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CN114433220B - Preparation method of benzene and synthesis gas alkylation catalyst - Google Patents

Preparation method of benzene and synthesis gas alkylation catalyst Download PDF

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Publication number
CN114433220B
CN114433220B CN202011197862.XA CN202011197862A CN114433220B CN 114433220 B CN114433220 B CN 114433220B CN 202011197862 A CN202011197862 A CN 202011197862A CN 114433220 B CN114433220 B CN 114433220B
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acid
pore volume
molecular sieve
carrier
solution
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CN114433220A (en
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王京
刘中勋
周震寰
康承琳
梁战桥
王志强
岳欣
盖月庭
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • 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
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
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    • 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
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    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
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    • 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
    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7073—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
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    • 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
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    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a preparation method of a benzene and synthesis gas alkylation catalyst. According to the preparation method of the catalyst, two composite molecular sieves are adopted to prepare the catalyst carrier, the prepared catalyst has high catalytic activity and good selectivity, the molecular sieve pore structure and the pore size distribution are optimized through acid-base treatment, the loading and effective utilization of metals are facilitated, the conversion rate of benzene and the selectivity and yield of toluene and C8 aromatic hydrocarbon are improved, and the preparation method has the advantages of simplicity, sufficient raw material sources, low cost, easiness in operation and suitability for large-scale industrial application.

Description

Preparation method of benzene and synthesis gas alkylation catalyst
Technical Field
The invention relates to the field of alkylation of benzene and synthesis gas, in particular to a preparation method of a benzene and synthesis gas alkylation catalyst.
Background
Benzene, toluene and xylene (BTX) in aromatics are important basic chemical raw materials. Toluene and xylene, especially paraxylene PX, derivatives thereof are widely used in chemical products such as polyesters, petrochemicals, plastics and rubber. With the rapid development of the industries of ethylene, reforming, coal chemical industry and the like in China in recent years, the yield of domestic pure benzene is gradually increasing.
The synthetic gas is one of main products of coal chemical industry, can be obtained through a coal gasification process, and has rich relative resources. Thus, on the one hand, inexpensive synthesis gas is used as a feedstock; on the other hand, the application of pure benzene is enlarged, toluene and xylene with higher economic value are increased, and a new route for preparing aromatic hydrocarbon is developed.
The route to methanol alkylation reactions currently in existence in the industry is syngas to methanol to aromatics. The synthesis gas alkylation reaction can directly skip the synthesis process of intermediate methanol and directly flow from synthesis gas to aromatic hydrocarbon, so that the synthesis gas alkylation reaction can save the step of preparing methanol from synthesis gas, shorten the whole flow and save the whole investment. But the activities of hydrogen and carbon monoxide are low relative to the high activities of methanol, so that more research is still required.
CN104945219a discloses a method for preparing toluene and para-xylene from benzene and synthesis gas and a catalyst therefor. The patent adopts metal oxide and solid acid catalyst, the metal oxide is noble metal and transition metal, the solid acid can be silicon aluminum molecular sieve or Nb, zr and Sn phosphate, and the reduction is not needed before the use. When the catalyst catalyzes benzene and synthesis gas to carry out alkylation reaction, the conversion rate of benzene is less than 20%, and the reaction activity is low.
CN109776249a and CN109776250a disclose a method for directly preparing para-xylene from synthesis gas and aromatic hydrocarbon. The acidic molecular sieve is at least one of modified acidic ZSM-5 and ZSM-11 molecular sieves, and the metal oxide is at least one oxide of zinc, chromium, zirconium, copper, manganese, platinum and palladium and one of graphite powder and a dispersing agent. Toluene can be converted into xylene by the method, and the selectivity of the para-xylene reaches more than 90 percent. Because the catalyst is prepared by adopting a mode of blending metal and an acid center, the uniformity after mixing is poor, and the conversion rate of reactants is limited.
CN107999118A discloses an aromatic hydrocarbon and synthesis gas alkylation catalyst comprising a support and a supported active component, said support comprising 20-80 wt.% of MFI or IMF structured hydrogen-type molecular sieve, and 20-80 wt.% of alumina, said active component comprising a first metal and a second metal, said first metal being zinc, said second metal being at least one selected from chromium, copper, magnesium and silver. The catalyst can be used for preparing toluene and xylene by reacting benzene with synthesis gas.
Disclosure of Invention
The invention provides a preparation method of a benzene and synthesis gas alkylation catalyst with high activity and high selectivity in order to fully utilize low-price synthesis gas and expand the application of pure benzene and increase the production of toluene and xylene with higher economic value.
