CN112058304B - A bifunctional catalyst capable of adjusting solid acidity, preparation method and application thereof - Google Patents

Abstract

The invention provides a double-function catalyst capable of adjusting solid acidity, a preparation method and application thereof, comprising the following steps: carrying out depolymerization reaction and hydrothermal crystallization reaction on a Y-type zeolite molecular sieve serving as a raw material to obtain YZCZ solid powder; carrying out ion exchange on the YZCZ solid powder to obtain H-type YZCZ solid powder; the H-type YZCZ solid powder is used as a carrier to load a hydrogenation transition metal component, so that the adjustable solid acidity bifunctional catalyst is prepared; the adjustable solid acidity bifunctional catalyst of the supported metal salt is applied to clean liquid fuel produced by directly liquefying low-metamorphic coal, and can efficiently complete the selective fracture of the Car-O in the cracking process under the synergistic effect of the adjustable solid acid and the metal Ni, thereby completing the aim of converting the low-metamorphic coal into the clean liquid fuel.

Description

A bifunctional catalyst capable of adjusting solid acidity, preparation method and application thereof

technical field

The invention relates to the technical field of catalyst preparation, in particular to a bifunctional catalyst capable of adjusting solid acidity, a preparation method and an application thereof.

Background technique

At present, the relatively abundant coal resources and scarce oil resources, as well as the increasing dependence on foreign oil each year, have brought huge challenges to the strategic security of energy. The direct liquefaction of coal and the conversion of low metamorphic coal into clean liquid fuels and high-value organic chemical fine products are an important process route.

Low-metamorphic coal is a mixture of macromolecular compounds composed of various chemical bonds and functional groups, and low molecular weight molecular compounds. It is mainly composed of heteroatoms such as C, H, O, and N, forming an extremely complex three-dimensional macromolecular structure. . The energy required for the breakage of the bridges connecting the basic structural units is much lower than the energy required for the breakage of the aromatic ring structure, so the use of acid-catalyzed breakage of the bridges is crucial to the coal liquefaction process. In addition, the content of heteroatoms (mainly O, N, S, etc.) and saturated aromatics in liquefied products are the main indicators for evaluating high-value liquid fuels. Under relatively mild conditions, while efficiently removing heteroatoms, saturated aromatics are technical difficulties in direct coal liquefaction, and are also a huge challenge for direct coal liquefaction to produce clean liquid fuels, especially the removal of oxygenates. Therefore, the development of Solid hydrogenation catalyst with acid catalytic function is the key technology to realize direct coal liquefaction under mild conditions.

Although transition metals have good hydrogenation performance at low temperature, they are extremely sensitive to heteroatoms and expensive. Metal sulfides and metal oxides exhibit good heteroatom tolerance, chemical stability, and low cost during hydrogenation, but the S loss of metal sulfides and the phase transition of metal oxides will lead to clean fuel quality decline.

Contents of the invention

The object of the present invention is a dual-functional catalyst capable of adjusting solid acidity, a preparation method and its application, which solves the defect that the quality of clean fuel decreases when the existing hydrogenation catalyst removes oxygen-containing compounds.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A method for preparing a bifunctional catalyst capable of adjusting solid acidity provided by the invention comprises the following steps:

Y-type zeolite molecular sieve is used as raw material for depolymerization reaction, followed by hydrothermal crystallization reaction to obtain YZCZ solid powder;

The H-type YZCZ solid powder is obtained by ion-exchanging the YZCZ solid powder;

The H-type YZCZ solid powder is used as a carrier, and a hydrogenation transition metal component is loaded to prepare a bifunctional catalyst that can adjust the acidity of the solid.

