CN112058304A - Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof - Google Patents

Abstract

The invention provides a dual-function catalyst with adjustable solid acidity, a preparation method and an application thereof, comprising the following steps: using Y-type zeolite molecular sieve as a raw material to carry out a depolymerization reaction, and then to carry out a hydrothermal crystallization reaction to obtain a YZCZ solid powder; the YZCZ solid powder is subjected to ion exchange to obtain H-type YZCZ solid powder; the H-type YZCZ solid powder is used as a carrier and a hydrogenation transition metal component is loaded to obtain a dual-function catalyst with adjustable solid acidity; The obtained bifunctional catalyst with adjustable solid acidity loaded with metal salts is applied to direct liquefaction of low-metamorphic coal to produce clean liquid fuel. Under the synergistic effect of adjustable solid acid and metallic Ni, it can efficiently complete the Car‑ Selective fracture of O to complete the transformation of low-metamorphic coal into clean liquid fuel.

Description

A kind of bifunctional catalyst with adjustable 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 with adjustable solid acidity, a preparation method and application thereof.

Background technique

At present, relatively abundant coal resources and scarce oil resources, as well as the increasing dependence on foreign oil, have brought great 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 fines is an important process route.

Low-metamorphic coal is a mixture of macromolecular compounds and low-molecular-weight molecular compounds composed of various chemical bonds and functional groups, mainly composed of C, H, O, N and other heteroatoms, forming a very complex three-dimensional macromolecular structure. . The energy required to break the bridge bonds connecting the basic structural units is much lower than the energy required to break the aromatic ring structure. Therefore, acid-catalyzed cleavage of bridge bonds is crucial to the coal liquefaction process. In addition, the content of heteroatoms (mainly O, N, S, etc.) and saturated aromatic hydrocarbons in the liquefied products are the main indicators for evaluating high-value liquid fuels. Under relatively mild conditions, while removing heteroatoms efficiently, saturated aromatic hydrocarbons are a technical difficulty in direct coal liquefaction, and also a huge challenge for direct coal liquefaction to produce clean liquid fuels, especially the removal of oxygenates. Acid-catalyzed solid hydrogenation catalysts are the key technologies to realize direct coal liquefaction under mild conditions.

Although transition metals have good hydrogenation properties at low temperatures, they are extremely sensitive to heteroatoms and are expensive. Metal sulfides and metal oxides show good heteroatom tolerance, chemical stability, and low price during hydrogenation, but the loss of S in metal sulfides and the phase transition of metal oxides can lead to clean fuel quality decline.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a dual-function catalyst with adjustable solid acidity, a preparation method and an application thereof, 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 with adjustable solid acidity provided by the invention comprises the following steps:

Using Y-type zeolite molecular sieve as raw material to carry out depolymerization reaction, then carry out hydrothermal crystallization reaction to obtain YZCZ solid powder;

H-type YZCZ solid powder is prepared by ion exchange of YZCZ solid powder;

Using H-type YZCZ solid powder as a carrier and supporting hydrogenated transition metal components, a bifunctional catalyst with adjustable solid acidity was prepared.

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

S1, the Y-type zeolite molecular sieve is added to the alkaline solution to carry out a depolymerization reaction, and at the same time, a template agent and a silicon source are added thereto to obtain a gel solution, followed by stirring at room temperature to obtain a gel liquid;

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

S3, the solid precipitate obtained in S2 is washed repeatedly until the pH is 7, and then oven-dried to obtain YZCZ solid powder;

Wherein, the mass ratio of alkaline 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, the prepared YZCZ solid powder is roasted, until the template agent embedded in the YZCZ solid powder is removed to obtain the roasted YZCZ solid powder;

S2, take the roasting YZCZ solid powder obtained in part S1 and join it to 1mol/L ammonium nitrate solution, then carry out ion exchange to obtain solid precipitate;

S3, the solid precipitate obtained in S2 is dried, and then roasted to obtain H-type YZCZ solid powder;

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

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

Preferably, the specific method for preparing the metal-supported tunable solid acidity bifunctional catalyst is:

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

S2, slowly adding 3wt% of dilute ammonia water to the carrier aqueous solution obtained in S1 and stirring to obtain a mixed solution, 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 in an H atmosphere to obtain a metal _- loaded adjustable solid acidity bifunctional catalyst;

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

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

A bifunctional catalyst with adjustable solid acidity is prepared based on the method for preparing a bifunctional catalyst with adjustable solid acidity.