In order to achieve the above object, the present invention provides a process for preparing benzene and synthesis gas alkylation catalysts comprising a support and the following active metal oxides in amounts based on the support: 10 to 30 mass% of zinc oxide, 10 to 30 mass% of a first metal oxide, and 7 to 30 mass% of a second metal oxide;
the carrier comprises 30-70 mass percent of hydrogen type MFI structure molecular sieve, 1-25 mass percent of hydrogen type EUO structure molecular sieve and 20-60 mass percent of alumina;
the first metal and the second metal are respectively and independently selected from one of Cu, ce, cr, zr and La;
the preparation method of the catalyst comprises the following steps:
(1) Mixing the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, pseudo-boehmite and peptizing agent, molding, and then performing first drying and first roasting to obtain a molded carrier;
(2) Carrying out acid treatment on the molded carrier by using an organic acid solution to obtain an acid-treated carrier; then, the acid-treated carrier is subjected to alkali treatment by using an inorganic alkali solution to obtain an acid-alkali-treated carrier;
(3) Carrying out ammonium exchange treatment on the acid-alkali treated carrier, and then washing, drying and roasting to obtain an ammonium exchanged carrier;
(4) The carrier is impregnated with a soluble zinc salt solution after ammonium exchange, then dried and roasted, then impregnated with a solution containing a first metal salt and a second metal salt, and then dried and roasted.
Optionally, in the step (1), the peptizing agent is an aqueous solution of an inorganic acid, and the inorganic acid is one or more selected from nitric acid, phosphoric acid and boric acid; in the peptizing agent, the content of the inorganic acid is 2-6 mass percent, and the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve and the pseudo-boehmite is 0.6-0.9 mL/g.
Optionally, the hydrogen type MFI structure molecular sieve is a hydrogen type ZSM-5 molecular sieve; siO of the hydrogen type MFI structure molecular sieve 2 /Al 2 O 3 The molar ratio is (20-150): 1, a step of;
the hydrogen EUO structure molecular sieve is a hydrogen EU-1 molecular sieve; siO of the hydrogen type EUO structure molecular sieve 2 /Al 2 O 3 The molar ratio is (20-150): 1.
optionally, the alumina in the carrier is macroporous alumina, the pseudo-boehmite in the step (1) is macroporous pseudo-boehmite, and the specific surface area of the macroporous pseudo-boehmite is 340-400 m 2 Per gram, the pore volume is 0.7-1 mL/g.
Optionally, in the macroporous pseudo-boehmite, the pore volume with the pore diameter of less than 3nm accounts for 0-1% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 5-15% of the total pore volume.
Optionally, in the step (1), the temperature of the first drying is 100-180 ℃ and the time is 1-12 h; the temperature of the first roasting is 520-600 ℃ and the time is 1-10 h.
Optionally, in step (2), the acid treatment comprises: acid treatment is carried out on the molded carrier by using the organic acid solution, washing is carried out until the pH value of an eluate is 6-8, and then drying is carried out at 100-180 ℃ to obtain the carrier after the acid treatment;
the temperature of the acid treatment is 30-70 ℃ and the time is 1-10 h, and the liquid/solid ratio of the acid treatment is 5-40 mL/g;
the organic acid in the organic acid solution is one or more selected from acetic acid, oxalic acid, citric acid, tartaric acid and benzoic acid; in the organic acid solution, the content of the organic acid is 0.01-1 mol/L.
Optionally, in step (2), the alkali treatment comprises: the inorganic strong alkali solution is used for carrying out alkali treatment on the acid-treated carrier, washing is carried out until the pH value of an eluate is 6-8, and then drying is carried out at 100-180 ℃ to obtain the acid-alkali-treated carrier;
the temperature of the alkali treatment is 30-70 ℃ and the time is 1-10 h, and the liquid/solid ratio of the alkali treatment is 5-40 mL/g;
the inorganic strong base in the inorganic strong base solution is selected from sodium hydroxide and/or potassium hydroxide; in the inorganic strong alkali solution, the content of the inorganic strong alkali is 0.05-0.3 mol/L.
Optionally, in step (3), the ammonium exchange process comprises: ion-exchanging the acid-base treated support with an ammonium salt solution; the ammonium salt solution is selected from one or more of ammonium chloride solution, ammonium nitrate solution and ammonium sulfate solution.
Optionally, in the step (3) and the step (4), the drying temperature is 100-180 ℃ respectively, and the drying time is 4-12 hours respectively; the roasting temperature is 350-500 ℃ and the roasting time is 3-6 hours respectively.
Optionally, in the step (4), the soluble zinc salt is one or more of nitrate, acetate, sulfate and chloride of zinc; the first metal salt is selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the first metal; the second metal salt is selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the second metal.
