CN114433218B - Benzene and synthesis gas alkylation catalyst and preparation method and application thereof - Google Patents

Benzene and synthesis gas alkylation catalyst and preparation method and application thereof Download PDF

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CN114433218B
CN114433218B CN202011193896.1A CN202011193896A CN114433218B CN 114433218 B CN114433218 B CN 114433218B CN 202011193896 A CN202011193896 A CN 202011193896A CN 114433218 B CN114433218 B CN 114433218B
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pore volume
molecular sieve
catalyst
mass
carrier
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CN114433218A (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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • B01J35/615—
    • B01J35/633—
    • B01J35/695—
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    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • 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
    • 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
    • B01J29/48—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
    • 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
    • B01J29/70—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
    • 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
    • B01J29/70—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
    • B01J29/7646—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/7846—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • 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

Abstract

The invention relates to a benzene and synthesis gas alkylation catalyst, a preparation method and application thereof. The catalyst carrier adopts two composite molecular sieves, the catalyst pore structure and the acid distribution are enriched through the collocation of the two molecular sieves, so that the catalyst has the advantages of high catalytic activity and good selectivity, and the element distribution is more uniform when metal is immersed by adopting pseudo-boehmite as a binder, so that the conversion rate of benzene, the selectivity and the yield of toluene and C8 aromatic hydrocarbon are improved, and the preparation method is simple, the raw material sources are sufficient, the cost is low, the operation is easy, and the catalyst carrier is suitable for large-scale industrial application.

Description

Benzene and synthesis gas alkylation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of benzene and synthesis gas alkylation, in particular to a benzene and synthesis gas alkylation catalyst, a preparation method and application thereof.
Background
Benzene, toluene and xylene (BTX) in aromatics are important basic chemical raw materials. Toluene and xylene, especially para-xylene, 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.
CN110116022a is a preparation method of a bifunctional composite catalyst for preparing light aromatic hydrocarbon by benzene and synthesis gas in one step. The composite catalyst consists of an acidic molecular sieve and metal oxides, wherein the acidic molecular sieve adopts HZSM-5, and the metal oxides are one or more of Ti, V, cr, mn, fe, co, ni, cu, zn, mo, in, W, re. The co-precipitated metal oxide is mixed with a molecular sieve by ball milling, and the resulting composite catalyst can convert benzene to toluene and xylenes.
US4487984 discloses a process for the preparation of alkylaromatic compounds by reacting an aromatic compound with synthesis gas under alkylation conditions in the presence of a bifunctional catalyst comprising a complex oxide of copper, zinc and aluminium or chromium and an aluminosilicate.
The above patents all use metal co-precipitation followed by blending with molecular sieves to prepare catalysts. However, the catalyst prepared by this method has uneven distribution of metal and acid center, thus resulting in lower reactivity.
CN107999118A discloses an aromatic hydrocarbon and synthesis gas alkylation catalyst comprising a support and a supported active component, said support comprising 20-80 mass% of MFI or IMF structured hydrogen-type molecular sieve, and 20-80 mass% 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 benzene and synthesis gas alkylation catalyst with high activity and high selectivity, a preparation method and application thereof, and aims to fully utilize low-price synthesis gas, 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, a first aspect of the present invention provides a benzene and synthesis gas alkylation catalyst comprising a support and an active metal oxide having the following content on a support basis: 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 20-80 mass percent of hydrogen type MFI structure molecular sieve, 1-60 mass percent of hydrogen type EUO structure molecular sieve and 15-60 mass percent of alumina;
the first metal and the second metal are each independently selected from one of Cu, ce, cr, zr and La.
Alternatively, the carrier contains 25 to 70 mass% of the hydrogen type MFI structure molecular sieve, 1 to 30 mass% of the hydrogen type EUO structure molecular sieve, and 20 to 60 mass% of the alumina.
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.
alternatively, the content of active metal oxides, based on the support, is as follows: 15 to 28 mass% of zinc oxide, 10 to 26 mass% of a first metal oxide, and 7 to 26 mass% of a second metal oxide.
Alternatively, the first metal oxide is selected from oxides of Cr or Zr, and the second metal oxide is selected from one of oxides of La, ce, and Cu.
