CN1098915C - Hydrorefining catalyst and its preparing process - Google Patents

Abstract

This invention describes a method for preparing a hydrorefining catalyst. The catalyst uses silica-containing alumina as a support, group VIII and group VIB metals as active components, and boron as a promoter. It mainly contains tungsten, molybdenum, and nickel as active components. The catalyst is prepared by simultaneously loading the active components and promoters through a single solution impregnation method, followed by drying and calcination to obtain the catalyst.

Description

A kind of hydrorefining catalyst and preparation method thereof

The invention relates to a hydrorefining catalyst and a preparation method thereof, in particular to a hydrodesulfurization and hydrodenitrogenation catalyst for distillate oil and a preparation method thereof.

A typical hydrorefining catalyst uses alumina as a carrier and VIII and VIB group metal elements as active components. In order to further improve the activity and stability of the hydrorefining catalyst, various methods have been adopted, such as carrier Carry out modification, improve preparation conditions, add additives, etc. Among them, the selected additives often include P, F, B, Si, Ti, Zr, etc. The addition of silicon, especially the introduction of a certain amount of silicon into the alumina carrier, is beneficial to improve the acidity of the catalyst carrier. The addition of boron can also increase the acidity of the carrier and catalyst, but there is an optimum value for the content of boron, and the presence of too much boron will actually reduce the acidity (Bulletin of the chemical society of Japan, 37(12), 1797-1809(1964)) , if boron is added during the molding process of the alumina carrier, it will cause the pore distribution of the carrier to disperse, so it is best to add boron during the impregnation process.

It is generally believed that the hydrogenation performance of the tungsten-nickel system is higher than that of the molybdenum-nickel system. Further research has found that the three-component system of tungsten, molybdenum and nickel is mixed in a certain proportion, and its catalytic activity is higher than that of the tungsten-nickel system. In the invention patents CN1052501A and CN1086534A, tungsten, molybdenum, nickel are selected as active components and boron is used as auxiliary agent, wherein silicon is added in the process of alumina molding, while tungsten, molybdenum, nickel and boron are used secondary or tertiary, After four times of spray dipping (saturated impregnation), each spray dipping must be dried, roasted and other steps to make the catalyst. The main problem in these two patents is that the preparation process of the catalyst is complicated, and the yield of the catalyst decreases and the cost increases after repeated impregnation, drying and roasting.

The purpose of the present invention is to address the shortcomings of the above-mentioned prior art, and propose a hydrorefining catalyst and its preparation method. The formed silicon-containing alumina carrier is only impregnated once, so that the active components and additives are loaded on the carrier at the same time. , the preparation process is simplified and the catalyst cost is reduced.

Catalyst of the present invention and preparation method are as follows:

The distillate hydrotreating catalyst of the present invention uses metal elements of group VIII and group VIB as active components, adds boron additives, uses silicon-containing alumina as a carrier, and uses 3% to 10% of _SiO2 as a basis on the basis of weight percentage. MoO ₃ 5-10%, WO ₃ 10-25%, NiO2-5%, B ₂ O ₃ 2-5%; the catalyst is prepared by using a mixed solution containing active components and additives on the formed carrier. It is obtained by impregnating, drying and roasting once.

The pore volume of the catalyst is 0.20-0.50 cm ³ /g, and the specific surface area is 100-200 m ² /g.

The silicon in the above-mentioned silicon-containing alumina is preferably added during the molding process of the alumina carrier, and the ratio of silicon to aluminum is 1:5-25.

The preparation method of described hydrorefining catalyst comprises:

a. Forming of silicon-containing alumina carrier;

b. Prepare mixed solution;

c. impregnating the shaped alumina carrier in step a with the mixed solution described in step b;

d. drying and roasting to obtain the catalyst;

The mixed solution contains tungsten, molybdenum, nickel and boron components at the same time, and the impregnation of the shaped alumina carrier is one-time impregnation.

To realize the one-time impregnation and loading of active components and additives on the carrier, the key technology is to prepare a mixed solution containing active components and additives.

