CN112058302B - Preparation method and application of ZSM-5 molecular sieve catalyst - Google Patents
Preparation method and application of ZSM-5 molecular sieve catalyst Download PDFInfo
- Publication number
- CN112058302B CN112058302B CN202011155400.1A CN202011155400A CN112058302B CN 112058302 B CN112058302 B CN 112058302B CN 202011155400 A CN202011155400 A CN 202011155400A CN 112058302 B CN112058302 B CN 112058302B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular sieve
- zsm
- drying
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a ZSM-5 molecular sieve catalyst, which comprises the following steps: (1) Adding the empty-shell type small-crystal-grain ZSM-5 molecular sieve into an ammonium molybdate solution, carrying out constant-temperature bath and stirring, adding a nitrate solution of a second element into the solution, and stirring until the color of the solution is not changed; (2) Performing suction filtration, namely ventilating and standing the solid obtained by suction filtration at room temperature, drying and grinding to obtain catalyst dry powder; (3) Adding catalyst dry powder into a dispersant aqueous solution, and diluting with deionized water; (4) ball milling, and separating slurry; (5) spray drying; (6) Drying and roasting the mixture in a nitrogen atmosphere, and naturally cooling the mixture to room temperature; wherein, the second element is any one or two of Fe, co, mn, cu, zn, ga, cr and Ag. The invention also discloses the application of the catalyst in methane dehydroaromatization. The second element is introduced in the synthesis process of the catalyst, so that the wear-resisting strength of the catalyst can be improved.
Description
Technical Field
The invention belongs to the technical field of petrochemical catalysts, and particularly relates to a preparation method and application of a ZSM-5 molecular sieve catalyst.
Background
The molding refers to a unit process of preparing solid particles with certain shape, size and strength by mutually aggregating various powders, particles, solutions or molten raw materials under the action of certain external force. Solid catalysts, regardless of the method of preparation, are ultimately used in catalytic reactors in the form of particles of various shapes and sizes, and molding is an important process in catalyst preparation.
Spray forming is a forming method of preparing a microspherical catalyst from a suspension or paste material by using a drying device similar to milk powder production by applying a spray drying principle. The solution is usually dispersed into fine droplets by an atomizer, and the purpose of atomization is to disperse the slurry into fine droplets having an average diameter of 20 to 60 μm, and when the droplets come into contact with hot air, the droplets are rapidly vaporized and dried into a powder or granular product.
In the existing catalyst spray forming, a binder is required to be added in the forming process so as to improve the mechanical strength and the wear resistance of the formed catalyst. The addition of the binder has a certain influence on the activity of the catalyst, a catalyst evaluation device and the aftertreatment of the product to a certain extent, and the binder also has an influence on the external specific surface area of the catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a ZSM-5 molecular sieve catalyst, wherein a hollow shell type small crystal grain ZSM-5 molecular sieve is taken as a carrier, and a second element is introduced in the synthesis process of the catalyst, so that the wear-resisting strength of the catalyst is improved.
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding a carrier hollow shell type small crystal grain ZSM-5 molecular sieve into an ammonium molybdate solution, stirring for 28-46h at the constant temperature of 50-90 ℃ and the rotating speed of 90-120r/min, then adding a nitrate solution of a second element into the solution under the stirring state, and continuously stirring until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration for 24-36h at room temperature, drying and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 5-6%, and the loading amount of a second element is 2-5%;
(3) Adding the catalyst dry powder into a dispersant aqueous solution with the mass concentration of 4-7%, diluting with deionized water until the solid content of the catalyst slurry is 35-45%, and stirring in the diluting process;
(4) Adding the catalyst slurry into a ball mill for ball milling, and then separating the slurry;
(5) Spray drying the slurry obtained in the step (4);
(6) Drying the product obtained in the step (5) at 120-150 ℃ for 3-5h in nitrogen atmosphere, then heating to 450-500 ℃ for roasting for 4-5h, continuing heating to 550 ℃ for roasting for 0.5-1h, and naturally cooling to room temperature;
wherein the second element is any one or two of Fe, co, mn, cu, zn, ga, cr and Ag.