Optionally, the specific surface area of the catalyst is 250-340 m 2 And/g, the total pore volume is 0.1-0.5 mL/g.
Optionally, in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 30-60% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 5-20% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 20-50% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 0-5% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 0-5% of the total pore volume.
Optionally, in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 30-50% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 10-20% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 30-50% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 0.1-2% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 0-1% of the total pore volume.
In a second aspect, the present invention provides a process for preparing the catalyst according to the first aspect of the invention, the process comprising:
(1) Mixing the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, pseudo-boehmite and a peptizing agent, molding, and then performing first drying and first roasting to obtain a carrier;
(2) Carrying out steam treatment on the carrier to obtain a carrier after steam treatment;
(3) Impregnating the carrier subjected to the vapor treatment in the step (2) by using a soluble zinc salt solution, drying and roasting to obtain a carrier loaded with zinc oxide,
(4) Impregnating the zinc oxide-loaded carrier in the step (3) with a solution containing a first metal salt and a second metal salt, and then drying and roasting.
Optionally, in the step (1), the specific surface area of the pseudo-boehmite is 250-320 m 2 Per gram, the pore volume is 0.3-0.5 mL/g; wherein the pore volume with the pore diameter of less than 3nm accounts for 0-10% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 5-25% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 60-90% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 0.1-5% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 0.1-4% of the total pore volume.
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; the content of the inorganic acid in the peptizing agent is 2 to 6 mass percent; 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 0.4-0.9 mL/g.
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 the step (2), the temperature of the water vapor treatment is 400-500 ℃ and the time is 2-8 h.
Optionally, in the step (3) and the step (4), the drying temperature is 100-180 ℃ and the drying time is 1-12 h; the roasting temperature is 350-500 ℃ and the roasting time is 2-8 h.
Optionally, in step (4), 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.
A third aspect of the invention provides the use of the catalyst of the first aspect of the invention in a benzene and synthesis gas alkylation reaction at a temperature of from 250 to 550℃and a pressure of from 0.5 to 5MPa, the benzene mass space velocity being from 0.5 to 4 hours -1 Benzene to CO molar ratio 1: (1-4) benzene and H 2 The molar ratio of (2) is 1: (2-8).
The catalyst carrier adopts two composite molecular sieves, improves the pore structure distribution and acid distribution of the catalyst by compounding the two molecular sieves, adopts pseudo-boehmite as a binder, and has higher catalytic activity and selectivity by loading metal active components in the carrier, namely, the conversion rate of benzene, the selectivity and the yield of toluene and C8 aromatic hydrocarbon are improved. The catalyst has the advantages of simple preparation method, sufficient raw material sources, low cost and easy operation, and is suitable 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 first aspect of the invention provides a benzene and synthesis gas alkylation catalyst comprising a carrier and an active metal oxide with the following content 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 20-80 mass percent of hydrogen type MFI structure molecular sieve, 1-60 mass percent of hydrogen type EUO structure molecular sieve and 15-60 mass percent of alumina; the first metal and the second metal are each independently selected from one of Cu, ce, cr, zr and La.
In order to further improve the catalytic activity and selectivity of the catalyst, in a preferred embodiment according to the present invention, the support may comprise 25 to 70 mass% of the hydrogen type MFI structure molecular sieve, 1 to 30 mass% of the hydrogen type EUO structure molecular sieve, and 20 to 60 mass% of the alumina.
According to the present invention, the hydrogen-type MFI structure molecular sieve used in preparing the catalyst carrier may be selected from hydrogen-type ZSM-5 molecular sieves; 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.
in a preferred embodiment according to the invention, the active metal oxide content may be, based on the support: 15 to 28 mass% of zinc oxide, 10 to 26 mass% of a first metal oxide, and 7 to 26 mass% of a second metal oxide.
In a preferred embodiment, the first metal oxide is selected from oxides of Cr or Zr, and the second metal oxide is selected from one of oxides of La, ce and Cu.
In one embodiment according to the invention, the catalyst may have a specific surface area of 250 to 340m 2 Per gram, the total pore volume may be 0.1 to 0.5mL/g; preferably, the specific surface area of the catalyst may be 300 to 340m 2 And/g, the total pore volume may be 0.2 to 0.4mL/g.
