixed aqueous solution, then dry it at 120℃ for 5h. Add 60ml of 60% ethylene glycol aqueous solution to the dried support and use 60 The solid obtained above was irradiated with a Co γ radiation source at a dose rate of 80 Gy / min for 6 hours, and then dried at 120° C. for 5 hours to obtain a modified inorganic oxide support A7.

[0045] Example 8

[0046] Take 200g of tooth-shaped α-phase inorganic oxide support with a water absorption rate of 100%. Prepare 180ml of ferric sulfate (concentration of 0.5mol / L) aqueous solution. Impregnate the inorganic oxide support with the mixed aqueous solution unsaturatedly, then dry at 110℃ for 3h. Add 70ml of 50% ethylene glycol aqueous solution to the dried support and use 60 The solid obtained above was irradiated with a Co γ radiation source at a dose rate of 50 Gy / min for 8 hours, and then dried at 120° C. for 3 hours to obtain a modified inorganic oxide support A8.

[0047] Examples 9-16 Preparation of Catalysts Containing Modified Inorganic Oxide Supports A1 to A8

[0048] Example 9:

[0049] 60 ml of PdCl 2 solution (concentration of 700 mg / L) was loaded on 100 g of the carrier A1 prepared in Example 1, and then dried at 110° C. for 3 h to obtain catalyst AC1.

[0050] Examples 10 to 16

[0051] Catalysts AC2 to AC8 were prepared using the modified inorganic oxide supports A2 to A8 according to the preparation method in Example 9.

[0052] Comparative Examples 1-8 Preparation of Modified Inorganic Oxide Support Comparative Samples B1 to B8

[0053] Comparative Example 1

[0054] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of a 1mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry at 110°C for 3 hours. Calcinate the resulting solid at 400°C for 4 hours, then reduce it with H2 at 400°C for 3 hours to obtain modified inorganic oxide support B1.

[0055] Comparative Example 2

[0056] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of a 1mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry at 110°C for 3 hours. Calcinate the resulting solid at 400°C for 4 hours, then reduce it with H2 at 600°C for 3 hours to obtain modified inorganic oxide support B2.

[0057] Comparative Example 3

[0058] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of a 1mol / L aqueous solution of potassium titanium oxalate. Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry at 110°C for 3 hours. Calcinate the resulting solid at 400°C for 6 hours, then reduce it with H2 at 600°C for 6 hours to obtain modified inorganic oxide support B3.

[0059] Comparative Example 4

[0060] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of a mixed aqueous solution of potassium titanium oxalate (concentration: 1 mol / L) and potassium tungstate (concentration: 0.2 mol / L). Impregnate an equal volume of this mixed aqueous solution into the inorganic oxide support, then dry it at 110°C for 3 hours. The resulting solid is calcined at 500°C for 6 hours and then reduced with H2 at 600°C for 3 hours to obtain modified inorganic oxide support B4.

[0061] Comparative Example 5

[0062] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of potassium titanium oxalate aqueous solution (concentration of 1mol / L). Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry it at 110°C for 3h, and calcine the resulting solid at 400°C for 6h. Prepare another 120ml of potassium tungstate aqueous solution (concentration of 0.2mol / L), impregnate an equal volume of the potassium tungstate aqueous solution into the above-obtained solid, then dry it at 110°C for 3h. Then calcine at 400°C for 6h, and then reduce it with H2 at 700°C for 3h to obtain a modified inorganic oxide support B5.

[0063] Comparative Example 6

[0064] Take 200g of a clover-shaped γ-phase inorganic oxide support with a water absorption rate of 60%. Prepare 120ml of potassium titanium oxalate aqueous solution (concentration of 1mol / L). Impregnate an equal volume of the potassium titanium oxalate aqueous solution into the inorganic oxide support, then dry it at 110°C for 3h, and then reduce it with H2 at 600°C for 5h. Prepare another 120ml of potassium tungstate aqueous solution (concentration of 0.2mol / L), impregnate an equal volume of the potassium tungstate aqueous solution into the above-obtained solid, and then dry it at 110°C for 3h. Then calcine it at 400°C for 6h, and then reduce it with H2 at 600°C for 5h to obtain a modified inorganic oxide support B6.