According to the preparation method of the catalyst, two composite molecular sieves are adopted to prepare the carrier, and acid-base treatment is carried out, so that the acid distribution of the carrier can be improved, the pore structure and the pore size distribution are optimized, the catalyst prepared by loading active metal components has high catalytic activity and good selectivity, the conversion rate of benzene and the selectivity and yield of toluene and C8 aromatic hydrocarbon are high, and the preparation method of the catalyst has the advantages of simplicity, sufficient raw material sources, low cost, easiness in operation and suitability for large-scale industrial application.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the present disclosure, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The invention provides a preparation method of a benzene and synthesis gas alkylation catalyst, which comprises a carrier and active metal oxides with the following contents based on the carrier: 10 to 30 mass% of zinc oxide, 10 to 30 mass% of a first metal oxide, and 7 to 30 mass% of a second metal oxide; the carrier comprises 30-70 mass percent of hydrogen type MFI structure molecular sieve, 1-25 mass percent of hydrogen type EUO structure molecular sieve and 20-60 mass percent of alumina; the first metal and the second metal are respectively and independently selected from one of Cu, ce, cr, zr and La; the preparation method of the catalyst comprises the following steps: (1) Mixing the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, pseudo-boehmite and peptizing agent, molding, and then performing first drying and first roasting to obtain a molded carrier; (2) Carrying out acid treatment on the molded carrier by using an organic acid solution to obtain an acid-treated carrier; then, the acid-treated carrier is subjected to alkali treatment by using an inorganic alkali solution to obtain an acid-alkali-treated carrier; (3) Carrying out ammonium exchange treatment on the acid-alkali treated carrier, and then washing, drying and roasting to obtain an ammonium exchanged carrier; (4) The carrier is impregnated with a soluble zinc salt solution after ammonium exchange, then dried and roasted, then impregnated with a solution containing a first metal salt and a second metal salt, and then dried and roasted.
The invention is not limited to the kind and solute content of the peptizing agent, in one embodiment, the peptizing agent can be an aqueous solution of inorganic acid, and the inorganic acid can be one or more selected from nitric acid, phosphoric acid and boric acid; further, the content of the inorganic acid in the peptizing agent may be 2 to 6 mass%, preferably may be 3 to 5 mass%; still further, the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen form MFI structure molecular sieve, the hydrogen form EUO structure molecular sieve, and the pseudo-boehmite may be 0.6 to 0.9mL/g, preferably 0.65 to 0.85mL/g.
According to the present invention, preferably, the catalyst comprises a support and an active metal oxide in the following content on a support basis: 12 to 28 mass% of zinc oxide, 11 to 27 mass% of a first metal oxide, and 7.1 to 28 mass% of a second metal oxide; further preferably, the catalyst comprises a support and an active metal oxide in the following amounts, based on the support: 15 to 26 mass% of zinc oxide, 11.5 to 26 mass% of a first metal oxide, and 7.2 to 26 mass% of a second metal oxide.
According to the present invention, preferably, the carrier contains 30 to 68 mass% of the hydrogen type MFI structure molecular sieve, 2 to 22 mass% of the hydrogen type EUO structure molecular sieve, and 23 to 55 mass% of alumina.
According to the invention, the hydrogen type MFI structure molecular sieve used in preparing the catalyst carrier is preferably hydrogen type ZSM-5 molecular sieve; the EUO structural molecular sieve in hydrogen form may be selected from EU-1 molecular sieves in hydrogen form. In a specific embodiment, the hydrogen type EUO structure molecular sieve is SiO 2 /Al 2 O 3 The molar ratio can be (20-150): 1, preferably (25 to 75): 1, a step of; siO of the hydrogen type MFI structure molecular sieve 2 /Al 2 O 3 The molar ratio can be (20-150): 1, preferably (25 to 100): 1.
according to the invention, the alumina in the carrier can be macroporous alumina, and is obtained by roasting and converting macroporous pseudo-boehmite. In one embodiment, in order to increase the specific surface area and pore volume of the catalyst, the performance of the catalyst is improved, and the selectivity and yield of toluene and C8 aromatic hydrocarbon are further improved, (1) the pseudo-boehmite in the step (1) is macroporous pseudo-boehmite, and the specific surface area of the macroporous pseudo-boehmite can be 340-400 m 2 Per gram, the pore volume can be 0.7-1 mL/g; preferably, in the macroporous pseudo-boehmite, the pore volume with the pore diameter of less than 3nm accounts for 0-1% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 5-15% of the total pore volume.
In order to further increase the specific surface area and the total pore volume of the catalyst and increase the distribution ratio of macropores in the catalyst, in a preferred embodiment, the specific surface area of the macroporous pseudo-boehmite may be 345-380 m 2 Per gram, the pore volume can be 0.75-0.85 mL/g; in the macroporous pseudo-boehmite, the pore volume with the pore diameter of less than 3nm can account for 0-1% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm can account for 40-60% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm can account for 20-35% of the total pore volume, and the pore diameter of more than 15nm and less than 30nmThe volume can be 8-15% of the total pore volume, and the pore volume with the pore diameter above 30nm can be 5-10% of the total pore volume.
In one embodiment according to the invention, in step (1), the temperature of the first drying is 100 to 180 ℃, preferably may be 110 to 150 ℃, for a time of 1 to 12 hours, preferably may be 4 to 6 hours; the temperature of the first firing is 520 to 600 ℃, preferably 540 to 580 ℃, and the time is 1 to 10 hours, preferably 4 to 6 hours.
According to the present invention, in order to adjust the acid amount and acid distribution of the molecular sieve and remove part of silicon using a subsequent alkali treatment, part of framework aluminum is removed using an acid treatment method, (2) in step, the molded carrier is acid-treated with an organic acid solution, and in one embodiment, the acid treatment may include: and (3) carrying out acid treatment on the molded carrier by using the organic acid solution, washing until the pH value of an eluate is 6-8, and then drying at 100-180 ℃ to obtain the carrier after the acid treatment. The present invention is not limited in the kind of the washing liquid, and may be conventional in the art, preferably deionized water.