In order to improve the reactivity of the catalyst, increase the conversion rate of benzene and the yield of the product, in a specific embodiment according to the present invention, the catalyst may have a pore volume of less than 3nm of 30 to 60% of the total pore volume, a pore volume of more than 3nm and less than 5nm of 5 to 20% of the total pore volume, a pore volume of more than 5nm and less than 15nm of 20 to 50% of the total pore volume, a pore volume of more than 15nm and less than 30nm of 0 to 5% of the total pore volume, and a pore volume of more than 30nm of 0 to 5% of the total pore volume; in a further preferred embodiment, in the catalyst, the pore volume having a pore diameter of less than 3nm may occupy 30 to 50% of the total pore volume, the pore volume having a pore diameter of 3nm or more and less than 5nm may occupy 10 to 20% of the total pore volume, the pore volume having a pore diameter of 5nm or more and less than 15nm may occupy 30 to 50% of the total pore volume, the pore volume having a pore diameter of 15nm or more and less than 30nm may occupy 0.1 to 2% of the total pore volume, and the pore volume having a pore diameter of 30nm or more may occupy 0 to 1% of the total pore volume.
In a second aspect, the present invention provides a process for preparing the catalyst according to the first aspect of the invention, the process comprising: (1) Mixing the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, pseudo-boehmite and a peptizing agent, molding, and then performing first drying and first roasting to obtain a carrier; (2) Carrying out steam treatment on the carrier to obtain a carrier after steam treatment; (3) And (4) impregnating the carrier subjected to the vapor treatment in the step (2) by using a soluble zinc salt solution, drying and roasting to obtain a zinc oxide-loaded carrier, and (4) impregnating the zinc oxide-loaded carrier in the step (3) by using a solution containing a first metal salt and a second metal salt, and then drying and roasting.
The invention adopts pseudo-boehmite as a binder for carrier molding, and in a specific implementation mode, the specific surface area of the pseudo-boehmite can be 250-320 m 2 Per gram, the pore volume can be 0.3-0.5 mL/g; in the pseudo-boehmite, the pore volume with the pore diameter of less than 3nm can occupy 0-10% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm can occupy 5-25% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm can occupy 60-90% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm can occupy 0.1-5% of the total pore volume, and the pore volume with the pore diameter of more than 30nm can occupy 0.1-4% of the total pore volume.
In one embodiment, the peptizing agent in step (1) may be an aqueous solution of an inorganic acid, and the inorganic acid may 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%, and preferably may be 3 to 5 mass%. In one embodiment, 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 0.4 to 0.9mL/g.
In one embodiment according to the present invention, the temperature of the first drying of step (1) is 100 to 180 ℃, preferably may be 110 to 150 ℃, and the time may be 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.
In one embodiment according to the invention, the temperature of the steam treatment of step (2) may be 400 to 500 ℃, preferably 420 to 480 ℃, for a period of time of 2 to 8 hours, preferably 2 to 6 hours. The support after the water vapor treatment is preferably dried, and the drying temperature may be 110 to 150 ℃ and the time may be 1 to 12 hours.
The invention is not limited to the kind and solute content of the soluble zinc salt solution in the step (3), and in one embodiment, the soluble zinc salt solution may be one or more of a nitrate solution, an acetate solution, a sulfate solution, a chloride solution, a gluconate solution and a citrate solution containing zinc element, and preferably may be one or more of a nitrate solution, a sulfate solution, a chloride solution and a citrate solution containing zinc element.
In one embodiment according to the present invention, the drying temperature in step (3) and step (4) may be 100 to 180 ℃, preferably 110 to 150 ℃, for 1 to 12 hours, preferably 2 to 6 hours, respectively; (3) The temperatures of the calcination in step (a) and (b) may be 350 to 500 ℃, preferably 350 to 500 ℃, and the times may be 2 to 8 hours, preferably 4 to 6 hours, respectively.
In one embodiment according to the invention, the temperature of the impregnation described in step (3) and (4) may be 15 to 40 ℃, preferably 20 to 30 ℃, respectively, and the time may be 6 to 24 hours, preferably 10 to 20 hours, respectively.
According to the present invention, the oxidation state catalyst obtained in step (4) is preferably 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.
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.
In a third aspect, the present invention provides the use of the catalyst of the first aspect of the invention in the alkylation of benzene with synthesis gas.