[0065] Comparative Example 7

[0066] Take 200g of a spherical α-phase inorganic oxide support with a water absorption rate of 70%. Prepare 160ml of a 1mol / L aqueous solution of sodium metavanadate. Excessively impregnate the inorganic oxide support with the mixed aqueous solution, then dry at 120°C for 5h. The resulting solid is calcined at 500°C for 6h and then reduced with H2 at 500°C for 3h to obtain modified inorganic oxide support B7.

[0067] Comparative Example 8

[0068] Take 200g of a toothed α-phase inorganic oxide support with a water absorption rate of 100%. Prepare 180ml of an aqueous solution of 0.5mol / L ferric sulfate. Impregnate the inorganic oxide support with the mixed aqueous solution, then dry at 110°C for 3h. The resulting solid is calcined at 500°C for 4h and then reduced with H2 at 500°C for 4h to obtain modified inorganic oxide support B8.

[0069] Comparative Examples 9-16 Preparation of Catalysts Containing Modified Inorganic Oxide Support Comparative Samples B1 to B8

[0070] Comparative Examples 9 to 16

[0071] Catalysts BC1 to BC8 were prepared according to the preparation method in Example 9 using modified inorganic oxide supports B1 to B8, respectively.

[0072] Testing of modified inorganic oxide supports

[0073] X-ray diffractometer (Cu Kα radiation, Bruker D8 Advance) ) The crystal structure of the modified inorganic oxide carrier prepared in the examples and comparative examples was characterized. The carrier surface was lightly scraped with a blade, ground into powder and then pressed into tablets for testing. The test range was 5°-90° and the scanning speed was 5°min -1 Jade software was used for phase retrieval, background subtraction, smoothing, and fitting calculation of the characteristic peak areas of variable-valence metals. Data such as the half-width at half-maximum of the characteristic diffraction peaks were obtained. The grain size of the corresponding variable-valence metal oxides was then calculated using the Scherrer formula. The test results are listed in Table 1.

[0074] The variable-valence metal elements on the surface of the modified inorganic oxide supports prepared in the Examples and Comparative Examples were analyzed using a Thermofisher ESCALAB250 X-ray spectrometer (X-ray source: Al Ka, 15 kV, 150 W). Background subtraction was performed using ThermoAvantage software, and the characteristic peaks of the variable-valence metal elements were peak-fitted. The software's built-in sensitivity factor method was then used to calculate the number of atoms in different valence states of the corresponding elements. The Ti2p peak was selected for Ti, the W4f peak for W, the V2p peak for V, and the Fe2p peak for Fe. The test results are listed in Table 1.

[0075] Table 1. Test results of modified inorganic oxide supports

[0076]

[0077]

[0078] According to the data in Table 1, the particle size of the variable valence metal on the inorganic oxide support of Examples (A1-A7) is significantly smaller than that of Comparative Examples (B1-B6), indicating that the technical solution of the present invention can significantly weaken the agglomeration tendency of the variable valence metal on the alumina support, improve the distribution of the variable valence metal on the alumina and enhance the modification effect; at the same time, although extending the hydrogen reduction time or increasing the reduction temperature can also increase the number of low-valent variable valence metal atoms, the degree of increase and effect are very limited, and the lower valence subvalent and sub-subvalent variable valence metals are also more difficult to obtain. At the same time, the uniform distribution of the variable valence metal and its oxide on the alumina will be greatly reduced. The method provided by the present invention can more conveniently, finely and widely control the amount of low-valent variable valence metal by adjusting the irradiation time and irradiation dose rate.