Preferably, the specific process of the ball milling is as follows: ball material ratio (3-5): 1, the ball milling time is 3-4h, and the ball milling frequency is 90-120Hz.
Preferably, agate balls are filled in the ball mill, and the mass ratio of the agate balls to the raw material is 1:2 are composed of 10mm and 6mm agate balls respectively.
Preferably, when the spray drying is carried out in the step (5), the feeding speed is 50-100mL/min, the temperature of a drying air inlet is 220-230 ℃, the temperature of an air outlet is 100-105 ℃, the system pressure is-50 Pa, and the frequency converter frequency of the atomizer is 70Hz.
Preferably, the conditions for drying in step (2) are: drying at 100-120 deg.C for 4-6 hr.
Preferably, the dispersant is polyvinyl alcohol.
Preferably, in the step (6), the temperature rise rate is 100 ℃/h.
The application of a ZSM-5 molecular sieve catalyst in methane dehydroaromatization comprises the following steps: the method is characterized in that: the application is as follows: carbonizing the catalyst, and reacting for 4-7h at 700-900 ℃ in a circulating fluidized bed reaction device by taking methane as a raw material, wherein the loading capacity of the catalyst is 30-200g, and the flow rate of the methane is 1.5L/min;
wherein the catalyst is prepared by the preparation method.
Preferably, the carbonization conditions are: the carbonization temperature is 650 ℃, and the carbonization time is 120min.
The solid content is the mass content of the catalyst dry powder in the catalyst slurry.
The invention has the advantages that:
the preparation method of the ZSM-5 molecular sieve catalyst provided by the invention is simple to operate, does not need an adhesive, takes the hollow shell type small-crystal-grain ZSM-5 molecular sieve as a carrier, introduces the second element in the synthesis process of the catalyst, can improve the wear-resisting strength of the catalyst, and has high selectivity of the total aromatic hydrocarbon of the raw materials when the prepared catalyst is used for the methane dehydrogenation aromatization reaction.
Detailed Description
The hollow shell type small crystal grain ZSM-5 molecular sieve adopted in the embodiment of the invention is the catalyst prepared in the patent CN104150507A in the embodiment 1.
Example 1
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 46h at constant temperature bath 50 ℃ under 90r/min, and then adding nitrate solution of second element Fe (NO) into the solution under stirring state 3 ) 3 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying at 100 ℃ for 6 hours, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 5%, and the loading amount of a second element Fe is 2%;
(3) Adding the catalyst dry powder into a polyvinyl alcohol aqueous solution with the mass concentration of 4%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 35%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 3 hours, wherein the frequency of a ball mill is 90Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 50mL/min, the temperature of a drying air inlet is 220 ℃, the temperature of an air outlet is 100 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 120 ℃ for 5h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 0.5h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 2
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 28h at constant temperature of 90 ℃ and 120r/min, and then adding nitrate solution of a second element Co, namely Co (NO) into the solution under stirring 3 ) 3 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 36h, drying at 120 ℃ for 4h, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amount of the second element Co is 5%;
(3) Adding the catalyst dry powder into a polyvinyl alcohol aqueous solution with the mass concentration of 7%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 5:1, ball milling for 4 hours, wherein the frequency of a ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed during spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, then heating to 500 ℃ for roasting for 4h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 3
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 36h at the constant temperature of 70 ℃ and the rotating speed of 100r/min, and then stirring downwards under the stirring stateTo which a nitrate solution of a second element Mn, i.e. Mn (NO), is added 3 ) 2 The aqueous solution of (2) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration for 30 hours at room temperature, drying the solid for 5 hours at 110 ℃, and grinding the solid to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 5 percent, and the loading amount of a second element Mn is 4 percent;
(3) Adding the catalyst dry powder into a polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 40%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 4:1, ball milling for 3 hours, wherein the frequency of the ball mill is 100Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in the spray drying process is 80mL/min, the temperature of a drying air inlet is 225 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 130 ℃ for 4h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 4
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 36h at constant temperature bath of 80 ℃ and 100r/min, and then adding a nitrate solution of a second element Cu, namely Cu (NO) into the solution under the stirring state 3 ) 2 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying the solid at 110 ℃ for 6 hours, and grinding the solid to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6 percent, and the loading amount of a second element Cu is 5 percent;