The invention is not limited by the reaction conditions of the benzene and synthesis gas alkylation reaction, and in one embodiment, the benzene and synthesis gas alkylation reactionThe temperature of (2) may be 250-550 ℃, preferably 400-500 ℃, the pressure may be 0.5-5 MPa, preferably 2-4 MPa, and the mass space velocity of the benzene may be 0.5-4 h -1 Preferably 1 to 3 hours -1 The benzene to CO molar ratio is preferably 1: (1-4) benzene and H 2 The molar ratio is 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, content of alumina 70% by mass) used in the following 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 pseudo-boehmite powder (SB) are fully and uniformly mixed, then 80mL of dilute nitric acid solution with a 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 carrier containing 65% by mass of HZSM-5, 5% by mass of HEU-1 and 30% by mass of gamma-alumina.
The carrier was subjected to steam treatment at 440℃for 4 hours, followed by drying at 120℃for 4 hours, to give 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 molar ratio of 70 and pseudo-thin water57.1g of alundum powder (SB) 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 for molding. Drying at 120 deg.C for 4h, and calcining at 540 deg.C for 4h in air atmosphere to obtain carrier containing 50% by mass of HZSM-5, 10% by mass of HEU-1 and 40% by mass of gamma-alumina.
The support was subjected to steam treatment at 460℃for 2 hours, followed by drying at 120℃for 4 hours, to give support b.
Preparation example 3
Preparing a carrier c.
SiO is made of 2 /Al 2 O 3 30g of hydrogen ZSM-5 molecular sieve with the molar ratio of 70 and SiO 2 /Al 2 O 3 The EU-1 molecular sieve in the hydrogen form with the molar ratio of 25, namely 20g, and 71.4g of pseudo-boehmite powder (SB) are fully and uniformly mixed, and then 100mL of dilute nitric acid solution with the concentration of 3.5 mass percent is added, kneaded and extruded into strips for molding. Drying at 120 deg.C for 4h, and calcining at 540 deg.C for 4h in air atmosphere to obtain carrier containing 30% by mass of HZSM-5, 20% by mass of HEU-1 and 50% by mass of gamma-alumina.
The carrier was subjected to steam treatment at 480℃for 6 hours, followed by drying at 120℃for 4 hours, to give 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 is dissolved in 100g of deionized water at 50 ℃, 65g of carrier a 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.
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.
0.09mol of zirconium nitrate and 0.04mol 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 then baked for 4h in an air atmosphere at 400 ℃ 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.
0.11mol of zirconium nitrate and 0.03mol 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 then baked for 4h in an air atmosphere at 400 ℃ 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 the 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. Physical properties are shown in Table 3. The zinc oxide and first metal oxide and second metal oxide contents in table 2 were measured by XRF fluorescence; 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. At a reaction temperature of 440 ℃, a reaction pressure of 3MPa and a benzene feeding mass space velocity of 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 data of the reaction results of the respective catalysts 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
From the data of application example 1 and application example 7, the catalyst a prepared in the present invention further contains EU-1 molecular sieve in the carrier, compared with the catalyst G in the prior art described in application example 7, which can improve the reactivity and the product yield.
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 provided by the invention has higher benzene conversion rate, selectivity and higher toluene and C8 aromatic hydrocarbon yields.
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 (15)

1. A benzene and synthesis gas alkylation catalyst comprising a support and an active metal oxide in the following amounts on a support basis: 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 20-80 mass percent of hydrogen type MFI structure molecular sieve, 1-60 mass percent of hydrogen type EUO structure molecular sieve and 15-60 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 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 method for preparing 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 a peptizing agent, molding, and then performing first drying and first roasting to obtain a carrier;
(2) Carrying out steam treatment on the carrier to obtain a carrier after steam treatment;
(3) Impregnating the carrier subjected to the vapor treatment in the step (2) by using a soluble zinc salt solution, drying and roasting to obtain a carrier loaded with zinc oxide,
(4) Impregnating the zinc oxide-loaded carrier in the step (3) with a solution containing a first metal salt and a second metal salt, and then drying and roasting.
2. The catalyst according to claim 1, wherein the carrier comprises 25 to 70 mass% of the hydrogen-type MFI structure molecular sieve, 1 to 30 mass% of the hydrogen-type EUO structure molecular sieve, and 20 to 60 mass% of the alumina.