Preferably, the specific method for preparing YZCZ solid powder is:

S1, adding Y-type zeolite molecular sieve into the alkali solution to carry out depolymerization reaction, and at the same time, adding template agent and silicon source to it to obtain a gel solution, and then stirring at room temperature to obtain a gel liquid;

S2, hydrothermally crystallizing the gel liquid obtained in S1 to obtain a solid precipitate;

S3, washing the solid precipitate obtained in S2 with water several times until the pH is 7, and then drying to obtain YZCZ solid powder;

Wherein, the mass ratio of alkali solution, Y-type zeolite molecular sieve, silicon source and template agent is 50:(3-5):(3.5-4.5):(0.7-1.2).

Preferably, in S1, the template agent is tetrapropylammonium bromide, tetraethylammonium bromide or tetrapropylammonium hydroxide; the silicon source is calcined fumed silica.

Preferably, the specific method for preparing H-type YZCZ solid powder is:

S1, roasting the prepared YZCZ solid powder until the template agent embedded in the YZCZ solid powder is removed to obtain the roasted YZCZ solid powder;

S2, taking the roasted YZCZ solid powder obtained in part S1 and adding it to a 1mol/L ammonium nitrate solution, and then performing ion exchange to obtain a solid precipitate;

S3, drying the solid precipitate obtained in S2, and then roasting to obtain the H-type YZCZ solid powder;

Among them, the solid-liquid ratio of roasted YZCZ solid powder and ammonium nitrate solution is 20:1.

Preferably, the process parameters of roasting in S1 are: heating up to 600°C, heating rate of 10°C/min, and roasting for 5 hours; the process parameters of roasting in S3 are: heating up to 550°C, heating rate of 10°C/min, roasting for 5 hours.

Preferably, the specific method for preparing a metal-loaded adjustable solid acidic bifunctional catalyst is:

S1, adding distilled water to the prepared H-type YZCZ solid powder, then slowly adding a transition metal salt, stirring evenly, to obtain a carrier aqueous solution;

S2, slowly adding 3 wt% dilute ammonia water into the carrier aqueous solution obtained in S1 and stirring to obtain a mixed solution, and then filtering and drying to obtain a solid precipitate, wherein the pH of the mixed solution is 9-10.5;

S3, placing the solid precipitate obtained in S2 in an atmosphere reduction furnace, and heating it under an _H2 atmosphere to obtain a metal-loaded bifunctional catalyst capable of adjusting solid acidity;

Among them, the solid-liquid ratio of H-type YZCZ solid powder to distilled water is 1:50.

Preferably, in S1, the transition metal salt is one or more of Pd, Pt, Ru and Ni, and the metal loading is (3-20)wt%.

A bifunctional catalyst capable of modulating solid acidity is prepared based on the preparation method of a bifunctional catalyst capable of modulating solid acidity.

An application of a dual-functional catalyst that can adjust solid acidity, based on the preparation method of a dual-functional catalyst that can adjust solid acidity, the dual-functional catalyst that can adjust solid acidity can be used in hydrogenation and hydrogenation of aromatic hydrocarbons Removal of heteroatoms.

Compared with prior art, the beneficial effect of the present invention is:

The present invention provides a dual-functional catalyst capable of adjusting solid acidity and its preparation method. In the prepared YZCZ, the ratio of Y zeolite molecular sieve to ZSM-5 zeolite molecular sieve can be changed by changing the addition amount of Y zeolite molecular sieve, two At the same time, the ratio of Y zeolite molecular sieve to ZSM-5 zeolite molecular sieve can also be adjusted through the crystallization time, because the longer the crystallization time, the greater the depolymerization of Y-type zeolite. YZCZ with different proportions of Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve can also be obtained by adjusting different crystallization time;

The dual-function catalyst capable of adjusting solid acidity prepared by the present invention is a zeolite composite with two structures, which can combine the structures of two different zeolites, Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve, by adjusting the two zeolite The proportion of molecular sieves in the zeolite composite can realize the adjustment of the acidity (B acid and L acid) of the zeolite composite through the coordinated action of different B/L values.

