CN103041869B - Preparation method of spherical catalyst carrier - Google Patents

Abstract

The invention discloses a preparation method of a spherical catalyst carrier. According to the method, a spherical size stabilization method is adopted for preparation, and a gemini surfactant is added into an aluminum oxide precursor, so that the physical properties of the surface of an aluminum oxide carrier are improved, the adhesion and rheology of materials during the carrier forming process are regulated, the plastic deformation of the carrier after forming is reduced, the yield of the spherical carrier is greatly improved, the strength of the spherical carrier is improved, and the proportion of complete particles in the spherical carrier is improved. In addition, the gemini surfactant is adopted, so that Na<+>, Ca<2+>, K<+>, Cl<->, Br<->, F<->, I<-> and other negative and positive hetero ions can not be introduced; and furthermore, the gemini surfactant is larger in molecular weight and good in reaming effect.

Description

Preparation method of spherical catalyst carrier

technical field

The invention relates to a method for preparing a spherical catalyst carrier, in particular to a spherical hydrogenation catalyst carrier. The method can be used for the catalyst carrier of petroleum wax hydrotreating, and can also be used for the hydrotreating catalyst carrier of heavy distillate oil, and is especially suitable for reactors with large aspect ratio and small reactor diameter.

Background technique

In recent years, with the increasing reduction and inferiority of high-waxy crude oil resources, the shortage and inferiority of paraffin resources have been caused; at the same time, the increase in domestic paraffin production and the increase in market demand have resulted in the processing of inferior paraffin and high-melting point waxes. The demand is increasing; while the requirements of environmental protection regulations are becoming increasingly stringent, the production and use of catalysts are required to be as pollution-free as possible and to achieve clean operation. Therefore, it is necessary to study high activity, low cost and environment-friendly catalysts for paraffin hydrotreating.

At present, the petroleum wax hydrorefining catalysts used in industry are basically cylindrical or three- and four-leaf clover strips. This type of catalyst has the advantages of high molding efficiency and large production capacity. However, since the petroleum wax hydrogenation reactor is characterized by a large height-to-diameter ratio and a small reactor diameter (0.80-1.40m), it is not conducive to the loading and unloading of the catalyst. It is difficult to achieve uniform dense-phase packing of the catalyst, because the dense-phase packing cannot be installed in such a small-diameter reactor, so dense-phase packing cannot be realized. Therefore, the petroleum wax hydrorefining catalyst should be prepared in a spherical shape. The loading and unloading of the spherical catalyst is easy, and it is easy to meet the requirements of dense phase packing.

At present, industrial hydrotreating catalysts are usually supported by alumina or alumina containing a small amount of additives. The preparation methods of spherical particle catalysts mainly include: spray drying molding, rolling molding, molding in oil, spherical sizing method, etc.

Spray drying molding is a method of producing powdery and microspherical products using the principle of spray drying. That is, an atomizer is used to disperse the raw material slurry into droplets, and the droplets are dried with hot air. The key technology of spray molding lies in the micronization (atomization) of slurry solids, which requires finer atomized droplets. Therefore, spray molding is suitable for the preparation of microsphere (several microns or tens of microns) catalysts, fluid catalytic cracking catalysts It is mostly prepared by spray drying method.

Rotational molding is to send powder and appropriate amount of water (or other binders) into a low-speed rotating container. The powder particles are agglomerated under the action of liquid bridge and capillary force to form micronuclei. Under the action of rolling and rolling impact, it continuously turns and grows in the powder layer, and finally becomes spherical particles of a certain size and leaves the container. Rotational molding has a large processing capacity, less equipment investment, and high operating rate, but the particle density is not high, the strength is poor, it is difficult to prepare smaller particle balls, and the dust is relatively large during operation. Due to the above-mentioned shortcomings of this method, its application has gradually decreased.

Molding in oil is to use the characteristics of gelation of sol at an appropriate pH value and concentration. The sol is dropped into a medium such as kerosene in the form of small droplets. Due to the effect of surface tension, it shrinks into a ball and then gels to form small particles. . This kind of method exists the problem of environmental pollution, and its application is also gradually reduced.