The present invention proposes to prepare a stable molybdenum-boron ammonia solution first, acidify under certain conditions to obtain an acidic molybdenum-boron solution, then add tungsten compound and nickel compound, or mix with tungsten-nickel solution to obtain tungsten, molybdenum, Nickel, boron mixed solution.

Molybdate ions and borate ions in aqueous solution are all easy to polymerize. As the acidity of the solution increases, molybdenum mainly exists in the form of polyacid ions, while boron not only easily forms polyions, but also decreases with temperature, and borate ions (or Boronic acid molecules) will form an association structure due to hydrogen bonding and precipitate out of the solution. When the molybdenum and boron compounds are dissolved in the ammonia solution, if the acidification is carried out immediately, the molybdenum and boron in the solution will separate out of the solution in a polymerized state. To effectively solve the problem of coagulation during acidification, it is necessary to find a way to disperse molybdate ions and borate ions evenly in the solution, that is, to form boron molybdenum heteropoly compounds, so that they can exist stably in acidic solution. In order to facilitate the formation of molybdenum boron heteropoly compounds in the molybdenum boron ammonia solution, if the heating and boiling method is used to form molybdenum boron heteropoly compounds, the method will increase the equipment requirements in industrial applications, increase energy consumption, and when the concentration of molybdenum boron solution When the temperature is higher and the temperature drops to room temperature, due to the large temperature difference, there will be re-precipitation of molybdenum boron precipitation.

The present invention adopts the method of placing the molybdenum boron solution for a period of time under different acidity values. Because the degree of polymerization of molybdate ions and borate ions is different when the acidity is different, it is more conducive to the mutual diffusion and penetration between molecules when the solution is left for a period of time.

The method is as follows: after the molybdenum boron ammonia solution is formed, first place the solution at a pH value of 6 to 9 for 50 to 200 hours, and then place the solution at a pH value of 3 to 6 for 50 to 300 hours; then mix the tungsten compound and The nickel compound is mixed with the molybdenum-boron ammonia solution to prepare a mixed solution containing molybdenum, tungsten, nickel and boron.

Wherein the mixing mode of tungsten compound and nickel compound and described molybdenum-boron ammonia solution can be to adopt the mode that prepares tungsten-nickel solution and molybdenum-boron solution to mix; also can adopt a kind of in tungsten compound and nickel compound and molybdenum-boron solution to mix, wait After it is completely dissolved, another is added, or the tungsten compound is mixed directly with the molybdenum-boron solution together with the nickel compound.

The above-mentioned tungsten-nickel solution can be prepared by taking tungsten compound and nickel compound and adding water.

The preparation of described molybdenum, tungsten, nickel, boron mixed solution is preferably prepared according to the following conditions:

(1) Add molybdenum compound and boron compound into ammonia solution, adjust the pH value between 6 and 9 with ammonia water, keep the temperature of the solution at 50-90°C for 2-8 hours, and place the solution for 50-200 hours (preferably placed within the temperature range of 20-60°C), acidified with inorganic acid or/and organic acid between 40-80°C to make the pH value of the solution between 3-6, and keep the temperature of the solution at 40-80°C for 2~ 8 hours, place the solution for 50 to 300 hours (preferably placed in the temperature range of 20 to 60 ° C), and obtain a molybdenum boron solution;

(2) Between 20°C and 80°C, mix molybdenum-boron solution with tungsten compound and nickel compound to prepare a mixed solution containing tungsten, molybdenum, nickel, and boron;

After preparing the molybdenum, tungsten, nickel and boron mixed solution, it is best to adjust the temperature of the mixed solution to be between 40-80° C. and maintain it for 1-4 hours.

Mixed solution of tungsten, molybdenum, nickel and boron, combined with the actual situation of industrial application, the most effective source of boron compound is boric acid or ammonium borate, which can be dissolved in alkaline solution, and heating is more conducive to dissolution. Molybdenum compound is the most effective The source is ammonium molybdate or molybdenum trioxide, which can be dissolved in alkaline solution. The nickel compound can be selected from acidic nickel salts such as nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, and the most effective source of tungsten compound It is ammonium metatungstate, which can be dissolved in acidic solution.