Application of a bifunctional catalyst with adjustable solid acidity, the bifunctional catalyst with adjustable solid acidity prepared based on the method for preparing a bifunctional catalyst with adjustable solid acidity is used in aromatic hydrocarbon hydrogenation and Removal of heteroatoms.

Compared with the prior art, the beneficial effects of the present invention are:

The invention provides a dual-function catalyst with adjustable solid acidity and a preparation method thereof. In the prepared YZCZ, the ratio of Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve can be changed by changing the addition amount of Y zeolite molecular sieve, the ratio of two zeolite molecular sieves The addition amount of silica can be adjusted. At the same time, the ratio of Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve can also be adjusted by the crystallization time, because the longer the crystallization time, the greater the depolymerization of Y-type zeolite, YZCZ with different ratios of Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve can also be obtained by adjusting different crystallization times;

The dual-function catalyst with adjustable solid acidity prepared by the invention is a zeolite compound with two structures, which can combine the structures of two different zeolites, namely Y zeolite molecular sieve and ZSM-5 zeolite molecular sieve, and by adjusting the two kinds of zeolite The proportion of molecular sieves in the zeolite complex can be adjusted to the acidity (B acid and L acid) of the zeolite complex through the coordination of different B/L values.

The application of the adjustable solid acidity bifunctional catalyst provided by the invention is to use the prepared metal salt-loaded adjustable solid acidity bifunctional catalyst for the efficient hydrogenation of aromatic 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 metal salt-loaded dual-function catalyst with adjustable solid acidity prepared by the invention is applied to low-metamorphic coal direct liquefaction In the production of clean liquid fuel, under the synergistic effect of tunable solid acid and metallic Ni, the selective fracture of Car-O in the cracking process can be efficiently completed, so as to achieve the purpose of converting low-metamorphic coal into clean liquid fuel.

Description of drawings

Fig. 1 is the YZCZ electron microscope image and energy scattering spectrum obtained in the embodiment of the present invention;

FIG. 2 is an electron microscope image and an energy scattering spectrum of Ni/YZCZ prepared in the embodiment of the present invention.

Detailed ways

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

A method for preparing a bifunctional catalyst with adjustable solid acidity provided by the invention comprises the following steps:

The Y-type zeolite molecular sieve is used as the raw material to carry out depolymerization reaction, and then hydrothermal crystallization reaction is carried out to obtain YZCZ (Y/ZSM-5 compositezeolite, referred to as YZCZ) solid powder;

Then the YZCZ solid powder is ion-exchanged to obtain H-type YZCZ with acid catalytic activity (H-type Y/ZSM-5 compositezeolite, 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 obtain a bifunctional catalyst with adjustable solid acidity (M/YZCZ for short, M represents the transition metal component).

Further, the preparation method specifically comprises the following steps:

a. Preparation of YZCZ solid powder

a1. Add a certain amount of Y-type zeolite molecular sieve into the alkaline solution, and control the pH to be 10.5-11.5, so that the Y-type zeolite molecular sieve is slowly depolymerized, and at the same time, a template agent and a silicon source are added to it to obtain a gel solution, which is stirred at room temperature and controlled The aging time is 1-3 hours to obtain gel liquid;

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

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

b. Preparation of H-type YZCZ

b1. The YZCZ solid powder obtained in step a is placed in a muffle furnace, calcined at 550 °C for 5 hours by introducing air, and the heating rate is 10 °C/min for roasting, and the template agent embedded in the YZCZ structure is completely removed;

b2. Take a certain amount of calcined YZCZ solid powder and add it to 1 mol/L ammonium nitrate solution, carry out ion exchange at 40°C, and obtain solid precipitate after ion exchange three times;

b3. The precipitate obtained in step b2 is first dried at 100°C for 6 hours, then the dried precipitate is put into a muffle furnace, and air is introduced 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 obtained in step b as the carrier, first add a certain amount of distilled water, then slowly add the transition metal salt, stir evenly, heat the carrier aqueous solution to 50-60°C, and seal and stir for 30-60min;

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

c3. Place the solid precipitate obtained in step c2 in an atmosphere reduction furnace, and under _H2 atmosphere, control the heating rate to 2-3 °C/min, heat up to 400-500 °C, and maintain for 3-5h to obtain a metal-loaded A bifunctional catalyst for modulating solid acidity.