(3) Adding the catalyst dry powder into a polyvinyl alcohol aqueous solution with the mass concentration of 7%, diluting the catalyst dry powder with deionized water to obtain catalyst slurry with the solid content of 40%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersing agent;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 5:1, ball milling for 3 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 100mL/min, the temperature of a drying air inlet is 220 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 140 ℃ for 4h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 0.5h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 5
A preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into an ammonium molybdate solution, stirring for 28 hours at the constant temperature of 60 ℃ and the rotating speed of 120r/min, and then adding a nitrate solution of a second element Zn (namely Zn (NO) into the solution under the stirring state 3 ) 2 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying at 100 ℃ for 5 hours, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amount of a second element Zn is 5%;
(3) Adding the catalyst dry powder into a dispersant polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 4 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 6
The second element is Ga, and the other examples are the same as example 5, specifically as follows:
a preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into an ammonium molybdate solution, stirring for 28 hours at the constant temperature of 60 ℃ and the rotating speed of 120r/min, and then adding a nitrate solution of a second element Ga (namely Ga (NO) into the solution under the stirring state 3 ) 3 The aqueous solution of (2) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying at 100 ℃ for 5 hours, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amount of the second element Ga is 5%;
(3) Adding the catalyst dry powder into a dispersant polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 4 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 7
The second element is Cr, and the other elements are the same as those in example 5, specifically as follows:
a preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 28h at the constant temperature of 60 ℃ and the rotating speed of 120r/min, and then adding nitrate solution of second element Cr, namely Cr (NO) into the solution under the stirring state 3 ) 3 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying at 100 ℃ for 5 hours, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amount of a second element Cr is 5%;
(3) Adding the catalyst dry powder into a dispersant polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the mixture of the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 4 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 8
The second element is Ag, and the other steps are the same as those in example 5, specifically as follows:
a preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding the carrier hollow shell type small crystal grain ZSM-5 molecular sieve into ammonium molybdate solution, stirring for 28h at the constant temperature of 60 ℃ and the rotating speed of 120r/min, and then adding nitrate solution of second element Ag, namely AgNO into the solution under the stirring state 3 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration at room temperature for 24 hours, drying at 100 ℃ for 5 hours, and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amount of the second element Ag is 5%;
(3) Adding the catalyst dry powder into a dispersant polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 4 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed in spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Example 9
The second elements are Cu and Zn, and the others are the same as those in the embodiment 5, and the specific contents are as follows:
a preparation method of a ZSM-5 molecular sieve catalyst comprises the following steps:
(1) Adding a carrier hollow shell type small crystal grain ZSM-5 molecular sieve into an ammonium molybdate solution, stirring for 28 hours at the constant temperature of 60 ℃ and the rotating speed of 120r/min, and then respectively adding nitrate solutions of a second element Cu and Zn, namely Cu (NO) into the solution under the stirring state 3 ) 2 And Zn (NO) 3 ) 2 The aqueous solution of (1) is continuously stirred until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration for 24 hours at room temperature, drying the solid for 5 hours at 100 ℃, and grinding the solid to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 6%, and the loading amounts of the second elements Cu and Zn are 5% in total;
(3) Adding the catalyst dry powder into a dispersant polyvinyl alcohol aqueous solution with the mass concentration of 5%, diluting the catalyst dry powder with deionized water until the solid content of the catalyst slurry is 45%, and stirring the catalyst slurry in the diluting process; the polyvinyl alcohol is a dispersant;
(4) Adding the catalyst slurry into a ball mill for ball milling, wherein the ball mill is filled with agate balls, and the mass ratio of the agate balls to the agate balls is 1:2, the diameters of the agate balls are respectively 10mm and 6 mm; ball material ratio 3:1, ball milling for 4 hours, wherein the frequency of the ball mill is 120Hz, and then separating slurry;
(5) Spray drying the slurry obtained in the step (4), wherein the feeding speed during spray drying is 100mL/min, the temperature of a drying air inlet is 230 ℃, the temperature of an air outlet is 105 ℃, the system pressure is-50 Pa, and the frequency of a frequency converter of an atomizer is 70Hz;
(6) Drying the product obtained in the step (5) at 150 ℃ for 3h in a nitrogen atmosphere, then heating to 450 ℃ for roasting for 5h, continuing heating to 550 ℃ for roasting for 1h, and naturally cooling to room temperature; the rate of temperature rise is 100 ℃/h.