The ammonia solution with a certain concentration refers to a concentration in the range of 2.0-9.0 mol/dm ³ calculated in the form of NH ₃ . The concentration of the ammonia solution used is related to the pH value of the required molybdenum-boron solution. If the pH value of the molybdenum-boron solution is required to be higher, the concentration of the corresponding ammonia solution is larger. On the contrary, if the pH value of the molybdenum-boron solution is required to be lower, the corresponding The concentration of ammonia solution is small; and the concentration of ammonia solution is also related to the amount of dissolved ammonium molybdate (or molybdenum trioxide) and boric acid (or ammonium borate, calculated in the form of H ₃ BO ₃ ), requiring molybdenum boron solution The ratio of ammonia (NH ₃ ) to boric acid (H ₃ BO ₃ ) and ammonium molybdate (calculated as MoO ₃ ) is NH ₃ : (H ₃ BO ₃ +MoO ₃ )=0.4～3.0:1.0 within the range.

If the concentration of ammonia water selected during the preparation of the molybdenum-boron solution is small and the amount of boric acid is large, the molybdenum-boron solution with a pH value between 6 and 7 can be prepared.

According to the above method, a mixed solution including the following components can be prepared: MoO ₃ 0.3～1.5mol/dm ³ , WO ₃ 0.4～1.8mol/dm ³ , NiO 0.4～1.8mol/dm ^-3 , B ₂ O ₃ 0.3～1.5 mol/dm ^-3

The concrete preparation steps of catalyst of the present invention are:

(1) Forming of silicon-containing alumina carrier;

(2) Preparation of a mixed solution containing tungsten, molybdenum, nickel and boron;

(3) impregnate with a mixed solution containing tungsten, molybdenum, nickel and boron, dry at 100-130°C for 2-8 hours, and bake at 400-550°C for 2-6 hours to make the catalyst of the present invention .

The molding of silicon-containing alumina carrier can be carried out as follows:

Preparation of spherical silicon-containing alumina carrier: take the required amount of dry aluminum hydroxide powder and low-sodium silica sol (preferably silica sol with a sodium ion content of less than 1000ppm), mix well and then use inorganic acid and/or organic Pseudosol is kneaded with acid, and then balled and solidified by oily ammonia column. The wet rubber ball is dried at 90-130°C for 2-6 hours, and roasted at 500-700°C for 2-6 hours.

Preparation of cylindrical and special-shaped alumina carrier: take the required amount of dry aluminum hydroxide powder, low-sodium silica sol (preferably silica sol with a sodium ion content less than 1000ppm), and knead with peptizer, water and extrusion aid It is made into a paste and extruded on the extrusion machine. The shape of the carrier can be adjusted by replacing the orifice of the extruder. It can be cylindrical or special-shaped. The formed carrier is under the same conditions as the spherical alumina carrier Drying and calcining under low temperature can produce a variety of strip-shaped silica-containing alumina supports. Wherein the peptizer can be inorganic acid, organic acid, aluminum salt of strong acid anion, etc., such as: nitric acid, hydrochloric acid, oxalic acid, formic acid, acetic acid, aluminum nitrate, etc., and can also be an organic combination of several peptizers wherein; The extruding agent can be combustible substances such as kale powder, starch, cellulose, etc.

The ratio of the amount of silicon-aluminum substances in the prepared silicon-containing alumina carrier is 1:5-25. The physical and chemical properties of the pore structure are as follows: the specific surface area is 200-300m ² /g, the pore volume is 0.40-0.70cm ³ /g, and the average pore diameter is 4-14nm.

Among them, the pore structure properties of the carrier can be adjusted according to the requirements of the finished catalyst, by selecting different dry aluminum hydroxide powders and changing the molding conditions of the carrier, such as the amount of peptizing agent, calcination temperature and time, and other factors.