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

Further, in step a1, the mass ratio of alkaline 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 alkali solution is a 0.15 mol/L NaOH solution.

Further, in step b1, during one calcination, the temperature is raised to 600°C, the heating rate is 10°C/min, and the calcination is performed for 5h.

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

Further, in step b3, during the secondary roasting, the temperature is raised to 550°C, the heating rate is 10°C/min, and the roasting is performed for 5 hours.

Further, in step c1, the solid-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 reduce slowly and prevent the metal particles from agglomerating.

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

The application of the adjustable solid acid bifunctional catalyst provided by the 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 bifunctional catalyst with adjustable solid acidity supported by metallic nickel, which specifically comprises the following steps:

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

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

3. Wash the above-mentioned solid precipitate with water for several times, wash to pH=7, and dry at 100° C. for 6 hours to obtain YZCZ solid powder, whose electron microscope image is shown in Figure 1.

4. Put the YZCZ solid powder obtained in step 3 into a muffle furnace, and pass in air to conduct a calcination to remove the template agent; during the first calcination, the temperature is raised to 600°C, the heating rate is 10°C/min, and the calcination is performed for 5h.

5. Add a certain amount of calcined YZCZ solid powder into 1 mol/L ammonium nitrate solution, carry out ion exchange at 40 °C, and undergo ion exchange three times to obtain a precipitate; the solid-to-liquid ratio of YZCZ solid powder to ammonium nitrate solution is 20 :1.

6. The precipitate obtained in step 5 was first dried at 100°C for 6 hours, then the dried precipitate was put into a muffle furnace, and air was introduced for secondary roasting. During the secondary roasting, the temperature was raised to 550 °C. ℃, the heating rate is 10℃/min, and the calcination is carried out for 5h to obtain H-type YZCZ solid powder.

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-liquid ratio of H-type YZCZ solid powder and distilled water is 1:50, then slowly add Ni salt, stir evenly, and mix the carrier aqueous solution The temperature was raised to 60°C, and the airtight stirring was carried out for 30min;

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

9. Place the solid precipitate obtained in step 8 in an atmosphere reduction furnace, control the heating rate to 2 °C/min under the _H2 atmosphere, heat it up to 400 °C, and maintain it for 3 h to obtain a metal-loaded adjustable solid acid bicarbonate. Functional catalyst (Ni/YZCZ), the metallic nickel in Fig. 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, silica, 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, silica, 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 content is shown in Table 1.

Table I

The modulation 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.; wherein C represents adsorption on the acid site of B acid or L acid pyridine concentration (mmolg ^-1 ).

Example 6

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

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

3. The prepared solid precipitate is placed in an atmosphere reduction furnace, and in the _H2 atmosphere, the temperature rise rate is controlled to 3°C/min, the temperature is raised to 500°C, and maintained for 5h to obtain a variable solid acidity with a Ni loading of 5%. The bifunctional catalyst (Ni _10% /YZCZ).

Example 7

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

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

Reaction conditions: The catalysts were evaluated in a programmed temperature-controlled high-pressure mechanically stirred micro-reactor.

Taking diphenyl ether 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 1ml, the reaction solvent is n-hexane as the solvent, and the addition amount is 20ml , the amount of catalyst added is 0.05g.

In this way, the ability of Ni/YZCZ to catalyze hydrogenation and the ability to break C-O bonds was evaluated.

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

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

Table 3

Example 9

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

Example 10

The difference from Example 6 is that the nickel nitrate hexahydrate was replaced by platinum nitrate, and 0.327 g of platinum nitrate was added to obtain a dual-function catalyst (Pt _10% /YZCZ) with adjustable solid acidity with a Pt loading of 10%.

Application Example 1

Taking diphenyl ether 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 1ml, the solvent is cyclohexane, and the addition amount is 20ml , the amount of catalyst added is 0.05g.

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

Table 4

Application Example 2

The Ni _10% /YZCZ prepared in Example 6 was applied to the hydrogenation of subbituminous coal extracted with equal volume of acetone/carbon disulfide.

Reaction conditions: The catalysts were evaluated in a programmed temperature-controlled high-pressure mechanically stirred micro-reactor.

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 products extracted from sub-bituminous coal were used to evaluate the application effect of Ni _10% /YZCZ in direct coal liquefaction.