The application of a dual-functional catalyst capable of adjusting solid acidity provided by the present invention is to use the prepared dual-functional catalyst loaded with metal salts for the efficient hydrogenation of aromatic hydrocarbon macromolecules and the removal of heteroatoms. In addition to the reaction, it has the characteristics of low reaction temperature (≤160°C), high conversion rate, and excellent recovery and regeneration performance; the bifunctional catalyst loaded with metal salts and adjustable solid acidity prepared by the present invention is applied to the direct liquefaction of low-deterioration coal In the production of clean liquid fuels, under the synergistic effect of adjustable solid acid and metal Ni, the selective cleavage of Car-O in the cracking process can be efficiently completed, thereby completing the purpose of converting low-modified coal into clean liquid fuels.

Description of drawings

Fig. 1 is the YZCZ electron micrograph and the energy scatter spectrum that make in the embodiment of the present invention;

Fig. 2 is the Ni/YZCZ electron micrograph and energy scattering spectrum obtained in the embodiment of the present invention.

Detailed ways

The present invention will be described in further detail below in conjunction with the accompanying drawings.

A method for preparing a bifunctional catalyst capable of adjusting solid acidity provided by the invention comprises the following steps:

Using Y-type zeolite molecular sieve as raw material to carry out depolymerization reaction, followed by hydrothermal crystallization reaction, to obtain YZCZ (Y/ZSM-5compositezeolite, referred to as YZCZ) solid powder;

Then YZCZ solid powder was ion-exchanged to obtain H-type YZCZ with acid catalytic activity (H-type Y/ZSM-5compositezeolite, referred to as H-type YZCZ);

Finally, the H-type YZCZ solid powder is used as the carrier, and the hydrogenation transition metal component is supported to prepare a dual-functional catalyst that can adjust the acidity of the solid (abbreviated as M/YZCZ, and M represents the transition metal component).

Further, the preparation method specifically includes the following steps:

a. Preparation of YZCZ solid powder

a1. Add a certain amount of Y-type zeolite molecular sieve into the alkali solution, control the pH to 10.5-11.5, and slowly depolymerize the Y-type zeolite molecular sieve. At the same time, add template agent and silicon source to it to obtain a gel solution, stir at room temperature, and control The aging time is 1-3 hours to obtain a gel liquid;

a2. Add the above-mentioned gel liquid into an autoclave for hydrothermal crystallization, the crystallization temperature is 175-185°C, the crystallization time is 10-18h, and a solid precipitate is obtained;

a3. Wash the above solid precipitate with water several times until the pH is 7, and then dry it at 100° C. for 6 hours to obtain YZCZ solid powder.

b. Preparation of H-type YZCZ

b1. Put the YZCZ solid powder prepared in step a in a muffle furnace, and bake it with air at 550°C for 5 hours, and bake at a heating rate of 10°C/min to completely remove the template embedded in the YZCZ structure;

b2. Take a certain amount of roasted YZCZ solid powder and add it to 1mol/L ammonium nitrate solution, and perform ion exchange at 40°C. After ion exchange three times, a solid precipitate is obtained;

b3. Dry the precipitate obtained in step b2 at 100°C for 6 hours, then put the dried precipitate into the muffle furnace, and pass in air for secondary roasting to obtain acid catalytic activity. H-type YZCZ solid powder;

c. Preparation of metal-supported bifunctional catalysts with adjustable solid acidity

c1. Using the H-type YZCZ solid powder prepared in step b as a carrier, first add a certain amount of distilled water, then slowly add transition metal salt, stir evenly, heat the carrier aqueous solution to 50-60°C, and stir in a closed manner for 30-60 minutes;

c2. Slowly add a certain amount of 3wt% dilute ammonia water into the carrier aqueous solution, adjust the pH to 9-10.5, continue to stir for 30-60min, maintain 50-60°C, filter the mixed solution to obtain a solid precipitate, at 80°C Dry for 6 hours and set aside;

c3. Put the solid precipitate obtained in step c2 in an atmosphere reduction furnace, and under _H2 atmosphere, control the heating rate of 2-3°C/min, raise the temperature to 400-500°C, and maintain it for 3-5h to obtain a metal-loaded product. A bifunctional catalyst that modulates solid acidity.

