CN115400785B - Core-shell structure catalyst for propane aromatization and preparation method and application thereof - Google Patents

Core-shell structure catalyst for propane aromatization and preparation method and application thereof Download PDF

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CN115400785B
CN115400785B CN202211179411.2A CN202211179411A CN115400785B CN 115400785 B CN115400785 B CN 115400785B CN 202211179411 A CN202211179411 A CN 202211179411A CN 115400785 B CN115400785 B CN 115400785B
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propane
core
molecular sieve
catalyst
aromatization
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CN115400785A (en
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康金灿
李世航
张庆红
王野
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Xiamen University
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    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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    • B01J35/391—Physical properties of the active metal ingredient
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    • B01J37/08—Heat treatment
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
    • B01J29/405—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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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
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Abstract

A core-shell structured catalyst for aromatization of propane, a preparation method and application thereof, wherein the core layer of the catalyst is ZSM-5 molecular sieve, the shell layer is Silicate-1 molecular sieve, and Pt and an auxiliary agent M metal element are encapsulated in the shell layer of Silicate-1 molecular sieve. The mass percentage of the shell layer Silicate-1 molecular sieve is 30% -70%, the mass percentage of the metal Pt is 0.01% -3%, the mass percentage of the M metal element is 0.01% -10%, and the balance is the core layer ZSM-5 molecular sieve. The catalyst is prepared by adopting a hydrothermal synthesis method, the preparation mode is simple, the catalyst can be directly used in propane aromatization reaction, the selectivity of aromatic hydrocarbon products can reach 70%, and the light aromatic hydrocarbon accounts for more than 80%. The catalyst has simple preparation process, low cost and good catalytic performance.

Description

Core-shell structure catalyst for propane aromatization and preparation method and application thereof
Technical Field
The invention relates to the fields of catalytic material preparation and low-carbon alkane conversion and utilization, in particular to a core-shell structure catalyst for propane aromatization and a preparation method and application thereof.
Background
Aromatic hydrocarbon is an extremely important basic chemical product and has wide application in various aspects of national economy such as chemistry, biological medicine, light industry electronics and the like. The main sources of the aromatic hydrocarbon are naphtha reforming and coal tar fractionation, the production efficiency is lower, the energy consumption is larger, and the aromatic hydrocarbon supply in the market becomes uncontrollable due to the increasingly prominent global environment problem and the reduction of crude oil resources. Propane is used as a byproduct obtained by processing natural gas or refining crude oil, and has a large specific gravity in shale gas, so that the technical development of preparing aromatic hydrocarbon by aromatization of propane has important significance.
The ZSM-5 molecular sieve is widely applied to various aromatization reactions due to the excellent shape selective catalytic capability, and the catalysts for aromatization of propane reported in the current literature are mostly further modified on the ZSM-5 molecular sieve. Although such catalysts exhibit a certain catalytic activity, they still do not meet the industrial needs. On one hand, the low-carbon hydrocarbon products in the product occupy larger specific gravity, and the aromatic hydrocarbon selectivity is not high; on the other hand, the generated aromatic hydrocarbon is easy to be further aromatized on the acidic site on the surface of the ZSM-5 molecular sieve to generate heavy aromatic hydrocarbon with lower added value, and carbon deposition reaction is easy to occur.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a core-shell catalyst for propane aromatization, a preparation method and application thereof, wherein the core-shell catalyst has higher propane aromatization performance and can inhibit further aromatization on the surface of the catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the core-shell structured catalyst for aromatization of propane has a core layer of ZSM-5 molecular sieve, a shell layer of Silicate-1 molecular sieve, and metal Pt and an auxiliary agent M metal element are encapsulated in the shell layer of Silicate-1 molecular sieve; the mass percentage of the shell layer Silicate-1 molecular sieve is 30% -70%, the metal Pt is 0.01% -3%, the M metal element is 0.01% -10%, and the balance is the nuclear layer ZSM-5 molecular sieve.
The M metal element is at least one of Sn, zn, ga, ir, cu, ag, co.