Spherical granulation method is to add water, peptizer and forming aids to the material, knead it into a soft block plastic body, then add it to the extruder, extrude the cylindrical strip through the cylindrical orifice plate, pelletize, roll the ball , dried and calcined to obtain a spherical catalyst carrier. This method has no pollution to the environment, and the preparation of spherical carriers is developing in this direction.

CN1085594A discloses a kind of wax material hydrogenation refining catalyst, with Mo, Ni as active components, the preparation process of this catalyst: neutralize the silica-alumina mixed sol after low-temperature aging with ammonia water, after filtering, washing, with phosphoric acid and nitric acid Peptization, and then forming through the oily ammonia column, and the carrier is formed through the oily ammonia column. This ball forming process is complicated, and there is ammonia nitrogen pollution problem, which does not meet the environmental protection requirements. Manual operation is adopted in the forming process of drop ball and oil ammonia column, and workers are exposed to the environment full of ammonia gas for a long time, which will cause great harm to their health.

CN01114183.2 discloses a wax hydrorefining catalyst and its preparation method. This method adopts SiO ₂ -P ₂ O ₅ -Al ₂ O ₃ with large pore volume, large specific surface area, highly concentrated pore distribution and weak acidity as the carrier, and W and Ni as the active metal components. Ni/W( Mole) ratio is 0.30～0.80. The pore volume of the catalyst is 0.40-0.55 cm ³ /g, and the pore volume fraction within the pore diameter range of 4-15 nm accounts for 95%-99% of the pore volume fraction within the pore diameter range of 0-100 nm. The catalyst has higher activity and selectivity when it is used for hydrofinishing of wax. However, this method also adopts the process of forming into balls through the oily ammonia column at room temperature, the process is complicated, and there is ammonia nitrogen pollution in the production process, and the ball size is not uniform, the strength is low, the yield is low, and the molding efficiency is low.

CN200910079772.8 discloses a toothed spherical heavy oil hydrotreating catalyst and a preparation method thereof. Preparation of alumina carrier precursor: add peptizer, pore expander and forming aid to aluminum hydroxide, after mixing evenly, add deionized water and nitric acid, mix evenly, and obtain soft block plastic body; said peptizer It is nitric acid, citric acid, acetic acid or tartaric acid or a mixture of any two or more of the foregoing. In this way, the strong acid and alumina will inevitably have a strong interaction, which will cause serious loss of pore volume and specific surface area, and reduce the pore volume and specific surface area of the final catalyst.

CN03134003.2 discloses a petroleum wax hydrorefining catalyst and its preparation method. The catalyst uses tungsten, molybdenum and nickel (or cobalt) as active metals, and alumina containing two additives of silicon and phosphorus as a carrier , and its preparation method is prepared by respectively impregnating an aqueous solution containing tungsten-nickel or cobalt and an aqueous solution containing molybdenum-boron on an alumina carrier containing silicon and phosphorus. The alumina carrier containing silicon and phosphorus is prepared by adding silicon-containing aluminum hydroxide prepared by _CO2 neutralization method as a raw material, and adding a phosphorus-containing compound during the carrier molding process. The method can effectively adjust the physical and chemical properties of the catalyst through the synergistic adjustment effect of the two composite additives, so that the catalyst has a reasonable pore structure and suitable surface acid properties. The catalyst can process petroleum wax materials including high melting point wax materials, and can produce food-grade petroleum wax products. CN03133997.2 discloses a petroleum wax hydrogenation catalyst and its preparation method. The method is to use the silicon-containing and phosphorus-containing aluminum hydroxide prepared by the _CO2 neutralization method as the carrier material of the catalyst, wherein the two additives of silicon and phosphorus in the silicon-containing and phosphorus-containing aluminum hydroxide are added step by step, and part of the silicon-containing It is mixed with phosphorus-containing compounds and sodium metaaluminate solution to form a gel. Part of the silicon-containing compound is added after the gel is formed or during the aging process. Most of the phosphorus-containing compounds are formed in the gel after the aluminum hydroxide is formed and washed. Added in the process of dissolving or slurrying, so that most of the silicon and phosphorus are distributed on the surface of aluminum hydroxide, and effectively play the role of silicon and phosphorus in synergistically adjusting the physical and chemical properties and pore structure of the catalyst surface. The catalyst has good activity and selectivity when processing petroleum wax materials, including high melting point petroleum wax. The petroleum wax hydrorefining catalysts in the above two patents are formed by extrusion, which has high molding efficiency, can prepare catalysts with relatively small particle equivalent diameters, and solves the problem of diffusion and mass transfer of heavy components. If it is made into a spherical catalyst, the molding efficiency will not be too high and needs to be improved.