Comparative examples 1-9, which do not contain a second element, are otherwise the same as examples 1-9, with comparative examples 1-9 being provided for examples 1-9, respectively.
Wear resistance detection
The abrasion index of the catalyst finally prepared in each example was measured by an abrasion index measuring instrument, and the results are shown in Table 1.
Table 1 abrasion resistance index results
As can be seen from Table 1, the abrasion resistance of the prepared molecular sieve catalyst is improved by adding the second element.
2. Application of methane dehydroaromatization
The catalysts prepared in examples 1-9 were used in the dehydroaromatization of methane, with the following specific reactions: carbonizing the catalyst at 650 ℃ for 120min, reacting for 7h at 900 ℃ in a circulating fluidized bed reaction device by using methane as a raw material, wherein the loading capacity of the catalyst is 200g, and the flow rate of the methane is 1.5L/min.
The conversion of methane and the selectivity of total aromatics were measured and the results are shown in tables 2 and 3.
TABLE 2 conversion of methane (%)
Table 3 total aromatics selectivity (%)
As can be seen from tables 2 and 3, the catalyst provided by the invention has high selectivity of total aromatic hydrocarbon when used in methane dehydrogenation aromatization reaction.
Claims (8)
1. An application of a ZSM-5 molecular sieve catalyst in methane dehydroaromatization is characterized in that: the application is as follows: carbonizing the catalyst, and reacting for 4-7h at 700-900 ℃ in a circulating fluidized bed reaction device by taking methane as a raw material, wherein the loading capacity of the catalyst is 30-200g, and the flow rate of the methane is 1.5L/min;
wherein, the catalyst is prepared by the following method:
(1) Adding a carrier hollow shell type small crystal grain ZSM-5 molecular sieve into an ammonium molybdate solution, stirring for 28-46h at the constant temperature of 50-90 ℃ and the rotating speed of 90-120r/min, then adding a nitrate solution of a second element into the solution under the stirring state, and continuously stirring until the color of the solution is not changed;
(2) Performing suction filtration, namely ventilating and standing the solid obtained after suction filtration for 24-36h at room temperature, drying and grinding to obtain catalyst dry powder, wherein the loading amount of molybdenum in the catalyst dry powder is 5-6%, and the loading amount of a second element is 2-5%;
(3) Adding the catalyst dry powder into a dispersant aqueous solution with the mass concentration of 4-7%, diluting with deionized water until the solid content of the catalyst slurry is 35-45%, and stirring in the diluting process;
(4) Adding the catalyst slurry into a ball mill for ball milling, and then separating the slurry;
(5) Spray drying the slurry obtained in the step (4);
(6) Drying the product obtained in the step (5) at 120-150 ℃ for 3-5h in nitrogen atmosphere, then heating to 450-500 ℃ for roasting for 4-5h, continuing heating to 550 ℃ for roasting for 0.5-1h, and naturally cooling to room temperature;
wherein, the second element is any one or two of Co, mn, cu, zn, ga, cr or Ag.