The preparation method of the core-shell catalyst for aromatization of propane comprises the following steps:
1) Mixing a silicon source, a template agent, an aluminum source and deionized water, stirring at a certain temperature to form a mixed sol, transferring the mixed sol into a hydrothermal kettle for crystallization, and centrifuging, washing, drying and roasting the obtained product to obtain a ZSM-5 molecular sieve;
2) Mixing a silicon source, a template agent and deionized water, stirring at a certain temperature, adding a metered Pt salt solution and an M metal precursor solution, stirring, adding the metered ZSM-5 molecular sieve prepared in the step 1) to obtain a mixture, transferring the obtained mixture into a hydrothermal kettle for crystallization, and centrifuging, washing, drying and roasting the obtained product to obtain the core-shell catalyst.
In the step 1), the silicon source is at least one of tetraethyl orthosilicate, silica sol and white carbon black, the template agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrabutylphosphonium hydroxide, the aluminum source is at least one of aluminum isopropoxide, aluminum nitrate nonahydrate and aluminum chloride hexahydrate, the molar amount of the template agent is 0.01-2 times of the molar amount of the silicon source, the molar amount of the aluminum source is 1/300-1/10 of the molar amount of the silicon source, and the molar amount of deionized water is 10-300 times of the molar amount of the silicon source; stirring temperature is 20-80 ℃, and stirring time is 3-48 h.
In the step 1), the temperature of the hydrothermal crystallization process is 120-220 ℃ and the crystallization time is 24-120 h; drying comprises at least one of vacuum drying and air drying, wherein the drying temperature is 50-120 ℃ and the drying time is 3-12 h; the roasting temperature is 400-650 ℃ and the roasting time is 3-10 h.
In the step 2), the silicon source is at least one of tetraethyl orthosilicate, silica sol and fumed silica, the template agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrabutylphosphonium hydroxide, the molar quantity of the template agent is 0.01-2 times of the molar quantity of the silicon source, and the molar quantity of deionized water is 10-300 times of the molar quantity of the silicon source; stirring temperature is 20-80 ℃, and stirring time is 3-48 h.
In the step 2), the Pt salt is one or more of nitrate, ammonium salt and halide, and the mass concentration of the solution is 0.01-50 mg/mL; the M metal element precursor is at least one of an oxide, an inorganic salt and a complex of the M metal element, and the molar concentration of the M metal element precursor solution is 0.1-50 mmol/L.
In the step 2), the temperature of the hydrothermal crystallization process is 80-220 ℃ and the crystallization time is 20-120 h; drying comprises at least one of vacuum drying and air drying, wherein the drying temperature is 50-120 ℃ and the drying time is 3-12 h; the roasting temperature is 400-650 ℃ and the roasting time is 3-10 h.
The application of the core-shell structure catalyst for propane aromatization is used for preparing aromatic hydrocarbon by propane aromatization reaction.
Before the reaction, hydrogen-argon or hydrogen-nitrogen mixed gas with 5 to 100 percent of hydrogen is used for treatment for 1 to 4 hours at the temperature of 300 to 600 ℃, then raw material gas is introduced, and propane aromatization reaction is carried out at a certain pressure and temperature; the reaction is carried out in a fixed bed, a fixed fluidized bed, a circulating fluidized bed or a moving bed reactor, the raw material gas is pure propane, propane/nitrogen or propane/hydrogen mixture, the volume content of propane is not less than 25 percent, the reaction temperature is 350-650 ℃, the reaction pressure is 0.1-1 MPa, and the reaction airspeed is 1000-12000 mL/h/g.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The core-shell structured catalyst disclosed by the invention has the advantages that the active metal Pt and the auxiliary agent element are packaged in the shell layer Silicate-1 molecular sieve, and a dehydrogenation site can be provided for propane to generate propylene.
(2) The core-shell structured catalyst core layer is a ZSM-5 molecular sieve, and can provide aromatization acid sites for propylene to generate aromatic hydrocarbon.