In the prior art, the method of preparing spherical catalysts by extruding and pelletizing generally involves adding peptizers and forming aids to the materials. Peptizers are generally nitric acid, citric acid, acetic acid or tartaric acid. Forming aids are generally safflower powder or polyethylene glycol, etc. The adhesion and rheological properties of the cylindrical strips extruded through the cylindrical orifice plate are not good, resulting in low molding efficiency.         

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides a method for preparing a spherical catalyst carrier. The method has the advantages of uniform particle size, high strength, high yield and small loss.

The preparation method of spherical catalyst carrier of the present invention comprises:

(1) Mix the alumina precursor, gemini surfactant and adhesive evenly, wherein the amount of adhesive added is 2.0% to 15.0% of the weight of alumina, and the amount of gemini surfactant added is 0.5% to 8.0% of the weight of alumina %;

(2) After the mixture obtained in step (1) is kneaded, extruded and pre-dried, it is pelletized and pelletized by a spherical granulator, and then dried and calcined to obtain a spherical catalyst carrier.

The spherical catalyst carrier of the present invention may also contain auxiliary components, and the auxiliary agent is one or more of silicon, zirconium, titanium, iron, phosphorus, boron and the like. The way in which the auxiliary agent is introduced into the carrier can be introduced in any way in the prior art, such as the method of introducing silicon and phosphorus in CN01114183.2, CN03133997.2, CN03134003.2, the introduction of boron, phosphorus, silicon, zirconium and titanium in CN 200410050777.5 method.

In step (1), the order of adding the alumina precursor, gemini surfactant and adhesive is not limited. The adhesive is prepared by mixing one or more of small-pore alumina, aluminum nitrate and aluminum sulfate with inorganic acid and/or organic acid, wherein the amount of inorganic acid and/or organic acid accounts for 30% of the weight of the adhesive. %~60%. Among them, the properties of small-pore alumina are generally as follows: the specific surface area is 200m ² /g~400m ² /g, and the pore volume is 0.3ml/g~0.6ml/g. The inorganic acid can be selected from one or more of nitric acid, phosphoric acid, sulfuric acid and hydrochloric acid, preferably nitric acid, and the organic acid can be selected from one or more of acetic acid, citric acid and oxalic acid.

The Gemini surfactant can be selected from one or more of the quaternary ammonium salt gemini surfactant series and the acetylenic diol gemini surfactant 400 series. Quaternary ammonium salt gemini surfactant series commonly used dibromide-N,N'-di(dimethyldodecyl)propylene diammonium, N,N'-dimethyl carboxybetaine, 1,3- Didodecyl-N,N-dimethyl bromide-2-propanol, 1,3-ditetradecyl-N,N-dimethyl bromide-2-propanol, etc. One or more, acetylenic diol gemini surfactant 400 series commonly used one or more of Cido-420, Cido-440, Cido-465, Cido-485 surfactants.

In the process of mixing and kneading, in order to further facilitate extrusion molding, extrusion aids, such as one or more of safflower powder, polyethylene glycol, etc., can also be added. In order to ensure that the catalyst carrier has the required macropore ratio, a pore-enlarging agent can be added during the preparation process, and the amount of the pore-enlarging agent added is 0.1% to 5.0% of the weight of the alumina precursor. The pore-enlarging agent can be selected from conventional types, such as one or more of conventional combustible solid powders such as methylcellulose, starch derivatives, sodium polyacrylate, and carbon black, preferably sodium polyacrylate.

The pre-drying temperature in step (2) is 20-70°C, the time is 0.2-1.0 hours, the drying is at a temperature of 90-130°C for 2-4 hours, and the roasting is at a temperature of 600-900°C Roast for 3 to 6 hours.

The spherical granulator described in step (2) adopts the existing spherical granulator.

