CN112295590B - Composite metal modified hierarchical pore molecular sieve catalyst and preparation method and application thereof - Google Patents

Composite metal modified hierarchical pore molecular sieve catalyst and preparation method and application thereof Download PDF

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CN112295590B
CN112295590B CN201910711283.3A CN201910711283A CN112295590B CN 112295590 B CN112295590 B CN 112295590B CN 201910711283 A CN201910711283 A CN 201910711283A CN 112295590 B CN112295590 B CN 112295590B
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aluminum
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CN112295590A (en
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荆开石
高学顺
张金强
姜晓锋
张晓露
张宏科
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Wanhua Chemical Group Co Ltd
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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
    • 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
    • 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
    • B01J29/48—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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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a composite metal modified hierarchical pore molecular sieve catalyst and a preparation method thereof, wherein the composite metal modified hierarchical pore molecular sieve catalyst comprises the following components in percentage by mass: metal oxide a: 1-10%, metal oxide b: 1-10% (all by metal simple substance), and the balance of hierarchical pore HZSM-5 molecular sieve, wherein the pore size distribution of the catalyst is as follows: micropores are less than 2nm, mesopores are 2-10 nm, and the pore volume of the micropores is as follows: and (2.5-1) mesoporous volume: 1. the catalyst is a composite metal modified hierarchical pore molecular sieve synthesized by an in-situ one-step method, and has the characteristics of high catalytic activity, good olefin selectivity and long reaction stability in the reaction of preparing low-carbon olefin from halogenated methane. The method for preparing the catalyst is low in price, green and environment-friendly, and has a good industrial application prospect.

Description

Composite metal modified hierarchical pore molecular sieve catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of environment-friendly catalytic materials, and relates to a composite metal modified hierarchical pore molecular sieve catalyst for reaction of preparing low-carbon olefin from methyl halide and a preparation method thereof.
Background
Lower olefins (ethylene, propylene and butylene) are important feedstocks for the production of various chemicals. With the rapid development of modern industries in recent years, the demand of low carbon olefins is rapidly increasing. The traditional method for producing the low-carbon olefins utilizes a petroleum route to produce the low-carbon olefins, and mainly relies on steam cracking of naphtha, but the yield of ethylene and propylene produced by the route is low. With the shortage of global petroleum resources, the seeking of non-petroleum routes for preparing low-carbon olefins has very important strategic significance. The process for preparing the low-carbon olefin by converting methane into methyl halide by taking natural gas (methane) as a raw material has the advantages of simple process, mild conditions, no need of using synthesis gas to greatly reduce energy consumption and the like, gradually becomes a research hotspot, and has good development prospect.
Olah et al [ J.Am.chem.Soc,1985,107: 7097-.]A three-step process for the preparation of hydrocarbon products via methyl chloride using methane is reported. The methane is catalytically converted on a solid acid catalyst to generate the methane chloride, and the methane chloride is modified by gamma-Al 2 O 3 Further converting into methanol, and finally converting the methanol into hydrocarbon products. Taylor et al (U.S. Pat. No. 4,4652688, 1988)]A two-step process for the synthesis of gasoline products from methane via methane chloride is disclosed. In Cu-K-La/Al 2 O 3 The methane is subjected to oxychlorination reaction and converted into methane chloride, the methane chloride is converted into a gasoline product on ZSM-5, and the products in the work are mainly alkane and aromatic hydrocarbon.
Process for preparing olefins by using molecular sieves to catalyze halogenated methanes due to HZSM-5 molecular sieve surface
Figure BDA0002153834210000021
In the presence of acid, the initial product of low-carbon olefin can further generate secondary reactions such as hydrogen transfer, aromatization and the like to generate alkane and aromatic hydrocarbon, so that the selectivity of the low-carbon olefin is reduced; the microporous structure of the HZSM-5 molecular sieve is not beneficial to the diffusion of macromolecular species, so that carbon deposition is caused to deposit in a catalyst pore channel, and the service life of the catalyst is influenced.
In the current research, the inventors mostly adopt the acid treatment dealuminization or alkali treatment desilication mode to form mesopores, but the micropore structure of the molecular sieve is damaged; and the single or composite metal is adopted to load the modified microporous HZSM-5 molecular sieve, although the product selectivity is improved, the reaction stability is poor. Therefore, it is necessary to develop a new molecular sieve catalyst, which has a micro-mesoporous composite pore channel structure, can enhance the mass transfer of carbon deposition, prolong the service life of the catalyst, and can improve the conversion rate of methyl halide and the selectivity of low-carbon olefin.
Disclosure of Invention
The invention aims to provide a composite metal modified hierarchical pore molecular sieve catalyst and application of the catalyst in the reaction of preparing low-carbon olefin from methyl halide.