(3) The core-shell structured catalyst has the advantages that a layer of Silicate-1 molecular sieve continuously grows on the surface of the ZSM-5 molecular sieve, and the surface acidic sites of the ZSM-5 molecular sieve are covered, so that high-value light aromatic hydrocarbon generated on the surface acidic sites of the ZSM-5 molecular sieve can be prevented from further aromatizing to generate heavy aromatic hydrocarbon.
(4) The core-shell catalyst prepared by the invention has better propane aromatization performance, the total aromatic hydrocarbon selectivity in the product can reach 70%, and the light aromatic hydrocarbon accounts for more than 80%.
(5) The core-shell catalyst prepared by the method has the advantages of easily available raw materials, simple preparation process and excellent performance, and is suitable for industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of the ZSM-5 (30) molecular sieve of example 2 and the core-shell structured catalyst PtZn-S1@ZSM-5 (30) of example 2.
FIG. 2 is a ZSM-5 (30) molecular sieve of example 2 and the core of example 2NH of shell catalyst PtZn-S1@ZSM-5 (30) 3 -TPD map.
FIG. 3 is an SEM image of ZSM-5 (30) molecular sieve of example 2.
FIG. 4 is an SEM image of the core-shell catalyst PtZn-S1@ZSM-5 (30) of example 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
2.08g of tetraethyl orthosilicate, 5.29g of tetrapropylammonium hydroxide (25% aqueous solution), 0.07g of aluminum isopropoxide and 5.03g of deionized water are placed in a 100mL beaker, stirred for 10 hours at 25 ℃ to form mixed sol, the mixed sol is moved into a 100mL hydrothermal kettle, crystallized for 72 hours in a 170 ℃ oven, and after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged and washed, and dried in vacuum for 6 hours at 80 ℃; then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain a ZSM-5 (30) molecular sieve; 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water are placed in a 100mL beaker, after stirring for 6 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of gallium nitrate aqueous solution (the concentration of the gallium nitrate aqueous solution is 10 mmol/L) are added, after stirring for 4 hours, 0.5g of prepared ZSM-5 (30) molecular sieve is added, then the mixture is moved into a 100mL hydrothermal kettle, crystallization is carried out in an oven at 100 ℃ for 24 hours, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged, washed and dried in vacuum at 80 ℃ for 6 hours; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as PtGa-S1@ZSM-5 (30).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600deg.C at a heating rate of 10deg.C/min, and then introducing raw gas n (propane) n (nitrogen)) The pressure in the fixed bed reactor was 0.1MPa and the reaction space velocity was 6000mL/h/g =1:1. The catalytic properties of the catalyst are shown in table 1.
Example 2
ZSM-5 (30) molecular sieve was prepared as in example 1; 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water are placed in a 100mL beaker, after stirring for 6 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of zinc nitrate aqueous solution (the concentration of the zinc nitrate aqueous solution is 10 mmol/L) are added, after stirring for 4 hours, 0.5g of prepared ZSM-5 (30) molecular sieve is added, then the mixture is moved into a 100mL hydrothermal kettle, crystallization is carried out in an oven at 100 ℃ for 24 hours, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged, washed and dried in vacuum at 80 ℃ for 6 hours; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as PtZn-S1@ZSM-5 (30).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600 ℃ at a heating rate of 10 ℃/min, and then introducing raw material gas n (propane): n (nitrogen) =1:1, wherein the pressure in the fixed bed reactor is 0.1MPa, and the reaction space velocity is 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Example 3
ZSM-5 (30) molecular sieve was prepared as in example 1; 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water are placed in a 100mL beaker, after stirring for 6 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of stannous chloride aqueous solution (the concentration of the stannous chloride aqueous solution is 10 mmol/L) are added, after stirring for 4 hours, 0.5g of prepared ZSM-5 (30) molecular sieve is added, then the mixture is transferred to a 100mL hydrothermal kettle, crystallization is carried out in an oven at 100 ℃ for 24 hours, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged and washed, and vacuum drying is carried out for 6 hours at 80 ℃; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as PtSn-S1@ZSM-5 (30).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600 ℃ at a heating rate of 10 ℃/min, and then introducing raw material gas n (propane): n (nitrogen) =1:1, wherein the pressure in the fixed bed reactor is 0.1MPa, and the reaction space velocity is 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Example 4