2. Use of the ZSM-5 molecular sieve catalyst of claim 1 in dehydroaromatization of methane characterized by: the specific process of ball milling is as follows: ball-material ratio (3-5): 1, the ball milling time is 3-4h, and the ball milling frequency is 90-120Hz.
3. Use of the ZSM-5 molecular sieve catalyst of claim 2 in dehydroaromatization of methane characterized by: the ball mill is filled with agate balls, and the mass ratio of the agate balls to the water is 1:2 are composed of 10mm and 6mm agate balls respectively.
4. Use of a ZSM-5 molecular sieve catalyst as claimed in claim 3 in dehydroaromatization of methane characterized in that: and (5) during spray drying, the feeding speed is 50-100mL/min, the temperature of a drying air inlet is 220-230 ℃, the temperature of an air outlet is 100-105 ℃, the system pressure is-50 Pa, and the frequency converter frequency of the atomizer is 70Hz.
5. Use of the ZSM-5 molecular sieve catalyst of claim 4 in dehydroaromatization of methane characterized by: the drying conditions in the step (2) are as follows: drying at 100-120 deg.C for 4-6h.
6. Use of the ZSM-5 molecular sieve catalyst of claim 1 in dehydroaromatization of methane characterized by: the dispersing agent is polyvinyl alcohol.
7. Use of the ZSM-5 molecular sieve catalyst of claim 5 in dehydroaromatization of methane characterized by: in the step (6), the temperature rise rate is 100 ℃/h.
8. Use of a ZSM-5 molecular sieve catalyst as claimed in any of claims 1-7 in dehydroaromatization of methane characterized in that: the carbonization conditions are as follows: the carbonization temperature is 650 ℃, and the carbonization time is 120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011155400.1A CN112058302B (en) | 2020-10-26 | 2020-10-26 | Preparation method and application of ZSM-5 molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011155400.1A CN112058302B (en) | 2020-10-26 | 2020-10-26 | Preparation method and application of ZSM-5 molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112058302A CN112058302A (en) | 2020-12-11 |
| CN112058302B true CN112058302B (en) | 2023-02-28 |
Family
ID=73655990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011155400.1A Active CN112058302B (en) | 2020-10-26 | 2020-10-26 | Preparation method and application of ZSM-5 molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112058302B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385242A (en) * | 2002-05-30 | 2002-12-18 | 汕头大学 | Catalyst for methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen and preparation process thereof |
| JP2008260006A (en) * | 2007-03-20 | 2008-10-30 | Meidensha Corp | Atalyst for aromatization of lower hydrocarbon, and method for preparing aromatic compound |
| JP2009028710A (en) * | 2007-06-29 | 2009-02-12 | Meidensha Corp | Catalyst for aromatization of lower hydrocarbon |
| CN104275205A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Preparation method of catalyst for improving yield of diesel oil produced by catalytic cracking |
| CN105498829A (en) * | 2015-12-10 | 2016-04-20 | 大唐国际化工技术研究院有限公司 | Methanol aromatized catalyst as well as preparation method and application thereof |
| CN108479858A (en) * | 2018-04-27 | 2018-09-04 | 陕西延长石油(集团)有限责任公司研究院 | A kind of binder free spray forming technique improving molecular sieve catalyst intensity |
| CN108636445A (en) * | 2018-04-27 | 2018-10-12 | 陕西延长石油(集团)有限责任公司研究院 | A kind of preparation method and applications of high stability catalyst for aromatizing low-carbon paraffin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5736633B2 (en) * | 2008-04-18 | 2015-06-17 | 株式会社明電舎 | Catalyst and production method thereof |
| EA024439B1 (en) * | 2009-09-03 | 2016-09-30 | Басф Се | Process for producing benzene from methane |
-
2020
- 2020-10-26 CN CN202011155400.1A patent/CN112058302B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385242A (en) * | 2002-05-30 | 2002-12-18 | 汕头大学 | Catalyst for methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen and preparation process thereof |