The invention also aims to provide the preparation method of the composite metal modified hierarchical pore molecular sieve catalyst, which adopts an in-situ one-step method to synthesize the composite metal modified hierarchical pore molecular sieve catalyst, and has simple preparation process and low price.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the composite metal modified hierarchical pore molecular sieve catalyst comprises the following components in percentage by mass: metal oxide a: 1-10%, metal oxide b: 1-10% (all by metal simple substance), and the balance of a hierarchical pore HZSM-5 molecular sieve, preferably, the pore size distribution of the catalyst is as follows: the pore diameter of the micropores is less than 2nm, the pore diameter of the mesopores is 2-10 nm, and the pore volume of the micropores is as follows: and (2.5-1) mesoporous volume: 1. carbon deposition can be generated in the reaction process, and the large molecular weight of the carbon deposition can block micropores of the molecular sieve, so that the catalyst is quickly deactivated; because the catalyst contains mesopores, the mass transfer of carbon deposition can be enhanced, thereby prolonging the service life of the catalyst.
In the catalyst, a and b are any two of calcium, magnesium, zinc, potassium, sodium, cerium, lanthanum and manganese which exist in oxide form.
A preparation method of a composite metal modified hierarchical pore molecular sieve catalyst comprises the following steps:
A. dissolving an aluminum source in water, gradually adding a template agent, preferably tetrapropylammonium hydroxide (TPAOH), and a growth inhibitor into an aluminum source aqueous solution, adding a silicon source, continuously stirring uniformly, preferably stirring for 4-8 hours to prepare a sol solution I;
B. dissolving nitrate a 'in water, adding nitrate b', and uniformly stirring to prepare a solution II;
C. adding the solution II into the sol solution I, adding linoleic acid, and performing ultrasonic dissolution at 20-50 ℃ to prepare a sol solution III;
D. pre-crystallizing the sol liquid III for 1-24 h at 60-120 ℃ under infrared radiation;
E. transferring the pre-crystallized solution III into an autoclave, and carrying out hydrothermal crystallization at 120-200 ℃ for 24-144 h; filtering, drying and calcining to obtain the catalyst.
As an embodiment, the specific preparation steps of the catalyst are as follows:
A. under magnetic stirring, dissolving a certain amount of aluminum source in distilled water, then gradually adding TPAOH and a certain amount of growth inhibitor into the mixed solution, stirring until the mixed solution is clear, slowly adding a silicon source under vigorous stirring, and continuously stirring for 4-8 hours to prepare a sol solution I;
B. dissolving a certain amount of nitrate a 'in distilled water, stirring for dissolving, adding a certain amount of nitrate b', and uniformly stirring to prepare a solution II;
C. slowly adding the solution II into the sol solution I, adding a certain amount of linoleic acid, continuously stirring for 0.5-4 h, ultrasonically dissolving for 0.5-8 h at the temperature of 20-50 ℃, and continuously stirring for 0.5-4 h to prepare a sol solution III;
D. pre-crystallizing the sol liquid III for 1-24 h at 60-120 ℃ under infrared radiation;
E. transferring the sol solution III into an autoclave, and carrying out hydrothermal crystallization at 120-200 ℃ for 24-144 h; collecting a sample through filtration, and drying at 90-150 ℃ for 5-20 h; calcining at 450-750 ℃ for 2-10 h to remove the template; tabletting and crushing the mixture into 20-30 meshes for later use.
In the preparation method of the catalyst of the present invention, in the step a, an aluminum source is used, including but not limited to the following species: one or more of aluminum sulfate, aluminum isopropoxide, aluminum acetate, aluminum chloride, aluminum nitrate and sodium metaaluminate, preferably aluminum sulfate.
In the preparation method of the catalyst of the present invention, in the step a, the growth inhibitor used includes, but is not limited to, the following species: 3-Aminopropyltriethoxysilane (APTEO), Vinyltriethoxysilane (VTES), 3-Chloropropyltriethoxysilane (CPTEO), 3-mercaptopropyltriethoxysilane (CPTES), 3-Aminopropyltrimethoxysilane (APTMO), N- (. beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane (APAMS), N-diethyl-3-aminopropyltrimethoxysilane (DPAMS), preferably VTES.
In the preparation method of the catalyst of the present invention, in the step a, the silicon source includes but is not limited to the following species: one or more of methyl silicate, ethyl silicate, propyl silicate, butyl silicate and silica sol, preferably ethyl silicate.