The spherical catalyst carrier of the present invention is prepared by a spherical sizing method. By adding gemini surfactants to the alumina precursor, the physical properties of the surface of the alumina carrier are improved, and the adhesion of the material in the carrier molding process is adjusted. Rheology, reducing the plasticity of the carrier after molding, greatly increasing the yield of the spherical carrier, improving the strength of the spherical carrier, and increasing the proportion of complete particles of the spherical carrier, which not only reflects the advantages of anionic and cationic surfactants, but also does not Introduce Na ⁺ , Ca ²⁺ , K ⁺ , Cl ^- , Br ^- , F ^- , I ^- and other anions and cations. In addition, the gemini surfactant has a large molecular weight and has a good pore expansion effect.

Detailed ways

The method of the invention prepares the spherical catalyst carrier, which is used in the paraffin hydrogenation refining process, preferably using silicon and boron additives. The catalyst carrier is mainly composed of alumina and contains boron oxide and silicon dioxide. The weight content of boron oxide in the carrier is generally 0.5% to 10.0%, preferably 2.0% to 8.0%. The weight content is generally 0.5% to 20.0%, preferably 2.0% to 15.0%. In the preparation process of the spherical catalyst carrier, the silicon source and the boron source are added in step (1), wherein the silicon source is water glass or silica sol, and the boron source is boric acid. The boric acid is preferably added in the form of boric acid aqueous solution or boric acid acidic solution, wherein the temperature of the solution is 30-100°C, preferably 40-80°C.

During the preparation process of the spherical catalyst carrier, the silicon source can be added in any step of mixing the alumina precursor, the gemini surfactant, and the adhesive, and the boron source can be added after the above materials are uniformly mixed.

The properties of the above-mentioned spherical catalyst carrier are as follows: the specific surface area is 200-350 m ² /g, preferably 250-300 m ² /g, the pore volume is 0.5-1.0 cm ³ /g, preferably 0.60-0.90 cm ³ /g, the average pore The diameter is 6-20nm, preferably 7-12nm, the amount of infrared acid is 0.20-0.80mmol/g, preferably 0.30-0.70mmol/g, and the mechanical strength is ≥35.0 N/grain.

To further illustrate the method of the present invention, the following examples are cited. wt% is mass fraction.

Example 1

Weigh 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3wt %) prepared by carbonization, add 20.0 grams of water glass, 8.0 grams of sodium polyacrylate and 15.0 grams of polyethylene glycol, mix, and then add 14 grams of adhesive (35.0wt% of small-pore alumina , 34.4wt% of concentrated nitric acid, and 30.6wt% of water) and a mixture of gemini surfactants (4 grams of N, N'-dimethylcarboxybetaine), and then add Dissolve 6.5 grams of boric acid in 100ml of 50°C water, mix thoroughly, knead into a plastic shape, and then extrude into strips (the diameter of the strip orifice is 1.9mm). Then it was pre-dried in a drying oven at 30°C for 0.35 hours, cut into balls by a spherical granulator, dried at 110°C for 3 hours, and roasted at a constant temperature of 600°C for 3.0 hours to obtain a spherical hydrogenation catalyst carrier.

Example 2

Take 200g of pseudo-boehmite powder prepared by carbonization (containing Al(OH) ₃ <3wt%), mix 25.0 grams of silica sol, 10.0 grams of methylcellulose and 3.0 grams of scallop powder, mix well, add 18 grams of adhesive (of which 30.0wt% small pore alumina, 39.1wt% concentrated phosphoric acid, 30.9wt% water) and a mixture of gemini surfactants (gemini surfactant is 1,3-didodecyl-N,N -Dimethylammonium bromide-2-propanol is 6 grams ) , then add 6.5 grams of boric acid dissolved in 100ml of 70°C water, mix thoroughly, knead into a plastic shape and extrude into strips (the diameter of the strip orifice is 2.1mm). It was then pre-dried in a drying oven at 40° C. for 0.3 hours. After cutting and pelletizing by a spherical granulator, drying at 110° C. for 4 hours, and constant temperature roasting at 600° C. for 4.0 hours, the spherical hydrogenation catalyst carrier was made.