Further, in step a1, tetrapropylammonium bromide, tetraethylammonium bromide or tetrapropylammonium hydroxide is selected as the templating agent, and calcined fumed silica is selected as the supplementary silicon source.

Further, in step a1, the mass ratio of alkali solution, Y-type zeolite molecular sieve, supplementary silicon source and template agent is 50:(3-5):(3.5-4.5):(0.7-1.2).

Further, in step a1, the alkaline solution is 0.15 mol/L NaOH solution.

Further, in step b1, during the primary calcination, the temperature is raised to 600° C. at a heating rate of 10° C./min, and the calcination is performed for 5 hours.

Further, in step b2, the solid-to-liquid ratio of the YZCZ solid powder to the ammonium nitrate solution is 20:1.

Further, in step b3, during the second calcination, the temperature is raised to 550° C. at a heating rate of 10° C./min, and the calcination is performed for 5 hours.

Further, in step c1, the solid-to-liquid ratio of H-type YZCZ to distilled water is 1:50.

Further, in step c3, the control of the heating rate can make the reaction slowly reduce and prevent the aggregation of metal particles.

Further, the transition metal salt is one or more metal salts among Pd, Pt, Ru and Ni, and the metal loading is (3-20)wt%.

The application of the adjustable solid acid bifunctional catalyst provided by the present invention is the application of the adjustable solid acid bifunctional catalyst prepared by the above preparation method in the hydrogenation of aromatic hydrocarbons and the removal of heteroatoms.

Example 1

A method for preparing a dual-functional catalyst with adjustable solid acidity loaded with metallic nickel, specifically comprising the following steps:

1. Add a certain amount of Y-type zeolite molecular sieve into 0.15mol/L NaOH alkali solution, while depolymerizing, add tetrapropylammonium bromide (TPABr) and silicon dioxide to it to obtain a gel solution, stir at room temperature, and control The aging time is 2 hours; wherein, the mass ratio of alkaline solution, Y-type zeolite molecular sieve, silicon dioxide, and tetrapropylammonium bromide (TPABr) is 50:4:4:1.

2. Put the above gel into an autoclave for hydrothermal crystallization, the crystallization temperature is 180° C., and the crystallization time is 16 hours to obtain a solid precipitate.

3. Wash the above solid precipitate with water several times until pH = 7, and dry at 100°C for 6 hours to obtain YZCZ solid powder. The electron micrograph is shown in Fig. 1 .

4. Put the YZCZ solid powder prepared in step 3 into the muffle furnace, and carry out a calcination with air to remove the template agent; during the 1st calcination, heat up to 600°C at a heating rate of 10°C/min, and calcine for 5 hours.

5. Add a certain amount of roasted YZCZ solid powder into 1mol/L ammonium nitrate solution, and conduct ion exchange at 40°C. After ion exchange three times, a precipitate is obtained; the solid-liquid ratio of YZCZ solid powder and ammonium nitrate solution is 20 :1.

6. Dry the precipitate obtained in step 5 at 100°C for 6 hours, then put the dried precipitate into the muffle furnace, and put air into it for secondary roasting. During the secondary roasting, raise the temperature to 550 ℃, the heating rate is 10℃/min, and calcined for 5h, the H-type YZCZ solid powder can be obtained.

7. Use the H-type YZCZ solid powder prepared in step 6 as a carrier, first add a certain amount of distilled water, the solid-to-liquid ratio of the H-type YZCZ solid powder to distilled water is 1:50, then slowly add Ni salt, stir evenly, and dissolve the carrier aqueous solution Raise the temperature to 60°C, and stir for 30 minutes under airtight;

8. Slowly add a certain amount of 3% dilute ammonia water into the carrier aqueous solution, adjust the pH to 9, continue to stir for 40 minutes, maintain 50°C, filter the mixed solution to obtain a solid precipitate, and dry it at 80°C for 6 hours before use.

