CN100413582C - A kind of preparation method of catalyst composition - Google Patents

Abstract

The invention relates to a preparation method of a catalyst composition. The Ni _{x Wy} O _z composite oxide precursor was generated by co-precipitation method, and then mixed with MoO ₃ , filtered, shaped, and activated to become the final catalyst. Wherein the coprecipitation method generates the Ni _x W _y O _z composite oxide precursor as follows: add the salt mixture containing active metal Ni and W components in the reaction tank according to the proportion of catalyst components, and then add concentrated ammonia water, Make the pH value of the solution reach 10.0-13.0 to form a uniform material, then heat the material to evaporate ammonia until the pH value reaches 7.5-9.0, and at the same time generate a precipitate, which is the composite oxide Ni _x W _y O _z predecessor. The catalyst prepared by the method of the invention has high usability, especially higher activity for the process of deeply removing impurities from hydrocarbons. Moreover, the method of the invention is simple and convenient, and the metal loss rate is low. The method of the invention is mainly used for preparing bulk phase catalysts with higher metal content.

Description

A kind of preparation method of catalyst composition

technical field

The present invention relates to a preparation method of a catalyst composition, in particular to a preparation method of a bulk catalyst composition, in particular to a preparation method of a bulk catalyst for hydroconversion or hydrotreating of hydrocarbon oil, in particular The invention relates to a method for preparing a bulk catalyst for deep desulfurization, denitrogenation and other impurity removal processes of hydrocarbon oil.

Background technique

Fuel contains S, N and other impurities and aromatics (especially polycyclic aromatics), which will form harmful substances such as SOx, NOx and solid particles during use, which not only endanger human health, but also form acid rain in the air, causing greater pollution and destruction. In the past ten years, many countries including North America, Europe, and Japan have proposed the concept of ultra-low sulfur diesel (ULSD) and continuously formulated new fuel specifications to limit the content of sulfur and aromatics in gasoline and diesel for vehicles, and improve the quality of oil products. ,reduce environmental pollution.

While the worldwide fuel oil regulations are more stringent on the indicators of transportation fuels, the inferior quality of raw materials makes refineries need to find new catalysts to meet product demand under the premise of ensuring the refinery's profitability. Due to the decline in crude oil quality and the increasingly stringent requirements for sulfur content in diesel fractions in products, conventional hydrotreating catalysts that can only remove general sulfur-containing compounds are somewhat insufficient, so there is a need for removal of the most difficult-to-convert sulfur-containing compounds It's getting stronger and stronger. Therefore, catalysts with higher hydrodesulfurization performance are required. Ordinary hydrodesulfurization catalysts are easier to remove sulfur-containing compounds with no steric hindrance or small steric hindrance, but when dealing with sulfur-containing compounds with larger steric hindrance, such as 4,6-dimethyldibenzo The effect of thiophene (4,6-DMDBT) is not good. Therefore, improving the ultra-deep hydrodesulfurization ability of the catalyst, especially the conversion of difficult-to-remove sulfur-containing species is the key to realizing ultra-clean fuels.

Industrial hydrodesulfurization catalysts include supported hydrodesulfurization catalysts and bulk hydrodesulfurization catalysts. The former uses refractory metal oxides such as alumina as the carrier, and metals such as Ni, Co, Mo, and W are the most commonly used active components. Due to the limitation of the loading amount of metal components, when this type of catalyst processes ordinary diesel, it is difficult to obtain low-sulfur diesel with a sulfur content of less than 50 μg/g, and it is even more difficult to meet the future ultra-low-sulfur diesel standard with a sulfur content of less than 10 μg/g. The bulk method catalyst can get rid of the metal content limit, and at the same time, the ratio of each active component in the catalyst can be adjusted arbitrarily, the hydrogenation performance of the catalyst can be improved, and the ultra-deep desulfurization conversion of diesel can be achieved, and the sulfur content is less than 10 μg/g, or even Lower ultra-low sulfur diesel.

U.S. Patent No. 4,880,526 discloses a bulk catalyst containing Ni, Mo, W, and Co with high activity for hydroprocessing and a preparation method thereof. In the method, the aluminum oxide colloid is firstly prepared, and then soluble salts containing active metal components are added for mixing, dried and roasted. In addition, alumina colloids can also be prepared first, dried, mixed with insoluble salts containing active metal components, rolled, dried and roasted. Or different active metal components are prepared by any one of the above two methods. This method is similar to the kneading method, but has the problem of low metal utilization.