| JP2008260006A (en) * | 2007-03-20 | 2008-10-30 | Meidensha Corp | Atalyst for aromatization of lower hydrocarbon, and method for preparing aromatic compound |
| JP2009028710A (en) * | 2007-06-29 | 2009-02-12 | Meidensha Corp | Catalyst for aromatization of lower hydrocarbon |
| CN104275205A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Preparation method of catalyst for improving yield of diesel oil produced by catalytic cracking |
| CN105498829A (en) * | 2015-12-10 | 2016-04-20 | 大唐国际化工技术研究院有限公司 | Methanol aromatized catalyst as well as preparation method and application thereof |
| CN108479858A (en) * | 2018-04-27 | 2018-09-04 | 陕西延长石油(集团)有限责任公司研究院 | A kind of binder free spray forming technique improving molecular sieve catalyst intensity |
| CN108636445A (en) * | 2018-04-27 | 2018-10-12 | 陕西延长石油(集团)有限责任公司研究院 | A kind of preparation method and applications of high stability catalyst for aromatizing low-carbon paraffin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112058302A (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102239677B1 (en) | Catalyst for oxidative dehydrogenation reaction, method for preparing thereof and oxidative dehydrogenation method using the same catalyst | |
| CN102755897A (en) | Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process | |
| CN112742362B (en) | Coke oven gas hydrodesulfurization catalyst and preparation method and application thereof | |
| CN114768863B (en) | Heavy oil hydrodesulfurization catalyst and preparation method thereof | |
| CN108671934A (en) | A kind of preparation method of the Hydrobon catalyst of high mechanical properties | |
| CN112058302B (en) | Preparation method and application of ZSM-5 molecular sieve catalyst | |
| CN107930644A (en) | A kind of high-performance methanol synthesis catalyst and preparation method thereof | |
| CN110142060B (en) | Silicon carbide/silicon nitride carrier and preparation method thereof, Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
| CN111468048A (en) | Preparation method of high-strength gamma-alumina microspheres | |
| CN108579742B (en) | Dehydrogenation catalyst and method for preparing same | |
| CN112657504B (en) | Coating type catalyst for preparing formaldehyde by oxidizing methanol with iron-molybdenum method and preparation method thereof | |
| CN110732342A (en) | Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof | |
| CN108479858A (en) | A kind of binder free spray forming technique improving molecular sieve catalyst intensity | |
| CN109894121B (en) | Preparation method of catalyst for preparing 1, 3-butadiene from butylene | |
| CN112742408B (en) | Dry gas hydrogenation saturated olefin and desulfurization catalyst, and preparation method and application thereof | |
| US3855153A (en) | Unsupported catalyst for the oxidation of methanol to formaldehyde | |
| CN109894119B (en) | Preparation method of catalyst for preparing 1, 3-butadiene from butylene | |
| CN110614108B (en) | Isobutane dehydrogenation catalyst with carrier being mesoporous molecular sieve with three-dimensional cage-shaped pore channel distribution structure, preparation method and application | |
| JPS63315148A (en) | Catalyst of synthesis of methacrylic acid and preparation thereof showing excellent reproducibility | |
| CN109201070B (en) | Catalyst for preparing 1, 3-butadiene from butylene | |
| CN109201062B (en) | Fischer-Tropsch synthesis precipitated iron-based catalyst, preparation method thereof and Fischer-Tropsch synthesis method | |
| CN107537508B (en) | Compound iron zinc catalyst presoma, by its catalyst synthesized and its preparation method and application | |
| CN109201056B (en) | Catalyst for preparing 1, 4-butanediol from dimethyl maleate | |
| CN111644172A (en) | Catalyst for liquid phase hydrogenation and preparation method and application thereof | |
| CN111072486A (en) | Method for synthesizing lower aliphatic amine based on ultrasonic deoxygenation ethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |