Preparation method and application of alumina carrier

Abstract

The invention relates to a preparation method of an alumina carrier and application of the alumina carrier in hydrogenation reaction of aromatic raffinate oil and heavy aromatics. The preparation method of the alumina carrier comprises the following steps: carrying out hydrothermal treatment on a mixture of an aluminum source and an inorganic ammonium salt aqueous solution and / or ammonia water; carrying out solid-liquid separation on the hydrothermal treatment product to obtain a solid material; kneading, forming and roasting the solid material and a mixture of a peptizing agent and an auxiliary agent; and loading a metal additive on the roasted product to obtain the alumina carrier. By adopting the preparation method of the modified alumina carrier, Na ion impurities in raw materials can be effectively removed, the pore structure of the carrier can be effectively adjusted, and a nickel-based hydrogenation catalyst prepared by taking the modified alumina carrier as the carrier is high in metal loading capacity, has excellent hydrogenation activity and stability, and meets the industrial production of alumina carriers and hydrogenation catalysts.

Description

Technical Field

[0001] The invention belongs to the field of catalysts, and specifically relates to an alumina carrier and a preparation method and application thereof. Background Art

[0002] Alumina is widely used as a carrier of hydrogenation catalysts due to its unique pore structure and surface properties. In particular, hydrogenation catalysts in the oil refining industry generally use alumina to load metal active components, so the properties of the carrier are particularly important during preparation. Alumina carriers play the role of loading active components and obtaining high dispersion rates of active components in supported hydrogenation catalysts. The carrier should have a large pore volume and pore size, can load more metal active components, and at the same time have anti-coking and anti-carbon deposition properties. Impurity elements in alumina carriers, especially excessive Na content, will have an adverse effect on the interaction between active metals and carriers.

[0003] The preparation of alumina carrier generally uses pseudo-boehmite and alumina powder as raw materials, which are fully mixed with binders, pore expanders, etc., and then an appropriate amount of acidic solution is added to react and dissolve to obtain a viscous material that is easy to extrude and shape. After subsequent drying, roasting and other processes, the carrier product is finally obtained.

[0004] The existing technology focuses on the modification of the pore structure of the alumina carrier to obtain a larger pore volume and pore size, or to obtain a carrier with a double pore distribution for application in a specific reaction. However, it does not involve the mutual influence of the pore structure and surface properties of the alumina carrier, and the synergistic effect on the loaded active metal, nor does it mention the treatment method of impurities in the alumina raw material. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a modified alumina carrier and a modification method thereof, as well as a hydrogenation catalyst prepared from the alumina carrier. The preparation method of the modified alumina carrier of the present invention can effectively remove Na ion impurities in the raw material, and can effectively adjust the pore structure of the carrier. The nickel-based hydrogenation catalyst prepared using the modified alumina carrier as a carrier has the characteristics of high metal loading. The addition of alkaline earth metal oxides and rare earth oxides can improve the surface properties of the alumina carrier, produce synergistic effects with active metals, promote the dispersion of active metals on the surface of the carrier, and improve the hydrogenation activity and stability of the catalyst. The nickel-based catalyst of the present invention is applied to the hydrogenation reaction of aromatic raffinate oil and heavy aromatics, and exhibits excellent hydrogenation activity and stability, mild reaction conditions, and large process operation flexibility.

[0006] In order to achieve the above object, the present invention adopts the following technical solution.

[0007] In a first aspect, the present invention provides a method for preparing an alumina carrier, comprising the following steps:

[0008] a) subjecting a mixture of an aluminum source and an aqueous solution of an inorganic ammonium salt and / or aqueous ammonia to a hydrothermal treatment;

[0009] b) subjecting the product of the hydrothermal treatment to solid-liquid separation to obtain a solid material;

[0010] c) kneading, shaping and calcining the solid material with a mixture of a peptizing agent and an auxiliary agent;

[0011] d) loading a metal additive on the calcined product to obtain the alumina carrier.