After the silicon-containing alumina carrier is formed and the mixed solution is prepared, the active components and additives can be loaded. Specifically, it can be carried out as follows:

The catalyst of the present invention can be obtained by impregnating a silicon-containing alumina carrier with a mixed solution containing tungsten, molybdenum, nickel and boron, drying and calcining. The impregnation can be supersaturated impregnation or saturated impregnation. The saturated impregnation method refers to putting the silicon-containing alumina carrier into a rotatable container (drum), and spraying the impregnation solution with the saturated adsorption amount of the carrier onto the carrier in the form of mist while rotating. Supersaturated impregnation refers to impregnation with a solution of 1.5 to 3.0 times the volume of the saturated adsorption capacity of the carrier for 0.5 to 2.0 hours.

In a word, the present invention adopts the method of placing the molybdenum-boron solution under different acidities for a period of time, first prepares the acidic molybdenum-boron solution, and then mixes tungsten compound and nickel compound with the acidic molybdenum-boron solution under certain conditions to prepare The mixed solution containing tungsten, molybdenum, nickel and boron has a high concentration and good stability, and does not contain alkali metal and alkaline earth metal ions. There is no special requirement for equipment, which is conducive to industrial implementation. On the basis of solving the preparation of the mixed solution of tungsten, molybdenum, nickel and boron, the mixed solution is further used to obtain the hydrofinishing catalyst of the present invention through impregnation, drying and roasting only once, and at least twice through impregnation, drying and roasting. Compared with the technology of preparing the catalyst by roasting, the activity of the catalyst is equivalent, which simplifies the preparation process of the catalyst and reduces the cost.

The advantages, technical characteristics and catalyst preparation process of the present invention are further illustrated below through examples and comparative examples, but it should not be considered that the present invention is limited thereto.

Example 1

This example describes the molding process of a silicon-containing alumina support.

Get aluminum hydroxide dry rubber powder 1000g (production of No. 3 Catalyst Factory of Fushun Petrochemical Company, Liaoning Province, containing Al ₂ O _62.0m %) and ^160cm Silica sol (production of Xinguang Release Agent Factory in Shenyang City, pH value is 9.3, Containing SiO ₂ is 30.0m%, Na ⁺ concentration is 300ppm) After mixing evenly, add 1800cm ³ of nitric acid solution with a concentration of 1.25mol/dm ³ , stir to make a pseudosol, and then drip the ball through the oil ammonia column and solidify into a ball Type carrier, dried at 90°C for 4 hours and calcined at 550°C for 4 hours to make silicon-containing alumina carrier A, whose physical and chemical properties are listed in Table 1.

Take 1000g of aluminum hydroxide dry rubber powder (produced by the No. 1 Fertilizer Factory of Qilu Petrochemical Company in Shandong Province, containing Al ₂ O ₃ 66.0m%) and 250cm ³ of silica sol and mix evenly, then add 700cm ³ of a mixed solution containing nitric acid and acetic acid , wherein the concentration of nitric acid is 0.70mol/dm ³ , the concentration of acetic acid is 0.40mol/dm ³ , knead evenly to form a paste-like plastic, extrude into 1.2mm clover-shaped strips on an extruder, and dry at 120°C for 4 hours. Calcined at 550°C for 4 hours to obtain silicon-containing alumina carrier B, whose physical and chemical properties are listed in Table 1.

Table 1 Physicochemical properties of silica-containing alumina supports carrier SiO ₂ m% Specific surface area m ² /g Pore volume cm ³ /g Average pore size nm Si-Al Ratio Shape and diameter mm A 8.2 260 0.57 8.8 1:13.2 Spherical 1.5～2.5 B 12.6 220 0.60 11.0 1:8.1 Clover 1.2

Example 2

This example introduces the preparation process and method of molybdenum boron solution.

Measure the ammonia solution, add ammonium molybdate (industrial grade, containing _MoO3 82.7m%) and boric acid (industrial grade) successively, heat and place for a period of time, measure the pH value of the solution, and prepare molybdenum boron solutions D and E. Preparation conditions and solution properties are shown in Table 2.