Bulk phase catalyst refers to the supported catalyst whose active components are dispersed on the carrier. It does not use an inactive carrier as a carrier. Even if it contains a certain amount of inactive components, it also plays a role in improving the strength of the bond. Most of the catalyst is composed of active components, and the content of active components is generally not limited, sometimes called bulk catalysts.

Chinese patents CN1253988A and CN1253989A disclose a bulk phase catalyst for the conversion of heavy hydrocarbons and a preparation method thereof. The catalyst is prepared by the co-gel method, which can obtain more uniform metal dispersion, and adopts the process of extruding and then washing. The metal salt solution is mixed with the molecular sieve slurry, and then the precipitant is added. The hydrocracking catalyst prepared by the method has strong nitrogen tolerance and can produce more middle distillates. The catalyst prepared by the above method is mainly aimed at the hydrocracking reaction of heavy distillate oil, and the hydrofinishing process is not described.

US patents US6299760, US6156695, US6537442, US6440888, and US6652738 disclose a bulk catalyst containing VIII/VIB active metal components for hydroprocessing and a preparation method thereof. The preparation of the catalyst can adopt the solution route or the solid route. The metal content can reach 50wt%-100wt%. The active metal component can be Ni-Mo or Ni-Mo-W. The catalyst may or may not contain a binder component. Binders are mainly used to bind metals and improve the strength of catalysts. The catalyst prepared by this method has high performance of HDS and HDN.

The preparation method disclosed in U.S. Patent No. 4,880,526 adopts the metal kneading preparation technology, and the microscopic distribution of different metal components in the bulk phase is not uniform. The methods disclosed in U.S. Patent No. 6,299,760 and other patents are a relatively excellent bulk catalyst for hydrotreating and its preparation method, but in the preparation of the catalyst involved in the patent, the molding of the catalyst adopts the method of first preparing the Ni-Mo Or Ni-Mo-W metal powder, then bonded with alumina or mix Ni-Mo or Ni-Mo-W metal powder with alumina colloid, then dehydrate, extrude, and dry. Due to the high metal content of the catalyst prepared by this method, there is often a lack of sufficient interaction between the metal and alumina, resulting in poor catalyst strength. The active component part is composed of a large number of metals, and some internal metal components cannot be fully utilized during the formation of Ni-Mo or Ni-Mo-W powder, resulting in loss of activity, and this problem cannot be solved by simple bonding. CN1342102A discloses a mixed metal catalyst, which is obtained by co-precipitating three active metals. Its main disadvantage is that no coordination effect between different active metals has been found. US6162350 and CN1339985A disclose a mixed metal catalyst composition. During the preparation process, at least one metal is kept in a solid state, and the surface of the solid metal compound reacts to form another solid oxide, and finally forms a core-shell composition. This method does not allow good coordination of dissimilar metals.

In the catalyst prepared by the bulk method, due to the high metal content, the coordination between different types of metals is very important. In the prior art, only the types and contents of metals are emphasized, and how to improve the coordination and cooperation between different metals is not involved.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a method for preparing a bulk catalyst. Through a special preparation process, different metals in the bulk catalyst can achieve good coordination and coordination, and further improve the performance of the catalyst.

Through research, it is found that in bulk catalysts, in the case of similar metal types and contents, the coordinated coordination of different metals will make the catalysts have different performances. Based on the above findings, the present invention proposes a method for preparing a bulk catalyst.

The preparation process of the bulk catalyst of the present invention includes the following contents: (1) the coprecipitation method generates the Ni _x W _y O _z composite oxide precursor; (2) the Ni _x W _y O _z composite oxide precursor is beaten and mixed with _MoO , Filtration; (3) Forming and activation are final catalysts.

Wherein (1) described co-precipitation method generates the process of Ni _x W _y O _z composite oxide precursor, adopts following process: in reaction tank, add the active metal Ni, W component containing Salt mixture, then add concentrated ammonia water to make the pH value of the material reach 10.0-13.0, forming a uniform material, the color is generally dark blue. Then heat the material to evaporate ammonia until the pH value of the solution reaches 7.5-9.0, and at the same time a precipitate is formed, which is the precursor of the composite oxide Ni _x W _y O _z .

The required catalyst aids and additional components can be added in one or more of the above steps. Auxiliaries generally include one or more of P, F, Ti, Si, B, Zr, etc. The added components are generally refractory porous substances and their precursors, such as one or more of alumina and its precursors (aluminum hydroxide, aluminum salt solution, etc.), clay, silica-alumina, titanium oxide-magnesia, and molecular sieves. species, preferably adding alumina or its precursors. The method of adding additives and adding components adopts conventional methods in this field.