9. Put the solid precipitate obtained in step 8 in an atmosphere reduction furnace, under H ₂ atmosphere, control the heating rate of 2°C/min, raise the temperature to 400°C, and keep it for 3h to obtain a metal-loaded adjustable solid acid bismuth Functional catalyst (Ni/YZCZ), metal nickel in Figure 2 is distributed in granular form.

Example 2

The difference from Example 1 is that the mass ratio of alkaline solution, Y-type zeolite molecular sieve, silicon dioxide, and tetrapropylammonium bromide (TPABr) is 50:3:3.5:0.7.

Example 3

The difference from Example 1 is that the mass ratio of alkaline solution, Y-type zeolite molecular sieve, silicon dioxide, and tetrapropylammonium bromide (TPABr) is 50:5:4.5:1.2.

Example 4

The difference from Example 1 is that the crystallization time is 12 hours.

Example 5

The difference from Example 1 is that the crystallization time is 18 hours.

The adjustment of the acidity of the prepared YZCZ with different Y-type zeolite contents is shown in Table 1.

Table I

The adjustment of the acidity of the prepared YZCZ with different crystallization times is shown in Table 2.

Table II

L酸为Lewis，C(B酸)＝1.88IA(B)R²/W；C(L酸)＝1.42IA(L)R²/W.；其中C表示吸附在B酸或L酸酸位上的吡啶浓度(mmolg^-1)。In the table, B acid is

L acid is Lewis, C (B acid) = 1.88IA (B) R ² /W; C (L acid) = 1.42IA (L) R ² /W.; where C means adsorption on the acid site of B acid or L acid The concentration of pyridine (mmolg ^-1 ).

Example 6

1. Add 2g of the H-type YZCZ solid powder obtained in Example 1 into 100ml of distilled water, slowly add 1.02g of nickel nitrate hexahydrate, stir evenly, raise the temperature of the carrier aqueous solution to 50°C, and stir for 35 minutes;

2. Slowly add a certain amount of 3% dilute ammonia water into the carrier aqueous solution, adjust the pH to 10.5, continue to stir for 60 minutes, maintain 60°C, filter the mixed solution to obtain a solid precipitate, and dry it at 80°C for 6 hours before use.

3. Put the obtained solid precipitate in an atmosphere reduction furnace, under the _H2 atmosphere, control the heating rate of 3°C/min, raise the temperature to 500°C, and maintain it for 5h to obtain a tunable solid acid with a Ni loading of 5%. Bifunctional catalyst (Ni _10% /YZCZ).

Example 7

The difference from Example 6 is that the addition amount of nickel nitrate hexahydrate is 0.51 g, and a bifunctional catalyst (Ni _5% /YZCZ) with adjustable solid acidity with a Ni loading of 5% is prepared.

Example 8

The difference from Example 6 is that the addition amount of nickel nitrate hexahydrate is 1.53 g, and a bifunctional catalyst (Ni _15% /YZCZ) with adjustable solid acidity with a Ni loading of 15% is prepared.

The catalysts prepared in Examples 6, 7 and 8 were applied to the catalytic hydrogenation of diphenyl ether.

Reaction conditions: Catalysts were evaluated in a programmed temperature-controlled high-pressure mechanically stirred microreactor.

Take diphenyl ether as the reaction substrate, the reaction conditions are as follows: the initial hydrogen pressure is 5Mpa, the reaction temperature is 160°C, the reaction time is 120 minutes, the reaction substrate is 1ml, the reaction solvent is n-hexane, and the addition amount is 20ml , The addition of catalyst is 0.05g.

This was used to evaluate the Ni/YZCZ catalytic hydrogenation ability and the ability to break the C-O bond.

