CN116786155A - Preparation method and application of high-activity HZSM-5 supported solid super acidic catalyst - Google Patents

Preparation method and application of high-activity HZSM-5 supported solid super acidic catalyst Download PDF

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CN116786155A
CN116786155A CN202310748173.0A CN202310748173A CN116786155A CN 116786155 A CN116786155 A CN 116786155A CN 202310748173 A CN202310748173 A CN 202310748173A CN 116786155 A CN116786155 A CN 116786155A
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hzsm
catalyst
zro
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曹景沛
江玮
赵小燕
胡鑫
宦祖兴
陈晨旭
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China University of Mining and Technology CUMT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method and application of a high-activity HZSM-5 supported solid super acidic catalyst. HZSM-5 is selected as a carrier, and ZrO is prepared by an impregnation method 2 And S is 2 O 8 2‑ Load on loadIn vivo, high activity S is obtained 2 O 8 2‑ /X％ZrO 2 HZSM-5 (x=5, 10, 15 or 20) solid super acid catalyst; series of solid superacids S 2 O 8 2‑ /X％ZrO 2 The activity difference of the HZSM-5 catalyst is smaller, and the solid superacid S 2 O 8 2‑ /10％ZrO 2 The activity of the-HZSM-5 catalyst was slightly higher at 180℃for 120min and 2MPa H 2 When the conversion rate of catalytic benzyl phenyl ether hydrogenation conversion reaches 100%, the obtained products are mainly toluene, phenol, 2-benzyl phenol and 4-benzyl phenol. The solid superacid S without active metal provided by the invention 2 O 8 2‑ /X％ZrO 2 The HZSM-5 catalyst can efficiently catalyze the conversion of benzyl phenyl ether under the participation of hydrogen, so that the cost is greatly saved, the safety is higher, and the catalyst has good application prospect.

Description

Preparation method and application of high-activity HZSM-5 supported solid super acidic catalyst
Technical Field
The invention belongs to the technical field of catalysts, relates to a solid super acidic catalyst, and in particular relates to a preparation method and application of a high-activity HZSM-5 supported solid super acidic catalyst.
Background
Renewable resources will dominate future energy structures due to environmental pollution effects and the crisis of fossil energy. As the most abundant natural phenolic biopolymers, lignin is highly likely to be an alternative renewable resource for sustainable production of high value-added organic chemicals and liquid fuels. A number of lignin depolymerization processes, for example, typical reduction catalytic fractionation techniques have been developed to convert lignin to low molecular weight feedstocks. Among them, benzyl phenyl ether represents a typical alpha-O-4 bond model compound in lignin, and researchers have also developed a large number of benzyl phenyl ether conversion routes, with the most extensive studies being conducted with supported active metal catalysts.
Different kinds of nickel-based, cobalt-based, ruthenium-based, palladium-based and platinum-based metal catalysts are used in large amounts for the hydrocatalytic conversion of benzyl phenyl ether, the use of active metals increases the cost of the catalyst, and development of high-activity catalysts without active metals has been attracting attention. The solid super acid catalyst has excellent characteristics, can effectively convert active hydrogen to carry out hydrogenation reaction, and is an efficient catalyst for the hydrogenation conversion of lignin model compounds.
Disclosure of Invention
The invention aims to provide a preparation method of a high-activity HZSM-5 supported solid super acidic catalyst.
