CN114433217A - Benzene and synthesis gas alkylation catalyst, preparation method and application thereof - Google Patents

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

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Publication number
CN114433217A
CN114433217A CN202011193807.3A CN202011193807A CN114433217A CN 114433217 A CN114433217 A CN 114433217A CN 202011193807 A CN202011193807 A CN 202011193807A CN 114433217 A CN114433217 A CN 114433217A
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pore volume
catalyst
mass
accounts
molecular sieve
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CN114433217B (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
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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
    • B01J29/80—Mixtures of different zeolites
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615—100-500 m2/g
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    • B01J35/695—Pore distribution polymodal
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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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
    • B01J29/405—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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    • B01J29/40—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
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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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    • B01J29/00—Catalysts comprising molecular sieves
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    • 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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    • B01J29/70—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
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    • 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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    • 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
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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, optimizes the pore structure and acid distribution of the catalyst, has the advantages of high catalytic activity and good selectivity, increases the specific surface area and pore volume of the catalyst by adopting macroporous alumina as a binder, improves the mass transfer and heat transfer effects of the catalyst, improves the conversion rate of benzene and the selectivity and yield of toluene and C8 aromatic hydrocarbon, has simple preparation method, sufficient raw material sources and low cost, is easy to operate, and is suitable for large-scale industrial application.

Description

Benzene and synthetic gas alkylation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of alkylation of benzene and synthesis gas, in particular to a benzene and synthesis gas alkylation catalyst and a preparation method and application thereof.
Background
Benzene, toluene and xylene (BTX) among aromatic hydrocarbons are important basic chemical raw materials. Toluene and xylene, especially p-xylene, derivatives of which are widely used in chemical products such as polyesters, petrochemicals, plastics and rubbers. With the rapid development of the industries such as ethylene, reforming, coal chemical industry and the like in China in recent years, the yield of domestic pure benzene is gradually increased; on the other hand, the environmental protection standard of China is increasingly strict and the standards of gasoline and diesel oil are continuously improved, the benzene content in the gasoline is reduced from 1 percent of the national V standard to 0.8 percent of the national VI standard, and the benzene is difficult to be used as a blending component of the gasoline.
China is a country with more coal and less oil, the coal reserves are huge, the price is low, and the development of the coal chemical industry has attracted wide attention in recent years. The synthesis gas is one of main products of coal chemical industry, can be obtained through a coal gasification process, and is relatively rich in resources. Therefore, on the one hand, the synthesis gas with low price is used as the raw material; on the other hand, the application of pure benzene is enlarged, the yield of toluene and xylene with higher economic value is increased, and a new route for preparing aromatic hydrocarbon is developed, so that the significance is great.
The current commercial route for methanol alkylation is syngas → methanol → aromatics. The synthetic gas alkylation reaction can directly skip the intermediate methanol synthesis process and directly go from synthetic gas → aromatic hydrocarbon, so the synthetic gas alkylation reaction can not only save the step of preparing methanol by synthetic gas, but also shorten the whole process and save the whole investment. But the activities of hydrogen and carbon monoxide are low relative to the high activity of methanol, and thus much research is still required.
CN110116022A is a preparation method of a bifunctional composite catalyst for preparing light aromatic hydrocarbon by one-step method of benzene and synthesis gas. The composite catalyst consists of an acidic molecular sieve and a metal oxide, wherein the acidic molecular sieve adopts HZSM-5, and the metal oxide is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, In, W and Re. The coprecipitated metal oxide and the molecular sieve are mixed by a ball milling method, and the obtained composite catalyst can convert benzene into toluene and xylene.
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 dual function catalyst comprising complex oxides of copper, zinc and aluminium or chromium and an aluminosilicate.