In the preparation method of the catalyst composition of the present invention, the consumption of each raw material is determined according to needs, and the weight ratio of general composite oxide Ni _x W _y O _z and oxide MoO is 1: 10～10: ₁ , preferably 1: 5～ 5:1. The total weight content of the composite oxide Ni _x W _y O _z and the oxide MoO ₃ in the bulk catalyst is 40% to 100%, preferably 50% to 80%, and may contain other additives and additive components. In said Ni _x W _y O _z z=x+3y, the ratio of x and y in the composite oxide Ni _x W _y O _z is 1:8-8:1, preferably 1:4-4:1. The specific surface area of the prepared bulk catalyst is 120-400m ² /g, and the pore volume is 0.10-0.50ml/g.

Although W, Mo, and Ni are commonly used active components of hydrogenation catalysts, it has been found through a large number of experiments that the performance of catalysts with different compounding methods is very different. Especially in bulk catalysts with a large total metal content, the different coordination methods of these metals have a greater impact on the performance of the catalyst. The present invention finds through a large number of experiments that the bulk hydrogenation catalyst used for the deep removal of impurities from hydrocarbon materials first co-precipitates W and Ni to make the precursor of the Ni _x W _y O _z composite oxide, the precursor of the composite oxide The material is then mixed with MoO ₃ and then prepared by conventional methods. This preparation process combines elements W and Ni organically to form a composite oxide, which is then combined with MoO ₃ to form Ni _x W _y O Composition of _z complex oxide and Mo oxide. The results show that the catalyst with the microstructure of the present invention has outstanding impurity removal activity when used for hydrogenation of hydrocarbons, especially when it is used for deep removal of impurities from hydrocarbons, the activity of the catalyst is significantly higher than that of catalysts with similar chemical composition. The mechanism that the composition of Ni-W composite oxide and Mo oxide of the present invention can improve catalyst activity is not yet very clear, and, in bulk catalyst, the content of active metal is higher, and the existence form of active metal is different from that of traditional loaded catalyst. The catalysts are completely different, and therefore, the metal complexing theory of traditional supported catalysts cannot be applied. For example, it is generally believed that Ni can promote the activity of Mo, and it is hoped that there will be a stronger interaction between Ni and Mo. However, the present invention has found in experiments that for bulk catalysts, fully combining Mo and Ni can remove impurities in depth. did not exhibit desirable performance. The possible reason for the unexpected improvement in the performance of the catalyst composed of Ni-W composite oxide and Mo oxide in the deep impurity removal of the present invention is that in the bulk catalyst with a high metal content, the existence form of the active metal is different from that of the supported catalyst. Different, in the deep impurity removal process of hydrocarbon raw materials, Ni-W composite oxides have strong hydrogenation activity after sulfidation, which makes hydrocarbon molecules with complex structures hydrogenation effectively and eliminates the steric hindrance of the impurity removal reaction. Mo in the bulk catalyst has strong impurity removal activity after sulfidation, and heteroatom-containing hydrocarbons with simple structure and small steric hindrance are easy to react, reducing the interference of these heteroatom hydrocarbons on Ni-W hydrogenation activity , which is beneficial for the hydrogenation of complex structural molecules by Ni-W highly active centers. After the complex structure hydrocarbon molecules containing heteroatoms are effectively hydrogenated by the Ni-W high active center, the steric hindrance of de-impurity is greatly reduced, and can be easily removed in the de-impurity active center. Therefore, the active centers of the Ni-W composite oxide and the Mo oxide in the present invention are coordinated, and the combined catalyst has outstanding activity in the deep impurity removal reaction. The method of the present invention does not use the salt solution of Mo, because the reaction product of the Mo salt solution and the precipitation agent generally has a certain solubility, thus avoiding the loss of Mo. The bulk phase catalyst obtained by the method of the invention is more uniform.

Description of drawings

Fig. 1 is the catalyst A electron scanning microscope JSM-6301F figure (magnification 80,000 times) prepared by the method of the present invention.