It is another object of the present invention to provide the use of the solid superacid catalyst prepared by the above-described preparation method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a method for preparing a high activity HZSM-5 supported solid super acidic catalyst, comprising the following steps:
(1) Placing the commercial HZSM-5 carrier into a muffle furnace for calcination, and removing impurities and template agent;
(2) Weighing a precursor of soluble zirconia, adding the precursor into deionized water, and stirring the solution at room temperature by ultrasonic waves to prepare a uniform solution; then adding the calcined HZSM-5 powder in the step (1), and stirring for 4 hours;
(3) Immersing the mixture obtained in the step (2) for 24 hours at room temperature; after the impregnation is completed, the mixture is dried to remove water;
(4) Grinding the solid obtained in the step (3) into powder, then placing the powder into a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature at 550 ℃ for 5 hours, and cooling to room temperature to obtain ZrO 2 -HZSM-5 powder;
(5) Preparing a 1mol/L ammonium persulfate solution, and adding the ZrO prepared in the step (4) 2 HZSM-5 powder, stirring for 2h, filtering, and drying a filter cake;
(6) Placing the solid obtained in the step (5) into a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, maintaining at 550 ℃ for 3 hours, and cooling to room temperature to obtain S 2 O 8 2- /ZrO 2 HZSM-5 catalyst.
Preferably, the HZSM-5 carrier in step (1) is calcined by heating to 550 ℃ at a heating rate of 10 ℃/min and maintaining at 550 ℃ for 5 hours.
Preferably, the precursor of the soluble zirconia in the step (2) is zirconium nitrate pentahydrate.
Preferably, in the step (4), the ZrO 2 The amount of zirconia in HZSM-5 is based on ZrO 2 The amount of HZSM-5 is 5-20%.
Preferably, the temperature of the drying in the step (3) is 110 ℃ and the drying time is 24 hours.
In a second aspect, the invention provides the use of HZSM-5 supported solid superacid catalysts prepared by the preparation method described above in benzyl phenyl ether hydrogenation catalysis.
The specific application steps comprise: putting a reaction substrate benzyl phenyl ether, a catalyst and n-hexane into a reactor, sealing, and replacing tertiary air with hydrogen; subsequently, the reactor was pressurized to 2MPa with hydrogen at room temperature; then the temperature is raised to 180 ℃ to 200 ℃ and is vigorously stirred for 15min to 120min; after the experiment was completed, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst and the organic phase obtained by gas chromatography and gas phase analysis.
Preferably, the catalyst is S 2 O 8 2- /10％ZrO 2 HZSM-5 catalyst.
Preferably, the catalyst comprises 50% of the substrate mass.
Preferably, the reaction conditions for the hydrogenation reaction are: 180 ℃ for 120min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention selects HZSM-5 as a carrier and uses ZrO by an impregnation method 2 And S is 2 O 8 2- Loaded on a carrier to obtain high-activity S 2 O 8 2- /X％ZrO 2 HZSM-5 (x=5, 10, 15 or 20) solid superacid catalysts, the series of catalysts having the morphology typical of HZSM-5, a large number of micropores and mesopores being present in the catalyst.
2. The solid superacid S without active metal provided by the invention 2 O 8 2- /X％ZrO 2 HZSM-5 catalystCan efficiently catalyze benzyl phenyl ether to be converted under the participation of hydrogen, and is a series of solid superacid S 2 O 8 2- /X％ZrO 2 The activity difference of the HZSM-5 catalyst is smaller, and the solid superacid S 2 O 8 2- /10％ZrO 2 The activity of the-HZSM-5 catalyst was slightly higher at 180℃for 120min and 2MPa H 2 When the method is used, the conversion rate of catalytic benzyl phenyl ether hydrogenation conversion reaches 100%, the obtained products are mainly toluene, phenol, 2-benzyl phenol and 4-benzyl phenol, the cost is greatly saved, the safety is higher, a new mode is provided for the high added value utilization of lignin model compounds, and the method has good application prospects.