In the preparation method of the catalyst, in the step A, a silicon source, an aluminum source, a template agent, a growth inhibitor and H 2 The adding molar ratio of O is as follows: silicon source: an aluminum source: template agent: growth inhibitors: h 2 O＝10～100：1～10：1～10：1～5：800～2000。
In the preparation method of the catalyst, in the step B, the nitrate a 'and the nitrate B' are Ca (NO) 3 ) 2 ·4H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、KNO 3 、NaNO 3 、Ce(NO 3 ) 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O、Mn(NO 3 ) 2 Any two of them.
In the preparation method of the catalyst of the invention, in the step B, nitrate a ', nitrate B' and nitrate H 2 The adding molar ratio of the O, the linoleic acid and the production inhibitor is as follows: a' nitrate salt: a nitrate salt b': h 2 O: linoleic acid: 1-15% of growth inhibitor: 1-15: 300-1500: 1-5: 1 to 5.
In the preparation method of the catalyst, in the step C, linoleic acid is added as a dispersing complexing agent, so that the metal can be uniformly dispersed in the molecular sieve pore canal in the subsequent crystallization synthesis, and the high-efficiency activity of the catalyst is ensured.
In the preparation method of the catalyst, in the step D, the catalyst is pre-crystallized at 60-120 ℃ by using 100-1000 mu m infrared radiation, the pre-crystallization time is 1-24 h, and the temperature gradient of a precursor is reduced and the diameter uniformity and the product purity are improved by pre-crystallization treatment.
The invention also relates to the composite metal modified hierarchical pore molecular sieve catalyst prepared by the preparation method. Preferably, the composite metal modified hierarchical pore molecular sieve catalyst comprises the following components in percentage by mass: metal oxide a: 1-10%, metal oxide b: 1-10% (all by metal simple substance), and the balance of hierarchical pore HZSM-5 molecular sieve. More preferably, a and b are any two of calcium, magnesium, zinc, potassium, sodium, cerium, lanthanum and manganese in the form of oxides. Further preferably, the pore size distribution of the catalyst is: the pore diameter of the micropores is less than 2nm, the pore diameter of the mesopores is 2-10 nm, and the pore volume of the micropores is as follows: and (2.5-1) mesoporous volume: 1.
the composite metal modified hierarchical pore molecular sieve catalyst is filled in a fixed bed reaction tube, reaction raw material methyl halide is diluted by nitrogen and enters the reaction tube, the volume flow ratio of methyl halide to nitrogen is 1: 5-10, the mass space velocity of methyl halide is 0.1-3 h -1 The reaction temperature is 350-500 ℃, and the pressure is 0.1-0.5 MPa. The preparation of the low-carbon olefin from the methyl halide mainly refers to the preparation of the low-carbon olefin from methyl chloride and methyl bromide. The pressure in the present invention is absolute pressure.
The invention has the positive effects that:
(1) the catalyst of the invention modifies the acidity of the surface of the molecular sieve through the composite metal, so that the surface of the catalyst is modified
Figure BDA0002153834210000051
The acid is converted into Lewis acid which is more beneficial to generating low-carbon olefin, and the selectivity of the low-carbon olefin is improved(ii) a In the reaction of catalyzing chloromethane to prepare low-carbon olefin by the catalyst, the chloromethane conversion rate can reach more than 99%, the low-carbon olefin selectivity can reach more than 89%, and the reaction stabilization time can reach more than 200 h; in the reaction of preparing low-carbon olefin by catalyzing methyl bromide, the conversion rate of methyl bromide can reach more than 93 percent, the selectivity of the low-carbon olefin is as high as more than 83 percent, the reaction stabilization time reaches more than 170 hours, and the method has good industrial application prospect.
(2) The preparation process of the composite metal modified hierarchical pore molecular sieve catalyst synthesized by the in-situ one-step method is simple, the cost is low, the growth inhibitor is used for controlling the growth process of molecular sieve crystals, particularly, organosilane is used as the growth inhibitor to be combined with an infrared pre-crystallization and hydrothermal crystallization method to synthesize the catalyst with a microporous and mesoporous dual-pore-channel structure, so that the mass transfer capacity of the catalyst is enhanced, and the service life of the catalyst is prolonged.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the invention. Any combination of the different embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
The gas products were analyzed using an Agilent-7890B gas chromatograph. Analysis conditions were as follows: keeping the column temperature at 70 ℃ for 10 minutes, heating to 180 ℃ at 10 ℃/min, keeping for 9min, keeping the injection port temperature at 170 ℃, keeping the flow rate of the spacer purge gas at 3mL/min, and shunting and injecting samples, wherein the shunting ratio is 10: 1.
the pore volume and pore diameter are measured by N on a BELSORBII analyzer 2 And (4) carrying out physical adsorption. The analysis conditions are as follows: the samples were pre-treated in vacuo at 200 ℃ for 2h before the adsorption measurement. Calculated using the Brunauer-Emmet-teller (bet) equation.