Example 3

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3 wt %) prepared by the aluminum nitrate method, mix 20.0g of silica sol, 6.0g of carbon black and 3.0g of scallop powder, and then add 20g of adhesive ( in which small Porous alumina is 40.0 wt% , citric acid is 38.6 wt%, water is 21.4 wt%) and the mixture of gemini surfactant (alkyne diol gemini surfactant Cido-420 is 4 grams) after mixing evenly, then add 100ml of boric acid 6.0 dissolved in water at 60°C, fully mixed, kneaded into a plastic shape, extruded into strips (diameter of the strip orifice plate is 2.3mm), and then pre-dried in a drying oven at 20°C for 0.7 hours. After being cut and pelletized by a spherical sizing machine, it was then dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Example 4

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3 wt %) prepared by the aluminum nitrate method, mix 22.0 grams of silica sol, 6.1 grams of carbon black and 2.8 grams of scallop powder, and then add 22 grams of adhesive ( in which small 40.0 wt % porous alumina , 38.6 wt % citric acid, 21.4 wt % water) and a mixture of gemini surfactants (1,3-Ditetradecyl-N,N-dimethylammonium bromide- 2-propanol is 4 grams) after mixing evenly, add boric acid 6.0 dissolved in 100ml 60 ℃ water, mix well, knead into a plastic shape and extrude into strips (the diameter of the strip-shaped orifice plate is 2.3mm) and then in 20 ℃ Pre-dried in a drying oven for 0.7 hours. After being cut and pelletized by a spherical sizing machine, it was then dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Comparative example 1

Weigh 200g of pseudo-boehmite powder prepared by carbonization (containing Al(OH) ₃ <3wt%), add 20.0 grams of water glass, 8.0 grams of sodium polyacrylate and 15.0 grams of polyethylene glycol, mix, then add 14 grams of adhesive (among them 35.0 wt % of small-pore alumina , 34.4 wt % of concentrated nitric acid, and 30.6 wt % of water), then add 6.5 grams of boric acid dissolved in 100 ml of 50 °C water, mix thoroughly, knead into a plastic shape, and extrude into strips ( The diameter of the strip orifice is 1.9mm). It was then pre-dried in a drying oven at 40° C. for 0.3 hours. It was cut and formed into balls by a spherical granulator, dried at 110°C for 3 hours, and calcined at 600°C for 3.0 hours at a constant temperature to obtain a spherical hydrogenation catalyst carrier.

Comparative example 2

Take 200g of pseudo-boehmite powder (containing Al(OH) ₃ < 3wt%) prepared by carbonization method, mix 25.0g of silica sol, 10.0g of methylcellulose and 3.0g of turmeric powder, add 4.2g of hexadecyl Trimethyl ammonium chloride, after mixing evenly, add 12 grams of adhesive (30.0wt% of small-pore alumina, 39.1wt% of concentrated phosphoric acid, 30.9wt% of water), and then add 6.5% of boric acid dissolved in 100ml of 70°C water gram, fully mixed, kneaded into a plastic shape and then extruded into strips (the diameter of the strip orifice is 2.1mm). It was then pre-dried in a drying oven at 30° C. for 0.35 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 4 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical hydrogenation catalyst carrier.

Comparative example 3

Get 200g of pseudo-boehmite powder (containing Al(OH) ₃ <3wt%) prepared by 200g aluminum nitrate method, 20.0 grams of silica sol, 6.0 grams of carbon black and 3.5 grams of asparagus powder and mix, then add 20 grams of adhesive (wherein the pores are oxidized Aluminum is 40.0 wt % , citric acid is 38.6 wt %, water is 21.4 wt %) and a mixture of surfactant (sodium octadecylbenzene sulfonate content is 4 grams), after mixing well, add 100ml of 60 ℃ water Dissolved boric acid 6.0 grams, fully mixed, kneaded into a plastic shape and then extruded into strips (the diameter of the strip orifice is 2.3mm). It was then pre-dried in a drying oven at 50° C. for 0.2 hours. After being cut and pelletized by a spherical granulator, it was dried at 110°C for 3 hours, and then calcined at a constant temperature of 600°C for 4.0 hours to make a spherical catalyst carrier.