Drawings
FIG. 1 is S 2 O 8 2- /10％ZrO 2 NH of-HZSM-5 catalyst 3 -TPD profile;
FIG. 2 is S 2 O 8 2- /10％ZrO 2 SEM image of HZSM-5 catalyst;
FIG. 3 is S 2 O 8 2- /10％ZrO 2 TEM image of HZSM-5 catalyst;
FIG. 4 is S 2 O 8 2- /10％ZrO 2 XRD pattern of HZSM-5 catalyst;
FIG. 5 is S 2 O 8 2- /10％ZrO 2 N of-HZSM-5 catalyst 2 Adsorption-desorption isotherms.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Example 1: synthesis of solid superacid S by impregnation method 2 O 8 2- /10％ZrO 2 HZSM-5 catalyst
Synthesis of solid superacid S by impregnation method 2 O 8 2- /10％ZrO 2 HZSM-5 catalyst. Firstly, placing a commercial HZSM-5 carrier in a muffle furnace for calcination, heating to 550 ℃ at a heating rate of 10 ℃/min, and keeping at 550 ℃ for 5 hours to remove impurities and template; 0.5242g of zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O) adding 50mL of deionized water into a beaker, and stirring ultrasonically for 5min to prepare a uniform solution; subsequently, 1g of calcined HZSM-5 powder is weighed, added into a beaker, stirred for 4 hours, and after the completion, the mixture is immersed for 24 hours at normal temperature; after the impregnation was completed, the mixture was dried in an oven at 110℃for 24 hours, the water was removed, the resulting solid was ground into powder, and then put into a muffle furnace, heated to 550℃at a heating rate of 3℃per minute, and kept at 550℃for 5 hours, the resulting solid was labeled as 10% ZrO 2 -HZSM-5；
4.5640g of ammonium persulfate ((NH) was weighed out 4 ) 2 S 2 O 8 ) The solid was placed in a beaker and added with 20mL of deionized water to prepare 1mol/L (NH) 4 ) 2 S 2 O 8 1g of 10% ZrO solution was weighed out 2 Adding HZSM-5 solid powder into a beaker, stirring for 2 hours, directly filtering, and drying the obtained solid in an oven at 110 ℃ for 2 hours; then the solid was placed in a muffle furnace, heated to 550 ℃ at a heating rate of 3 ℃/min, and kept at 550 ℃ for 3 hours, finally, the obtained white solid powder was marked as S 2 O 8 2- /10％ZrO 2 HZSM-5 catalyst.
As shown in FIG. 1, NH 3 TPD characterization shows S 2 O 8 2- /10％ZrO 2 The HZSM-5 catalyst has stronger acidity, and obvious desorption peak appears at 600-800 ℃, which shows S 2 O 8 2- /10％ZrO 2 The HZSM-5 catalyst is a solid super acid catalyst.
As shown in FIG. 2, SEM characterization shows S 2 O 8 2- /10％ZrO 2 The HZSM-5 solid super acid catalyst still has the typical morphology of HZSM-5, and the series of treatments can not damage the morphology of HZSM-5.
As shown in FIG. 3, the TEM characterization shows S 2 O 8 2- /10％ZrO 2 The HZSM-5 solid super acid catalyst still has the typical morphology of HZSM-5, and the series of treatments can not damage the morphology of HZSM-5.
As shown in FIG. 4, XRD characterization reveals S 2 O 8 2- /10％ZrO 2 The HZSM-5 solid superacid catalyst still has typical characteristic diffraction peaks of HZSM-5, the structure of the HZSM-5 is not damaged by serial treatment, and the catalyst has obvious characteristic diffraction peaks at the positions of which the 2 theta values are 30.40 DEG, 35.25 DEG, 50.71 DEG and 60.28 DEG, which are respectively attributed to ZrO 2 The crystal planes (111), (200), (220) and (311) of (C) confirm that zirconium is present as ZrO on the surface of the molecular sieve 2 Is present in the form of (c).
As shown in fig. 5, N 2 Adsorption-desorption characterization showed S 2 O 8 2- /10％ZrO 2 The HZSM-5 solid superacid catalyst has an isotherm of type IV with a hysteresis curve of type H4, exhibiting typical porosity, and a large number of micropores and mesopores are present in the catalyst. Specific analysis results show S 2 O 8 2- /10％ZrO 2 The specific surface area, the pore volume and the pore diameter of the HZSM-5 solid super acid catalyst are 320m respectively 2 /g、0.22cm 3 /g and 2.76nm.