Hydrogenation product analysis method: Agilent7890/5973 quadrupole gas chromatography/mass spectrometry was used to analyze the composition of catalytic hydrogenation conversion products, and the chromatographic column was a 60m×0.25mm×0.25μm HP-5MS capillary cross-linked column.

Under the same reaction conditions, the conversion rate and product distribution of the three bifunctional catalysts prepared in Examples 6, 7 and 8 for catalytic hydrogenation of diphenyl ether are shown in Table 3.

Table three

Example 9

The difference from Example 6 is that nickel nitrate hexahydrate is replaced by rubidium nitrate, and 0.345 g of rubidium nitrate is added to prepare a dual-functional catalyst (Ru _10% /YZCZ) with a Ru loading of 10% and an adjustable solid acidity.

Example 10

The difference from Example 6 is that nickel nitrate hexahydrate is replaced by platinum nitrate, and 0.327g platinum nitrate is added to obtain a dual-functional catalyst (Pt _10% /YZCZ) with a Pt load of 10% that can be adjusted to solid acidity

Application Example 1

Take diphenyl ether as the reaction substrate, the reaction conditions are as follows: the initial hydrogen pressure is 5Mpa, the reaction temperature is 160°C, the reaction time is 120 minutes, the reaction substrate is 1ml, the solvent is cyclohexane, and the addition amount is 20ml , The addition of catalyst is 0.05g.

The three bifunctional catalysts prepared in Examples 6, 9 and 10 were applied to the catalytic hydrogenation process, and the conversion rate of the reactants was shown in Table 4.

Table four

Application Example 2

The Ni _10% /YZCZ prepared in Example 6 was applied to the hydrogenation of sub-bituminous coal extracted by an equal volume of acetone/carbon disulfide.

Reaction conditions: Catalysts were evaluated in a programmed temperature-controlled high-pressure mechanically stirred microreactor.

Take the extract as the reaction substrate, the reaction conditions are that the initial hydrogen pressure is 5Mpa, the reaction temperature is 160°C, the reaction time is 120 minutes, the reaction substrate is 0.5g, the solvent is n-hexane as the solvent, and the addition amount is 20ml. The amount of catalyst added was 0.05 g.

The product extracted from subbituminous coal was used to evaluate the application effect of Ni _10% /YZCZ in direct coal liquefaction.

Hydrogenation product analysis method: Agilent7890/5973 quadrupole gas chromatography/mass spectrometry was used to analyze the composition of catalytic hydrogenation conversion products, and the chromatographic column was a 60m×0.25mm×0.25μm HP-5MS capillary cross-linked column.

Table five

From examples 1, 2 and 3, it is illustrated that this method can be prepared by regulating the content of Y-type zeolite molecular sieves in the gel system to obtain different proportions of B /L acid YZCZ complex; From examples 1, 4 and 5, it is confirmed that in the gel system of the same ratio, by controlling the crystallization time, the amount of depolymerized Y is different, and the same ratio can also be obtained by ZSM-5 Type molecular sieves are prepared into YZCZ complexes with Y morphology and different ratios of B/L acid.

The above example shows that the acidity adjustment of YZCZ can be realized by precisely controlling the content of Y-type zeolite molecular sieve in the gel system and regulating the depolymerization amount of Y-type zeolite molecular sieve by controlling the crystallization time.

From examples 6, 7 and 8, using the same method to load different amounts of metal Ni, in the catalytic hydrogenation reaction of the model compound diphenyl ether, Ni _10% /YZCZ has more advantages; examples 6, 9 and 10 show that the loading The effect of metal Ni, Ru and Pt on the catalytic hydrogenation reaction of the model compound diphenyl ether proves that Ni _10% /YZCZ has more advantages in terms of cost; Example 11 shows that the catalytic hydrogenation effect of sub-bituminous coal extracts shows that Ni _10% /YZCZ can effectively saturate aromatics and remove compounds containing heteroatoms.

Of course, the above descriptions are not intended to limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or replacements made by those skilled in the art within the scope of the present invention shall also belong to the present invention. protection scope of the invention.