[0012] In the preparation scheme of the present invention, the role of ammonium ions is to form soluble Na salts with the Na element present in the aluminum source under heating, and to be removed in the subsequent solid-liquid separation process; at the same time, the addition of metal additives further improves the pore structure and surface properties of the alumina carrier, thereby increasing the pore size and pore volume of the alumina carrier.

[0013] In some embodiments, the aluminum source includes at least one of pseudo-boehmite, aluminum hydroxide, aluminum oxide, or aluminum sol.

[0014] In some embodiments, the inorganic ammonium salt includes at least one of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium nitrate, or aluminum ammonium sulfate.

[0015] In some embodiments, the peptizing agent is selected from at least one of nitric acid, acetic acid or citric acid.

[0016] In some embodiments, the auxiliary agent is selected from at least one of hydroxypropyl cellulose, hydroxymethyl cellulose or sesbania powder.

[0017] In some embodiments, the metal promoter includes alkaline earth metal and / or rare earth metal. In some embodiments, the alkaline earth metal includes Mg and / or Ca. In some embodiments, the rare earth metal includes La and / or Ce.

[0018] In some embodiments, in step a), the ratio of the mass of the aluminum source to the sum of the mass of the inorganic ammonium salt aqueous solution and the ammonia water is 1:(5-20). In some specific embodiments, in step a), the ratio of the mass of the aluminum source to the sum of the mass of the inorganic ammonium salt aqueous solution and the ammonia water is 1:5, 1:7.5, 1:10, 1:12.5, 1:15, 1:17.5, 1:20 or any value therebetween.

[0019] In some embodiments, the mass concentration of the inorganic ammonium salt aqueous solution and / or the ammonia water is 1-10%, preferably 3-8%. In some embodiments, the mass concentration of the inorganic ammonium salt aqueous solution and / or the ammonia water is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value therebetween.

[0020] In some embodiments, in step c), the amount of the peptizing agent added is 0.5-10% of the mass of the solid material. In some specific embodiments, in step c), the amount of the peptizing agent added is 0.5%, 1%, 2%, 4%, 6%, 8%, 10% of the mass of the solid material or any value thereof.

[0021] In some embodiments, in step c), the amount of the additive added is 0.5-10% of the mass of the aluminum source. In some specific embodiments, in step c), the amount of the additive added is 0.5%, 1%, 2%, 4%, 6%, 8%, 10% of the mass of the aluminum source or any value thereof.

[0022] In some embodiments, in step d), the amount of the metal additive added is 0.5-3.0% of the mass of the product after calcination, calculated as the oxide of the metal additive. In some embodiments, in step d), the amount of the metal additive added is 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or any value therebetween, calculated as the oxide of the metal additive, of the mass of the product after calcination.

[0023] In some embodiments, in step a), the temperature of the hydrothermal treatment is 30-90° C., preferably 70-90° C. In some specific embodiments, in step a), the temperature of the hydrothermal treatment is 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C. or any value therebetween.

[0024] In some embodiments, in step a), the hydrothermal treatment time is 0.5-5h, preferably 1-3h. In some specific embodiments, in step a), the hydrothermal treatment time is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 4h, 5h or any value therebetween.

[0025] In some embodiments, in step c), the calcination temperature is 450-850° C., preferably 500-700° C. In some specific embodiments, in step c), the calcination temperature is 450° C., 550° C., 600° C., 650° C., 700° C., 800° C., 850° C. or any value therebetween.

[0026] In some embodiments, in step c), the calcination time is 0.5-10 h, preferably 1-6 h. In some specific embodiments, in step c), the calcination time is 0.5 h, 1 h, 2 h, 4 h, 6 h, 8 h, 10 h or any value therebetween.

[0027] In some embodiments, step c) further comprises drying the formed product and then calcining it. Preferably, the drying temperature is 60-100° C. and the drying time is 0.5-5 h.