Table 2 the solution Ammonia solution Ammonium molybdate boric acid heating temperature time Place temperature time pH value Composition (mol/dm ³ ) cm ³ mol/l g g ℃ Hour ℃ Hour MoO ₃ B ₂ O ₃ D. 840 6.70 280 203 60 4 30 80 9.0 1.59 1.64 E. 800 3.43 331 183 70 6 40 150 6.5 1.90 1.48

Measure the above-mentioned molybdenum-boron solution, acidify and heat at the specified temperature, measure the pH value of the solution, place it at the specified temperature for the required time, and prepare acidified molybdenum-boron solutions _D1 , _E1 , _E1 ', The results are shown in Table 3.

table 3 the solution Molybdenum boron solution cm ³ Acidification and heating acid type Acid dosage acid concentration place pH value Composition (mol/dm ³ ) temperature(℃) time (h) cm ³ mol/ ^dm3 temperature(℃) time (h) MoO ₃ B ₂ O ₃ D ₁ 800 50 3 nitric acid 160 14.3 30 100 4.5 1.32 1.37 E ₁ 500 60 6 nitric acid 50 14.3 40 200 5.0 1.73 1.35 E ₁ ' 100 55 4 oxalic acid 8g - 40 150 6.0 1.79 1.40

Example 3

This example introduces the preparation method of tungsten-nickel solution.

Measure 225cm ^of water, add 438g of ammonium metatungstate (industrial grade, containing 85.2m% WO ₃ ) and 344g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O, produced by the No. 1 Chemical Reagent Factory of Kaiyuan City, Liaoning Province) in sequence , stirring and dissolving to obtain tungsten-nickel solution G, whose composition is WO ₃ 3.22mol/dm ³ , NiO 2.37mol/dm ³ .

Measure 373cm ^of water, add 176g of ammonium metatungstate (industrial grade, containing 85.2m% WO ₃ ) and 132g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O, produced by the No. 1 Chemical Reagent Factory of Kaiyuan City, Liaoning Province) in sequence , stirring and dissolving to obtain a tungsten-nickel solution H, whose composition is WO ₃ 1.29 mol/dm ³ , NiO 0.91 mol/dm ³ .

Example 4

This example further illustrates the preparation method and process of the mixed solution containing tungsten, molybdenum, nickel and boron in combination with examples 2 and 3.

Measure the molybdenum-boron solution D ₁ 300cm ³ in Example 2, first add 168g of ammonium metatungstate and heat at 70°C for 1 hour, then add 134g of nickel nitrate, and heat for another 1 hour to obtain tungsten, molybdenum, The composition of nickel and boron mixed solution D ₂ is listed in Table 4.

Measure the molybdenum-boron solution E ₁ 200cm ³ in Example 2 and the tungsten-nickel solution G200cm ³ in Example 3, add the molybdenum-boron solution to the tungsten-nickel solution under stirring at 60°C, and then at this temperature Heated for 2 hours to obtain a mixed solution E ₂ containing tungsten, molybdenum, nickel, and boron, the composition of which is listed in Table 4

Measure the molybdenum-boron solution E ₁ 200cm ³ in Example 2 and the tungsten-nickel solution G100cm ³ in Example 3, add the molybdenum-boron solution into the tungsten-nickel solution under stirring at 50°C, and then at this temperature After heating for 3 hours, a mixed solution G ₁ containing tungsten, molybdenum, nickel, and boron was obtained, and its composition is listed in Table 4.

Measure the molybdenum-boron solution D ₁ 200cm ³ in Example 2 and the tungsten-nickel solution H200cm ³ in Example 3, add the tungsten-nickel solution into the molybdenum-boron solution under stirring at 55°C, and then at this temperature After heating for 4 hours, a mixed solution H ₁ containing tungsten, molybdenum, nickel and boron was obtained, and its composition is listed in Table 4.

Table 4 Composition of tungsten, molybdenum, nickel, boron mixed solution the solution Composition (mol/dm ³ ) WO ₃ MoO ₃ NiO B ₂ O _{3 D2} 1.58 1.02 1.18 1.05 E ₂ 1.61 0.87 1.18 0.68 G ₁ 1.07 1.15 0.79 0.90 H ₁ 0.65 0.64 0.45 0.70

Example 5

This example describes the method and process of adding active components and adjuvants to the carrier.