Table 1 The physicochemical properties of each embodiment carrier

the Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Specific surface area, ^m2 /g 290 284 278 275 243 280 300 Pore volume, cm ³ /g 0.775 0.752 0.764 0.758 0.490 0.660 0.685 Average pore diameter, nm 10.7 10.6 11.0 11.0 8.1 9.4 9.1 Strength, N/grain 55 60 65 53 30 32 35 Particle size, mm 1.84 2.02 2.23 2.22 1.84 2.01 2.24 Qualified product, wt% 90 95 98 95 75 80 78 Plasticity, wt% 2.6 2.4 2.1 2.0 4.5 3.5 4.0 acid distribution the the the the the the the Weak acid center, mmol/g 0.30 0.31 0.31 0.30 0.35 0.34 0.38 Medium strong acid center, mmol/g 0.25 0.27 0.30 0.29 0.30 0.32 0.35 Strong acid center, mmol/g 0.03 0.05 0.03 0.02 0.08 0.10 0.07

[Note]: Determination by ammonia adsorption-TPD method, where 150~250℃, 250~400℃, 400~500℃ correspond to the desorption temperature of ammonia in weak acid center, medium strong acid center and strong acid center respectively.

Claims (1)

1. A preparation method for a spherical catalyst carrier, comprising: (1) Mix the alumina precursor with gemini surfactant and adhesive evenly, wherein the amount of adhesive added is 2.0%~15.0% of the weight of alumina, and the amount of gemini surfactant added is 0.5%~8.0% of the weight of alumina %; the gemini surfactant is one or more of the quaternary ammonium salt gemini surfactant series and the acetylene glycol gemini surfactant 400 series; the adhesive uses small-pore alumina, aluminum nitrate and sulfuric acid One or more of aluminum is mixed with inorganic acid and/or organic acid, wherein the amount of inorganic acid and/or organic acid accounts for 30%~60% of the weight of the adhesive; the inorganic acid is selected from nitric acid, phosphoric acid One or more in , sulfuric acid, hydrochloric acid; Described organic acid selects one or more in acetic acid, citric acid, oxalic acid; (2) After the mixture obtained in step (1) is kneaded, extruded and pre-dried, it is pelletized and pelletized with a spherical granulator, then dried and roasted to obtain a spherical catalyst carrier; the pre-drying temperature is 20~ 70°C, the time is 0.2~1.0 hours. 2, according to the described method of claim 1, it is characterized in that described quaternary ammonium salt gemini surfactant series is dibromide-N,N'-di(dimethyldodecyl)propylene diammonium, N , N′-Dimethylcarboxybetaine, 1,3-Didodecyl-N,N-Dimethylamine bromide-2-propanol, 1,3-Ditetradecyl-N,N -One or more of dimethyl bromide amines -2-propanol, the acetylenic diol gemini surfactant 400 series are Cido-420, Cido-440, Cido-465, Cido-485 surface active one or more of the agents. 3. The method according to claim 1, characterized in that the spherical catalyst carrier contains additive components, and the additive is one or more of silicon, zirconium, titanium, iron, phosphorus, boron . 4. The method according to claim 1, characterized in that during the preparation of the spherical carrier, extrusion aids and/or pore-enlarging agents are added. 5. The method according to claim 1, characterized in that the drying in step (2) is at a temperature of 90-130°C for 2-4 hours, and the roasting is at a temperature of 600-900°C for 3-3 hours. 6 hours. 6. The method according to claim 1, characterized in that the spherical catalyst carrier is mainly composed of alumina and contains boron oxide and silicon dioxide, and the weight content of boron oxide in the carrier is 0.5% to 10.0%. The weight content of silica in the carrier is 0.5% to 20.0%. 7. The method according to claim 6, characterized in that in the spherical catalyst carrier, the weight content of boron oxide is 2.0% to 8.0%, and the weight content of silicon dioxide is 2.0% to 15.0%. 8. The method according to claim 6 or 7, characterized in that during the preparation of the spherical catalyst carrier, silicon source and boron source are added in step (1), wherein the silicon source is water glass or silica sol, Boron source adopts boric acid. 9. The method according to claim 8, characterized in that the boric acid is added in the form of boric acid aqueous solution or boric acid acidic solution, and the temperature of the solution is 30-100°C. 10. The method according to claim 8, characterized in that during the preparation of the spherical catalyst carrier, the silicon source is added in any step of mixing the alumina precursor, the gemini surfactant, and the adhesive, and the boron source is to be added as described above. Add the material after mixing evenly. the