CN108636441B - Nano metal fiber doped molecular sieve, and preparation method and application thereof - Google Patents
Nano metal fiber doped molecular sieve, and preparation method and application thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 67
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 46
- 239000010457 zeolite Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 71
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910017816 Cu—Co Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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- 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
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- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C07—ORGANIC CHEMISTRY
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- C07C2529/00—Catalysts comprising molecular sieves
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- C07C2529/068—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- C07C2529/072—Iron group metals or copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a nano metal fiber doped molecular sieve, a preparation method and application thereof, belonging to the field of chemistry and materials. Dispersing zeolite particles in a solvent in the form of colloidal particles to obtain zeolite sol gel with solid content; and (3) uniformly mixing the zeolite sol gel and the nano metal fibers, carrying out closed reaction on the uniformly mixed solution under a vacuum condition, and drying and calcining after the reaction is finished to obtain the nano metal fiber doped zeolite molecular sieve. The zeolite molecular sieve doped with the nano metal fibers prepared by the invention has high strength, high selectivity and adsorption performance. Because the nanometer metal fiber is supported in the pore canal of the template after roasting, the structure of the molecular sieve is effectively strengthened, and the strength of the molecular sieve can completely meet the use requirement.
Description
Technical Field
The invention relates to the field of chemistry and materials, in particular to a nano metal fiber doped molecular sieve, a preparation method and application thereof.
Background
In recent years, an assembly method using a template technique has been widely studied in material research, and the template technique is also one of effective methods for preparing zeolite molecular sieves. For example, the method adopts the space generated by the close packing of polystyrene pellets as a template, the porous structure of bacteria or tree tissues as a template, polyurethane foam as a template, and anion exchange resin micropores as a template, etc.
However, since zeolite particles are bonded together by electrostatic force during the assembly process, voids are inevitably present between the particles, and although the silicon hydroxyl groups on the zeolite surface can be partially condensed by calcination, the strength of the assembly material is weak due to the limited contact area between the particles, and it is difficult to meet practical requirements. Therefore, it is very critical to improve the strength of zeolite molecular sieves prepared by the template assembly method by various methods.
Disclosure of Invention
The invention aims to provide a nano metal fiber doped molecular sieve, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a molecular sieve doped with nano metal fibers is prepared by the following method: dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in a solvent in the form of colloidal particles to obtain zeolite sol gel with the solid content of 1-30 wt%; mixing the following components in a mass ratio of 12-20: 0.1-13 of zeolite sol gel and nano metal fibers are uniformly mixed, the uniformly mixed liquid is subjected to closed reaction under the vacuum condition, and after the reaction is finished, drying and calcining are carried out to obtain the nano metal fiber doped zeolite molecular sieve, wherein: the nano metal fiber is nano Cu-Co alloy fiber, nano Fe-Ag alloy fiber, nano Ni fiber, nano Cu fiber, nano Pd fiber or nano Co-Ag alloy fiber. .
A method for preparing a molecular sieve doped with nano metal fibers comprises the steps of dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in a solvent in the form of colloidal particles to obtain zeolite sol gel with the solid content of 1-30 wt%; mixing the following components in a mass ratio of 12-20: 0.1-1 of zeolite sol gel and nano metal fibers are uniformly mixed, the uniformly mixed liquid is subjected to closed reaction under the vacuum condition, and after the reaction is finished, drying and calcining are carried out to obtain the nano metal fiber doped zeolite molecular sieve, wherein: the nano metal fiber is nano Cu-Co alloy fiber, nano Fe-Ag alloy fiber, nano Ni fiber, nano Cu fiber, nano Pd fiber or nano Co-Ag alloy fiber. .
The technical scheme of the invention is as follows: the solvent is an alcohol solvent containing 1-3 carbon atoms.
The technical scheme of the invention is as follows: the temperature of the closed reaction under the vacuum condition is 60-75 ℃, and the reaction time is 2-4 h.
The technical scheme of the invention is as follows: the calcining temperature is 400-460 ℃, and the calcining time is 1-5 h.
A kind ofThe method for catalytically synthesizing the p-xylene by using the molecular sieve takes dimethyl carbonate and toluene as raw materials, takes the molecular sieve doped with the nano metal fibers as a catalyst, and has the temperature of 200-220 ℃, the pressure of 0.1-0.4 MPa and the mass space velocity of 2-6 h-1The reaction is carried out under the condition that the molar ratio of the raw materials of toluene and dimethyl carbonate is 1: 1 to 5.