All the drugs were purchased from national drug group chemical reagents, Inc. or Xiong chemical Co., Ltd.
The infrared radiation uses WS70-1 far infrared dryer, Shanghai Soxhlet apparatus Limited, wavelength is 100-1000 μm.
The catalyst is synthesized by hydrothermal method by using an autoclave with the model of KH-200mL, which is a company with finite responsibilities of instruments sold in China.
Example 1
Under magnetic stirring, dissolving 5mol of aluminum sulfate in 800mol of distilled water, then gradually adding 4mol of TPAOH and 3mol of APTEO into the mixed solution, stirring until the mixed solution is clear, slowly adding 50mol of ethyl silicate under vigorous stirring, and continuously stirring for 4 hours to prepare a sol solution I; adding 7mol of Ca (NO) 3 ) 2 ·4H 2 Dissolving O in 500mol of distilled water, stirring to dissolve, adding 10mol of Mg (NO) 3 ) 2 ·6H 2 O, stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 5mol of linoleic acid, continuously stirring for 4h, ultrasonically dissolving for 4h at 50 ℃, and continuously stirring for 4h to prepare a sol solution III; pre-crystallizing the sol solution III for 4h at 60 ℃ under 100-micron infrared radiation, transferring the solution III into a high-pressure kettle, and thermally crystallizing for 72h at 180 ℃; collecting solid sample by filtration, and drying at 120 deg.C for 80 hr; calcining at 550 ℃ for 10 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Ca-Mg/hierarchical pore HZSM-5 molecular sieve, the content of calcium is 6.2 percent, and the content of magnesium is 5.4 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 2.5: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature-controlled fixed bed, Ca-Mg/hierarchical pore HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the catalyst is filled in the fixed bed reaction tube, the reaction temperature is 450 ℃, the pressure is 0.1MPa, and the mass space velocity of the methyl chloride is 0.45h -1 The volume flow ratio of the methyl chloride to the nitrogen is 1:8, the product analysis of the reaction product is completed through gas chromatography, the methyl chloride conversion rate is 99.9%, the low-carbon olefin selectivity is 90%, and the reaction is stably operated for 210 h.
Example 2:
under magnetic stirring, 1mol of aluminum chloride is dissolved in 1000mol of distilled water, then 8mol of TPAOH and 2mol of VTES are gradually added into the mixed solution, the mixture is stirred until the mixture is clear, 10mol of methyl silicate is slowly added under vigorous stirring and the mixture is continuously stirred for 4 hours to prepare sol solutionI, performing primary filtration; 2mol of Mg (NO) 3 ) 2 ·6H 2 Dissolving O in 300mol of distilled water, stirring to dissolve, adding 1mol of Zn (NO) 3 ) 2 ·6H 2 O, stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 3mol of linoleic acid, continuously stirring for 0.5h, ultrasonically dissolving at 20 ℃ for 0.5h, and continuously stirring for 0.5h to prepare a sol solution III; pre-crystallizing the sol solution III for 24h at 120 ℃ under 500-micron infrared radiation, transferring the solution III into a high-pressure kettle, and thermally crystallizing for 144h at 120 ℃; collecting solid sample by filtration, drying at 90 deg.C for 20 h; calcining at 450 ℃ for 10 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Mg-Zn/hierarchical pore HZSM-5 molecular sieve, the magnesium content is 5.2 percent, and the zinc content is 7.0 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 1.8: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Mg-Zn/multi-stage hole HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the reaction raw material methyl chloride is diluted by nitrogen and then enters the reaction tube, and the reaction conditions are as follows: the reaction temperature is 500 ℃, the pressure is 0.1MPa, and the mass space velocity of the chloromethane is 0.20h -1 The volume flow ratio of the chloromethane to the nitrogen is 1:5, the product analysis of the reaction product is completed through gas chromatography, the chloromethane conversion rate is 99.2%, the low-carbon olefin selectivity is 89%, and the reaction is stably operated for 230 hours.