The present invention is not limited in the amount of the organic acid solution used for the acid treatment and the treatment conditions, and in one embodiment according to the present invention, the liquid/solid ratio of the acid treatment may be 5 to 40mL/g, preferably 10 to 20mL/g; further, the temperature of the acid treatment may be 30 to 70 ℃, preferably 40 to 60 ℃, and the time may be 1 to 10 hours, preferably 2 to 6 hours.
The invention has no requirement on the type of organic acid in the organic acid solution, and can be conventional in the field, for example, the organic acid can be one or more of acetic acid, oxalic acid, citric acid, tartaric acid and benzoic acid; further, the organic acid may be contained in an amount of 0.01 to 1mol/L, preferably 0.1 to 0.5mol/L.
According to the invention, inorganic alkali treatment can be adopted to remove part of silicon in the molecular sieve framework, so that the molecular sieve forms certain mesopores, and as the silicon removal and mesopore formation process is related to the framework aluminum distribution, particularly the more framework aluminum is, the more framework silicon is difficult to remove, part of aluminum can be removed by acid treatment before the inorganic alkali treatment, so that the framework silicon removal is more effective, and meanwhile, the acid distribution can be improved. In a specific embodiment, in step (2), the acid-treated support is subjected to a base treatment using an inorganic strong base solution, and in one embodiment, the base treatment may comprise: and (3) carrying out alkali treatment on the acid-treated carrier by using the inorganic alkali solution, washing until the pH value of an eluate is 6-8, and then drying at 100-180 ℃ to obtain the acid-alkali treated carrier.
The present invention is not limited to the amount of the inorganic strong alkali solution used for the alkali treatment and the treatment conditions, and in one embodiment according to the present invention, the liquid/solid ratio of the alkali treatment may be 5 to 40mL/g, preferably 10 to 20mL/g; further, the temperature of the alkali treatment may be 30 to 70 ℃, preferably 40 to 60 ℃, and the time may be 1 to 10 hours, preferably 2 to 8 hours.
The invention has no requirement on the inorganic strong base type in the inorganic strong base solution, and can be conventional in the field, for example, the inorganic strong base can be sodium hydroxide and/or potassium hydroxide; further, the content of the inorganic strong base in the inorganic strong base solution may be 0.05 to 0.3mol/L, and preferably may be 0.1 to 0.25mol/L.
The invention is not limited to the steps of the ammonium exchange process, which may be conventional in the art, and in one embodiment may include: ion-exchanging the acid-base treated support with an ammonium salt solution; further, the ammonium salt may be selected from one or more of ammonium chloride, ammonium nitrate and ammonium sulfate, and preferably may be selected from ammonium chloride; further, the temperature of the ammonium exchange treatment may be 65 to 95 ℃ and the time may be 1 to 10 hours.
In a specific embodiment according to the present invention, in the step (3) and the step (4), the drying temperature may be 100 to 180 ℃ and the drying time may be 4 to 12 hours, respectively; further, the roasting temperatures may be 350 to 500 ℃, preferably 400 to 450 ℃, respectively, and the time may be 3 to 6 hours, respectively.
The invention is not limited to the type and solute content of the soluble zinc salt solution in the step (4), and in one embodiment, the soluble zinc salt may be one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate thereof, and preferably may be one or more of nitrate, sulfate, chloride and citrate containing zinc element.
According to the present invention, the first metal salt in step (4) may be selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the first metal; the second metal salt may be selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the second metal.
Preferably, the specific surface area of the catalyst prepared by the invention can be 350-400 m 2 The total pore volume may be 0.65 to 0.85mL/g. In the catalyst, the pore volume with the pore diameter of less than 3nm can account for 20-42% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm can account for 8-30% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm can account for 18-35% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm can account for 8-15% of the total pore volume, and the pore volume with the pore diameter of more than 30nm can account for 5-20% of the total pore volume;
further, the pore volume with a pore diameter of less than 3nm may account for 30 to 40% of the total pore volume, the pore volume with a pore diameter of more than 3nm and less than 5nm may account for 10 to 20% of the total pore volume, the pore volume with a pore diameter of more than 5nm and less than 15nm may account for 20 to 30% of the total pore volume, the pore volume with a pore diameter of more than 15nm and less than 30nm may account for 10 to 14% of the total pore volume, and the pore volume with a pore diameter of more than 30nm may account for 8 to 15% of the total pore volume.
According to the present invention, preferably, the oxidation state catalyst obtained in step (4) is heated to the reaction temperature in a hydrogen-containing gas before use, and in a specific embodiment, the hydrogen-containing gas may include hydrogen and optionally an inert atmosphere gas, and the inert atmosphere gas may be one or more selected from nitrogen, helium and argon.
The catalyst prepared by the invention is suitable for alkylation reaction of benzene and synthesis gas, in one embodiment, the alkylation reaction temperature can be 250-550 ℃, preferably 400-500 ℃, the pressure can be 0.5-5 MPa, preferably 2-4 MPa, and the mass airspeed of benzene can be 0.5-4 h -1 Preferably 1 to 3 hours -1 The molar ratio of benzene to CO is preferably 1: (1-4) benzene and H 2 Preferably 1: (2-8).