Example 2: synthesis of solid superacid S by impregnation method 2 O 8 2- /5％ZrO 2 HZSM-5 catalyst
Preparation of solid superacid S by the same impregnation method as in example 1 2 O 8 2- /5％ZrO 2 HZSM-5 catalyst except for Zr (NO) 3 ) 4 ·5H 2 The O mass was 0.2483g.
Example 3: synthesis of solid superacid S by impregnation method 2 O 8 2- /15％ZrO 2 HZSM-5 catalyst
Preparation of solid superacid S by the same impregnation method as in example 1 2 O 8 2- /15％ZrO 2 HZSM-5 catalyst except for Zr (NO) 3 ) 4 ·5H 2 The O mass was 0.8326g.
Example 4: synthesis of solid superacid S by impregnation method 2 O 8 2- /20％ZrO 2 HZSM-5 catalyst
Preparation of solid superacid S by the same impregnation method as in example 1 2 O 8 2- /20％ZrO 2 HZSM-5 catalyst except for Zr (NO) 3 ) 4 ·5H 2 The O mass was 1.1795g.
Example 5: hydrogenation application of solid super acidic catalyst
Take the catalytic reaction of benzyl phenyl ether as an example:
all catalytic reactions were performed in a 100mL stainless steel autoclave. In a typical experiment, 0.1g of the reaction substrate (benzyl phenyl ether), a quantity of catalyst (50 mg) and n-hexane (20 mL) were placed in the reactor. After sealing, residual air was removed by passing hydrogen 3 times. Subsequently, the reactor was pressurized to the desired pressure (2 MPa) with hydrogen at room temperature. The temperature was then raised to the desired reaction temperature (180℃or 200 ℃) and maintained for a period of time (15 min or 120 min) with vigorous stirring at 800 rpm. After the experiment was completed, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst and the obtained organic phase was analyzed by gas chromatography-mass spectrometry (GC-MS) and gas phase (GC).
TABLE 1 hydrogenation catalytic conversion Properties of different catalysts for p-benzyl phenyl ether
Reaction conditions: 0.1g of benzyl phenyl ether, 50mg of catalyst, 2MPaH 2 20mL of n-hexane.
Table 1 summarizes the different solid superacids 2 O 8 2- /X％ZrO 2 Results of the hydroconversion reaction of p-benzyl phenyl ether with HZSM-5 catalyst. Obviously, when no catalyst was added or only HZSM-5 was present, the benzyl phenyl ether was not hydroconverted under the reaction conditions studied, whereas after addition of the prepared solid superacid catalyst, the benzyl phenyl ether exhibited a different degree of conversion. Under the reaction conditions of 180 ℃, 15min and 2MPa H 2 The conversion rate of the catalyst to benzyl phenyl ether reaches more than 80%, and the obtained products are mainly toluene, phenol, 2-benzyl phenol and 4-benzyl phenol, wherein the 2-benzyl phenol and the 4-benzyl phenol are mainlyTo be formed by rearrangement and isomerisation of benzyl phenyl ether, the aromatic ring structure is preserved without hydrogenation. In contrast, a series of solid superacids 2 O 8 2- /X％ZrO 2 The activity difference of the HZSM-5 catalyst is smaller, and the solid superacid S 2 O 8 2- /10％ZrO 2 The activity of the-HZSM-5 catalyst was slightly higher at 180℃for 120min and 2MPa H 2 When the catalyst is used, the conversion rate of catalyzing the hydrogenation conversion of benzyl phenyl ether reaches 100 percent. Under the reaction conditions of 200 ℃,120min and 2MPa H 2 Series of solid superacids S 2 O 8 2- /X％ZrO 2 The conversion of the HZSM-5 catalyst to benzyl phenyl ether reaches a maximum of 100%, and the obtained products are mainly toluene, phenol, 2-benzyl phenol and 4-benzyl phenol.