Example 3:
under magnetic stirring, dissolving 7mol of aluminum acetate in 2000mol of distilled water, then gradually adding 1mol of TPAOH and 5mol of CPTEO into the mixed solution, stirring until the mixed solution is clear, slowly adding 100mol of butyl silicate under vigorous stirring, and continuously stirring for 8 hours to prepare a sol solution I; adding 10mol Zn (NO) 3 ) 2 ·6H 2 Dissolving O in 1500mol of distilled water, stirring to dissolve, adding 5mol of KNO 3 Stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 1mol of linoleic acid, continuously stirring for 4h, ultrasonically dissolving at 50 ℃ for 0.5h, and continuously stirring for 4h to prepare a sol solution III; subjecting sol solution III to 800 μm infrared radiation 1Pre-crystallizing at 20 ℃ for 1h, transferring the solution III into an autoclave, and performing hydrothermal crystallization at 200 ℃ for 24 h; collecting solid sample by filtration, drying at 150 deg.C for 5 hr; calcining at 750 ℃ for 2 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Zn-K/hierarchical pore HZSM-5 molecular sieve, the zinc content is 8.4 percent, and the potassium content is 2.5 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 2: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Zn-K/multi-stage hole HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl bromide to prepare low-carbon olefin, the reaction raw material methyl bromide enters the reaction tube after being diluted by nitrogen, and the reaction conditions are as follows: the reaction temperature is 400 ℃, the pressure is 0.2MPa, and the mass space velocity of methyl bromide is 1.0h -1 The volume flow ratio of the methyl bromide to the nitrogen is 1:10, the product analysis of the reaction product is completed through gas chromatography, the conversion rate of the methyl bromide is 93 percent, the selectivity of the low-carbon olefin is 85 percent, and the reaction is stably operated for up to 170 hours.
Example 4:
under magnetic stirring, dissolving 3mol of aluminum nitrate in 1000mol of distilled water, then gradually adding 3mol of TPAOH and 3mol of CPTES into the mixed solution, stirring until the mixed solution is clear, slowly adding 20mol of propyl silicate under vigorous stirring, and continuously stirring for 7 hours to prepare a sol solution I; adding 5mol of NaNO 3 Dissolving in 500ml distilled water, stirring to dissolve, adding 5mol Ce (NO) 3 ) 3 ·6H 2 O, stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 2mol of linoleic acid, continuously stirring for 2h, ultrasonically dissolving at 30 ℃ for 6h, and continuously stirring for 2h to prepare a sol solution III; pre-crystallizing the sol solution III for 5h at 100 ℃ under 1000-micron infrared radiation, transferring the solution III into a high-pressure kettle, and thermally crystallizing for 96h at 180 ℃; collecting solid sample by filtration, drying at 100 deg.C for 10 hr; calcining at 550 ℃ for 6 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Na-Ce/hierarchical pore HZSM-5 molecular sieve, the sodium content is 4.5 percent, and the cerium content is 2.7 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume is 2.1: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Na-Ce/hierarchical pore HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the reaction raw material methyl chloride is diluted by nitrogen and then enters the reaction tube, and the reaction conditions are as follows: the reaction temperature is 450 ℃, the pressure is 0.1MPa, and the mass space velocity of the chloromethane is 0.45h -1 The volume flow ratio of the methyl chloride to the nitrogen is 1:8, the product analysis of the reaction product is completed through gas chromatography, the methyl chloride conversion rate is 99%, the low-carbon olefin selectivity is 92%, and the reaction is stably operated for up to 215 h.
Example 5:
under magnetic stirring, dissolving 10mol of aluminum isopropoxide in 1500mol of distilled water, then gradually adding 10mol of TPAOH and 4mol of APTMO into the mixed solution, stirring until the mixed solution is clear, slowly adding 70mol of ethyl silicate under vigorous stirring, and continuously stirring for 6 hours to prepare a sol solution I; 2molLa (NO) 3 ) 3 ·6H 2 Dissolving O in 700mol of distilled water, stirring to dissolve, adding 10mol of Mn (NO) 3 ) 3 Stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 4mol of linoleic acid, continuously stirring for 3h, ultrasonically dissolving for 7h at 40 ℃, and continuously stirring for 3h to prepare a sol solution III; pre-crystallizing the sol solution III for 10h at 80 ℃ under 500-micron infrared radiation, transferring the solution III into a high-pressure kettle, and thermally crystallizing for 120h at 160 ℃; collecting solid sample by filtration, drying at 130 deg.C for 7 h; calcining at 650 ℃ for 4 h; tabletting and crushing to 20-30 meshes for later use; in the prepared La-Mn/hierarchical pore HZSM-5 molecular sieve, the lanthanum content is 4.6 percent, and the manganese content is 9.2 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume is 1: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature-controlled fixed bed, the La-Mn/hierarchical-hole HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl bromide to prepare low-carbon olefin, the reaction raw material methyl bromide enters the reaction tube after being diluted by nitrogen, and the reaction conditions are as follows: the reaction temperature is 450 ℃, the pressure is 0.1MPa, and the mass space velocity of methyl bromide is 0.45h -1 The volume flow ratio of the bromomethane to the nitrogen is 1:8,the product analysis of the reaction product is completed by gas chromatography, the conversion rate of methyl bromide is 94%, the selectivity of low-carbon olefin is 83%, and the reaction is stably operated for up to 180 h.