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

Table 5

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

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

From Examples 6, 7 and 8, using the same method and loading 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 catalytic hydrogenation effect of metal Ni, Ru and Pt on the model compound diphenyl ether proves that Ni _10% /YZCZ has more advantages in cost; _10% /YZCZ can effectively saturate aromatic hydrocarbons and remove heteroatom-containing compounds.

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

Claims (9)

1. a bifunctional catalyst preparation method of adjustable solid acidity, is characterized in that, comprises the following steps: Using Y-type zeolite molecular sieve as raw material to carry out depolymerization reaction, then carry out hydrothermal crystallization reaction to obtain YZCZ solid powder; H-type YZCZ solid powder is prepared by ion exchange of YZCZ solid powder; Using H-type YZCZ solid powder as a carrier and supporting hydrogenated transition metal components, a bifunctional catalyst with adjustable solid acidity was prepared. 2. the bifunctional catalyst preparation method of a kind of adjustable solid acidity according to claim 1, is characterized in that, the concrete method of preparing YZCZ solid powder is: S1, the Y-type zeolite molecular sieve is added to the alkaline solution to carry out a depolymerization reaction, and at the same time, a template agent and a silicon source are added thereto to obtain a gel solution, followed by stirring at room temperature to obtain a gel liquid; S2, hydrothermally crystallizing the gel liquid obtained in S1 to obtain a solid precipitate; S3, the solid precipitate obtained in S2 is washed repeatedly until the pH is 7, and then oven-dried to obtain YZCZ solid powder; Wherein, the mass ratio of alkaline solution, Y-type zeolite molecular sieve, silicon source, and template agent is 50:(3-5):(3.5-4.5):(0.7-1.2). 3. a kind of adjustable solid acidity bifunctional catalyst preparation method according to claim 2, is characterized in that, in S1, described templating agent is tetrapropyl ammonium bromide, tetraethyl ammonium bromide or tetraethylammonium bromide Propyl ammonium hydroxide; calcined fumed silica as the silicon source. 4. the bifunctional catalyst preparation method of a kind of adjustable solid acidity according to claim 1 is characterized in that, the concrete method of preparing H-type YZCZ solid powder is: S1, the prepared YZCZ solid powder is roasted, until the template agent embedded in the YZCZ solid powder is removed to obtain the roasted YZCZ solid powder; S2, take the roasting YZCZ solid powder obtained in part S1 and join it to 1mol/L ammonium nitrate solution, then carry out ion exchange to obtain solid precipitate; S3, the solid precipitate obtained in S2 is dried, and then roasted to obtain H-type YZCZ solid powder; Among them, the solid-liquid ratio of the calcined YZCZ solid powder and the ammonium nitrate solution is 20:1. 5. a kind of adjustable solid acidity bifunctional catalyst preparation method according to claim 4, is characterized in that, the technological parameter of roasting in S1 is: be warming up to 600 ℃, heating rate 10 ℃/min, roasting 5h; The process parameters of the roasting in S3 are: heating to 550°C, heating rate of 10°C/min, and roasting for 5h. 6. a kind of adjustable solid acidity bifunctional catalyst preparation method according to claim 1 is characterized in that, the concrete method of preparing the metal-loaded adjustable solid acidity bifunctional catalyst is: S1, adding distilled water to the prepared H-type YZCZ solid powder, then slowly adding the transition metal salt, stirring uniformly, to obtain an aqueous carrier solution; S2, slowly adding 3wt% of dilute ammonia water to the carrier aqueous solution obtained in S1 and stirring to obtain a mixed solution, 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 in an H atmosphere to obtain a metal _- loaded adjustable solid acidity bifunctional catalyst; Among them, the solid-liquid ratio of H-type YZCZ solid powder and distilled water is 1:50. 7. a kind of adjustable solid acidity bifunctional catalyst preparation method according to claim 6 is characterized in that, in S1, transition metal salt is one or more metal salts in Pd, Pt, Ru and Ni , and the metal loading is (3-20) wt%. 8 . A bifunctional catalyst with adjustable solid acidity, characterized in that it is prepared based on the method for preparing a bifunctional catalyst with adjustable solid acidity according to any one of claims 1 to 7 . 9. the application of a kind of adjustable solid acidity bifunctional catalyst, it is characterized in that, based on the preparation method of a kind of adjustable solid acidity bifunctional catalyst preparation method described in any one of claim 1-7, obtained can be prepared. The bifunctional catalyst with modulating solid acidity is applied to the hydrogenation of aromatic hydrocarbons and the removal of heteroatoms.

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