2.08g of tetraethyl orthosilicate, 5.29g of tetrapropylammonium hydroxide (25% aqueous solution), 0.02g of aluminum isopropoxide and 5.03g of deionized water are placed in a 100mL beaker, stirred for 10 hours at 25 ℃ to form mixed sol, the mixed sol is moved into a 100mL hydrothermal kettle, crystallized for 72 hours in a 170 ℃ oven, and after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged and washed, and dried in vacuum for 6 hours at 80 ℃; then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain a ZSM-5 (100) molecular sieve; 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water are placed in a 100mL beaker, after stirring for 6 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of zinc nitrate aqueous solution (the concentration of the zinc nitrate aqueous solution is 10 mmol/L) are added, after stirring for 4 hours, 0.5g of prepared ZSM-5 (100) molecular sieve is added, then the mixture is moved into a 100mL hydrothermal kettle, crystallization is carried out in an oven at 100 ℃ for 24 hours, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged, washed and dried in vacuum at 80 ℃ for 6 hours; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as PtZn-S1@ZSM-5 (100).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min whileThe temperature rising rate of 10 ℃/min is raised to 600 ℃, then raw material gas n (propane): n (nitrogen) =1:1 is introduced, the pressure in the fixed bed reactor is 0.1MPa, and the reaction space velocity is 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Example 5
2.08g of tetraethyl orthosilicate, 5.29g of tetrapropylammonium hydroxide (25% aqueous solution), 0.01g of aluminum isopropoxide and 5.03g of deionized water are placed in a 100mL beaker, stirred for 10 hours at 25 ℃ to form mixed sol, the mixed sol is moved into a 100mL hydrothermal kettle, crystallized for 72 hours in a 170 ℃ oven, and after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged and washed, and dried in vacuum for 6 hours at 80 ℃; then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain a ZSM-5 (200) molecular sieve; 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water are placed in a 100mL beaker, after stirring for 6 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of zinc nitrate aqueous solution (the concentration of the zinc nitrate aqueous solution is 10 mmol/L) are added, after stirring for 4 hours, 0.5g of prepared ZSM-5 (200) molecular sieve is added, then the mixture is moved into a 100mL hydrothermal kettle, crystallization is carried out in an oven at 100 ℃ for 24 hours, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged, washed and dried in vacuum at 80 ℃ for 6 hours; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as PtZn-S1@ZSM-5 (200).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600 ℃ at a heating rate of 10 ℃/min, and then introducing raw material gas n (propane): n (nitrogen) =1:1, wherein the pressure in the fixed bed reactor is 0.1MPa, and the reaction space velocity is 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Comparative example 1
ZSM-5 (30) molecular sieve was prepared as in example 1; placing 2.28g of tetraethyl orthosilicate, 0.35g of tetrapropylammonium hydroxide (25% aqueous solution) and 41.0g of deionized water in a 100mL beaker, stirring at 25 ℃ for 6 hours, adding 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL), stirring for 4 hours, adding 0.5g of prepared ZSM-5 (30) molecular sieve, transferring the mixture into a 100mL hydrothermal kettle, crystallizing in an oven at 100 ℃ for 24 hours, centrifuging and washing the solid-liquid mixture in the hydrothermal kettle after natural cooling, and vacuum drying at 80 ℃ for 6 hours; and then grinding the solid, putting the ground solid into a muffle furnace, and roasting the ground solid at 550 ℃ for 6 hours in an air atmosphere to obtain the catalyst with the core-shell structure, which is marked as Pt-S1@ZSM-5 (30).
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600 ℃ at a heating rate of 10 ℃/min, and then introducing raw material gas n (propane): n (nitrogen) =1:1, wherein the pressure in the fixed bed reactor is 0.1MPa, and the reaction space velocity is 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Comparative example 2
2.08g of tetraethyl orthosilicate, 5.29g of tetrapropylammonium hydroxide (25% aqueous solution) and 5.03g of deionized water are placed in a 100mL beaker, after stirring for 10 hours at 25 ℃, 0.45mL of chloroplatinic acid aqueous solution (the concentration of the chloroplatinic acid aqueous solution is 10 mg/mL) and 3.47mL of zinc nitrate aqueous solution (the concentration of the zinc nitrate aqueous solution is 10 mmol/L) are added to form a mixed sol, after stirring for 4 hours, the mixed sol is transferred into a 100mL hydrothermal kettle, crystallization is carried out for 72 hours in an oven at 170 ℃, after natural cooling, the solid-liquid mixture in the hydrothermal kettle is centrifuged and washed, and vacuum drying is carried out for 6 hours at 80 ℃; then the solid is ground and put into a muffle furnace, and baked for 6 hours at 550 ℃ in air atmosphere to obtain the molecular sieve catalyst which is named PtZn-S1.
Filling 0.5g of the catalyst with 30-60 meshes into a quartz reaction tube of a constant pressure fixed bed, and firstly adding 20mL/min of pure H 2 The temperature of the air flow is raised to 500 ℃ at the heating rate of 5 ℃/min for pretreatment, the temperature is kept constant for 4 hours, and then the air flow is switched to N 2 (50 mL/min) purging for 10min while heating to 600deg.C at a heating rate of 10deg.C/min, followed by feeding of feed gas n (propane) N (nitrogen) =1:1, the pressure in the fixed bed reactor was 0.1MPa, and the reaction space velocity was 6000mL/h/g. The catalytic properties of the catalyst are shown in table 1.
Table 1 propane aromatization performance of the catalysts of examples 1-5 and comparative examples 1-2
FIG. 1 is an X-ray diffraction pattern of the ZSM-5 (30) molecular sieve of example 2 and the core-shell structured catalyst PtZn-S1@ZSM-5 (30) of example 2. It can be seen that the catalyst has characteristic diffraction peaks of the MFI molecular sieve, and no characteristic diffraction peaks of the metal particles, indicating that the metal nanoparticles are small in size and highly dispersed.
FIG. 2 shows the molecular sieve of ZSM-5 (30) of example 2 and the NH of the catalyst PtZn-S1@ZSM-5 (30) of example 2 in the core-shell structure 3 -TPD map. As can be seen from the above, the ZSM-5 (30) molecular sieve and the PtZn-S1@ZSM-5 (30) molecular sieve have a low temperature desorption peak and a high temperature desorption peak, and the acid content of the high temperature desorption peak of the ZSM-5 (30) molecular sieve is obviously higher than that of the PtZn-S1@ZSM-5 (30) molecular sieve, which indicates that the Silicate-1 molecular sieve at the outer layer of the core-shell structure catalyst covers the surface acid sites of the ZSM-5 molecular sieve at the inner layer.
FIG. 3 is an SEM image of ZSM-5 (30) molecular sieve of example 2. As can be seen, the ZSM-5 (30) molecular sieve is regular in shape and takes the shape of a hexagonal prism.
FIG. 4 is an SEM image of the core-shell catalyst PtZn-S1@ZSM-5 (30) of example 2. It can be seen that the PtZn-S1@ZSM-5 (30) catalyst has a similar structure to the ZSM-5 molecular sieve.

Claims (8)

1. A core-shell structured catalyst for aromatization of propane, characterized by: the core layer of the catalyst with the core-shell structure is a ZSM-5 molecular sieve, the shell layer is a Silicate-1 molecular sieve, and metal Pt and an auxiliary agent M metal element are encapsulated in the Silicate-1 molecular sieve; the shell layer Silicate-1 molecular sieve is 30% -70%, the metal Pt is 0.01% -3%, the M metal element is 0.01% -10% by mass, and the balance is the core layer ZSM-5 molecular sieve; the M metal element is at least one of Sn, zn, ga, cu, co;
the preparation method comprises the following steps:
1) Mixing and stirring a silicon source, a template agent, an aluminum source and deionized water to form a mixed sol, transferring the mixed sol into a hydrothermal kettle for crystallization, and centrifuging, washing, drying and roasting the obtained product to obtain a ZSM-5 molecular sieve;
2) Mixing and stirring a silicon source, a template agent and deionized water, adding a Pt salt solution and an M metal precursor solution, stirring, adding a ZSM-5 molecular sieve to obtain a mixture, transferring the obtained mixture into a hydrothermal kettle for crystallization, and centrifuging, washing, drying and roasting the obtained product to obtain the core-shell catalyst.
2. A core-shell structured catalyst for aromatization of propane as set forth in claim 1, wherein: in the step 1), the silicon source is at least one of tetraethyl orthosilicate, silica sol and white carbon black, the template agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrabutylphosphonium hydroxide, the aluminum source is at least one of aluminum isopropoxide, aluminum nitrate nonahydrate and aluminum chloride hexahydrate, the molar amount of the template agent is 0.01-2 times of the molar amount of the silicon source, the molar amount of the aluminum source is 1/300-1/10 of the molar amount of the silicon source, and the molar amount of deionized water is 10-300 times of the molar amount of the silicon source; stirring temperature is 20-80 ℃, and stirring time is 3-48 h.
3. A core-shell structured catalyst for aromatization of propane as set forth in claim 1, wherein: in the step 1), the crystallization temperature is 120-220 ℃ and the crystallization time is 24-120 h; the drying comprises at least one of vacuum drying and air-blast drying, wherein the drying temperature is 50-120 ℃, and the drying time is 3-12 h; the roasting temperature is 400-650 ℃, and the roasting time is 3-10 h.
4. A core-shell structured catalyst for aromatization of propane as set forth in claim 1, wherein: in the step 2), the silicon source is at least one of tetraethyl orthosilicate, silica sol and fumed silica, the template agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrabutylphosphonium hydroxide, the molar quantity of the template agent is 0.01-2 times of the molar quantity of the silicon source, and the molar quantity of deionized water is 10-300 times of the molar quantity of the silicon source; stirring temperature is 20-80 ℃, and stirring time is 3-48 h.
5. A core-shell structured catalyst for aromatization of propane as set forth in claim 1, wherein: in the step 2), the Pt salt is one or more of nitrate, ammonium salt and halide, and the mass concentration of the Pt salt solution is 0.01-50 mg/mL; the M metal element precursor is at least one of an oxide, an inorganic salt and a complex of the M metal element, and the molar concentration of the M metal element precursor solution is 0.1-50 mmol/L.
6. A core-shell structured catalyst for aromatization of propane as set forth in claim 1, wherein: in the step 2), the crystallization temperature is 80-220 ℃ and the crystallization time is 20-120 h; the drying comprises at least one of vacuum drying and air-blast drying, wherein the drying temperature is 50-120 ℃, and the drying time is 3-12 h; the roasting temperature is 400-650 ℃, and the roasting time is 3-10 h.
7. The application of the core-shell structured catalyst for propane aromatization as set forth in any one of claims 1 to 6, which is characterized in that: is used for preparing aromatic hydrocarbon by propane aromatization reaction.
8. The use according to claim 7, wherein: before the propane aromatization reaction, pure hydrogen is used for treatment for 1-4 hours at 300-600 ℃, then raw gas is introduced, and the propane aromatization reaction is carried out at a certain pressure and temperature; the reaction is carried out in a fixed bed, a fixed fluidized bed, a circulating fluidized bed or a moving bed reactor, raw material gas is pure propane, propane/nitrogen or propane/hydrogen mixture, the volume content of propane is not less than 25%, the reaction temperature is 350-650 ℃, the reaction pressure is 0.1-1 MPa, and the reaction airspeed is 1000-12000 mL/h/g.
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CN103418429A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Methane oxygen-free dehydrogenation aromatization catalyst and preparation method thereof
CN106607088A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Catalyst for producing aromatic hydrocarbon from methanol and preparation method and application thereof
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