[0079] Testing of catalyst products containing modified inorganic oxide supports

[0080] The hydrogenation activity and selectivity of AC1-AC8 and BC1-BC8 were evaluated in a 100 ml small fixed bed reactor using Yanshan Petrochemical's C2 component gas (acetylene content 0.1%, ethylene content 60-61%, ethane content 10-11%, hydrogen content 12-13%, propylene 15-20%, and CO content 600 ppm). Specifically, 100 ml of catalyst was loaded in the middle of the fixed bed reactor and the reaction was carried out at a reaction pressure of 1.5 MPa and a space velocity of 20,000 h / min. -1 Under the same conditions, the catalyst temperature is gradually increased by 0.5°C from 60°C, and the acetylene content at the reactor outlet is recorded. When the acetylene content at the reactor outlet remains at 0 ppm for 6 hours, the current reaction temperature and ethylene selectivity are regarded as the catalyst performance data. The ethylene selectivity is calculated as follows:

[0081]

[0082] The evaluation results are listed in Table 2.

[0083] Table 2. Evaluation results of catalysts AC1-8 and BC1-8

[0084] serial number catalyst Reaction temperature (℃) Ethylene selectivity (%) Example 1 AC1 68.5 9.6 Example 2 AC2 66.5 9.4 Example 3 AC3 66.0 10.4 Example 4 AC4 65.0 14.3 Example 5 AC5 63.0 15.4 Example 6 AC6 62.5 13.2 Example 7 AC7 69.0 7.2 Example 8 AC8 70.5 6.5 Comparative Example 1 BC1 75.5 -87.5 Comparative Example 2 BC2 76.5 -94.2 Comparative Example 3 BC3 75.0 -98.3 Comparative Example 4 BC4 73.5 -66.1 Comparative Example 5 BC5 70.0 -70.3 Comparative Example 6 BC6 68.5 -65.9 Comparative Example 7 BC7 76.0 -87.2 Comparative Example 8 BC8 77.5 -80.4

[0085] As can be seen from Table 2, the catalysts (AC1-AC8) prepared using the modified inorganic oxide support provided by the present invention have significantly better hydrogenation activity and selectivity than the catalysts (BC1-BC8) prepared using the comparative example support, and have great industrial application prospects.

Claims

1. A modified inorganic oxide support comprising an inorganic oxide and a variable valence metal, wherein: The inorganic oxide is selected from at least one of aluminum oxide and silicon dioxide, the variable-valent metal is selected from at least one of Sb, Ti, Mo, W, Ga, Re, and V, and the valence state of the variable-valent metal includes a highest valence state, a subvalent state, a subvalent state, and an optional sub-subvalent state; for the same metal, in its variable-valent metal: the molar ratio of the highest valence metal content to the total amount of variable-valent metal is (0.01-0.99):1, the molar ratio of the total content of the subvalent metal and / or subvalent metal to the total amount of variable-valent metal is (0.001-0.6):1, and the molar ratio of the sub-subvalent state content to the total amount of variable-valent metal is (0-0.2):

1.

2. The modified inorganic oxide support according to claim 1, characterized in that The inorganic oxide is selected from aluminum oxide; and / or Calculated by the weight of the metal element, the variable valence metal accounts for 0.001 to 30% of the weight of the inorganic oxide.

3. The modified inorganic oxide support according to claim 2, characterized in that The inorganic oxide is selected from aluminum oxide; and / or Calculated by the weight of the metal element, the variable valence metal accounts for 0.01 to 10% of the weight of the inorganic oxide.

4. The modified inorganic oxide support according to claim 2, characterized in that The aluminum oxide has a crystal form of at least one of the θ form, the α form, the γ form, the η form, the δ form, and the amorphous form; and / or The water absorption rate of the aluminum oxide is 30 to 150%.

5. The modified inorganic oxide support according to claim 4, characterized in that The aluminum oxide has a crystal form of at least one of the θ-type, α-type, and γ-type; and / or The water absorption rate of the aluminum oxide is 50-100%.