Example 6:
under magnetic stirring, dissolving 2mol of sodium metaaluminate in 800mol of distilled water, then gradually adding 7mol of TPAOH and 5mol of APAMS into the mixed solution, stirring until the mixed solution is clear, slowly adding 30mol of silica sol under vigorous stirring, and continuously stirring for 5 hours to prepare sol solution I; 5mol of Ca (NO) 3 ) 2 ·4H 2 Dissolving O in 300mol of distilled water, stirring to dissolve, adding 1.5mol of Ce (NO) 3 ) 3 ·6H 2 O, stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 3mol of linoleic acid, continuously stirring for 2h, ultrasonically dissolving at 30 ℃ for 6h, and continuously stirring for 4h to prepare a sol solution III; pre-crystallizing the sol solution III for 20h at 90 ℃ under 100-micron infrared radiation, transferring the solution III into a high-pressure kettle, and thermally crystallizing for 100h at 150 ℃; collecting solid sample by filtration, drying at 190 deg.C for 16 h; calcining at 700 ℃ for 3 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Ca-Ce/hierarchical pore HZSM-5 molecular sieve, the content of calcium is 7.3 percent, and the content of cerium is 7.7 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 1.6: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Ca-Ce/hierarchical pore HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the reaction raw material methyl chloride is diluted by nitrogen and then enters the reaction tube, and the reaction conditions are as follows: the reaction temperature is 500 ℃, the pressure is 0.1MPa, and the mass space velocity of the chloromethane is 0.5h -1 The volume flow ratio of the chloromethane to the nitrogen is 1:5, the reaction product is subjected to gas chromatography to obtain a product, the chloromethane conversion rate is 99.2%, the low-carbon olefin selectivity is 93%, and the reaction is stably operated for 240 hours.
Example 7:
dissolving 7mol of aluminum isopropoxide in 1200mol of distilled water under magnetic stirring, then gradually adding 2mol of TPAOH and 3.5mol of DPAMS into the mixed solution, stirring until the mixed solution is clear, and stirring until the mixed solution is clearSlowly adding 60mol of methyl silicate under vigorous stirring, and continuously stirring for 5 hours to prepare sol solution I; 15molMg (NO) 3 ) 2 ·6H 2 Dissolving O in 800mol of distilled water, stirring for dissolving, and adding 5mol of KNO 3 Stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 5mol of linoleic acid, continuously stirring for 4h, ultrasonically dissolving at 35 ℃ for 7h, and continuously stirring for 2.5h to prepare a sol solution III; pre-crystallizing the sol solution III for 15h at 100 ℃ under the infrared radiation of 500 mu m, transferring the solution III into a high-pressure kettle, and performing hydrothermal crystallization for 144h at 160 ℃; collecting solid sample by filtration, drying at 170 deg.C for 12 h; calcining at 600 deg.C for 4 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Mg-K/hierarchical pore HZSM-5 molecular sieve, the magnesium content is 7.2 percent, and the potassium content is 3.9 percent; through tests, the pore diameter of the micropore is 0.1-2 nm, the pore diameter of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 2.0: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Mg-K/hierarchical pore HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl bromide to prepare low-carbon olefin, the reaction raw material methyl bromide enters the reaction tube after being diluted by nitrogen, and the reaction conditions are as follows: the reaction temperature is 500 ℃, the pressure is 0.1MPa, and the mass space velocity of methyl bromide is 0.1h -1 The volume flow ratio of the methyl bromide to the nitrogen is 1:7, the product analysis of the reaction product is completed through gas chromatography, the conversion rate of the methyl bromide is 95 percent, the selectivity of the low-carbon olefin is 87 percent, and the reaction is stably operated for 175 hours.
Example 8:
under magnetic stirring, dissolving 4mol of aluminum acetate in 1000mol of distilled water, then gradually adding 5mol of TPAOH and 2mol of VTES into the mixed solution, stirring until the mixed solution is clear, slowly adding 100mol of butyl silicate under vigorous stirring, and continuously stirring for 7 hours to prepare a sol solution I; adding 10mol Zn (NO) 3 ) 2 ·6H 2 Dissolving O in 600mol of distilled water, stirring to dissolve, adding 2mol of La (NO) 3 ) 3 ·6H 2 O, stirring uniformly to prepare a solution II; slowly dripping the solution II into the sol solution I, adding 4mol of linoleic acid, continuously stirring for 3h, ultrasonically dissolving at 45 ℃ for 6h, continuously stirring for 3.5h,preparing sol liquid III; pre-crystallizing the sol solution III at 70 ℃ for 7h under 800 mu m infrared radiation, transferring the solution III into a high-pressure kettle, and performing hydrothermal crystallization for 100h at 150 ℃; collecting solid sample by filtration, drying at 160 deg.C for 10 hr; calcining at 650 ℃ for 6 h; tabletting and crushing to 20-30 meshes for later use; in the prepared Zn-La/hierarchical pore HZSM-5 molecular sieve, the zinc content is 8.7 percent, and the lanthanum content is 3.7 percent; through tests, the aperture of the micropore is 0.1-2 nm, the aperture of the newly added mesopore is 2-10 nm, and the pore volume of the micropore is as follows: mesoporous pore volume 1.2: 1.
the performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the Zn-La/hierarchical pore HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the reaction raw material methyl chloride is diluted by nitrogen and then enters the reaction tube, and the reaction conditions are as follows: the reaction temperature is 350 ℃, the pressure is 0.5MPa, and the mass space velocity of the chloromethane is 3h -1 The volume flow ratio of the methyl chloride to the nitrogen is 1:6, the product analysis of the reaction product is completed through gas chromatography, the methyl chloride conversion rate is 99.7%, the low-carbon olefin selectivity is 92%, and the reaction is stably operated for up to 232 h.
Comparative example 1
Taking a commercially available HZSM-5 molecular sieve (HZSM-5-80, model of catalyst factory of Tianjin Nankai university), tabletting and screening to 20-30 meshes, wherein the pore diameter of the micropores of the catalyst is 0.1-2 nm, the average pore diameter is 0.67nm, and no mesopores are formed.
The performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature-controlled fixed bed, the commercial HZSM-5 molecular sieve is used for catalyzing methyl chloride to prepare low-carbon olefin, the catalyst is filled in the fixed bed reaction tube, the reaction raw material, namely the methyl chloride, is diluted by nitrogen and then enters the reaction tube, and the reaction temperature is 450 ℃, the pressure is 0.1MPa, the mass airspeed of the methyl chloride is 0.45h -1 The volume flow ratio of the methyl chloride to the nitrogen is 1:8, the product analysis of the reaction product is completed through gas chromatography, the conversion rate of the methyl chloride is 89%, the selectivity of the low-carbon olefin is 50%, and the reaction is stably operated for 23 hours.
Comparative example 2
10g of the calcined HZSM-5 molecular sieve was taken, and by gradually dropping deionized water, the saturated water absorption of 10g of the HZSM-5 molecular sieve was measured to be 7.0 mL. 4.43g Ca (NO) 3 ) 2 ·4H 2 O and 7.00gMg (NO) 3 ) 2 ·6H 2 Dissolving O in 7mL of deionized water to prepare a nitrate aqueous solution, placing the nitrate aqueous solution in a 50mL beaker, adding 10g of HZSM-5 molecular sieve into the beaker under rapid stirring, uniformly mixing, performing ultrasonic dissolution at 40 ℃ for 1h, standing at room temperature for 20h, and drying at 120 ℃ for 80 h; calcining at 550 ℃ for 10 hours to remove the template, and obtaining the Ca-Mg/HZSM-5 molecular sieve, wherein the calcium content is 6.2 percent, and the magnesium content is 5.4 percent. The catalyst has micropore diameter of 0.1-2 nm, average pore diameter of 0.52nm and no mesopores.
The performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature-controlled fixed bed, the 5Ca-2Mg/HZSM-5 molecular sieve prepared by the method is used for catalyzing methyl chloride to prepare low-carbon olefin, the catalyst is filled in the fixed bed reaction tube, the reaction raw material methyl chloride is diluted by nitrogen and then enters the reaction tube, the reaction temperature is 450 ℃, the pressure is 0.1MPa, and the mass airspeed of the methyl chloride is 0.45h -1 The volume flow ratio of the methyl chloride to the nitrogen is 1:8, the product analysis of the reaction product is completed through gas chromatography, the conversion rate of the methyl chloride is 98%, the selectivity of the low-carbon olefin is 87%, and the reaction is stably operated for 50 h.
Comparative example 3:
under magnetic stirring, dissolving 5mol of aluminum sulfate in 800mol of distilled water, then gradually adding 3mol of APTEO into the mixed solution, stirring until the solution is clear, slowly adding 50mol of ethyl silicate under vigorous stirring, continuously stirring for 4 hours to prepare a sol solution I, transferring the solution I into a high-pressure kettle, and thermally crystallizing for 72 hours at 180 ℃; collecting solid sample by filtration, and drying at 120 deg.C for 80 hr; calcining at 550 ℃ for 10h to remove the template; the HZSM-5 molecular sieve catalyst is obtained, the aperture of the micropores is 0.1-2 nm, the average aperture is 0.71nm, and no mesopores are formed.