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The hydrogen-type ZSM-5 molecular sieve used below was purchased from China Petroleum smooth petrochemical company, and the hydrogen-type EU-1 molecular sieve was purchased from China petrochemical Kaolin catalyst division.
Physical properties of the pseudo-boehmite powder (trade name SB, manufactured by Condea, germany, 70% by mass of alumina) and the macroporous pseudo-boehmite powder (trade name HY-78, manufactured by China Petroleum smooth petrochemical Co., ltd.) used below are shown in Table 1.
TABLE 1
Preparation example 1
Preparing a carrier a.
SiO is made of 2 /Al 2 O 3 65g of hydrogen ZSM-5 molecular sieve with a molar ratio of 27 and SiO 2 /Al 2 O 3 5g of hydrogen EU-1 molecular sieve with a molar ratio of 35 and 42.9g of macroporous pseudo-boehmite (HY-78) are fully and uniformly mixed, and then 80mL of dilute nitric acid solution with a concentration of 3.5 mass percent is added, kneaded, extruded and molded. Drying at 120 deg.C for 4h, and calcining at 540 deg.C for 4h in air atmosphere to obtain the final product, wherein the final product contains 65% by mass of HZSM-5, 5% by mass of HEU-1 and 30% by mass of macroporous gamma-alumina.
Adding the molded carrier into oxalic acid solution with the concentration of 0.2mol/L, carrying out acid treatment for 2 hours at the temperature of 50 ℃ with the liquid/solid ratio of 15mL/g, then washing until the washing solution is neutral, drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid treatment, adding the carrier into sodium hydroxide solution with the concentration of 0.1mol/L with the liquid/solid ratio of 15mL/g, carrying out alkali treatment for 3 hours at the temperature of 50 ℃, washing until the washing solution is neutral, and drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid-alkali treatment.
And (3) carrying out ammonium exchange on 10g of the acid-base treated carrier by using 20g of an ammonium chloride solution with the concentration of 1mol/L, wherein the ammonium exchange temperature is 90 ℃, the time is 2 hours, then washing until a washing solution is neutral, drying at 120 ℃ for 4 hours, and roasting at 400 ℃ for 4 hours to obtain the carrier a.
Preparation example 2
Preparing a carrier b.
SiO is made of 2 /Al 2 O 3 50g of hydrogen ZSM-5 molecular sieve with a molar ratio of 38 and SiO 2 /Al 2 O 3 10g of hydrogen EU-1 molecular sieve with the molar ratio of 70 and 57.1g of macroporous pseudo-boehmite (HY-78) are fully and uniformly mixed, then 90mL of dilute nitric acid solution with the concentration of 3.5 mass percent is added, and the mixture is kneaded and extruded into strips. Drying at 120 deg.C for 4h, and calcining at 540 deg.C for 4h in air atmosphere to obtain the final product, which contains 50% by mass of HZSM-5, 10% by mass of HEU-1 and 40% by mass of macroporous gamma-alumina.
Adding the molded carrier into oxalic acid solution with the concentration of 0.2mol/L, carrying out acid treatment for 2 hours at the temperature of 50 ℃ with the liquid/solid ratio of 15mL/g, then washing until the washing solution is neutral, drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid treatment, adding the carrier into sodium hydroxide solution with the concentration of 0.1mol/L with the liquid/solid ratio of 15mL/g, carrying out alkali treatment for 6 hours at the temperature of 50 ℃, washing until the washing solution is neutral, and drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid-alkali treatment.
And (3) carrying out ammonium exchange on 10g of the acid-base treated carrier by using 20g of an ammonium chloride solution with the concentration of 1mol/L, wherein the ammonium exchange temperature is 90 ℃, the time is 2 hours, then washing until a washing solution is neutral, drying at 120 ℃ for 4 hours, and roasting at 400 ℃ for 4 hours to obtain the carrier b.
Preparation example 3
Preparing a carrier c.
SiO is made of 2 /Al 2 O 3 Hydrogen ZSM-5 fraction with a molar ratio of 7030g of sub-sieve, siO 2 /Al 2 O 3 20g of hydrogen EU-1 molecular sieve with a molar ratio of 25 and 71.4g of macroporous pseudo-boehmite (HY-78) are fully and uniformly mixed, and then 100mL of dilute nitric acid solution with a concentration of 3.5 mass percent is added, kneaded, extruded and molded. Drying at 120 deg.C for 4h, and calcining at 540 deg.C for 4h in air atmosphere to obtain the final product containing 30% by mass of HZSM-5, 20% by mass of HEU-1 and 50% by mass of macroporous gamma-alumina.
Adding the molded carrier into oxalic acid solution with the concentration of 0.2mol/L, carrying out acid treatment for 4 hours at the temperature of 50 ℃ with the liquid/solid ratio of 15mL/g, then washing until the washing solution is neutral, drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid treatment, adding the carrier into sodium hydroxide solution with the concentration of 0.1mol/L with the liquid/solid ratio of 15mL/g, carrying out alkali treatment for 5 hours at the temperature of 50 ℃, washing until the washing solution is neutral, and drying for 4 hours at the temperature of 120 ℃ to obtain the carrier after acid-alkali treatment.