The prior researches mainly focus on the hydrocracking of the active metal catalyst p-benzyl phenyl ether, and the obtained products mainly comprise cracked toluene, methylcyclohexane, cyclohexanol and phenol, while in the researches, solid superacid S with high activity and no active metal is developed 2 O 8 2- /X％ZrO 2 The HZSM-5 catalyst can effectively convert benzyl phenyl ether, and the obtained products are mainly toluene, phenol, 2-benzyl phenol and 4-benzyl phenol, and the contents of the phenol and the 2-benzyl phenol are higher.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (10)

1. The preparation method of the high-activity HZSM-5 supported solid super acidic catalyst is characterized by comprising the following steps of:
(1) Placing the commercial HZSM-5 carrier into a muffle furnace for calcination, and removing impurities and template agent;
(2) Weighing a precursor of soluble zirconia, adding the precursor into deionized water, and stirring the solution at room temperature by ultrasonic waves to prepare a uniform solution; then adding the calcined HZSM-5 powder in the step (1), and stirring for 4 hours;
(3) Immersing the mixture obtained in the step (2) for 24 hours at room temperature; after the impregnation is completed, the mixture is dried to remove water;
(4) Grinding the solid obtained in the step (3) into powder, then placing the powder into a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature at 550 ℃ for 5 hours, and cooling to room temperature to obtain ZrO 2 -HZSM-5 powder;
(5) Preparing a 1mol/L ammonium persulfate solution, and adding the ZrO prepared in the step (4) 2 HZSM-5 powder, stirring for 2h, filtering, and drying a filter cake;
(6) Placing the solid obtained in the step (5) into a muffle furnace, heating to 550 ℃ at a heating rate of 3 ℃/min, maintaining at 550 ℃ for 3 hours, and cooling to room temperature to obtain S 2 O 8 2- /ZrO 2 HZSM-5 catalyst.
2. The method for preparing a high activity HZSM-5 supported solid super acidic catalyst as claimed in claim 1, wherein in the step (1), the calcining process of the HZSM-5 carrier is performed by raising the temperature to 550 ℃ at a rate of 10 ℃/min and maintaining the temperature at 550 ℃ for 5 hours.
3. The method for preparing a high activity HZSM-5 supported solid super acidic catalyst as claimed in claim 1, wherein in the step (2), the precursor of the soluble zirconia is zirconium nitrate pentahydrate.
4. The method for preparing a high activity HZSM-5 supported solid super acidic catalyst as claimed in claim 1, wherein in the step (4), the ZrO 2 The amount of zirconia in HZSM-5 is based on ZrO 2 The amount of HZSM-5 is 5-20%.
5. The method for preparing a high activity HZSM-5 supported solid super acidic catalyst as claimed in claim 1, wherein in the step (3), the drying temperature is 110 ℃ and the drying time is 24 hours.
6. Use of HZSM-5 supported solid super acid catalyst prepared by the preparation method of any one of claims 1 to 5 in benzyl phenyl ether hydrogenation catalysis.
7. The application of claim 6, wherein the step of specifying the application comprises: putting a reaction substrate benzyl phenyl ether, a catalyst and n-hexane into a reactor, sealing, and replacing tertiary air with hydrogen; subsequently, the reactor was pressurized to 2MPa with hydrogen at room temperature; then the temperature is raised to 180 ℃ to 200 ℃ and is vigorously stirred for 15min to 120min; after the experiment was completed, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst and the organic phase obtained by gas chromatography and gas phase analysis.
8. The use according to claim 7, wherein the catalyst is S 2 O 8 2- /10％ZrO 2 HZSM-5 catalyst.
9. The use according to claim 7, wherein the catalyst comprises 50% by mass of the substrate.
10. The use according to claim 7, wherein the reaction conditions of the hydrogenation reaction are: 180 ℃ for 120min.
CN202310748173.0A 2023-06-22 2023-06-22 Preparation method and application of high-activity HZSM-5 supported solid super acidic catalyst Pending CN116786155A (en)

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