Detailed ways

The invention provides the preparation method of catalyst, a kind of concrete process step is as follows:

1. Preparation of Ni _x W _y O _z composite oxide precursor and MoO ₃ mixture

Add the salt mixture containing active metal Ni and W components into the reaction tank according to the ratio of catalyst components. Nickel-containing salts can be nickel sulfate, nickel nitrate, nickel chloride, basic nickel carbonate and the like. The tungsten-containing salt can be sodium tungstate, ammonium metatungstate, tungstic acid, etc. After mixing evenly, add concentrated ammonia water to the above mixture under stirring until dark blue material A is formed, and the pH value of material A is 10.0-13.0. The weight concentration of ammonia water is generally 15% to 35%. Heat the solution A to 80-100°C while stirring, distill ammonia and produce precipitation until the pH value of the slurry is 7.5-9.0. The precipitate in the slurry is the precursor of the Ni _x W _y O _z composite oxide. After the gel is formed, it can be filtered or not, then solid molybdenum trioxide is added, beaten and mixed, and then filtered to obtain a filter cake. The filter cake can be washed or not washed. The filter cake is dehydrated and dried at 50-150°C, and the drying time is After 0.5-24 hours, a mixture of Ni _x W _y O _z composite oxide precursor and MoO ₃ is obtained.

The temperature of the ammonia distillation is preferably 85-95° C., the ammonia distillation time is generally 1 to 5 hours, preferably 1 to 3 hours, and the pH value of the slurry is preferably 7.5-8.5 at the end of the ammonia distillation. The drying temperature is preferably 50-100°C, and the drying time is preferably 1-8 hours.

An aluminum salt solution can be added to the salt mixture composed of Ni and W, so that the precipitate contains the precursor of alumina. The aluminum salt solution can be aluminum nitrate, aluminum sulfate, aluminum chloride or aluminum acetate. Aluminum hydroxide can also be added directly after gelling. The purpose of introducing aluminum into the catalyst is mainly to increase the strength of the catalyst and improve the pore structure. During the preparation of the mixed material, auxiliary agents and additives can be added as required.

2. Catalyst preparation

The above-mentioned dried filter cake is rolled and extruded into strips. After forming, it can be washed with clean water or a solution containing decomposable salts (such as ammonium acetate). The final catalyst product is obtained by activating the strip after washing, and the activation includes drying and roasting. Drying and calcination can adopt conventional conditions in the art, such as drying at 50-200°C for 1-48 hours, and calcination at 450-600°C for 0.5-24 hours, preferably 1-8 hours. Auxiliaries and additives can also be introduced as needed during catalyst preparation.

The shape of the catalyst can be flake, spherical, cylindrical strip and special-shaped strip (clover, four-leaf clover) as required, preferably cylindrical strip and special-shaped strip (clover, four-leaf clover). The diameter of the carrier can be a thin strip of 0.8-2.0 mm and a thick strip of >2.5 mm.

The catalyst of the present invention has relatively high hydrodesulfurization and hydrodenitrogenation reaction performance, and can be used in hydrocracking pretreatment and diesel desulfurization processes, especially in processes such as diesel ultra-deep desulfurization for producing ultra-low sulfur clean fuels. The catalyst is also It can be used in other hydrorefining and hydrotreating processes. When the catalyst contains catalytic materials such as molecular sieves, it can also be used in reaction processes such as hydrocracking and hydroupgrading.

Although the catalyst of the present invention is a composition of Ni _{x Wy} O _z composite oxide and MoO ₃ from a microscopic point of view, the dispersion of the two materials is quite uniform, so two active centers can be formed to coordinate and cooperate.

Electron microscopy results of the catalyst in Table 1A

Table 1 is the electron microscope result of A catalyst, and A catalyst is the catalyst prepared by the method of this patent, and the catalyst is a strip catalyst with a diameter of 1.3 mm. Select 3 points from the catalyst center to the left and right edges to see the composition change of the catalyst. It can be seen from the results that the catalyst A prepared by this method exhibits very good metal dispersion performance from the center to the edge of the catalyst, and the metal composition of several points has little difference. Figure 1 is a JSM-6301F electron scanning microscope image of catalyst A (magnified by 80,000 times). It can also be seen from Figure 1 that the metal elements of Ni/Mo/W are very uniformly distributed in the entire bulk catalyst.

The solutions and effects of the present invention are further illustrated below through specific examples. The percentages involved are percentages by weight. The specific surface area of the catalyst is measured by the BET method, the pore volume is measured by the nitrogen adsorption method, and the strength is measured by the lateral pressure method.