3. The catalyst 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 catalyst according to claim 1, wherein the active metal oxide content is as follows, based on the support: 15 to 28 mass% of zinc oxide, 10 to 26 mass% of a first metal oxide, and 7 to 26 mass% of a second metal oxide.
5. The catalyst according to claim 1, wherein the first metal oxide is selected from oxides of Cr or Zr and the second metal oxide is selected from one of oxides of La, ce and Cu.
6. Root of Chinese characterThe catalyst according to claim 1, wherein the specific surface area of the catalyst is 250 to 340m 2 And/g, the total pore volume is 0.1-0.5 mL/g.
7. The catalyst according to claim 1, wherein in the catalyst, a pore volume having a pore diameter of less than 3nm is 30 to 60% of a total pore volume, a pore volume having a pore diameter of 3nm or more and less than 5nm is 5 to 20% of a total pore volume, a pore volume having a pore diameter of 5nm or more and less than 15nm is 20 to 50% of a total pore volume, a pore volume having a pore diameter of 15nm or more and less than 30nm is 0 to 5% of a total pore volume, and a pore volume having a pore diameter of 30nm or more is 0 to 5% of a total pore volume.
8. The catalyst according to claim 7, wherein in the catalyst, a pore volume having a pore diameter of less than 3nm is 30 to 50% of the total pore volume, a pore volume having a pore diameter of 3nm or more and less than 5nm is 10 to 20% of the total pore volume, a pore volume having a pore diameter of 5nm or more and less than 15nm is 30 to 50% of the total pore volume, a pore volume having a pore diameter of 15nm or more and less than 30nm is 0.1 to 2% of the total pore volume, and a pore volume having a pore diameter of 30nm or more is 0 to 1% of the total pore volume.
9. The catalyst according to claim 1, wherein in the step (1), the specific surface area of the pseudo-boehmite is 250 to 320m 2 Per gram, the pore volume is 0.3-0.5 mL/g; wherein the pore volume with the pore diameter of less than 3nm accounts for 0-10% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 5-25% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 60-90% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 0.1-5% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 0.1-4% of the total pore volume.
10. The catalyst according to claim 1, wherein in the step (1), the peptizing agent is an aqueous solution of an inorganic acid selected from one or more of nitric acid, phosphoric acid and boric acid; the content of the inorganic acid in the peptizing agent is 2 to 6 mass percent; 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 0.4-0.9 mL/g.
11. The catalyst according to claim 1, wherein in step (1), the temperature of the first drying is 100 to 180 ℃ for 1 to 12 hours; the temperature of the first roasting is 520-600 ℃ and the time is 1-10 h.
12. The catalyst according to claim 1, wherein in the step (2), the temperature of the water vapor treatment is 400 to 500 ℃ for 2 to 8 hours.
13. The catalyst according to claim 1, wherein in the steps (3) and (4), the drying temperature is 100 to 180 ℃ for 1 to 12 hours; the roasting temperature is 350-500 ℃ and the roasting time is 2-8 h.
14. The catalyst according to claim 1, wherein in step (4), 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.
15. Use of the catalyst of claim 1 in alkylation of benzene with synthesis gas at a temperature of 250-550 ℃ and a pressure of 0.5-5 MPa, the mass space velocity of benzene being 0.5-4 h -1 The molar ratio of benzene to CO is 1: (1-4) benzene and H 2 The molar ratio of (2) is 1: (2-8).
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101898145A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof
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
CN102671696A (en) * 2011-03-17 2012-09-19 中国石油化工股份有限公司 Composite zeolite catalyst containing modified NU-85 zeolite and preparation method
CN104549465A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4939947B2 (en) * 2003-12-30 2012-05-30 ユーオーピー エルエルシー Method and catalyst for isomerization of C8 alkyl aromatics
US7939701B2 (en) * 2007-12-12 2011-05-10 Uop Llc Aromatic isomerization catalyst and a process of use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101898145A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof
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
CN102671696A (en) * 2011-03-17 2012-09-19 中国石油化工股份有限公司 Composite zeolite catalyst containing modified NU-85 zeolite and preparation method
CN104549465A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst
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

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