Take the silicon-containing alumina carriers A and B in Example 1 respectively, place them in a rotating container, and take the mixed solutions D ₂ , E ₂ , and G ₁ and H ₁ were sprayed and soaked respectively (saturated impregnation), and the spraying speed was controlled so that the solution was sprayed onto the carrier in a mist form. After spraying and soaking, they were taken out and dried at 120°C for 4 hours, and then calcined at 450°C for 3 hours. The catalysts J ₁ , J ₂ , J ₃ and K ₁ , K ₂ , K ₃ of the present invention were prepared. The specific operating conditions and properties of the catalysts are listed in Table 5.

table 5 catalyst Carrier g Impregnation solution cm ³ Composition (m%) Pore volume cm ³ /g Specific surface area m ² /g SiO ₂ WO ₃ MoO ₃ NiO B ₂ O ₃ J ₁ A/200 D ₂ /150 5.3 18.3 7.3 4.4 3.6 0.34 155 J ₂ A/200 E ₂ /150 5.5 19.0 6.4 4.5 2.4 0.35 160 J ₃ A/200 G ₁ /150 5.8 13.3 8.9 3.2 3.4 0.38 166 K ₁ B/200 D ₂ /160 7.9 19.1 7.6 4.6 3.8 0.35 127 K ₂ B/200 E ₂ /160 8.0 19.8 6.6 4.7 2.5 0.36 131 K ₃ B/200 H _1/160 10.0 9.6 5.8 2.1 3.1 0.42 187

Comparative example 1

This comparative example compares the activity of the catalyst prepared by the present invention and the catalyst prepared according to the invention patents CN1052501A and CN1086534A.

Catalyst M was prepared according to the method of Chinese invention patent CN1052501A, and catalyst N was prepared according to the method described in CN1086534A. The physical and chemical properties of the reference catalyst are listed in Table 6.

Table 6 Physicochemical properties of reference catalyst catalyst Composition (m%) Pore volume cm ³ /g Specific surface area m ² /g SiO ₂ WO ₃ MoO ₃ NiO B ₂ O ₃ m 4.7 19.8 7.8 5.0 3.5 0.30 150 N 10.5 18.0 8.0 4.1 3.8 0.37 131

Get catalyst J ₁ of the present invention and reference catalyst M after carrying out presulfurization respectively on 100cm ³ small-scale hydrogenation units, use victory catalytic diesel oil as raw material, property is listed in table 7, at 340 ℃, hydrogen oil ratio (v/ The activity of the catalyst was evaluated under the conditions of v) of 600, volume space velocity of 1.0h ^-1 , and total pressure of 3.0Mpa, and the results are listed in Table 8.

Get catalyst _K1 of the present invention and reference catalyst N to carry out presulfurization respectively on 100cm ³ small-scale hydrogenation units, use victory coking gas oil (CGO) as raw material, properties are listed in Table 7, at 370 ℃, hydrogen oil The catalyst activity was evaluated under the conditions of ratio (v/v) of 800, volume space velocity of 1.0h ^-1 , and total pressure of 8.0Mpa, and the results are listed in Table 8.

Table 7 Raw Oil Properties Raw oil name victory catalytic diesel Victory CGO Density, (20℃)kg.m ^-3 875 913 Distillation range, ℃ initial boiling point 190 258 10% 223 374 50% 279 412 90% 335 476 95% 342 512 Sulfur, ppm 2970 9800 Nitrogen, ppm 591 6600

Table 8 Catalyst Activity Evaluation Results catalyst Desulfurization rate, % Nitrogen removal rate, % J ₁ 92.7 70.8 M (reference) 92.4 70.6 K ₁ 93.0 51.2 N (reference) 92.5 50.0 As can be seen from the catalyst activity evaluation results in Table 8, the catalyst of the present invention has comparable desulfurization and denitrogenation activities under the same operating conditions compared with the reference catalyst. For the preparation of the boron mixed solution, the mixed solution is used to prepare the catalyst only once through impregnation, drying and roasting. Therefore, the process flow of the catalyst prepared by the invention is simpler than that of the catalyst prepared by the prior art, thereby reducing the cost of the catalyst.