Example 1

Add 1000mL of water into the reaction tank, then add 40g of nickel chloride to dissolve, then add 32g of ammonium metatungstate to dissolve, then add 25% ammonia water until a dark blue solution A is formed, the pH value of the solution is 11.0, and the temperature of solution A is raised to 80°C , distill ammonia for 2 hours, the pH value is 8.0, then filter, add 600ml of clean water, 28g of molybdenum trioxide and 34g of aluminum hydroxide to the filter cake, beat and stir evenly, filter, dry the filter cake at 80°C for 5 hours, and then extrude , washed three times with clean water, dried the wet strip at 120°C for 5 hours, and calcined at 500°C for 4 hours to obtain the final catalyst A. The composition and main properties are shown in Table 2.

Example 2

According to the method of Example 1, according to the component content ratio of catalyst B in Table 2, add aluminum chloride, nickel chloride, sodium tungstate and zirconium oxychloride to the reaction tank, and then add 20% ammonia water to form dark blue solution, the pH value is 12.0, warming up to 95°C, distilling ammonia for 3 hours until the pH value is 7.5, then filtering, washing the filter cake twice with 500mL clean water, adding clean water and molybdenum trioxide, beating and stirring evenly, filtering, filtering The cake was dried at 70°C for 7 hours, then extruded into strips, washed twice with clean water, dried at 100°C for 8 hours, and calcined at 550°C for 3 hours to obtain the final catalyst B. The composition and main properties are shown in Table 2.

Example 3

According to the method of embodiment 1, according to the component content ratio of catalyst C in table 2, nickel nitrate, silica sol, ammonium metatungstate, aluminum hydroxide are added in the reaction tank, then add 30% ammonia water to form dark blue material, The pH value is 13.0, heat up to 80°C, distill ammonia for 5 hours until the pH value is 8.0, then add molybdenum trioxide, beat and stir evenly, filter, dry the filter cake at 120°C for 1 hour, and then extrude into strips, wet strips at 130 ℃ drying for 3 hours, and calcination at 600 ℃ for 3 hours to obtain the final catalyst C, whose composition and main properties are shown in Table 2.

Example 4

According to the method of Example 1, according to the component content ratio of catalyst D in Table 2, add 1000mL water into the reaction tank, then add 48g of nickel chloride to dissolve, then add 36g of ammonium metatungstate to dissolve, and then add 25% ammonia water into a dark blue solution A with a pH value of 12.0, heat up to 90°C, distill ammonia for 1 hour until the pH value is 9.0, then filter, and add 600ml of clean water, 16g of molybdenum trioxide, 6g of titanium trichloride and 37g of hydroxide to the filter cake Aluminum, beating and stirring evenly, filtering, drying the filter cake at 80°C for 5 hours, then extruding into strips, washing with clean water for 3 times, drying the wet strips at 120°C for 5 hours, and roasting at 500°C for 4 hours to obtain the final catalyst D. The composition and main properties are shown in Table 2.

comparative example

According to the catalyst composition of Example 1, the reference agent E was prepared according to the catalyst preparation method disclosed in Chinese patent CN1342102A.

Add 1000mL of water into the reaction tank, then add 45g of ammonium heptamolybdate to dissolve, then add 33g of ammonium metatungstate to dissolve, then add 25% ammonia water to form a gel until the pH value is 10.0, heat to a temperature of 90°C, and simultaneously A solution containing 40 g of nickel chloride was added dropwise in the tank. The resulting suspension was stirred for a further 30 minutes at 90°C. Then filter, wash the filter cake with hot water, dry at 100°C for 5 hours, then add 34g of aluminum hydroxide to extrude into a rod, dry the wet rod at 100°C for 8 hours, and roast at 500°C for 4 hours to obtain the final reference catalyst E. And the main properties are shown in Table 2. Prepare the catalyst by this method, the yield of molybdenum trioxide can only reach 80%, in order to ensure the metal content and proportioning in the catalyst, add 20% more ammonium heptamolybdate when feeding.

Catalyst and properties prepared by the method of the present invention in table 2

Example 5

This example is an evaluation of the performance of the hydrodesulfurization reaction of the catalyst.

In order to further illustrate the ultra-deep hydrodesulfurization ability of the catalyst of the present invention, a comparative evaluation test was carried out on a 200ml small-scale hydrogenation device using catalysts A and C of the present invention, catalysts of comparative example E, and the test material was Maoming blended diesel oil. The main properties of raw materials are shown in Table 3, and the process conditions and evaluation results of catalyst activity evaluation are shown in Table 4.