[0028] In some embodiments, in step d), the metal additive is loaded on the calcined product by an impregnation method.

[0029] In some embodiments, in step d), the immersion temperature is 25-90° C., preferably 25-60° C. In some specific embodiments, in step d), the immersion temperature is 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C. or any value therebetween.

[0030] In some embodiments, in step d), the immersion time is 0.5-5h, preferably 1-4h. In some specific embodiments, in step d), the immersion time is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 4h, 5h or any value therebetween.

[0031] In a second aspect, the present invention provides an alumina carrier prepared by the preparation method described in the first aspect.

[0032] In some embodiments, the pore volume of the alumina support is greater than 0.6 cm 2 / g, preferably greater than 0.65cm 2 / g, more preferably 0.65-0.75cm 2 / g.

[0033] In some embodiments, the pore size of the alumina support is greater than 10 nm, preferably greater than 12 nm, and more preferably 12-15 nm.

[0034] In some embodiments, the Na content in the alumina support is less than 0.5 wt %, preferably less than 0.1 wt %, and more preferably less than 0.08 wt %.

[0035] In a third aspect, the present invention provides a hydrogenation catalyst, which comprises an alumina carrier prepared by the preparation method described in the first aspect or the alumina carrier described in the second aspect, and Ni metal loaded on the alumina carrier.

[0036] In some embodiments, based on the total mass of the hydrogenation catalyst, the content of the Ni metal is greater than 20 wt %, preferably 20-25 wt %.

[0037] The hydrogenation catalyst of the invention has a higher Ni loading amount and better catalytic performance.

[0038] In a fourth aspect, the present invention provides a method for preparing the hydrogenation catalyst described in the third aspect, the preparation method comprising immersing the alumina carrier in a solution containing a nickel metal salt.

[0039] In some embodiments, the nickel metal salt includes at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, or nickel ammonia solution.

[0040] In some embodiments, the preparation method further comprises drying and calcining the impregnated product to obtain the hydrogenation catalyst. Preferably, the drying temperature is 60-100°C and the time is 0.5-5h. Preferably, the calcination temperature is 400-600°C and the time is 0.5-5h or any value therebetween.

[0041] In the fifth aspect, the present invention provides the use of the alumina carrier prepared by the preparation method described in the first aspect, the alumina carrier described in the second aspect, the hydrogenation catalyst described in the third aspect, or the hydrogenation catalyst prepared by the preparation method described in the fourth aspect in the hydrogenation reaction of aromatic raffinate or heavy aromatics.

[0042] In some embodiments, the temperature range of the hydrogenation reaction is 80-200° C., the pressure range is 0.6-4.0 MPa, and the hydrogen-to-oil volume ratio range is (100-600):1.

[0043] The method of the present invention comprises the following steps: a) mixing an aluminum source with at least one of an inorganic ammonium salt aqueous solution and ammonia water for hydrothermal treatment to obtain a hydrothermal treatment product; b) performing solid-liquid separation on the hydrothermal treatment product obtained in step a) to obtain a solid material and a separation liquid; c) adding a peptizing agent and an auxiliary agent to the solid material obtained in step b) for kneading, molding, and roasting to obtain an alumina carrier precursor; d) adding one or more metal auxiliary agents to the alumina carrier precursor obtained in step c) to further improve the pore structure and surface properties of the carrier to obtain an alumina carrier; e) roasting the alumina carrier obtained in step d) to load Ni metal to obtain a nickel-based hydrogenation catalyst. The preparation method of the modified alumina carrier of the present invention can effectively remove Na ion impurities in the raw material and can effectively adjust the pore structure of the carrier. The nickel-based hydrogenation catalyst prepared with the modified alumina carrier as a carrier has a high metal loading, excellent hydrogenation activity and stability, and meets the industrial production of alumina carriers and hydrogenation catalysts. DETAILED DESCRIPTION

[0044] The following examples will further illustrate the modification method of the alumina carrier provided by the present invention, as well as the nickel-based hydrogenation catalyst used as the carrier and the preparation method thereof, but the protection scope of the present invention is not limited to these examples.