Claims (8)

1, a kind of catalyst for hydrorefining distillate oil is an active ingredient with VIII family and group vib metallic element, adds boron additive, is carrier with siliceous aluminum oxide, it is characterized in that with the weight percent being benchmark, and catalyzer comprises SiO ₂3～10%, MoO ₃5～10%, WO ₃10～25%, NiO2～5%, B ₂O ₃2～5%; Described catalyzer is to make by in type carrier is only carried out single-steeping, drying and roasting with the mixing solutions that contains active ingredient and auxiliary agent.

2, according to the described catalyst for hydrorefining distillate oil of claim 1, the pore volume that it is characterized in that described catalyzer is 0.20～0.50cm ³/ g, specific surface area is 100～200m ²/ g.

3, according to the described catalyzer of claim 1, it is characterized in that the silicon in the described siliceous aluminum oxide adds in the alumina supporter moulding process, silica alumina ratio is 1: 5～25.

4, a kind of preparation method of Hydrobon catalyst comprises:

A. the moulding of siliceous alumina supporter;

B. prepare mixing solutions;

C. going on foot described mixing solutions with b floods a one-step forming alumina supporter;

D. dry, roasting makes catalyzer;

It is characterized in that described mixing solutions contains tungsten, molybdenum, nickel, boron component simultaneously, is disposable dipping to the dipping of formed alumina carrier, and wherein the preparation process of mixing solutions is:

(1) molybdenum compound and boron compound are added in the ammonia soln, regulate pH value between 6～9 with ammoniacal liquor, placement solution 50～200 hours, with mineral acid or/and the organic acid acidifying makes the pH value of solution value between 3～6, place solution 50～300 hours, and made Mo-B solution;

(2) Mo-B solution is mixed with tungsten compound and nickel compound, make and contain tungsten, molybdenum, nickel, boron mixing solutions.

5. according to the preparation method of the described Hydrobon catalyst of claim 4, it is characterized in that described molybdenum, tungsten, nickel, boron mixing solutions make by the following method:

(1) molybdenum compound and boron compound are added in the ammonia soln, regulate the pH value between 6～9 with ammoniacal liquor, keep the temperature of solution to descend 2～8 hours at 50～90 ℃, in 20～60 ℃ of scopes, placed solution 50～200 hours, between 40～80 ℃ with mineral acid or/and the organic acid acidifying makes the pH value of solution value between 3～6, the temperature that keeps mixing solutions in 40～80 ℃ of scopes 2～8 hours was placed solution 50～300 hours again in 20～60 ℃ of scopes, make Mo-B solution;

(2) between 20 ℃ to 80 ℃, Mo-B solution is mixed with tungsten compound and nickel compound, make and contain tungsten, molybdenum, nickel, boron mixing solutions.

6,, it is characterized in that described molybdenum compound is one or both in ammonium molybdate and the molybdic oxide according to the preparation method of the described Hydrobon catalyst of claim 5; Boron compound is one or both in boric acid and the ammonium borate; Tungsten compound is an ammonium metawolframate; Nickel compound is one or more in nickelous nitrate, nickelous chloride, the nickel acetate.

7,, it is characterized in that described mixing solutions comprises following component: MoO according to the preparation method of the described Hydrobon catalyst of claim 4 ₃0.3～1.5mol/dm ³, WO ₃0.4～1.8mol/dm ³, NiO0.4～1.8mol/dm ³, B ₂O ₃0.3～1.5mol/dm ³

8, according to the preparation method of the described Hydrobon catalyst of claim 5, it is characterized in that described preparation intact (2) goes on foot described molybdenum, tungsten, nickel, boron mixing solutions after, adjust the mixing solutions temperature that is made between 40～80 ℃, kept 1～4 hour.