Seulah Lee et al, in An in situ catalysis of cellulose using over biofunctional mix of Cr2O3The results of the reaction of toluene with synthesis gas to produce C8 aromatics are described in the article/ZnO and HZSM-5. The article uses mechanical mixing of a Zn-Cr metal oxide mixture with HZSM-5 to make the catalyst. Under the conditions of 400 ℃ and 3MPa, the conversion rate of toluene reaches 41.2 percent, the selectivity of xylene reaches 60 percent, but the byproduct C9+ aromatic hydrocarbon reaches 15 percent, and simultaneously 10 percent of benzene is also produced.
The above patents all employ metal coprecipitation followed by blending with molecular sieves to prepare the catalyst. However, the catalyst prepared by the method has uneven distribution of metal and acid centers, thereby resulting in lower reaction activity and lower selectivity of light aromatics.
CN107999118A discloses an aromatics and synthesis gas alkylation catalyst, which comprises a carrier and a supported active component, wherein the carrier comprises 20-80 wt% of MFI or IMF structure hydrogen type molecular sieve and 20-80 wt% of alumina, the active component comprises a first metal and a second metal, the first metal is zinc, and the second metal is at least one selected from chromium, copper, magnesium and silver. The catalyst can be used for preparing toluene and xylene by reacting benzene and synthesis gas.
Disclosure of Invention
The invention provides a high-activity high-selectivity benzene and synthesis gas alkylation catalyst, a preparation method and application thereof, in order to fully utilize synthesis gas with low price, 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 in an amount based on the total mass of the support as follows: 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% of hydrogen type MFI structure molecular sieve, 1-60 mass% of hydrogen type EUO structure molecular sieve and 15-60 mass% of macroporous alumina;
the first metal and the second metal are respectively and independently selected from one of Cu, Ce, Cr, Zr and La;
in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 20-45% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 10-30% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 20-35% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-20% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 8-20% of the total pore volume.
Optionally, the carrier comprises 25-70 mass% of the hydrogen MFI structure molecular sieve, 1-30 mass% of the hydrogen EUO structure molecular sieve and 20-60 mass% of the macroporous 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 sieve2/Al2O3The molar ratio is (20-150): 1;
the hydrogen type EUO structure molecular sieve is a hydrogen type EU-1 molecular sieve(ii) a SiO of the hydrogen type EUO structure molecular sieve2/Al2O3The molar ratio is (20-150): 1.
alternatively, the active metal oxides may be present in the following amounts, based on the support: 15 to 28 mass% of the zinc oxide, 10 to 26 mass% of the first metal oxide, and 7 to 26 mass% of the second metal oxide.
Optionally, the first metal oxide is selected from Cr or Zr oxides and the second metal oxide is selected from one of La, Ce and Cu oxides.
Optionally, the specific surface area of the catalyst is 345-450 m2The volume of the total pores is 0.6-0.9 mL/g.
Optionally, in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 30-45% 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 20-30% 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 8-15% of the total pore volume.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the invention, the process comprising:
(1) mixing and forming the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, the macroporous pseudo-boehmite and a peptizing agent, and then carrying out first drying and first roasting to obtain a carrier;
(2) carrying out water vapor treatment on the carrier to obtain a carrier subjected to the steam treatment;
(3) soaking the carrier subjected to the steam treatment in the step (2) by using a soluble zinc salt solution, and then drying and roasting to obtain a carrier loaded with zinc oxide;
(4) dipping the carrier loaded with the zinc oxide in the step (3) by using a solution containing a first metal salt and a second metal salt, and then drying and roasting;
the specific surface area of the macroporous pseudo-boehmite is 340-400 m2The pore volume is 0.70-1 mL/g; the diameter of the hole is less thanThe pore volume of 3nm accounts for 0-1% of the total pore volume, the pore volume of which the pore diameter is more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume of which the pore diameter is more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume of which the pore diameter is more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume of which the pore diameter is more than 30nm accounts for 5-15% of the total pore volume.
Optionally, (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%; the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen MFI structure molecular sieve, the hydrogen EUO structure molecular sieve and the macroporous 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 steam 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 350-600 ℃, and the roasting time is 2-8 h.
Optionally, in the 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.
The third aspect of the invention provides an application of the catalyst in the first aspect of the invention in the alkylation reaction of benzene and synthesis gas, wherein the temperature of the alkylation reaction of benzene and synthesis gas is 250-550 ℃, the pressure is 0.5-5 MPa, and the mass space velocity of benzene is 0.5-4 h-1The molar ratio of benzene to CO is preferably 1: (1-4), benzene and H2Is preferably 1: (2-8).
The catalyst carrier of the invention adopts two composite molecular sieves, optimizes the pore structure and acid distribution of the catalyst, and in addition, adopts macroporous pseudo-boehmite as a binder, increases the specific surface area and the proportion of macropores of the catalyst, improves the performance of the catalyst, and improves the conversion rate of benzene and the selectivity and yield of toluene and C8 aromatic hydrocarbon. The catalyst of the invention has simple preparation method, sufficient raw material source, 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 in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the terms "first and second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first, second" may explicitly or implicitly include one or more of that feature.
In a first aspect the present invention provides a benzene and synthesis gas alkylation catalyst comprising a support and an active metal oxide in an amount on the support of: 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% of hydrogen MFI structure molecular sieve, 1-60 mass% of hydrogen EUO structure molecular sieve and 15-60 mass% of macroporous alumina; the first metal and the second metal are respectively and independently selected from one of Cu, Ce, Cr, Zr and La; in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 20-45% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 10-30% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 20-35% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-20% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 8-20% of the total pore volume.
In order to further improve the catalytic activity and selectivity of the catalyst, in a preferred embodiment according to the present invention, the carrier may comprise 25 to 70 mass% of the hydrogen MFI structure molecular sieve, 1 to 30 mass% of the hydrogen EUO structure molecular sieve, and 20 to 60 mass% of the macroporous alumina, based on the total mass of the carrier.
According to the invention, the hydrogen-type MFI structure molecular sieve used in the preparation of the catalyst carrier can be selected from hydrogen-type ZSM-5 molecular sieves; the hydrogen EUO structural molecular sieve can be selected from hydrogen EU-1 molecular sieves. In one specific embodiment, the SiO of the molecular sieve with hydrogen type EUO structure2/Al2O3The molar ratio can be (20-150): 1, preferably (25-75): 1; SiO of the hydrogen type MFI structure molecular sieve2/Al2O3The molar ratio can be (20-150): 1, preferably (25-100): 1.
in a preferred embodiment according to the present disclosure, the active metal oxide may comprise, on a support basis: 15 to 28 mass% of the zinc oxide, 10 to 26 mass% of the first metal oxide, and 7 to 26 mass% of the second metal oxide.
In a preferred embodiment, the first metal oxide is selected from the group consisting of oxides of Cr or Zr, and the second metal oxide is selected from one of the oxides of La, Ce and Cu.
In one embodiment of the present invention, the specific surface area of the catalyst may be 345 to 450m2The total pore volume can be 0.6-0.9 mL/g; preferably, the specific surface area of the catalyst can be 348-390 m2The total pore volume can be 0.6-0.8 mL/g.
In a preferred embodiment of the present invention, in the catalyst, the pore volume having a pore diameter of less than 3nm accounts for 30 to 45% of the total pore volume, the pore volume having a pore diameter of 3nm or more and less than 5nm accounts for 10 to 20% of the total pore volume, the pore volume having a pore diameter of 5nm or more and less than 15nm accounts for 20 to 30% of the total pore volume, the pore volume having a pore diameter of 15nm or more and less than 30nm accounts for 8 to 15% of the total pore volume, and the pore volume having a pore diameter of 30nm or more accounts for 8 to 15% of the total pore volume.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the invention, the process comprising: (1) mixing and forming the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, the macroporous pseudo-boehmite and a peptizing agent, and then carrying out first drying and first roasting to obtain a carrier; (2) carrying out water vapor treatment on the carrier to obtain a carrier subjected to the steam treatment; (3) soaking the carrier subjected to the steam treatment in the step (2) by using a soluble zinc salt solution, and then drying and roasting to obtain a carrier loaded with zinc oxide; (4) dipping the carrier loaded with the zinc oxide in the step (3) by using a solution containing a first metal salt and a second metal salt, and then drying and roasting; the specific surface area of the macroporous pseudo-boehmite is 340-400 m2The pore volume is 0.70-1 mL/g; the pore volume of pores with the diameter of less than 3nm accounts for 0-1% of the total pore volume, the pore volume of pores with the diameter of more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume of pores with the diameter of more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume of pores with the diameter of more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume of pores with the 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, in the macroporous pseudoboehmite, the pore volume with a pore diameter of less than 3nm may account for 0 to 1% of the total pore volume, the pore volume with a pore diameter of more than 3nm and less than 5nm may account for 40 to 60% 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 35% of the total pore volume, the pore volume with a pore diameter of more than 15nm and less than 30nm may account for 8 to 15% of the total pore volume, and the pore volume with a pore diameter of more than 30nm may account for 5 to 10% of the total pore volume. The macroporous pseudo-boehmite is converted into the macroporous alumina in the carrier by roasting.
The invention has no limitation on the type and solute content of the peptizing agent, and in one embodiment, the peptizing agent in the step (1) 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% by mass, and preferably 3 to 5% by mass. In one embodiment, the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen MFI structure molecular sieve, the hydrogen EUO structure molecular sieve and the macroporous pseudo-boehmite can be 0.4-0.9 mL/g.
In one embodiment of the present invention, the temperature of the first drying in step (1) is 100 to 180 ℃, preferably 110 to 150 ℃, and the time is 1 to 12 hours, preferably 4 to 6 hours; the temperature of the first roasting is 520-600 ℃, preferably 540-580 ℃, and the time is 1-10 hours, preferably 4-6 hours.
In one embodiment of the present invention, the temperature of the steam treatment in step (2) is 400 to 500 ℃, preferably 420 to 480 ℃, and the time is 2 to 8 hours, preferably 2 to 6 hours. The carrier after the water vapor treatment is preferably dried, the drying temperature can be 110-150 ℃, and the drying time can be 1-12 hours.
The invention has no limitation on the type and solute content of the soluble zinc salt solution in 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 a zinc element, and preferably may be one or more of a nitrate solution, a sulfate solution, a chloride solution and a citrate solution containing a zinc element.
In one embodiment of the present invention, the drying temperature in the steps (3) and (4) may be 100 to 180 ℃, preferably 110 to 150 ℃, and the drying time may be 1 to 12 hours, preferably 4 to 6 hours; the roasting temperature can be 350-500 ℃, preferably 350-500 ℃, and the time can be 2-8 h, preferably 4-6 h.
In one embodiment of the present invention, the temperature of the impregnation in steps (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, preferably, the 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 comprise 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 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 invention provides the use of a catalyst according to the first aspect of the invention in the alkylation of benzene with synthesis gas.
The reaction conditions of the alkylation reaction of benzene and synthesis gas are not limited, in one embodiment, the temperature of the alkylation reaction can be 250-550 ℃, preferably 400-500 ℃, the pressure can be 0.5-5 MPa, preferably 2-4 MPa, and the mass space velocity of the benzene can be 0.5-4 h-1Preferably 1 to 3 hours-1The molar ratio of benzene to CO is preferably 1: (1-4), benzene and H2Is preferably 1: (2-8).
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The hydrogen type ZSM-5 molecular sieve used below was purchased from China Petroleum rectification petrochemical company, and the hydrogen type EU-1 molecular sieve was purchased from China petrochemical Long-ridge catalyst division.
The physical property data of the pseudo-boehmite powder (brand SB, produced by Condea, Germany, alumina content 70 mass%) and the macroporous pseudo-boehmite powder (brand HY-78, produced by Petroleum Fushun petrochemical company, China, alumina content 70 mass%) used are shown in Table 1.
TABLE 1
Figure BDA0002753446740000091
Preparation example 1
Preparing a carrier a.
Mixing SiO2/Al2O3Hydrogen type ZSM-5 molecular sieve 65g, SiO with molar ratio of 272/Al2O35g of hydrogen type EU-1 molecular sieve with the molar ratio of 35 and 42.9g of macroporous pseudo-thin water aluminum powder (HY-78) are fully and uniformly mixed, then 50mL of dilute nitric acid 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 in air atmosphere for 4h to obtain a carrier containing 65 wt% HZSM-5, 5 wt% HEU-1, and 30 wt% macroporous gamma-alumina.
The above carrier was subjected to steam treatment at 440 ℃ for 4h, followed by drying at 120 ℃ for 4h, to obtain carrier a.
Preparation example 2
Preparing a carrier b.
Mixing SiO2/Al2O3Hydrogen type ZSM-5 molecular sieve 50g, SiO with molar ratio of 382/Al2O310g of hydrogen type EU-1 molecular sieve with the molar ratio of 70 and 57.1g of macroporous pseudo-thin water aluminum powder (HY-78) are fully and uniformly mixed, and then 90mL of dilute nitric acid with the concentration of 3.5 mass percent is added for kneading and extrusion molding. Drying at 120 deg.C for 4h, and calcining at 540 deg.C in air atmosphere for 4h to obtain a carrier containing 50 wt% HZSM-5, 10 wt% HEU-1, and 40 wt% macroporous gamma-alumina.
The above carrier was subjected to steam treatment at 460 ℃ for 2h, followed by drying at 120 ℃ for 4h to obtain carrier b.
Preparation example 3
Preparing a carrier c.
Mixing SiO2/Al2O3Hydrogen type ZSM-5 molecular sieve 30g, SiO with molar ratio of 702/Al2O320g of hydrogen type EU-1 molecular sieve with the molar ratio of 25 and 71.4g of macroporous pseudo-thin water aluminum powder (HY-78) are fully and uniformly mixed, and then 100mL of dilute nitric acid with the concentration of 3.5 mass percent is added for kneading and extrusion molding. Drying at 120 deg.C for 4 hr with airRoasting at 540 ℃ in an atmosphere for 4h to obtain the carrier, wherein the carrier contains 30 mass percent of HZSM-5, 20 mass percent of HEU-1 and 50 mass percent of macroporous gamma-alumina.
The above carrier was subjected to steam treatment at 480 ℃ for 6h, followed by drying at 120 ℃ for 4h to obtain carrier c.
Preparation example 4
Preparing a carrier d.
Mixing SiO2/Al2O3Hydrogen type ZSM-5 molecular sieve 65g, SiO with molar ratio of 272/Al2O35g of hydrogen type EU-1 molecular sieve with the molar ratio of 35 and 42.9g of pseudo-boehmite powder (SB) are fully and uniformly mixed, and then 50mL of dilute nitric acid solution with the concentration of 3.5 mass percent is added for kneading and extrusion molding. Drying at 120 deg.C for 4h, and calcining at 540 deg.C in air atmosphere for 4h to obtain a carrier containing 65 wt% of HZSM-5, 5 wt% of HEU-1, and 30 wt% of gamma-alumina.
The above carrier was subjected to steam treatment at 440 ℃ for 4h, followed by drying at 120 ℃ for 4h to obtain carrier d.
Example 1
0.23mol of zinc nitrate is dissolved in 105 g of deionized water with the temperature of 50 ℃, 70g of carrier a is put into the zinc nitrate solution, the carrier a is soaked for 18h at the temperature of 25 ℃, dried for 2h at the temperature of 120 ℃, and then roasted for 4h at the temperature of 400 ℃ in the air atmosphere, and the carrier loaded with zinc oxide is obtained.
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 the zinc oxide into the solution, soaking the carrier at 25 ℃ for 18h, drying the carrier at 120 ℃ for 2h, and roasting the carrier 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 put into the zinc nitrate solution, and is soaked for 18h at 25 ℃, dried for 2h at 120 ℃, and then roasted for 4h at 400 ℃ in the air atmosphere, thus obtaining the carrier loaded with zinc oxide.
Dissolving 0.099mol of zirconium nitrate and 0.049mol of cerium nitrate in 100g of deionized water at 50 ℃, adding the carrier loaded with zinc oxide, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ in an air atmosphere for 4h to obtain the catalyst B.
Example 3
0.13mol of zinc nitrate is dissolved in 90 g of deionized water with the temperature of 50 ℃, then 60g of carrier a is put into the zinc nitrate solution, dipped for 18h at the temperature of 25 ℃, dried for 2h at the temperature of 120 ℃, and roasted for 4h at the temperature of 400 ℃ in the air atmosphere, thus obtaining 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 the zinc oxide into the solution, soaking the carrier at 25 ℃ for 18h, drying the carrier at 120 ℃ for 2h, and roasting the carrier 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 put into the zinc nitrate solution, dipped at 25 ℃ for 18h, dried at 120 ℃ for 2h, and then roasted at 400 ℃ for 4h in the air atmosphere 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 the zinc oxide into the solution, soaking the carrier at 25 ℃ for 18h, drying the carrier at 120 ℃ for 2h, and roasting the carrier at 400 ℃ in an air atmosphere for 4h to obtain a catalyst D.
Example 5
0.15mol of zinc nitrate is dissolved in 100g of deionized water with the temperature of 50 ℃, 65g of carrier c is put into the zinc nitrate solution, dipped for 18h at the temperature of 25 ℃, dried for 2h at the temperature of 120 ℃, and roasted for 4h at the temperature of 400 ℃ in the air atmosphere, thus obtaining 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 the zinc oxide into the solution, soaking the carrier at 25 ℃ for 18h, drying the carrier at 120 ℃ for 2h, and roasting the carrier at 400 ℃ for 4h in an air atmosphere to obtain the catalyst E.
Example 6
Dissolving 0.179mol of zinc nitrate in 100g of deionized water at 50 ℃, then putting 65g of the carrier a into the zinc nitrate solution, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ in an air atmosphere for 4h to obtain the zinc oxide-loaded carrier.
0.16mol of chromium nitrate and 0.049mol of cerium nitrate are dissolved in 100g of deionized water at 50 ℃, the carrier loaded with the zinc oxide is put into the solution to be soaked for 18h, the solution is dried for 2h at 120 ℃, and then the solution is roasted for 4h at 400 ℃ in the air atmosphere to obtain the catalyst F.
Comparative example 1
Dissolving 0.179mol of zinc nitrate in 100g of deionized water at 50 ℃, then putting 65g of carrier d into the zinc nitrate solution, soaking at 25 ℃ for 18h, drying at 120 ℃ for 2h, and roasting at 400 ℃ in air atmosphere for 4h to obtain the zinc oxide-loaded carrier.
Dissolving 0.099mol of zirconium nitrate and 0.049mol of cerium nitrate in 100G of deionized water at 50 ℃, putting the carrier loaded with the zinc oxide into the solution to be soaked for 18 hours, drying the carrier at 120 ℃ for 2 hours, and roasting the carrier at 400 ℃ in an air atmosphere for 4 hours to obtain the catalyst G.
Comparative example 2
The catalyst was prepared according to the method disclosed in CN107999118A of example 3 by mixing 60g of silica/alumina in a molar ratio of 25: 1 HZSM-5 and 57.1g of pseudo-boehmite powder (SB) are mixed uniformly, 80mL of dilute nitric acid solution with the concentration of 3.5 mass% is added, the mixture is kneaded and then extruded into strips for forming, the strips are dried at 120 ℃ for 4h, and the strips are roasted at 540 ℃ for 4h in air atmosphere to obtain a carrier e, wherein the carrier e contains 60 mass% of HZSM-5 and 40 mass% of gamma-alumina.
0.89mol of zinc nitrate and 0.38mol of chromium nitrate are dissolved in 200g of deionized water, and the solution is prepared by stirring the solution continuously until the zinc nitrate and the chromium nitrate are completely dissolved. And then 100g of the carrier e is put into the solution, impregnated for 12h, dried at 120 ℃ for 2h, and then roasted at 400 ℃ for 4h in an air atmosphere to obtain the carrier loaded with zinc and chromium.
Dissolving 0.01mol of lanthanum nitrate in 200g of deionized water, and continuously stirring until the lanthanum nitrate is completely dissolved to obtain a lanthanum nitrate solution. And (2) putting the carrier loaded with the zinc and the chromium into a lanthanum nitrate solution, soaking for 12H, drying for 2H at 120 ℃, and then roasting for 2H at 600 ℃ in an air atmosphere to obtain a catalyst H.
The compositions of the catalysts prepared in examples 1-6 and comparative examples 1-2 are shown in Table 2, wherein the active metal oxide content is based on the support. The physical property data are shown in Table 3. The contents of zinc oxide and the first and second metal oxides in table 2 were measured by XRF fluorescence; the specific surface area, the total pore volume and the 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
Figure BDA0002753446740000141
TABLE 3
Figure BDA0002753446740000151
Application examples 1 to 8
The alkylation of benzene with synthesis gas was carried out in a small fixed bed high pressure reactor. The catalyst was first heated to the reaction temperature in a hydrogen atmosphere. At the reaction temperature of 440 ℃, the reaction pressure of 3MPa and the benzene feeding mass space velocity of 1.5h-1And the molar ratio of benzene to CO is 1: 2. benzene and H2The molar ratio is 1: 4 under the condition of the reaction vessel. The product was analyzed by gas chromatography, and the data of the reaction results of the catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 4. The calculation method of each data in table 4 is as follows:
Figure BDA0002753446740000152
Figure BDA0002753446740000153
Figure BDA0002753446740000154
total yield of toluene and C8 aromatics
Benzene conversion × (toluene selectivity + C8 aromatics selectivity) × 100%
TABLE 4
Figure BDA0002753446740000161
From the data results of application examples 2 and 7, the EU-1 molecular sieve is added into the carrier, and the catalyst prepared by loading the active metal component by using the macroporous pseudo-boehmite as the binder has higher total yield of toluene and C8 aromatic hydrocarbon when benzene and synthesis gas alkylation reaction is carried out.
From the data of application examples 1 and 8, catalyst a prepared by the present invention has higher benzene conversion, selectivity and total yield of toluene and C8 aromatics compared to catalyst H of the prior art.
From the comparison of the data of application examples 1-6 and application examples 7-8, it can be seen that the benzene and syngas alkylation catalyst provided by the present invention has higher selectivity and yield for toluene and C8 aromatics.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (14)

1. A benzene and synthesis gas alkylation catalyst comprising a support and an active metal oxide in an amount on the support of: 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% of hydrogen type MFI structure molecular sieve, 1-60 mass% of hydrogen type EUO structure molecular sieve and 15-60 mass% of macroporous alumina;
the first metal and the second metal are respectively and independently selected from one of Cu, Ce, Cr, Zr and La;
in the catalyst, the pore volume with the pore diameter of less than 3nm accounts for 20-45% of the total pore volume, the pore volume with the pore diameter of more than 3nm and less than 5nm accounts for 10-30% of the total pore volume, the pore volume with the pore diameter of more than 5nm and less than 15nm accounts for 20-35% of the total pore volume, the pore volume with the pore diameter of more than 15nm and less than 30nm accounts for 8-20% of the total pore volume, and the pore volume with the pore diameter of more than 30nm accounts for 8-20% of the total pore volume.
2. The catalyst according to claim 1, wherein the carrier comprises 25 to 70 mass% of the hydrogen MFI structure molecular sieve, 1 to 30 mass% of the hydrogen EUO structure molecular sieve and 20 to 60 mass% of the macroporous alumina.
3. The catalyst of claim 1, wherein the hydrogen-form MFI structure molecular sieve is a hydrogen-form ZSM-5 molecular sieve; SiO of the hydrogen type MFI structure molecular sieve2/Al2O3The molar ratio is (20-150): 1;
the hydrogen type EUO structure molecular sieve is a hydrogen type EU-1 molecular sieve; SiO of the hydrogen type EUO structure molecular sieve2/Al2O3The molar ratio is (20-150): 1.
4. the catalyst of claim 1, wherein the active metal oxides are present in the following amounts, based on the support: 15 to 28 mass% of the zinc oxide, 10 to 26 mass% of the first metal oxide, and 7 to 26 mass% of the second metal oxide.
5. The catalyst of claim 1, wherein the first metal oxide is selected from the oxides of Cr or Zr and the second metal oxide is selected from one of the oxides of La, Ce and Cu.
6. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 345 to 450m2The total pore volume is 0.6-0.9 mL/g.
7. The catalyst according to claim 1, wherein in the catalyst, a pore volume having a pore diameter of less than 3nm accounts for 30 to 45% of the total pore volume, a pore volume having a pore diameter of 3nm or more and less than 5nm accounts for 10 to 20% of the total pore volume, a pore volume having a pore diameter of 5nm or more and less than 15nm accounts for 20 to 30% of the total pore volume, a pore volume having a pore diameter of 15nm or more and less than 30nm accounts for 8 to 15% of the total pore volume, and a pore volume having a pore diameter of 30nm or more accounts for 8 to 15% of the total pore volume.
8. A method of making the catalyst of claim 1, the method comprising:
(1) mixing and forming the hydrogen type MFI structure molecular sieve, the hydrogen type EUO structure molecular sieve, the macroporous pseudo-boehmite and a peptizing agent, and then carrying out first drying and first roasting to obtain a carrier;
(2) carrying out water vapor treatment on the carrier to obtain a carrier subjected to the steam treatment;
(3) soaking the carrier subjected to the steam treatment in the step (2) by using a soluble zinc salt solution, and then drying and roasting to obtain a carrier loaded with zinc oxide;
(4) dipping the carrier loaded with the zinc oxide in the step (3) by using a solution containing a first metal salt and a second metal salt, and then drying and roasting;
the specific surface area of the macroporous pseudo-boehmite is 340-400 m2The pore volume is 0.70-1 mL/g; the pore volume of pores with the diameter of less than 3nm accounts for 0-1% of the total pore volume, the pore volume of pores with the diameter of more than 3nm and less than 5nm accounts for 40-70% of the total pore volume, the pore volume of pores with the diameter of more than 5nm and less than 15nm accounts for 15-40% of the total pore volume, the pore volume of pores with the diameter of more than 15nm and less than 30nm accounts for 8-15% of the total pore volume, and the pore volume of pores with the diameter of more than 30nm accounts for 5-15% of the total pore volume.
9. The method according to claim 8, 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%; the liquid/solid ratio of the peptizing agent to the total mass of the hydrogen MFI structure molecular sieve, the hydrogen EUO structure molecular sieve and the macroporous pseudo-boehmite is 0.4-0.9 mL/g.
10. The method according to claim 8, wherein 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.
11. The method according to claim 8, wherein in the step (2), the temperature of the steam treatment is 400-500 ℃ and the time is 2-8 h.
12. The method according to claim 8, wherein in the steps (3) and (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.
13. The method according to claim 8, wherein in the 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.
14. The use of the catalyst of claim 1 in benzene and synthesis gas alkylation reactions at a temperature of 250-550 ℃, a pressure of 0.5-5 MPa, and a mass space velocity of benzene of 0.5-4 h-1The molar ratio of benzene to CO is 1: (1-4), benzene and H2In a molar ratio of1：(2～8)。
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