And (3) carrying out ammonium exchange on 10g of the acid-base treated carrier by using 20g of an ammonium chloride solution with the concentration of 1mol/L, wherein the ammonium exchange temperature is 90 ℃, the time is 2 hours, then washing until the washing solution is neutral, drying at 120 ℃ for 4 hours, and roasting at 400 ℃ for 4 hours to obtain the carrier c.
Example 1
0.23mol of zinc nitrate is dissolved in 105 g of deionized water at 50 ℃, then 70g of carrier a is put into the zinc nitrate solution, immersed for 18h at 25 ℃, dried for 2h at 120 ℃, and roasted for 4h under the air atmosphere at 400 ℃ to obtain the carrier loaded with zinc oxide.
Dissolving 0.11mol of chromium nitrate and 0.06mol of lanthanum nitrate in 105 g of deionized water at 50 ℃, putting the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain the catalyst A.
Example 2
0.179mol of zinc nitrate was dissolved in 100g of deionized water at 50℃and then 65g of carrier a was put into the above zinc nitrate solution, immersed at 25℃for 18 hours, dried at 120℃for 2 hours, and calcined at 400℃for 4 hours in an air atmosphere to obtain a zinc oxide-supported carrier.
0.099mol of zirconium nitrate and 0.049mol of cerium nitrate are dissolved in 100g of deionized water at 50 ℃, the carrier loaded with zinc oxide is put into the solution, immersed for 18h at 25 ℃, dried for 2h at 120 ℃, and baked for 4h in an air atmosphere at 400 ℃ to obtain the catalyst B.
Example 3
0.13mol of zinc nitrate is dissolved in 90 g of deionized water at 50 ℃, then 60g of carrier a is put into the zinc nitrate solution, immersed for 18h at 25 ℃, dried for 2h at 120 ℃, and roasted for 4h under the air atmosphere at 400 ℃ to obtain the carrier loaded with zinc oxide.
Dissolving 0.13mol of zirconium nitrate and 0.19mol of copper nitrate in 90 g of deionized water at 50 ℃, putting the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain the catalyst C.
Example 4
0.17mol of zinc nitrate is dissolved in 100g of deionized water at 50 ℃, 65g of carrier b is then put into the zinc nitrate solution, immersed for 18h at 25 ℃, dried for 2h at 120 ℃, and roasted for 4h under an air atmosphere at 400 ℃ to obtain the carrier loaded with zinc oxide.
Dissolving 0.09mol of zirconium nitrate and 0.04mol of cerium nitrate in 100g of deionized water at 50 ℃, putting the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain the catalyst D.
Example 5
0.15mol of zinc nitrate is dissolved in 100g of deionized water at 50 ℃, 65g of carrier c is then put into the zinc nitrate solution, immersed for 18h at 25 ℃, dried for 2h at 120 ℃, and roasted for 4h under an air atmosphere at 400 ℃ to obtain the carrier loaded with zinc oxide.
Dissolving 0.11mol of zirconium nitrate and 0.03mol of cerium nitrate in 100g of deionized water at 50 ℃, putting the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain the catalyst E.
Example 6
0.179mol of zinc nitrate was dissolved in 100g of deionized water at 50℃and then 65g of carrier a was put into the above zinc nitrate solution, immersed at 25℃for 18 hours, dried at 120℃for 2 hours, and calcined at 400℃for 4 hours in an air atmosphere to obtain a zinc oxide-supported carrier.
Dissolving 0.16mol of chromium nitrate and 0.049mol of cerium nitrate in 100g of deionized water at 50 ℃, putting the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain the catalyst F.
Comparative example 1
The catalyst was prepared according to the method of example 3 disclosed in CN107999118A by mixing 60g of silica/alumina in a molar ratio of 25:1 and 57.1g of pseudo-boehmite powder (SB), adding 80mL of dilute nitric acid solution with the concentration of 3.5 mass percent, kneading, extruding, forming, drying at 120 ℃ for 4 hours, and roasting at 540 ℃ for 4 hours in an air atmosphere to obtain a carrier d, wherein the carrier d contains 60 mass percent of HZSM-5 and 40 mass percent of gamma-alumina.
0.89mol of zinc nitrate and 0.38mol of chromium nitrate were dissolved in 200g of deionized water, and the solution was prepared by stirring until complete dissolution. Then 100g of the carrier d was put into the solution, immersed for 12 hours, dried at 120℃for 2 hours, and then baked for 4 hours in an air atmosphere at 400℃to obtain a zinc and chromium-loaded carrier.
0.01mol of lanthanum nitrate was dissolved in 200g of deionized water, and the solution was prepared by stirring until complete dissolution. And (3) putting the carrier loaded with zinc and chromium into a lanthanum nitrate solution, immersing for 12h, drying for 2h at 120 ℃, and roasting for 2h in an air atmosphere at 600 ℃ to obtain the catalyst G.