Claims (5)

1. The preparation method of the adjustable solid acidity bifunctional catalyst is characterized by comprising the following steps:

carrying out depolymerization reaction and hydrothermal crystallization reaction on a Y-type zeolite molecular sieve serving as a raw material to obtain YZCZ solid powder;

carrying out ion exchange on the YZCZ solid powder to obtain H-type YZCZ solid powder;

the H-type YZCZ solid powder is used as a carrier to load a hydrogenation transition metal component, so that the adjustable solid acidity bifunctional catalyst is prepared;

the specific method for preparing the YZCZ solid powder comprises the following steps:

s1, adding a Y-type zeolite molecular sieve into an alkali solution to carry out depolymerization reaction, simultaneously adding a template agent and a silicon source into the solution to obtain a gel solution, and stirring the gel solution at normal temperature to obtain gel liquid;

s2, carrying out hydrothermal crystallization on the gel liquid obtained in the step S1 to obtain a solid precipitate;

s3, washing the solid precipitate obtained in the S2 for a plurality of times until the pH value is 7, and then drying to obtain YZCZ solid powder;

wherein, the mass ratio of the alkali solution to the Y-type zeolite molecular sieve to the silicon source to the template agent is 50: (3-5): (3.5-4.5): (0.7-1.2);

the specific method for preparing the H-type YZCZ solid powder comprises the following steps:

s1, roasting the prepared YZCZ solid powder until the template agent embedded in the YZCZ solid powder is removed to obtain roasted YZCZ solid powder;

s2, adding the roasted YZCZ solid powder obtained in the step S1 into a 1mol/L ammonium nitrate solution, and then performing ion exchange to obtain a solid precipitate;

s3, drying the solid precipitate obtained in the step S2, and roasting to obtain H-type YZCZ solid powder; wherein, the solid-to-liquid ratio of the calcined YZCZ solid powder to the ammonium nitrate solution is 20:1, a step of;

the specific method for preparing the metal-supported adjustable solid acidity bifunctional catalyst is as follows:

s1, adding distilled water into the prepared H-type YZCZ solid powder, slowly adding transition metal salt, and uniformly stirring to obtain a carrier aqueous solution;

s2, slowly adding 3wt% of dilute ammonia water into the carrier aqueous solution obtained in the step S1, stirring to obtain a mixed solution, and then filtering and drying to obtain a solid precipitate, wherein the pH value of the mixed solution is 9-10.5;

s3, placing the solid precipitate obtained in S2 into an atmosphere reducing furnace, and placing the solid precipitate into H ₂ Heating in the atmosphere to obtain the metal-loaded bifunctional catalyst with adjustable solid acidity;

wherein the transition metal salt is one or more metal salts of Pd, pt, ru and Ni, the metal loading is (3-20) wt%, and the solid-liquid ratio of H-type YZCZ solid powder to distilled water is 1:50.

2. the method for preparing the dual-function catalyst with adjustable solid acidity according to claim 1, wherein in the step S1, the template agent is tetrapropylammonium bromide, tetraethylammonium bromide or tetrapropylammonium hydroxide; the silicon source is fumed silica.

3. The preparation method of the adjustable solid acidity bifunctional catalyst of claim 2, wherein in the process of preparing H-type YZCZ solid powder, the process parameters of calcination in S1 are: heating to 600 ℃, and roasting for 5 hours at a heating rate of 10 ℃/min; the roasting working parameters in S3 are as follows: heating to 550 ℃, heating at a speed of 10 ℃/min, and roasting for 5h.

4. A solid acidity-adjustable bifunctional catalyst prepared by the method of any one of claims 1 to 3.

5. The application of the adjustable solid acidity bifunctional catalyst is characterized in that the adjustable solid acidity bifunctional catalyst prepared by the adjustable solid acidity bifunctional catalyst preparation method according to any one of claims 1-3 is applied to aromatics hydrogenation and heteroatom removal.

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