[0045] The Na content of the alumina carrier and the Ni content of the hydrogenation catalyst were determined by X-ray fluorescence spectrometer from Bruker, Germany. The nitrogen physical adsorption and desorption of the samples were detected by Micromeritics Tristar 3000 physical adsorption instrument at 77K, and the pore volume and pore size data were calculated by formula.

[0046] In the present invention, the hydrogenation evaluation experiment of aromatic raffinate oil (the raw material comes from the aromatic extraction device of Zhenhai Refining and Chemical) is carried out on a fixed bed reactor device, 50 mL of catalyst is loaded into the adiabatic section of the reactor, and after the catalyst is pre-reduced, it is adjusted to the required reaction temperature, and the feeding reaction is started according to the set process conditions. The reactor is a multi-stage temperature-controlled quasi-adiabatic bed tubular fixed bed reactor.

[0047] The catalyst performance index is determined by the benzene content (wt%) and bromine index (mg / 100g) in the raffinate product. The benzene content is determined by Agilent 7890 gas chromatograph. The bromine index is determined by SY2123-77 (Method for determination of bromine value of petroleum products).

[0048] Example 1

[0049] a) ammonium carbonate is selected and prepared into 5000 g of a 3 wt% ammonium carbonate aqueous solution, which is then mixed with 1000 g of pseudo-boehmite and stirred for 2 h for hydrothermal treatment at a temperature of 80° C. After the hydrothermal treatment, solid-liquid separation is performed to obtain the treated pseudo-boehmite.

[0050] b) 10 g of nitric acid and 10 g of sesbania powder were mixed with the treated pseudo-boehmite and formed. The formed material was dried at 90° C. for 4 h and calcined at 600° C. for 4 h to obtain an alumina carrier precursor.

[0051] c) An aqueous solution of magnesium nitrate was selected and added to the alumina carrier precursor by impregnation at 30° C. for 3 hours in an amount of 5 g calculated as magnesium oxide to obtain an alumina carrier.

[0052] d) An aqueous solution of nickel nitrate was selected and added to an alumina carrier by a room temperature impregnation method for 4 hours, dried at 90° C. for 4 hours, and calcined at 500° C. for 4 hours to obtain a hydrogenation catalyst.

[0053] The evaluation conditions for raffinate oil hydrogenation are: reaction temperature 130°C, reaction pressure range 2.5Mpa, and hydrogen-to-oil volume ratio 150:1.

[0054] The pore volume of the alumina support is 0.72 cm 2 / g, pore size 13.69nm, Na content in the carrier is 0.054wt%, Ni content loaded on the carrier is 21.11wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 15.5mg / 100g.

[0055] Example 2

[0056] a) ammonium bicarbonate is selected and prepared into 5000 g of an 8 wt% ammonium bicarbonate aqueous solution, which is then mixed with 2500 g of aluminum hydroxide and stirred for 3 hours for hydrothermal treatment at a temperature of 45° C. After the hydrothermal treatment, solid-liquid separation is performed to obtain treated aluminum hydroxide.

[0057] b) 12.5 g of nitric acid and 10 g of sesbania powder were mixed with the treated pseudo-boehmite and formed. The formed material was dried at 90° C. for 4 h and calcined at 550° C. for 6 h to obtain an alumina carrier precursor.

[0058] c) A magnesium nitrate aqueous solution was selected and added to the alumina carrier precursor by an impregnation method at 80° C. The impregnation time was 2 hours and the added amount was 5 g in terms of magnesium oxide to obtain an alumina carrier.

[0059] d) An aqueous solution of nickel nitrate was selected and added to an alumina carrier by a room temperature impregnation method for 4 hours, dried at 90° C. for 4 hours, and calcined at 500° C. for 4 hours to obtain a hydrogenation catalyst.

[0060] The evaluation conditions for raffinate oil hydrogenation are: reaction temperature 130°C, reaction pressure range 2.5Mpa, and hydrogen-to-oil volume ratio 150:1.

[0061] The pore volume of the alumina support is 0.69 cm 2 / g, pore size 12.71nm, Na content in the carrier is 0.013wt%, Ni content loaded on the carrier is 20.65wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 17.8mg / 100g.

[0062] Example 3

[0063] a) 5000 g of ammonia water with a mass concentration of 1 wt % was selected, and then mixed with 1000 g of pseudo-boehmite and stirred for 2 h for hydrothermal treatment at a temperature of 60° C. After the hydrothermal treatment, solid-liquid separation was performed to obtain the treated pseudo-boehmite.

[0064] b) 10 g of acetic acid and 12.5 g of hydroxymethyl cellulose were mixed with the treated pseudo-boehmite and molded. The molded material was dried at 90° C. for 4 h and calcined at 600° C. for 4 h to obtain an alumina carrier precursor.

[0065] c) An aqueous solution of lanthanum nitrate was selected and added to the alumina carrier precursor by impregnation at 45° C. The impregnation time was 4 hours and the added amount was 5 g in terms of lanthanum oxide to obtain an alumina carrier.

[0066] d) An aqueous solution of nickel acetate was selected and added to an alumina carrier by a room temperature impregnation method for 4 hours. The mixture was dried at 90° C. for 4 hours and calcined at 500° C. for 4 hours to obtain a hydrogenation catalyst.

[0067] The evaluation conditions for raffinate oil hydrogenation are: reaction temperature 130°C, reaction pressure range 2.5Mpa, and hydrogen-to-oil volume ratio 150:1.

[0068] The pore volume of the alumina support is 0.70 cm 2 / g, pore size 13.01nm, Na content in the carrier is 0.073wt%, Ni content loaded on the carrier is 20.22wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 20.6mg / 100g.

[0069] Example 4

[0070] The alumina carrier and the hydrogenation catalyst were prepared according to the method of Example 1, except that in step a), the temperature of the hydrothermal reaction was 45°C.

[0071] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0072] The pore volume of the alumina support is 0.69 cm 2 / g, pore size 12.56nm, Na content in the carrier is 0.064wt%, Ni content loaded on the carrier is 20.94wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 23.7mg / 100g.

[0073] Example 5

[0074] The alumina carrier and the hydrogenation catalyst were prepared according to the method of Example 1, except that in step a), the temperature of the hydrothermal reaction was 60°C.

[0075] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0076] The pore volume of the alumina support is 0.70 cm 2 / g, pore size 13.01nm, Na content in the carrier is 0.073wt%, Ni content loaded on the carrier is 20.22wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 20.6mg / 100g.

[0077] Example 6

[0078] The alumina carrier and the hydrogenation catalyst were prepared according to the method of Example 1, except that in step a), the temperature of the hydrothermal reaction was 90°C.

[0079] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0080] The pore volume of the alumina support is 0.75 cm 2 / g, pore size 14.33nm, Na content in the carrier is 0.048wt%, Ni content loaded on the carrier is 21.64wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 19.3mg / 100g.

[0081] Example 7

[0082] The alumina carrier and hydrogenation catalyst were used in accordance with the method of Example 1, except that in step a), the mass concentration of the ammonium carbonate aqueous solution was 0.2 wt%.

[0083] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0084] The pore volume of the alumina support is 0.60 cm 2 / g, pore diameter 11.98nm, Na content in the carrier is 0.101wt%, Ni content loaded on the carrier is 20.06wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 26.0mg / 100g.

[0085] Example 8

[0086] The alumina carrier and hydrogenation catalyst were used in accordance with the method of Example 1, except that in step a), the mass concentration of the ammonium carbonate aqueous solution was 1 wt %.