6. The modified inorganic oxide support according to claim 1, characterized in that For the same metal, its variable valence metals: The molar ratio of the highest valence metal content to the total amount of variable valence metals is (0.35-0.85):1; and / or, The molar ratio of the total content of the subvalent metal and / or subvalent metal to the total amount of the variable valent metal is (0.05-0.55):1; and / or, The molar ratio of the sub-subvalent state content to the total amount of the variable valence metal is (0-0.15):

1.

7. A method for preparing the modified inorganic oxide support according to any one of claims 1 to 6, comprising loading the variable-valence metal on an inorganic oxide and irradiating the inorganic oxide to obtain the modified inorganic oxide support.

8. The preparation method according to claim 7, characterized in that The preparation method specifically comprises the following steps: Step (1) dissolving a soluble variable-valence metal salt compound in water to prepare a metal salt aqueous solution; Step (2) immersing the inorganic oxide in the metal salt aqueous solution prepared in step (1) to obtain an inorganic oxide loaded with a variable-valence metal salt; Step (3) irradiates the inorganic oxide loaded with the variable-valence metal salt obtained in step (2) to obtain the modified inorganic oxide carrier.

9. The preparation method according to claim 8, characterized in that When the variable-valence metal is two or more variable-valence metals, the modified inorganic oxide support is prepared by loading all variable-valence metals with inorganic oxides in one step and then irradiating them, or by loading inorganic oxides in steps according to different variable-valence metals and irradiating them in steps.

10. The preparation method according to claim 8, characterized in that The soluble variable-valence metal salt compound is selected from at least one of nitrates, acetates, sulfates, chlorides, and transition metal salts of variable-valence metals; and / or, The molar concentration of the metal salt aqueous solution is 0.01 to 5 mol / L.

11. The preparation method according to claim 10, characterized in that: The soluble variable-valence metal salt compound is selected from at least one of nitrates, acetates, chlorides, and transition metal salts of variable-valence metals; and / or, The molar concentration of the metal salt aqueous solution is 0.3 to 3 mol / L.

12. The preparation method according to claim 7 or 8, characterized in that: The irradiation source is selected from at least one of electron beam, X-ray, gamma ray and laser; and / or, The irradiation time is 0.1 to 24 hours; and / or, The inorganic oxide carrier loaded with the variable-valence metal salt obtained in step (2) further needs to be dried.

13. The preparation method according to claim 12, characterized in that The irradiation time is 2 to 20 hours.

14. The preparation method according to claim 12, characterized in that When the radiation source is an electron beam or X-ray, the radiation dose rate is 0.001 to 20 kGy / min; and / or, When the radiation source is gamma rays, the radiation dose rate is 5 to 200 Gy / min; and / or, When the radiation source is γ-rays, a free radical scavenger solution needs to be added; and / or, When the radiation source is laser, the wavelength of the laser is 200-1000nm and the power is 0.5-1000W.

15. The preparation method according to claim 14, characterized in that When the radiation source is an electron beam or X-ray, the radiation dose rate is 0.5 to 10 kGy / min; and / or, When the radiation source is gamma rays, the radiation dose rate is 30 to 100 Gy / min; and / or, When the radiation source is laser, the wavelength of the laser is 300-700nm and the power is 1-800W.

16. The preparation method according to claim 14, characterized in that The volume percentage concentration of the free radical scavenger solution is 1 to 99%; and / or, The free radical scavenger is selected from alcohol compounds.

17. The preparation method according to claim 16, characterized in that The volume percentage concentration of the free radical scavenger solution is 10 to 60%; and / or, The free radical scavenger is selected from at least one of methanol, ethanol, ethylene glycol and isopropanol.

18. A modified inorganic oxide support according to any one of claims 1 to 6 or a modified inorganic oxide support obtained by the preparation method according to any one of claims 7 to 17, for use in preparing a catalyst product.

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