Silica-alumina supported catalysts and methods of making and using same

Abstract

The application relates to the technical field of catalysts, and discloses a silicon-aluminum carrier catalyst, a preparation method and application. The preparation method of the silicon-aluminum carrier catalyst comprises the following steps: (1) mixing an acidic silicon-aluminum colloidal solution, low-silicon X molecular sieve, a precipitating agent, activated carbon and a soft template, drying silicon-aluminum mixed slurry obtained in the step, and obtaining a silicon-aluminum carrier; (2) mixing the silicon-aluminum carrier, colloidal pseudoboehmite and a binder, adjusting the pH value to 7-8, roasting the obtained mixture, and obtaining a strip-shaped silicon-aluminum carrier; (3) loading nickel-molybdenum-phosphorus on the strip-shaped silicon-aluminum carrier, and then reducing. The silicon-aluminum carrier catalyst prepared according to the method has the characteristics of high specific surface area, high activity, high stability and adjustable acidity, so that the catalytic activity in the application of heavy aromatic hydrocarbon pre-hydrogenation reaction is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a silicon-aluminum carrier catalyst, a preparation method and application thereof. BACKGROUND

[0002] With the intensification of the world's crude oil heavy and poor quality trend, and the continuous improvement of environmental protection regulations on the quality of gasoline and diesel, after delayed coking treatment of poor heavy aromatics, coking wax oil can be further treated by hydroprocessing, thereby further improving its light degree and improving its reaction efficiency and product quality in catalytic cracking or hydrocracking unit, which is an important technical route and the development trend of the refining industry. Pre-hydrogenation of heavy aromatics is an important chemical technology, mainly applied to efficient utilization of heavy aromatics resources. In this process, heavy aromatics are treated through a series of reactions to obtain lighter aromatic products, improving the utilization efficiency of heavy aromatics.

[0003] Most of the pre-hydrogenation catalysts used at home and abroad at present are alumina carriers with cobalt, molybdenum, nickel, tungsten as active components. In recent years, in order to improve the hydrogenation performance of the catalyst, some work has been done in carrier modification, the use of new materials and preparation methods. The conventional alumina carrier has too strong interaction between the active metals, which leads to high dispersion of the active metals, which is not conducive to the reduction of the active metals, resulting in problems such as poor hydrogenation activity of the supported hydrogenation catalyst with alumina carrier. Simply modifying the surface of the alumina carrier or adding organic additives in the metal impregnation solution all have the problem of unsatisfactory dispersion of the active metals. Patent CN117085729A discloses a catalyst for lightening of heavy aromatics and a preparation method and application thereof. The catalyst comprises HZSM-5 molecular sieve, and the preparation method of the HZSM-5 molecular sieve comprises the following steps: step 1, mixing a silicon source, a molecular sieve, water and an inorganic base to obtain a reaction product; step 2, mixing a silicon source, an aluminum source, water and an inorganic base to form a mixture, then adding the reaction product obtained in step 1, crystallizing, and washing, drying and calcining the crystallization product to obtain ZSM-5 molecular sieve; and step 3, ion exchanging the ZSM-5 molecular sieve to obtain HZSM-5 molecular sieve. The carrier of the method has low acid content, fewer strong acid centers and smaller specific surface area, thereby having low catalytic activity.

[0004] Therefore, it is urgent to develop a catalyst with adjustable acidity and high activity to improve the catalytic activity in the pre-hydrogenation reaction of heavy aromatics. SUMMARY

[0005] One of the purposes of the present application is to overcome the problems of small specific surface area, difficult to control acidity, poor stability and low catalytic activity of the catalyst in the pre-hydrogenation of heavy aromatic hydrocarbons in the prior art, and to provide a silicon-aluminum carrier catalyst, a preparation method and application thereof. The silicon-aluminum carrier catalyst prepared by the preparation method has adjustable acidity, high specific surface area, high activity and good stability.

[0006] To achieve the above-mentioned purpose, the first aspect of the present application provides a preparation method of a silicon-aluminum carrier catalyst, which comprises the following steps:

[0007] (1) mixing an acidic silicon-aluminum colloidal solution, a low-silicon X molecular sieve, a precipitating agent, activated carbon and a soft template, drying the obtained silicon-aluminum mixed slurry to obtain a silicon-aluminum carrier;

[0008] (2) mixing the silicon-aluminum carrier, colloidal pseudo-boehmite and a binder, adjusting the pH to 7-8, and calcining the obtained mixture to obtain a strip-shaped silicon-aluminum carrier;

[0009] (3) loading nickel-molybdenum-phosphorus on the strip-shaped silicon-aluminum carrier, and then reducing.

[0010] Preferably, the preparation method of the acidic silicon-aluminum colloidal solution in step (1) comprises the following steps:

[0011] (a) mixing a first aluminum source and a first inorganic acid to obtain a mixed solution, adding a first water glass solution to the mixed solution, and adjusting the pH to 1.5-2.0 to obtain a silicon-aluminum seed solution;

[0012] (b) performing first aging and second aging on the seed solution to obtain a silica sol;

[0013] (c) mixing a second aluminum source and a third inorganic acid and adding them to the silica sol, and adjusting the pH to 4.5-5.5 to obtain the acidic silicon-aluminum colloidal solution.

[0014] Preferably, in step (b), the process of the first aging comprises: mixing a second water glass solution and a second inorganic acid and adding them to the seed solution, and adjusting the pH to 2.0-2.5.

[0015] Preferably, the temperature of the first aging is lower than 15℃, preferably 10-12℃.

[0016] Preferably, in step (b), the process of the second aging comprises: performing the second aging on the obtained mixture after the first aging.

[0017] Preferably, the temperature of the second aging is 30-50℃.

[0018] Preferably, the first aluminum source and the second aluminum source each comprise at least one of aluminum sulfate, aluminum nitrate, and aluminum trichloride.

[0019] Preferably, the first inorganic acid, the second inorganic acid, and the third inorganic acid each comprise sulfuric acid and / or nitric acid.

[0020] Preferably, in step (a), the mass ratio of the first water glass solution and the first aluminum source is (2-5): 1, on an oxide basis.

[0021] Preferably, in step (b), the mass ratio of the second water glass solution and the seed crystal is (50-100): 1, on an oxide basis.

[0022] Preferably, in step (c), the mass ratio of the silica sol and the second aluminum source is (10-20): 1, on an oxide basis.

[0023] Preferably, in step (1), the precipitant comprises at least one of a basic carbonate.

[0024] Preferably, the precipitant comprises at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate.

[0025] Preferably, in step (1), the soft template comprises at least one of sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer.

[0026] Preferably, in step (1), the mass ratio of the acidic silica-alumina colloidal solution and the low-silica X molecular sieve is (5-10): 1, on an oxide basis.

[0027] Preferably, in step (1), the temperature at which the acidic silica-alumina colloidal solution, low-silica X molecular sieve, precipitant, activated carbon, and soft template are mixed is 50-70 °C.

[0028] Preferably, in step (2), the binder comprises at least one of hydroxymethylcellulose, soluble starch, and sodium polyacrylate.

[0029] Preferably, in step (2), the mass ratio of the silica-alumina support, the colloidal pseudoboehmite, and the binder is (60-80):(2-4): 1.

[0030] Preferably, in step (2), the conditions of the calcination comprise a temperature of 400-600 °C and a time of 3-6 h.

[0031] Preferably, in step (3), the process of loading the nickel-molybdenum-phosphorus to the strip-shaped silicon-aluminum carrier comprises: adding ammonia solution into molybdenum trioxide, nickel monoxide and phosphorus pentoxide, adjusting the pH value to 3-5 to obtain a nickel-molybdenum-phosphorus solution, and immersing the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution.

[0032] Preferably, in step (3), the mass ratio of the molybdenum trioxide, the nickel monoxide and the phosphorus pentoxide is (28-32):(4-6):1.

[0033] Preferably, in step (3), the reduction condition comprises: the temperature is 400-600℃, and the time is 2-5h.

[0034] The second aspect of the present application provides the silicon-aluminum carrier catalyst prepared by the preparation method.

[0035] The third aspect of the present application provides the application of the above-mentioned silicon-aluminum carrier catalyst in the pre-hydrogenation reaction of heavy aromatic hydrocarbon.

[0036] Compared with the prior art, the present application has the following beneficial effects:

[0037] Through the above technical solution, the seed solution plays a guiding role in the preparation process of the silica sol, guiding the chain growth of the silicon source, and the silica sol with high specific surface area and high activity is prepared, and the aluminum in the silicon-aluminum carrier is distributed in the center position of the carrier, having the advantage of adjustable acidity; the silicon-aluminum carrier prepared by introducing low-silicon X molecular sieve has the characteristics of high specific surface area and adjustable acidity; the precipitating agent prevents the silicon-aluminum source from depositing too fast and blocking the main pore channel of the silicon-aluminum body; the activated carbon and soft template make the pore size of the silicon-aluminum carrier more abundant, thereby improving the activity and stability of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is the naphthalene conversion rate of the example of the present application in a long period of 1000h;

[0039] Figure 2 is the tetralin selectivity of the example of the present application in a long period of 1000h. DETAILED DESCRIPTION

[0040] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0041] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values from the lower value to the upper value, inclusive of both values, and to sub-ranges falling within the specified range. In this context, individual points within a range should not be dismissed from the scope of the range. For numeric ranges, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to generate one or more new numeric ranges, which should be considered as specifically disclosed herein.

[0042] The preparation method of the silicon-aluminum carrier catalyst described in the present application comprises the following steps:

[0043] (1) mixing an acidic silicon-aluminum colloid solution, a low-silicon X molecular sieve, a precipitant, activated carbon and a soft template, drying the obtained silicon-aluminum mixed slurry to obtain a silicon-aluminum carrier;

[0044] (2) mixing the silicon-aluminum carrier, a colloidal pseudo-boehmite and a binder, adjusting the pH to 7-8, and roasting the obtained mixture to obtain a strip-shaped silicon-aluminum carrier;

[0045] (3) loading nickel-molybdenum-phosphorus on the strip-shaped silicon-aluminum carrier, and then reducing.

[0046] In the method described in the present application, the structure of the low-silicon X molecular sieve is destroyed under acidic conditions to release an active aluminum source, and the aluminum is coated on the surface of the silicon-aluminum colloid in a core-shell structure, thereby regulating the acidity of the carrier and improving the stability of the carrier; the molecular sieve body after the release of aluminum has high activity, and interacts with the acidic silicon-aluminum colloid to obtain a silicon-aluminum carrier with high specific surface area; and the deposition of the silicon-aluminum source is prevented from being too fast by the precipitant to block the pore channels of the silicon-aluminum body; the pore size of the silicon-aluminum carrier is made more abundant by the activated carbon and the soft template, thereby improving the activity and stability of the catalyst.

[0047] In the method described in the present application, the preparation method of the acidic silicon-aluminum colloid solution in step (1) comprises the following steps:

[0048] (a) mixing a first aluminum source and a first inorganic acid to obtain a mixed solution, adding a first water glass solution to the mixed solution, and adjusting the pH to 1.5-2.0 to obtain a silicon-aluminum seed solution;

[0049] (b) performing first aging and second aging on the seed solution to obtain a silica sol;

[0050] (c) mixing a second aluminum source and a third inorganic acid and adding the silica sol, and adjusting the pH to 4.5-5.5 to obtain the acidic silicon-aluminum colloid solution.

[0051] In the present application, the seed solution of silicon-aluminum plays a guiding role in the preparation of silica sol, breaks the growth mode of traditional spherical silica sol, guides the chain growth of silicon source, and obtains silica sol with high specific surface area and high activity. Moreover, the introduction of aluminum source makes the aluminum in the obtained silicon-aluminum carrier be distributed at the center position of the carrier, and has the advantage of adjustable acidity.

[0052] In the present application, in step (a), the process of adding the first water glass solution to the mixed solution can include: diluting the first water glass solution, and adding the diluted first water glass solution dropwise to the mixed solution.

[0053] In the method of the present application, in step (b), in order to chain growth of silicon source, the process of the first aging preferably includes: mixing the second water glass solution and the second inorganic acid and adding them to the seed solution, and adjusting the pH to 2.0-2.5.

[0054] In the present application, in step (b), in order to chain growth of silicon source, the second water glass solution and the second inorganic acid are mixed and preferably added dropwise to the seed solution.

[0055] In the method of the present application, the temperature of the first aging can be lower than 15°C, and is preferably 10-12°C.

[0056] In the method of the present application, in step (b), the process of the second aging can include: subjecting the obtained mixture after the first aging to the second aging.

[0057] In the method of the present application, in order to make the silica sol have the characteristics of high specific surface area and high activity, the temperature of the second aging is preferably 30-50°C, and more preferably 40-50°C.

[0058] In the present application, in step (c), in order to make the aluminum in the silicon-aluminum carrier be distributed at the center position of the carrier and have the characteristics of adjustable acidity, the second aluminum source and the third inorganic acid are mixed and preferably added dropwise to the silica sol.

[0059] In the method of the present application, the first aluminum source and the second aluminum source each include at least one of aluminum sulfate, aluminum nitrate, and aluminum chloride.

[0060] In the method of the present application, the first inorganic acid, the second inorganic acid, and the third inorganic acid include sulfuric acid and / or nitric acid.

[0061] In the present application, in step (a), the concentration of the first aluminum source in the first inorganic acid can be 5-15 g / L, and is preferably 8-10 g / L.

[0062] In the present application, in step (a), the concentration of the first water glass solution can be 240-260 g / L, preferably 245-255 g / L.

[0063] In the present application, in step (a), the concentration of the diluted first water glass solution can be 80-120 g / L, preferably 100-120 g / L.

[0064] In the present application, in step (a), the concentration of the first inorganic acid can be 5-10 wt%, preferably 6-8 wt%.

[0065] In the method of the present application, in step (a), the mass ratio of the first water glass to the first aluminum source, on an oxide basis, can be (2-5):1, preferably (2.5-4.5):1.

[0066] In the present application, in step (b), the concentration of the second water glass solution can be 120-180 g / L, preferably 140-160 g / L.

[0067] In the present application, in step (b), the concentration of the second inorganic acid can be 8-15 wt%, preferably 10-12 wt%.

[0068] In the method of the present application, in step (b), the mass ratio of the second water glass to the seed solution, on an oxide basis, can be (50-100):1, preferably (60-80):1.

[0069] In the present application, in step (c), the concentration of the second aluminum source in the third inorganic acid can be 15-25 g / L, preferably 18-22 g / L.

[0070] In the present application, in step (c), the concentration of the third inorganic acid can be 8-15 wt%, preferably 10-12 wt%.

[0071] In the method of the present application, in step (c), the mass ratio of the silica sol to the second aluminum source, on an oxide basis, can be (10-20):1, preferably (15-20):1.

[0072] In the method of the present application, in step (1), to prevent the silicon-aluminum source from being deposited too fast and clogging the silicon-aluminum body pores, the precipitant is preferably an alkaline carbonate.

[0073] In the method of the present application, the precipitant can be at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate, and the precipitant is preferably sodium carbonate and / or ammonium carbonate.

[0074] In the present application, in step (1), in order to make the pore size of the silicon-aluminum carrier more abundant, the particle size of the activated carbon is preferably 100-200 mesh, more preferably 150-200 mesh.

[0075] In the method of the present application, in step (1), in order to make the pore size of the silicon-aluminum carrier more abundant, the soft template is preferably at least one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and more preferably, the soft template is sodium dodecyl benzene sulfonate and / or cetyl trimethyl ammonium bromide.

[0076] In the present application, in step (1), the mass ratio of the low-silicon X molecular sieve, the precipitator, the activated carbon and the soft template can be (10-20):(40-80):(2-4):1.

[0077] In the method of the present application, in step (1), in order to make the silicon-aluminum carrier have high stability, high specific surface area and high activity, the mass ratio of the acidic silicon-aluminum colloidal solution and the low-silicon X molecular sieve is preferably (5-10):1 in terms of oxides.

[0078] In the method of the present application, in step (1), in order to make the silicon-aluminum carrier have the characteristics of adjustable acidity, the temperature of the process of mixing the acidic silicon-aluminum colloidal solution, the low-silicon X molecular sieve, the precipitator, the activated carbon and the soft template is preferably 50-70℃, more preferably 55-65℃.

[0079] In the method of the present application, in step (1), the drying conditions include that the temperature can be 100-200℃, preferably 120-150℃, and the time can be 8-15h, preferably 10-12h.

[0080] In the method of the present application, in step (2), the process of calcining the obtained mixture can further include extruding and drying the obtained mixture.

[0081] In the present application, in step (2), the drying conditions include that the temperature can be 100-200℃, preferably 120-150℃, and the time can be 8-15h, preferably 10-12h.

[0082] In the method of the present application, in step (2), in order to improve the activity and stability of the catalyst, the binder is preferably at least one of hydroxymethyl cellulose, soluble starch and sodium polyacrylate, and more preferably, the binder is hydroxymethyl cellulose.

[0083] In the method of the present application, in step (2), the mass ratio of the silicon-aluminum carrier, the peptized pseudo-boehmite and the binder can be (60-80):(2-4):1, preferably (60-70):(2-4):1.

[0084] In the method of the present application, in step (2), the calcination conditions include that the temperature can be 400-600℃, preferably 400-500℃; and the time can be 3-6h, preferably 4-5h.

[0085] In the method of the present application, in step (3), the process of loading nickel-molybdenum-phosphorus to the strip-shaped silicon-aluminum carrier can further include adding ammonia solution into molybdenum trioxide, nickel monoxide and phosphorus pentoxide, adjusting the pH value to 3-5 to obtain a nickel-molybdenum-phosphorus solution, and immersing the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution.

[0086] In the method of the present application, in step (3), in order to improve the activity of the catalyst, the ammonia solution is preferably added dropwise under stirring conditions in molybdenum trioxide, nickel monoxide and phosphorus pentoxide.

[0087] In the method of the present application, in step (3), the stirring rate can be 200-400r / min, preferably 300-400r / min.

[0088] In the method of the present application, in step (3), immersing the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution can adopt equal-volume impregnation.

[0089] In the method of the present application, in step (3), immersing the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution can be carried out in a sugar-coating machine.

[0090] In the method of the present application, in step (3), the rotating speed of the sugar-coating machine can be 20-46r / min, preferably 28-40r / min.

[0091] In the method of the present application, in step (3), the time for immersing the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution can be 1-3h, preferably 1.5-2.5h.

[0092] In the method of the present application, in step (3), the mass ratio of the molybdenum trioxide, the nickel monoxide and the phosphorus pentoxide can be (28-32):(4-6):1, preferably (30-32):(4-6):1.

[0093] In the present application, in step (3), the concentration of the ammonia solution can be 0.25-1wt%.

[0094] In the present application, in step (3), the concentration of the molybdenum trioxide in the ammonia solution can be 2-6 g / L.

[0095] In the present application, in step (3), the concentration of the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution can be 1.5-3.5 g / L.

[0096] In the present application, in step (3), the loading of the nickel-molybdenum-phosphorus on the strip-shaped silicon-aluminum carrier can further include drying.

[0097] In the present application, in step (3), the drying conditions include that the temperature can be 100-200 ℃, preferably 120-150 ℃, and the time can be 8-15 h, preferably 10-12 h.

[0098] In the method of the present application, in step (3), the reduction conditions include that the temperature can be 400-600 ℃, preferably 400-500 ℃, and the time can be 3-6 h, preferably 4-5 h.

[0099] In some embodiments, the method for preparing the silicon-aluminum carrier catalyst of the present application includes the following steps:

[0100] (1) mixing a first aluminum source and a first inorganic acid to obtain a mixed solution, diluting a first water glass solution, adding the diluted first water glass solution dropwise into the mixed solution, adjusting the pH to 1.5-2.0 to obtain a silicon-aluminum seed solution; mixing a second water glass solution and a second inorganic acid under the condition of a temperature lower than 15 ℃ and adding them dropwise into the seed solution, adjusting the pH to 2.0-2.5, and aging the obtained mixture under the condition of a temperature of 30-50 ℃ to obtain a silica sol; mixing a second aluminum source and a third inorganic acid and adding them dropwise into the silica sol, adjusting the pH to 4.5-5.5 to obtain the acidic silicon-aluminum colloidal solution; wherein the first aluminum source and the second aluminum source are each at least one of aluminum sulfate, aluminum nitrate and aluminum trichloride, the first inorganic acid, the second inorganic acid and the third inorganic acid are each sulfuric acid and / or nitric acid, the mass ratio of the first water glass and the first aluminum source is (2-5) : 1 in terms of oxides, the mass ratio of the second water glass and the seed is (50-100) : 1, and the mass ratio of the silica sol and the second aluminum source is (10-20) : 1;

[0101] (2) mixing the acidic silica-alumina colloidal solution, the low-silica X molecular sieve, a precipitant, 100-200 mesh activated carbon and a soft template at a temperature of 50-70°C, adjusting the pH value to 7-8, drying the obtained silica-alumina mixed slurry at a temperature of 100-200°C for 8-15h to obtain a silica-alumina carrier; wherein the precipitant is an alkaline carbonate, the soft template is at least one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, the mass ratio of the low-silica X molecular sieve, the precipitant, the activated carbon and the soft template is (10-20):(40-80):(2-4):1; the mass ratio of the acidic silica-alumina colloidal solution and the low-silica X molecular sieve is (5-10):1 in terms of oxides;

[0102] (3) mixing the silica-alumina carrier, colloidal pseudoboehmite and a binder, extruding the obtained mixture, drying at a temperature of 100-200°C for 8-15h, and calcining at a temperature of 400-600°C for 3-6h to obtain a strip-shaped silica-alumina carrier; wherein the binder is at least one of hydroxymethyl cellulose, soluble starch and sodium polyacrylate, the mass ratio of the silica-alumina carrier, the colloidal pseudoboehmite and the binder is (60-80):(2-4):1;

[0103] (4) adding ammonia solution drop by drop in the molybdenum trioxide, nickel monoxide and phosphorus pentoxide under stirring at a rate of 200-400r / min, adjusting the pH value to 3-5 to obtain a nickel-molybdenum-phosphorus solution, placing the strip-shaped silica-alumina carrier in a sugar-coating machine at a rotating speed of 20-46r / min, adding the nickel-molybdenum-phosphorus solution, impregnating for 1-3h, drying at a temperature of 100-200°C for 8-15h, and then calcining and reducing at a temperature of 400-600°C for 3-6h, wherein the mass ratio of the molybdenum trioxide, the nickel monoxide and the phosphorus pentoxide is (28-32):(4-6):1, the concentration of the molybdenum trioxide in the ammonia solution is 2-6g / L, and the concentration of the strip-shaped silica-alumina carrier in the nickel-molybdenum-phosphorus solution is 1.5-3.5g / L.

[0104] In some other embodiments, the preparation method of the silica-alumina carrier catalyst of the present application comprises the following steps:

[0105] (1) mixing a first aluminum source and a first inorganic acid to obtain a mixed solution, diluting a first water glass solution, adding the diluted first water glass solution dropwise into the mixed solution, adjusting pH to 1.5-2.0, to obtain a seed solution of silicon-aluminum; mixing a second water glass solution and a second inorganic acid under the condition of a temperature of 10-12℃ and adding the mixture dropwise into the seed solution, adjusting pH to 2.0-2.5, aging the obtained mixture under the condition of a temperature of 40-50℃, to obtain a silica sol; mixing a second aluminum source and a third inorganic acid and adding the mixture dropwise into the silica sol, adjusting pH to 4.5-5.5, to obtain the acidic silicon-aluminum colloidal solution; wherein the first aluminum source and the second aluminum source are each at least one of aluminum sulfate, aluminum nitrate and aluminum trichloride, the first inorganic acid, the second inorganic acid and the third inorganic acid are each sulfuric acid and / or nitric acid, the mass ratio of the first water glass and the first aluminum source is (2.5-4.5):1 in terms of oxides, the mass ratio of the second water glass and the seed is (60-80):1, and the mass ratio of the silica sol and the second aluminum source is (15-20):1;

[0106] (2) mixing the acidic silicon-aluminum colloidal solution, a low-silicon X molecular sieve, a precipitator, 120-180 mesh activated carbon and a soft template under the condition of a temperature of 55-65℃, adjusting pH to 7-8, drying the obtained silicon-aluminum mixed slurry under the condition of a temperature of 120-150℃ for 10-12h, to obtain a silicon-aluminum carrier; wherein the precipitator is sodium carbonate and / or ammonium carbonate, the soft template is sodium dodecyl benzene sulfonate and / or cetyl trimethyl ammonium bromide, the mass ratio of the low-silicon X molecular sieve, the precipitator, the activated carbon and the soft template is (10-20):(40-80):(2-4):1, and the mass ratio of the acidic silicon-aluminum colloidal solution and the low-silicon X molecular sieve is (5-10):1 in terms of oxides;

[0107] (3) mixing the silicon-aluminum carrier, a colloidal pseudo-boehmite and a binder, extruding the obtained mixture, drying the extruded mixture under the condition of a temperature of 120-150℃ for 10-12h, and calcining the dried mixture under the condition of a temperature of 400-500℃ for 4-5h, to obtain a strip-shaped silicon-aluminum carrier; wherein the binder is hydroxymethyl cellulose, and the mass ratio of the silicon-aluminum carrier, the colloidal pseudo-boehmite and the binder is (60-70):(2-4):1;

[0108] (4) adding ammonia solution drop by drop in molybdenum trioxide, nickel monoxide and phosphorus pentoxide under stirring at a speed of 300-400 r / min, adjusting pH value to 3-5 to obtain a nickel-molybdenum-phosphorus solution, placing the strip-shaped silicon-aluminum carrier in a sugar-coating machine at a rotating speed of 28-40 r / min, adding the nickel-molybdenum-phosphorus solution, impregnating for 1.5-2.5 h, drying at a temperature of 130-170 ℃ for 8-15 h, and then performing reduction roasting at a temperature of 450-550 ℃ for 3-6 h, wherein the mass ratio of the molybdenum trioxide, the nickel monoxide and the phosphorus pentoxide is (30-32):(4-6):1, the concentration of the molybdenum trioxide in the ammonia solution is 2-6 g / L, and the concentration of the strip-shaped silicon-aluminum carrier in the nickel-molybdenum-phosphorus solution is 1.5-3.5 g / L.

[0109] The application further provides the silicon-aluminum carrier catalyst prepared by the preparation method.

[0110] In the silicon-aluminum carrier catalyst, the specific surface area of the silicon-aluminum carrier catalyst can be 340-480 m 2 / g, and specifically can be 340 m 2 / g, 350 m 2 / g, 360 m 2 / g, 370 m 2 / g, 380 m 2 / g, 400 m 2 / g, 420 m 2 / g, 440 m 2 / g or 480 m 2 / g.

[0111] In the silicon-aluminum carrier catalyst, the pore volume of the silicon-aluminum carrier catalyst can be 0.60-0.90 cm 3 / g, and specifically can be 0.6 cm 3 / g, 0.65 cm 3 / g, 0.7 cm 3 / g, 0.8 cm 3 / g or 0.9 cm 3 / g.

[0112] In the silicon-aluminum carrier catalyst, the total acid amount of the silicon-aluminum carrier catalyst can be 0.4-0.8 mmol / g, and specifically can be 0.4 mmol / g, 0.5 mmol / g, 0.6 mmol / g, 0.7 mmol / g or 0.8 mmol / g.

[0113] In the silicon-aluminum carrier catalyst described in the present application, the strong acid amount of the silicon-aluminum carrier catalyst can be 0.12-0.20 mmol / g, and specifically can be 0.12 mmol / g, 0.14 mmol / g, 0.16 mmol / g, 0.18 mmol / g or 0.20 mmol / g.

[0114] In the silicon-aluminum carrier catalyst described in the present application, the silicon-aluminum carrier catalyst comprises the strip-shaped silicon-aluminum carrier, a nickel component, a molybdenum component and a phosphorus component.

[0115] In the silicon-aluminum carrier catalyst described in the present application, the content of the nickel component can be 2.5-5 wt%, preferably 2.5-4 wt%, based on the total weight of the silicon-aluminum carrier catalyst; the content of the molybdenum component can be 15-30 wt%, preferably 15-20 wt%; and the content of the phosphorus component can be 0.5-1 wt%, preferably 0.5-0.7 wt%.

[0116] The present application also provides the use of the above-mentioned silicon-aluminum carrier catalyst in catalyzing the pre-hydrogenation of heavy aromatic hydrocarbons. The silicon-aluminum carrier catalyst described in the present application has high catalytic activity in catalyzing the pre-hydrogenation of heavy aromatic hydrocarbons, and has high naphthalene conversion rate and tetrahydronaphthalene selectivity.

[0117] In the use described in the present application, the catalytic pre-hydrogenation of heavy aromatic hydrocarbons is carried out in a pre-hydrogenation reactor, and the conditions of the pre-hydrogenation reactor include: the inlet temperature can be 140-260°C, preferably 150-250°C; the reaction pressure can be 4-7 MPa, preferably 4-5 MPa; the hydrogen mass space velocity can be 1.5-4.0 h -1 , preferably 2.0-3.5 h -1 ; and the hydrogen-hydrocarbon volume ratio can be 600-1100 Nm 3 / m 3 , preferably 700-1000 Nm 3 / m 3 . In this context, the pressure is gauge pressure.

[0118] The silicon-aluminum carrier catalyst, the preparation method and the use described in the present application are further illustrated by the following examples. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following examples.

[0119] In the following examples, the experimental methods are all conventional methods in the art unless otherwise specified. The experimental materials used in the following examples are all commercially available unless otherwise specified.

[0120] Example 1

[0121] (1) 1 g of aluminum sulfate and sulfuric acid with a concentration of 7 wt% were mixed to obtain a mixed solution, a water glass solution with a concentration of 250 g / L was diluted to 100 g / L, and the diluted water glass solution was added dropwise to the mixed solution, the mass ratio of the water glass and the aluminum sulfate was 3: 1 in terms of oxides, the pH was adjusted to 2.0, and a seed solution of silicon aluminum was obtained; a water glass solution with a concentration of 150 g / L and sulfuric acid with a concentration of 11 wt% were mixed and added dropwise to the seed solution under the condition that the temperature was 11 ℃, the mass ratio of the water glass and the seed solution was 75: 1 in terms of oxides, the pH was adjusted to 2.5, and the obtained mixture was aged under the condition that the temperature was 50 ℃, and a silica sol was obtained; 2 g of aluminum sulfate and 100 mL of sulfuric acid with a concentration of 11 wt% were mixed and added dropwise to the silica sol, the mass ratio of the silica sol and the aluminum sulfate was 15: 1 in terms of oxides, the pH was adjusted to 4.5, and an acidic silica-aluminum colloidal solution was obtained;

[0122] (2) The acidic silica-aluminum colloidal solution obtained in step (1), low-silicon X molecular sieve, sodium carbonate, 150-mesh activated carbon, and sodium dodecylbenzenesulfonate were mixed under the condition that the temperature was 60 ℃, wherein the mass ratio of the acidic silica-aluminum colloidal solution: low-silicon X molecular sieve: activated carbon: sodium dodecylbenzenesulfonate was 75: 15: 60: 3: 1, the pH value was adjusted to 7, and the obtained silica-aluminum mixed slurry was dried under the condition that the temperature was 130 ℃ for 11 h to obtain a silica-aluminum carrier;

[0123] (3) The silica-aluminum carrier, peptized pseudoboehmite, and hydroxymethyl cellulose were mixed, wherein the mass ratio of the silica-aluminum carrier, the peptized pseudoboehmite, and the binder was 70: 3: 1, the obtained mixture was extruded, then dried under the condition that the temperature was 120 ℃ for 15 h, and calcined under the condition that the temperature was 500 ℃ for 4 h to obtain a strip-shaped silica-aluminum carrier;

[0124] (4) 0.5 wt% of ammonia solution was added dropwise to molybdenum trioxide, nickel monoxide, and phosphorus pentoxide under the condition of stirring at a speed of 300 r / min, the pH value was adjusted to 4, and a nickel-molybdenum-phosphorus solution was obtained, wherein the mass ratio of the molybdenum trioxide, the nickel monoxide, and the phosphorus pentoxide was 30: 5: 1. 100 g of the strip-shaped silica-aluminum carrier was placed in a sugar coating machine with a rotating speed of 35 r / min, 100 mL of the nickel-molybdenum-phosphorus solution was added, and impregnation was performed for 2 h, then drying was performed under the condition that the temperature was 150 ℃ for 10 h, and then reduction calcination was performed under the condition that the temperature was 500 ℃ for 4 h. The specific surface area, pore volume, total acid amount, and strong acid amount were tested and recorded in Table 1.

[0125] Catalytic C9 + The heavy aromatic hydrocarbon hydrogenation was performed in a pre-hydrogenation reactor, and the conditions of the pre-hydrogenation reactor included: the inlet temperature was 200 ℃, the reaction pressure was 5 MPa, the hydrogen mass space velocity was 3.0 h -1 -1, and the hydrogen hydrocarbon volume ratio was 850 Nm3 / m 3 Naphthalene conversion and tetralin selectivity are recorded in Table 1.

[0126] Example 2

[0127] (1) 0.5 g of aluminum sulfate and sulfuric acid with a concentration of 5 wt% were mixed to obtain a mixed solution, a water glass solution with a concentration of 240 g / L was diluted to 80 g / L, and the diluted water glass solution was added dropwise to the mixed solution, the mass ratio of the water glass and the aluminum sulfate was 2:1 in terms of oxides, the pH was adjusted to 1.5, and a seed solution of silicon aluminum was obtained; 100 mL of a water glass solution with a concentration of 120 g / L and 100 mL of sulfuric acid with a concentration of 10 wt% were mixed and added dropwise to the seed solution under the condition that the temperature was 10°C, the mass ratio of the water glass and the seed solution was 50:1 in terms of oxides, the pH was adjusted to 2, and the obtained mixture was aged under the condition that the temperature was 40°C to obtain a silica sol; 15 g of aluminum sulfate and 100 mL of sulfuric acid with a concentration of 10 wt% were mixed and added dropwise to the silica sol, the mass ratio of the silica sol and the aluminum sulfate was 10:1 in terms of oxides, the pH was adjusted to 4.5, and an acidic silicon aluminum colloidal solution was obtained;

[0128] (2) The acidic silicon aluminum colloidal solution obtained in step (1), a low-silicon X molecular sieve, ammonium carbonate, activated carbon with a mesh size of 100, and cetyltrimethylammonium bromide were mixed under the condition that the temperature was 50°C, the mass ratio of the acidic silicon aluminum colloidal solution, the low-silicon X molecular sieve, the ammonium carbonate, the activated carbon, and the cetyltrimethylammonium bromide was 50:10:40:2:1, the pH value was adjusted to 7, and the obtained silicon aluminum mixed slurry was dried under the condition that the temperature was 120°C for 15 h to obtain a silicon aluminum carrier;

[0129] (3) The silicon aluminum carrier, peptized pseudoboehmite, and hydroxymethyl cellulose were mixed, the mass ratio of the silicon aluminum carrier, the peptized pseudoboehmite, and the hydroxymethyl cellulose was 60:2:1, the obtained mixture was extruded, then dried under the condition that the temperature was 100°C for 15 h, and then calcined under the condition that the temperature was 400°C for 6 h to obtain a strip-shaped silicon aluminum carrier;

[0130] (4) 0.25 wt% of an ammonia solution was added dropwise to molybdenum trioxide, nickel monoxide, and phosphorus pentoxide under the condition of stirring at a rate of 200 r / min, the pH value was adjusted to 3, and a nickel-molybdenum-phosphorus solution was obtained, the mass ratio of the molybdenum trioxide, the nickel monoxide, and the phosphorus pentoxide was 28:4:1, 80 g of the strip-shaped silicon aluminum carrier was placed in a sugar-coating machine with a rotating speed of 20 r / min, 100 mL of the nickel-molybdenum-phosphorus solution was added, and the impregnation was performed for 1.5 h, then the obtained mixture was dried under the condition that the temperature was 100°C for 15 h, and then calcined and reduced under the condition that the temperature was 400°C for 6 h. The specific surface area, the pore volume, the total acid amount, and the strong acid amount were tested and recorded in Table 1.

[0131] Catalytic C9 + The heavy aromatic hydrocarbon hydrogenation was carried out in a pre-hydrogenation reactor, and the conditions of the pre-hydrogenation reactor included: an inlet temperature of 140℃, a reaction pressure of 4 MPa, a hydrogen mass space velocity of 3 h -1 , and a hydrogen hydrocarbon volume ratio of 600 Nm 3 / m 3 . The naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0132] Example 3

[0133] (1) 1.5 g of aluminum sulfate and concentrated sulfuric acid with a concentration of 10 wt% were mixed to obtain a mixed solution, a water glass solution with a concentration of 260 g / L was diluted to 120 g / L, and the diluted water glass solution was added dropwise to the mixed solution, the mass ratio of the water glass and the aluminum sulfate was 5:1 in terms of oxides, the pH was adjusted to 1.5, and a seed solution of silicon aluminum was obtained; 100 mL of a water glass solution with a concentration of 180 g / L and 100 mL of concentrated sulfuric acid with a concentration of 15 wt% were mixed and added dropwise to the seed solution, the mass ratio of the water glass and the seed solution was 100:1 in terms of oxides, the pH was adjusted to 2.5, and the obtained mixture was aged at a temperature of 40℃ to obtain a silica sol; 2.5 g of aluminum sulfate and 100 mL of sulfuric acid with a concentration of 25 g / L were mixed and added dropwise to the silica sol, the mass ratio of the silica sol and the aluminum sulfate was 20:1 in terms of oxides, the pH was adjusted to 5.5, and an acidic silicon aluminum colloidal solution was obtained;

[0134] (2) The acidic silicon aluminum colloidal solution obtained in step (1), low-silicon X molecular sieve, ammonium carbonate, activated carbon with a particle size of 200 mesh, and cetyltrimethylammonium bromide were mixed at a temperature of 70℃, and the pH was adjusted to 8, wherein the mass ratio of the acidic silicon aluminum colloidal solution, the low-silicon X molecular sieve, the ammonium carbonate, the activated carbon with a particle size of 200 mesh, and the cetyltrimethylammonium bromide was 200:20:80:4:1, and the obtained silicon aluminum mixed slurry was dried at a temperature of 200℃ for 8 h to obtain a silicon aluminum carrier;

[0135] (3) The silicon aluminum carrier, the colloidal pseudoboehmite, and the hydroxymethyl cellulose were mixed, wherein the mass ratio of the silicon aluminum carrier, the colloidal pseudoboehmite, and the hydroxymethyl cellulose was 80:4:1, the obtained mixture was extruded, then dried at a temperature of 200℃ for 3 h, and calcined at a temperature of 600℃ for 3 h to obtain a strip-shaped silicon aluminum carrier;

[0136] (4) 1wt% ammonia solution was added dropwise into molybdenum trioxide, nickel monoxide and phosphorus pentoxide under stirring at a rate of 400r / min, wherein the mass ratio of molybdenum trioxide, nickel monoxide and phosphorus pentoxide was 32:6:1, and the pH value was adjusted to 3, to obtain a nickel-molybdenum-phosphorus solution; 120g of the strip-shaped silicon-aluminum carrier was placed in a sugar-coating machine at a rotating speed of 40r / min, 100ml of the nickel-molybdenum-phosphorus solution was added, and impregnation was performed for 2.5h; then, drying was performed at a temperature of 200℃ for 8h, and then, calcination and reduction were performed at a temperature of 600℃ for 4h. The specific surface area, pore volume, total acid amount and strong acid amount were tested and recorded in Table 1.

[0137] The catalytic hydrogenation of α-methylnaphthalene was performed in a pre-hydrogenation reactor, and the conditions of the pre-hydrogenation reactor included: an inlet temperature of 260℃, a reaction pressure of 7MPa, a hydrogen mass space velocity of 4.0h -1 , and a hydrogen / hydrocarbon volume ratio of 1100Nm 3 / m 3 . The naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0138] Example 4

[0139] The silicon-aluminum carrier catalyst was prepared according to the method of Example 1, and the C9 + heavy aromatic hydrocarbon hydrogenation performance was tested according to the method of Example 1. The oil product evaluation and process condition selection were performed using a 100ml high-pressure hydrogenation reaction device. The reaction device reaction tube was a Φ43 (inner diameter) mm×1850mm stainless steel tube. The pre-hydrogenation catalyst 50ml was filled in the constant temperature zone of the reaction tube, and the upper and lower parts were filled with Φ3 inert porcelain balls.

[0140] The catalyst stability test conditions were: a reaction temperature of 380℃, a pressure of 5MPa, a hydrogen mass space velocity of 1.5h -1 , a hydrogen / oil volume ratio of 1000, and a long-period running time of 1000h. The naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Figure 1 and Figure 2 , respectively.

[0141] Comparative Example 1

[0142] The silicon-aluminum carrier catalyst was prepared according to the method of Example 1, except that in step (1), the seed solution preparation was not performed, and the seed solution was replaced with water. The data were recorded in Table 1.

[0143] The C9 + heavy aromatic hydrocarbon hydrogenation performance was tested according to the method of Example 1, and the naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0144] Comparative Example 2

[0145] The silicon-aluminum carrier catalyst was prepared according to the method of Example 1, except that no low-silicon X molecular sieve was added in step (2). The data are recorded in Table 1.

[0146] C9 + The heavy aromatic hydrocarbon hydrogenation performance was tested, and the naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0147] Comparative Example 3

[0148] The silicon-aluminum carrier catalyst was prepared according to the method of Example 1, except that no activated carbon was added in step (2). The data are recorded in Table 1.

[0149] C9 + The heavy aromatic hydrocarbon hydrogenation performance was tested, and the naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0150] Comparative Example 4

[0151] The silicon-aluminum carrier catalyst was prepared according to the method of Example 1, except that no sodium dodecyl benzene sulfonate was added in step (2). The data are recorded in Table 1.

[0152] The α-methylnaphthalene hydrogenation performance was tested according to the method of Example 1, and the naphthalene conversion rate and tetrahydronaphthalene selectivity were recorded in Table 1.

[0153] Table 1

[0154]

[0155] As can be seen from the results in Table 1, the silicon-aluminum carrier catalyst according to the present application has the characteristics of high specific surface area, high activity, high stability, and controllable acidity, and has high naphthalene conversion rate and tetrahydronaphthalene selectivity in the application of catalyzing heavy aromatic hydrocarbon pre-hydrogenation.

[0156] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A method for preparing a silicon-aluminum supported catalyst, characterized in that, The method includes the following steps: (1) Mix acidic silica-alumina colloidal solution, low-silica X molecular sieve, precipitant, activated carbon and soft template, and dry the resulting silica-alumina mixed slurry to obtain silica-alumina carrier; (2) The silica-alumina carrier, sol-bonded boehmite and binder are mixed, the pH is adjusted to 7-8, and the resulting mixture is calcined to obtain strip-shaped silica-alumina carrier; (3) Load nickel-molybdenum-phosphorus onto the strip-shaped silicon-aluminum carrier, and then reduce it; The preparation method of the acidic aluminosilicate colloidal solution in step (1) includes the following steps: (a) A first aluminum source and a first inorganic acid are mixed to obtain a mixed solution, and a first water glass solution is added to the mixed solution to adjust the pH to 1.5-2.0, thereby obtaining a silicon-aluminum seed solution; (b) The seed solution is subjected to a first aging and a second aging to obtain a silica sol; (c) The second aluminum source and the third inorganic acid are mixed and added to the silica sol, and the pH is adjusted to 4.5-5.5 to obtain the acidic silica-alumina colloidal solution; In step (b), the first aging process includes: mixing the second water glass solution and the second inorganic acid and adding them to the seed crystal solution, adjusting the pH to 2.0-2.5; The first aluminum source and the second aluminum source each include at least one of aluminum sulfate, aluminum nitrate and aluminum trichloride; The first inorganic acid, the second inorganic acid, and the third inorganic acid each comprise sulfuric acid and / or nitric acid.

2. The method according to claim 1, characterized in that, The temperature of the first aging process is below 15°C.

3. The method according to claim 2, characterized in that, The temperature for the first aging process is 10-12℃.

4. The method according to any one of claims 1-3, characterized in that, In step (b), the second aging process includes subjecting the mixture obtained after the first aging to the second aging.

5. The method according to claim 4, characterized in that, The second aging temperature is 30-50℃.

6. The method according to any one of claims 1-3 and 5, characterized in that, In step (a), the mass ratio of the first water glass solution to the first aluminum source, based on oxides, is (2-5):

1.

7. The method according to any one of claims 1-3 and 5, characterized in that, In step (b), the mass ratio of the second water glass solution to the seed crystal, based on oxides, is (50-100):

1.

8. The method according to any one of claims 1-3 and 5, characterized in that, In step (c), the mass ratio of the silica sol to the second aluminum source, based on oxides, is (10-20):

1.

9. The method according to claim 1, characterized in that, In step (1), the precipitant comprises an alkaline carbonate.

10. The method according to claim 9, characterized in that, The precipitant includes at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate.

11. The method according to claim 9 or 10, characterized in that, In step (1), the soft template includes at least one of sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.

12. The method according to claim 1, characterized in that, In step (1), the mass ratio of the acidic silica-alumina colloidal solution to the low-silica X molecular sieve, based on oxides, is (5-10):

1.

13. The method according to any one of claims 1-3, 5, 9, 10 and 12, characterized in that, In step (1), the acidic silica-alumina colloidal solution, low-silica X molecular sieve, precipitant, activated carbon and soft template are mixed at a temperature of 50-70°C.

14. The method according to claim 1, characterized in that, In step (2), the binder includes at least one of hydroxymethyl cellulose, soluble starch and sodium polyacrylate.

15. The method according to claim 14, characterized in that, In step (2), the mass ratio of the silica-alumina carrier, the sol-bonded pseudoboehmite, and the binder is (60-80):(2-4):

1.

16. The method according to claim 14 or 15, characterized in that, In step (2), the calcination conditions include a temperature of 400-600℃ and a time of 3-6h.

17. The method according to claim 1, characterized in that, In step (3), the process of loading nickel-molybdenum-phosphorus onto the strip-shaped silica-alumina support includes: adding ammonia solution to molybdenum trioxide, nickel monoxide and phosphorus pentoxide, adjusting the pH value to 3-5 to obtain a nickel-molybdenum-phosphorus solution, and immersing the strip-shaped silica-alumina support in the nickel-molybdenum-phosphorus solution.

18. The method according to claim 17, characterized in that, In step (3), the mass ratio of molybdenum trioxide, nickel monoxide and phosphorus pentoxide is (28-32):(4-6):

1.

19. The method according to claim 17 or 18, characterized in that, In step (3), the reduction conditions include: a temperature of 400-600℃ and a time of 2-5h.

20. The silica-alumina supported catalyst prepared by the method according to any one of claims 1-19.

21. The application of the silica-alumina supported catalyst according to claim 20 in the pre-hydrogenation reaction of heavy aromatics.

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