[0087] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0088] The pore volume of the alumina support is 0.68 cm 2 / g, pore size 12.78nm, Na content in the carrier is 0.064wt%, Ni content loaded on the carrier is 20.69wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 23.5mg / 100g.

[0089] Example 9

[0090] The alumina carrier and hydrogenation catalyst were used in accordance with the method of Example 1, except that in step a), the mass concentration of the ammonium carbonate aqueous solution was 8 wt %.

[0091] The raffinate oil hydrogenation evaluation was carried out under the same conditions as in Example 1.

[0092] The pore volume of the alumina support is 0.78 cm 2 / g, pore size 14.89nm, Na content in the carrier is 0.007wt%, Ni content loaded on the carrier is 22.55wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.00wt% and a bromine index of 13.4mg / 100g.

[0093] Comparative Example 1

[0094] The process is different from Example 1 only in that step a) is omitted, and the other steps are the same as Example 1. The specific process is as follows:

[0095] 1) 10 g of nitric acid, 10 g of sesbania powder and 1000 g of pseudo-boehmite were kneaded and formed, and the formed material was dried at 90° C. for 4 h and calcined at 600° C. for 4 h to obtain an alumina carrier precursor.

[0096] 2) An aqueous solution of magnesium nitrate was selected and added to the alumina carrier precursor by an impregnation method at 30° C. The impregnation time was 3 hours and the added amount was 5 g in terms of magnesium oxide to obtain an alumina carrier.

[0097] 3) An aqueous solution of nickel nitrate was selected and added to an alumina carrier by a room temperature impregnation method for 4 hours. The mixture was dried at 90° C. for 4 hours and calcined at 500° C. for 4 hours to obtain a hydrogenation catalyst.

[0098] The evaluation conditions for raffinate oil hydrogenation are: reaction temperature 130°C, reaction pressure range 2.5Mpa, and hydrogen-to-oil volume ratio 150:1.

[0099] The pore volume of the alumina support is 0.54 cm 2 / g, pore diameter 9.46nm, Na content in the carrier is 2.14wt%, Ni content loaded on the carrier is 16.41wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 1.32wt% and a bromine index of 127.7mg / 100g.

[0100] Comparative Example 2

[0101] The process is different from Example 1 only in that step c) is omitted, and the other steps are the same as Example 1. The specific process is as follows:

[0102] 1) Select ammonium carbonate and prepare it into 5000g of 3% ammonium carbonate aqueous solution, then repeatedly mix and stir with 1000g pseudo-boehmite for 2h, and the hydrothermal treatment temperature is 80° C. After the hydrothermal treatment, solid-liquid separation is performed to obtain the treated pseudo-boehmite.

[0103] 2) 10 g of nitric acid and 10 g of sesbania powder were mixed with the treated pseudo-boehmite and molded. The molded material was dried at 90° C. for 4 h and calcined at 600° C. for 4 h to obtain an alumina carrier.

[0104] 3) An aqueous solution of nickel nitrate was selected and added to an alumina carrier by a room temperature impregnation method for 4 hours. The mixture was dried at 90° C. for 4 hours and calcined at 500° C. for 4 hours to obtain a hydrogenation catalyst.

[0105] The evaluation conditions for raffinate oil hydrogenation are: reaction temperature 130°C, reaction pressure range 2.5Mpa, and hydrogen-to-oil volume ratio 150:1.

[0106] The pore volume of the alumina support is 0.70 cm 2 / g, pore size 12.98nm, Na content in the carrier is 0.10wt%, Ni content loaded on the carrier is 20.19wt%. The hydrogenation product of the hydrogenation catalyst prepared by the catalyst has a benzene content of 0.95wt% and a bromine index of 73.5mg / 100g.

[0107] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing an alumina carrier, comprising the following steps: a) subjecting a mixture of an aluminum source and an aqueous solution of an inorganic ammonium salt and / or aqueous ammonia to a hydrothermal treatment; b) subjecting the product of the hydrothermal treatment to solid-liquid separation to obtain a solid material; c) kneading, shaping and calcining the solid material with a mixture of a peptizing agent and an auxiliary agent; d) loading a metal additive on the calcined product to obtain the alumina carrier.

2. The preparation method according to claim 1, It is characterized in that The aluminum source comprises at least one of pseudo-boehmite, aluminum hydroxide, aluminum oxide or aluminum sol; and / or The inorganic ammonium salt comprises at least one of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium nitrate or aluminum ammonium sulfate; and / or The peptizing agent is selected from at least one of nitric acid, acetic acid or citric acid; and / or The auxiliary agent is selected from at least one of hydroxypropyl cellulose, hydroxymethyl cellulose or sesbania powder; and / or The metal additive includes alkaline earth metal and / or rare earth metal. Preferably, the alkaline earth metal comprises Mg and / or Ca, Preferably, the rare earth metal includes La and / or Ce.

3. The preparation method according to claim 1 or 2, It is characterized in that In step a), the ratio of the mass of the aluminum source to the sum of the mass of the inorganic ammonium salt aqueous solution and the ammonia water is 1:(5-20), preferably, the mass concentration of the inorganic ammonium salt aqueous solution and / or the ammonia water is 1-10%, preferably 3-8%; and / or In step c), the amount of the peptizing agent added is 0.5-10% of the mass of the solid material; and / or In step c), the amount of the additive added is 0.5-10% of the mass of the aluminum source; and / or In step d), the amount of the metal additive added is 0.5-3.0% of the mass of the calcined product, calculated as the oxide of the metal additive.

4. The preparation method according to any one of claims 1 to 3, It is characterized in that In step a), the temperature of the hydrothermal treatment is 30-90°C, preferably 70-90°C; and / or The hydrothermal treatment time is 0.5-5h, preferably 1-3h.

5. The preparation method according to any one of claims 1 to 4, It is characterized in that In step c), the calcination temperature is 450-850°C, preferably 500-700°C; and / or The calcination time is 0.5-10 h, preferably 1-6 h.

6. The preparation method according to any one of claims 1 to 5, It is characterized in that In step d), a metal additive is loaded on the calcined product by an impregnation method; Preferably, the impregnation temperature is 25-90°C, preferably 25-60°C; Preferably, the immersion time is 0.5-5 h, preferably 1-4 h.

7. An alumina carrier prepared according to the preparation method according to any one of claims 1 to 6, It is characterized in that The pore volume of the alumina carrier is greater than 0.6 cm 2 / g, preferably greater than 0.65cm 2 / g, more preferably 0.65-0.75cm 2 / g; and / or The pore size of the alumina support is greater than 10 nm, preferably greater than 12 nm, more preferably 12-15 nm; and / or The Na content in the alumina carrier is less than 0.5 wt %, preferably less than 0.1 wt %, and more preferably less than 0.08 wt %.

8. A hydrogenation catalyst, comprising an alumina carrier prepared by the preparation method according to any one of claims 1 to 6 or an alumina carrier according to claim 7, and Ni metal supported on the alumina carrier, Preferably, based on the total mass of the hydrogenation catalyst, the content of the Ni metal is 20 wt% or more, preferably 20-25 wt%.

9. The method for preparing the hydrogenation catalyst according to claim 8, It is characterized in that The preparation method comprises immersing the alumina support in a solution containing a nickel metal salt, Preferably, the nickel metal salt includes at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or nickel ammonia solution.

10. Use of the alumina carrier prepared by the preparation method according to any one of claims 1 to 6, the alumina carrier according to claim 7, the hydrogenation catalyst according to claim 8 or the hydrogenation catalyst prepared by the preparation method according to claim 9 in the hydrogenation reaction of aromatic raffinate or heavy aromatics.