The compositions of the catalysts prepared in examples 1 to 6 and comparative example 1 are shown in Table 2, wherein the active metal oxide content is based on the carrier, and the physical properties are shown in Table 3. Wherein, the zinc oxide and the first metal oxide and the second metal oxide contents in the table 2 are measured by an XRF fluorescence method; the specific surface area, total pore volume and pore size distribution described in tables 1 and 3 were measured by a static low temperature nitrogen adsorption capacity method, the specific surface area was calculated by a BET method, and the pore size distribution was calculated by a DFT method.
TABLE 2
TABLE 3 Table 3
Application examples 1 to 7
Alkylation of benzene with synthesis gas was carried out in a small fixed bed high pressure reactor. The catalyst is first heated to the reaction temperature in a hydrogen atmosphere. Then the reaction temperature is 440 ℃, the reaction pressure is 3MPa, and the benzene feeding mass space velocity is 1.5h -1 Benzene to CO molar ratio of 1: 2. benzene and H 2 The molar ratio is 1:4, carrying out alkylation reaction under the condition of 4. The products were analyzed by gas chromatography, and the reaction result data of each catalyst prepared in examples 1 to 6 and comparative example 1 are shown in Table 4. The calculation method of each data in table 4 is as follows.
Total toluene and C8 aromatics yield = benzene conversion x (toluene selectivity + C8 aromatics selectivity) x 100%
TABLE 4 Table 4
As can be seen from the comparison of the data obtained in application examples 1-6 and application example 7, the benzene and synthesis gas alkylation catalyst prepared by the method of the invention has higher benzene conversion rate and selectivity and yield of toluene and C8 aromatic hydrocarbon.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (11)

1. A process for the preparation of a benzene and synthesis gas alkylation catalyst comprising a support and an active metal oxide in the following amounts based on the support: 10 to 30 mass% of zinc oxide, 10 to 30 mass% of a first metal oxide, and 7 to 30 mass% of a second metal oxide;
the carrier comprises 30-70 mass percent of hydrogen type MFI structure molecular sieve, 1-25 mass percent of hydrogen type EUO structure molecular sieve and 20-60 mass percent of alumina;
the first metal and the second metal are respectively and independently selected from one of Cu, ce, cr, zr and La;
the preparation method of the catalyst comprises the following steps:
(1) Mixing the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, pseudo-boehmite and peptizing agent, molding, and then performing first drying and first roasting to obtain a molded carrier;
(2) Carrying out acid treatment on the molded carrier by using an organic acid solution to obtain an acid-treated carrier; then, the acid-treated carrier is subjected to alkali treatment by using an inorganic alkali solution to obtain an acid-alkali-treated carrier;
(3) Carrying out ammonium exchange treatment on the acid-alkali treated carrier, and then washing, drying and roasting to obtain an ammonium exchanged carrier;
(4) Impregnating the carrier after ammonium exchange by using a soluble zinc salt solution, drying and roasting, impregnating by using a solution containing a first metal salt and a second metal salt, and drying and roasting;
wherein, in the step (1), the peptizing agent is an aqueous solution of inorganic acid, and the inorganic acid is one or more selected from nitric acid, phosphoric acid and boric acid; in the peptizing agent, the content of the inorganic acid is 2-6 mass percent, and the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve and the pseudo-boehmite is 0.6-0.9 mL/g;
the hydrogen type MFI structure molecular sieve is a hydrogen type ZSM-5 molecular sieve; siO of the hydrogen type MFI structure molecular sieve 2 /Al 2 O 3 The molar ratio is (20-150): 1, a step of;
the hydrogen EUO structure molecular sieve is a hydrogen EU-1 molecular sieve; siO of the hydrogen type EUO structure molecular sieve 2 /Al 2 O 3 The molar ratio is (20-150): 1, a step of;
the alumina in the carrier is macroporous alumina, the pseudo-boehmite in the step (1) is macroporous pseudo-boehmite, and the specific surface area of the macroporous pseudo-boehmite is 340-400 m 2 Per gram, the pore volume is 0.7-1 mL/g;
in the macroporous pseudo-boehmite, the pore volume with the pore diameter of less than 3nm accounts for 0-1% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 5-15% of the total pore volume.
2. The method according to claim 1, wherein in the step (1), the content of the inorganic acid is 3 to 5 mass%, and the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen form MFI structure molecular sieve, the hydrogen form EUO structure molecular sieve, and the pseudo-boehmite is 0.65 to 0.85mL/g.
3. The method of claim 1, wherein the hydrogen form of the SiO of the MFI structure molecular sieve 2 /Al 2 O 3 The molar ratio is (25-100): 1, a step of;
SiO of the hydrogen type EUO structure molecular sieve 2 /Al 2 O 3 The molar ratio is (25-75): 1.
4. the method according to claim 1, wherein the specific surface area of the macroporous pseudo-boehmite is 345-380 m 2 Per gram, the pore volume is 0.75-0.85 mL/g.