Table 3 Main Properties of Raw Oil

Table 4 Catalyst hydrodesulfurization reaction process conditions and evaluation results

When the sulfur content of diesel oil is below 500μg/g, the sulfur-containing compounds are difficult to remove sulfur-containing species with steric hindrance. In industry, common hydrodesulfurization catalysts are precisely because it is difficult to combine 4-MDBT (4-methyldibenzothiophene), 4,6-DMDBT (4,6-dimethyldibenzothiophene) with steric positions Therefore, it is difficult to obtain ultra-clean fuel with a sulfur content of less than 50 μg/g in the product. It can be seen from Tables 2 and 4 that the bulk Ni, Mo and W catalysts of the present invention have a higher total metal content, and the atomic ratio of Ni, Mo and W can be adjusted in a wide range. Under the same reaction conditions, the sulfur content in the product using the bulk phase Ni, Mo, W catalyst of the present invention is far lower than that of the reference catalyst used. Therefore, the catalyst prepared by the method of the present invention has higher hydrogenation performance, and especially shows a more obvious removal effect on sulfides with steric hindrance. It can be seen from the results in the table that the bulk catalyst prepared by the method of the present invention has excellent hydrogenation and hydrodesulfurization capabilities, can be used in hydrodesulfurization and hydrodenitrogenation reactions, and is especially suitable for ultra-deep desulfurization in the production of ultra-clean diesel Reacting.

Claims (11)

1. a preparation method of catalyst composition, it is characterized in that comprising the following content: (1) co-precipitation method generates Ni _x W _y O _z composite oxide precursor; (2) Ni _x W _y O _z composite oxide precursor (3) forming and activating the final catalyst; wherein the co-precipitation method described in step (1 ₎ generates the Ni _x W _y O _z composite oxide precursor using the following process: according to the catalyst components Content ratio Add the salt mixture containing active metal Ni and W components into the reaction tank, and then add concentrated ammonia water to make the pH value of the solution reach 10.0-13.0 to form a uniform material, and then heat the material to evaporate the ammonia to the pH value Up to 7.5-9.0, a precipitate is generated simultaneously, and this precipitate is the precursor of the composite oxide Ni _x W _y O _z ; in the composite oxide Ni _x W _y O _z , z=x+3y, x and The ratio of y is 1:8 to 8:1. 2. according to the described method of claim 1, it is characterized in that in one or several steps in above-mentioned steps, add required catalyst auxiliary agent and add component, auxiliary agent comprises P, F, Ti, Si, B and Zr One or more of them, and the added component is one or more of alumina, clay, silica-alumina, titania-magnesia and molecular sieves. 3. according to the method for claim 1, it is characterized in that in the preparation method of catalyst composition, the consumption of each raw material is determined as required, composite oxide Ni _x W _y O _z and oxide compound MoO _The weight ratio is 1: 10 ~ 10:1, the total weight content of the composite oxide Ni _x W _y O _z and the oxide MoO ₃ in the catalyst is 40% ~ 100%. 4. according to the described method of claim 1, it is characterized in that in catalyst composition preparation method, each raw material consumption is determined by following ratio: composite oxide Ni _x W _y O _z and oxide compound MoO _The weight ratio is 1: 5 ~5:1, the total weight content of composite oxide Ni _x W _y O ₂ and oxide MoO ₃ in the catalyst is 50% ~ 80%, the ratio of x and y in the composite oxide Ni _x W _y O _z is 1: 4～4:1. 5. according to the method for claim 1, it is characterized in that active metal Ni is derived from nickel sulfate, nickel nitrate, nickel chloride or basic nickel carbonate, and active metal W is derived from sodium tungstate or ammonium metatungstate. 6. according to the described method of claim 1, it is characterized in that described concentrated ammonia water weight concentration is 15%～35%. 7. according to the described method of claim 1, it is characterized in that described ammonia evaporation temperature is 80-100 ℃. 8. according to the described method of claim 7, it is characterized in that described ammonia evaporation temperature is 85-95 ℃. 9. according to the method for claim 1, it is characterized in that the filter cake obtained by filtering described in step (2) is dehydrated and dried under the condition of 50-150 ℃, and the drying time is 0.5-24 hours. 10. according to the method for claim 1, it is characterized in that the pH value after ammonia evaporates is 7.5-8.5. 11. The method according to claim 1, characterized in that the activation described in step (3) includes drying and roasting, the drying is drying at 50-200°C for 1-48 hours, and the roasting is roasting at 450-600°C for 0.5- 24 hours.