The performance test of the catalyst is carried out in a glass reaction tube of a three-section temperature control fixed bed, the HZSM-5 molecular sieve prepared by the method is used for catalyzing chloromethane to prepare low-carbon olefin, the catalyst is filled in the fixed bed reaction tube, the reaction temperature is 450 ℃, the pressure is 0.1MPa, and the mass space velocity of the chloromethane is 0.45h -1 The volume flow ratio of chloromethane and nitrogen is 1:8, and the reaction product is finished by gas chromatographyAnd (3) analyzing a formed product, wherein the conversion rate of the chloromethane is 93%, the selectivity of the low-carbon olefin is 70%, and the reaction is stably operated for 58 hours.
TABLE 1
Figure BDA0002153834210000151

Claims (10)

1. The composite metal modified hierarchical pore molecular sieve catalyst is characterized by comprising the following components in percentage by mass: metal oxide a: 1-10%, metal oxide b: 1-10% of the molecular sieve, calculated by metal simple substance, and the balance of the molecular sieve is a multi-stage hole HZSM-5 molecular sieve;
the preparation method of the composite metal modified hierarchical pore molecular sieve catalyst comprises the following steps:
A. dissolving an aluminum source in water, gradually adding a template agent tetrapropylammonium hydroxide and a growth inhibitor into an aluminum source aqueous solution, adding a silicon source, uniformly stirring, and stirring for 4-8 hours to prepare a sol solution I;
B. dissolving nitrate a 'in water, adding nitrate b', and uniformly stirring to prepare a solution II;
C. adding the solution II into the sol solution I, adding linoleic acid, and performing ultrasonic dissolution at 20-50 ℃ to prepare a sol solution III;
D. pre-crystallizing the sol liquid III for 1-24 h at 60-120 ℃ under infrared radiation;
E. transferring the pre-crystallized solution III into an autoclave, and carrying out hydrothermal crystallization for 24-144 h at 120-200 ℃; filtering, drying and calcining to obtain a catalyst;
and a and b are any two of calcium, magnesium, zinc, potassium, sodium, cerium, lanthanum and manganese which exist in oxide form.
2. The catalyst of claim 1 wherein the catalyst pore size distribution is: the pore diameter of the micropores is less than 2nm, the pore diameter of the mesopores is 2-10 nm, and the pore volume of the micropores is as follows: mesoporous pore volume = 2.5-1: 1.
3. the catalyst of claim 1 or 2, wherein in the step A, the aluminum source comprises one or more of aluminum sulfate, aluminum isopropoxide, aluminum acetate, aluminum chloride, aluminum nitrate and sodium metaaluminate; the silicon source is selected from one or more of methyl silicate, ethyl silicate, propyl silicate, butyl silicate and silica sol.
4. The catalyst according to claim 1 or 2, wherein in step A, the growth inhibitor is selected from one or more of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, and N, N-diethyl-3-aminopropyltrimethoxysilane.
5. The catalyst according to claim 1 or 2, wherein in step a, the silicon source, the aluminum source, the templating agent, the growth inhibitor, and H 2 The molar ratio of O is: silicon source: aluminum source: template agent: growth inhibitors: h 2 O =10 to 100: 1-10: 1-10: 1-5: 800-2000; the aluminum source is Al 2 O 3 The silicon source is SiO 2 And (6) counting.
6. The catalyst according to claim 1 or 2, wherein in the step B, the nitrate a 'and the nitrate B' are Ca (NO) 3 ) 2 ·4H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、KNO 3 、NaNO 3 、Ce(NO 3 ) 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O、Mn(NO 3 ) 2 Any two of them.
7. Catalyst according to claim 1 or 2, characterized in that the nitrates a ', b', H 2 Adding mol of O, linoleic acid and growth inhibitorThe ratio is as follows: a' nitrate salt: a nitrate salt b': h 2 O: linoleic acid: growth inhibitor = 1-15: 1-15: 300-1500: 1-5: 1 to 5.
8. The catalyst according to claim 1 or 2, wherein in the step E, the catalyst is dried at 90-150 ℃ for 5-20 hours; calcining for 2-10 h at 450-750 ℃.
9. Use of a hierarchical pore molecular sieve catalyst according to any of claims 1-8 in the preparation of lower olefins from methyl halide.
10. The application of claim 9, wherein the composite metal modified hierarchical pore molecular sieve catalyst is filled in a fixed bed reaction tube, the reaction raw material, namely the halogenated methane is diluted by nitrogen and then enters the reaction tube, the volume flow ratio of the halogenated methane to the nitrogen is 1: 5-10, and the mass space velocity of the halogenated methane is 0.1-3 h -1 The reaction temperature is 350-500 ℃, and the pressure is 0.1-0.5 MPa.
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