5. The method of claim 4, wherein the pore volume of the macroporous pseudo-boehmite has a pore diameter of less than 3nm of 0 to 1% of the total pore volume, a pore volume of 3nm or more and less than 5nm of 40 to 60% of the total pore volume, a pore volume of 5nm or more and less than 15nm of 20 to 35% of the total pore volume, a pore volume of 15nm or more and less than 30nm of 8 to 15% of the total pore volume, and a pore volume of 30nm or more of 5 to 10% of the total pore volume.
6. The method of claim 1, wherein in step (1), the first drying is performed at a temperature of 100 to 180 ℃ for a time of 1 to 12 hours; the temperature of the first roasting is 520-600 ℃ and the time is 1-10 h.
7. The method of claim 1, wherein in step (2), the acid treatment comprises: acid treatment is carried out on the molded carrier by using the organic acid solution, washing is carried out until the pH value of an eluate is 6-8, and then drying is carried out at 100-180 ℃ to obtain the carrier after the acid treatment;
the temperature of the acid treatment is 30-70 ℃ and the time is 1-10 h, and the liquid/solid ratio of the acid treatment is 5-40 mL/g;
the organic acid is one or more selected from acetic acid, oxalic acid, citric acid, tartaric acid and benzoic acid; in the organic acid solution, the content of the organic acid is 0.01-1 mol/L.
8. The method of claim 1, wherein in step (2), the alkali treatment comprises: performing alkali treatment on the acid-treated carrier by using the inorganic alkali solution, washing until the pH value of an eluate is 6-8, and then drying at 100-180 ℃ to obtain the acid-alkali-treated carrier;
the temperature of the alkali treatment is 30-70 ℃ and the time is 1-10 h, and the liquid/solid ratio of the alkali treatment is 5-40 mL/g;
the inorganic strong base is selected from sodium hydroxide and/or potassium hydroxide; in the inorganic strong alkali solution, the content of the inorganic strong alkali is 0.05-0.3 mol/L.
9. The method of claim 1, wherein in step (3), the ammonium exchange process comprises: ion-exchanging the acid-base treated support with an ammonium salt solution; the ammonium salt solution is selected from one or more of ammonium chloride solution, ammonium nitrate solution and ammonium sulfate solution.
10. The method according to claim 1, wherein in the steps (3) and (4), the drying temperatures are 100 to 180 ℃ for 4 to 12 hours, respectively; the roasting temperature is 350-500 ℃ and the roasting time is 3-6 hours respectively.
11. The method of claim 1 wherein in step (4) the soluble zinc salt is one or more of nitrate, acetate, sulfate and chloride of zinc; the first metal salt is selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the first metal; the second metal salt is selected from one or more of nitrate, acetate, sulfate, chloride, gluconate and citrate of the second metal.
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Publication number Priority date Publication date Assignee Title
CN102107144A (en) * 2009-12-24 2011-06-29 中国石油化工股份有限公司 Method for preparing C8 aromatic isomerization catalyst
CN105435839A (en) * 2015-12-07 2016-03-30 中国海洋石油总公司 Methanol to aromatic catalyst containing two molecular sieves and preparation method
CN106140292A (en) * 2015-03-27 2016-11-23 中国石油化工股份有限公司 A kind of catalyst with composite molecular screen as carrier and its preparation method and application
WO2018010358A1 (en) * 2016-07-15 2018-01-18 中国科学院大连化学物理研究所 Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas
CN107999118A (en) * 2016-10-28 2018-05-08 中国石油化工股份有限公司 A kind of aromatic hydrocarbons and synthesis gas alkylation catalyst and preparation method and application
CN108786910A (en) * 2017-04-26 2018-11-13 中国石油化工股份有限公司 A kind of C8Arene isomerization catalyst and preparation method
CN110961143A (en) * 2018-09-29 2020-04-07 中国石油天然气股份有限公司 Molecular sieve catalyst, preparation method thereof and application thereof in ethylbenzene dealkylation and xylene isomerization

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11572283B2 (en) * 2017-10-26 2023-02-07 China Petroleum & Chemical Corporation Molecular sieve having mesopores, preparation method therefor, and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102107144A (en) * 2009-12-24 2011-06-29 中国石油化工股份有限公司 Method for preparing C8 aromatic isomerization catalyst
CN106140292A (en) * 2015-03-27 2016-11-23 中国石油化工股份有限公司 A kind of catalyst with composite molecular screen as carrier and its preparation method and application
CN105435839A (en) * 2015-12-07 2016-03-30 中国海洋石油总公司 Methanol to aromatic catalyst containing two molecular sieves and preparation method
WO2018010358A1 (en) * 2016-07-15 2018-01-18 中国科学院大连化学物理研究所 Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas
CN107999118A (en) * 2016-10-28 2018-05-08 中国石油化工股份有限公司 A kind of aromatic hydrocarbons and synthesis gas alkylation catalyst and preparation method and application
CN108786910A (en) * 2017-04-26 2018-11-13 中国石油化工股份有限公司 A kind of C8Arene isomerization catalyst and preparation method
CN110961143A (en) * 2018-09-29 2020-04-07 中国石油天然气股份有限公司 Molecular sieve catalyst, preparation method thereof and application thereof in ethylbenzene dealkylation and xylene isomerization

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