In some preferred embodiments: the pressure is 0.2-0.4 MPa, and the mass airspeed is 4-6 h-1The reaction is carried out under the condition, wherein the molar ratio of the raw materials of toluene to dimethyl carbonate is 1: 3 to 5.
The invention has the beneficial effects that:
the zeolite molecular sieve doped with the nano metal fibers prepared by the invention has high strength, high selectivity and adsorption performance. Because the nanometer metal fiber is supported in the pore canal of the template after roasting, the structure of the molecular sieve is effectively strengthened, and the strength of the molecular sieve can completely meet the use requirement. In addition, the zeolite molecular sieve doped with the nano metal fibers prepared by the invention can enable the molecular sieve to have specific catalytic function characteristics or selective adsorption characteristics.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
the nano Cu fiber and the nano Ni fiber in the technical scheme of the invention are prepared according to the contents reported in the following documents: motoyama M, Fukunaka Y, Sakka T, et al.electrochemical processing of Cu and Ni nanowire arrays [ J ]. Journal of electrochemical Chemistry 2005,584:84-91.
The nano Pd fiber in the technical scheme of the invention is prepared according to the contents reported in the following documents:
Wang D H,Zhou W L,McCaughy B F,et al.Electrodeposition of metallic nanowire thin films using mesoporous silica templates[J].Adv Mater,2003,15(2):130.
the nano Cu-Co alloy fiber, the nano Fe-Ag alloy fiber and the nano Co-Ag alloy fiber in the technical scheme of the invention are prepared according to the contents reported in the following documents:
Wang Y W,Zhang L D,Meng G W, et al.Fabrication of ordered ferromagnetic nonmagnetic alloy nanowire arrays and their magnetic property dependence on annealing temperature[J].J Phys Chem B, 2002,106(10):2502.
example 1
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 15 wt%; mixing zeolite sol gel with solid content of 15wt% and nano Cu-Co alloy fiber in a mass ratio of 12: 1, and carrying out vacuum closed reaction for 2.5 hours at the temperature of 60-65 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the zeolite molecular sieve doped with the nano Cu-Co alloy fibers.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Cu-Co alloy fibers prepared by the embodiment is 5.23 Kg/mm; determination of its H by the BET method2O and CO2Adsorption capacity, H at 25 ℃ at a relative humidity of 50%2O adsorption amount of 48.22%, and CO adsorption amount at 250mmHg column2The adsorption amount was 35.28%.
Catalytic preparation of p-xylene with toluene:
in a molar ratio of 4: dimethyl carbonate and toluene of 1 are used as raw materials, the zeolite molecular sieve doped with the nano Cu-Co alloy fiber prepared in the example 1 is used as a catalyst, the temperature is 210 ℃, the pressure is 0.2 MPa, and the mass space velocity is 5h-1The conversion rate of toluene reaches 96.3 percent, and the selectivity of p-xylene reaches 98.13 percent.
Example 2
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 10 wt%; mixing zeolite sol gel with solid content of 10wt% and nano Fe-Ag alloy fiber in a mass ratio of 20: 1, and carrying out vacuum sealing reaction for 2 hours at 70-75 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the zeolite molecular sieve doped with the nano Fe-Ag alloy fibers.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Fe-Ag alloy fiber prepared by the embodiment is 5.40 Kg/mm; determination of its H by the BET method2O and CO2Adsorption capacity, H at 25 ℃ relative humidity of 52%2O adsorption amount of 52.21%, and CO adsorption amount at 250mmHg column2The adsorption amount was 34.36%.
Catalytic preparation of p-xylene with toluene:
according to a molar ratio of 3: dimethyl carbonate and toluene of 1 are used as raw materials, the zeolite molecular sieve doped with the nano Fe-Ag alloy fiber prepared in the example 2 is used as a catalyst, the temperature is 200 ℃, the pressure is 0.3 MPa, and the mass space velocity is 4h-1The conversion rate of toluene reaches 95.2%, and the selectivity of p-xylene reaches 96.3%.
Example 3
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 20 wt%; mixing zeolite sol gel with solid content of 20wt% and nano Ni fiber in a mass ratio of 15: 0.5, and carrying out vacuum closed reaction for 2.5 hours at the temperature of 60-65 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the zeolite molecular sieve doped with the nano Ni fibers.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Ni fibers prepared by the embodiment is 5.02 Kg/mm; determination of its H by the BET method2O and CO2Adsorption capacity, H at 25 ℃ at a relative humidity of 50%2O adsorption amount of 47.29%, and CO adsorption amount at 250mmHg column2The adsorption amount was 38.24%.
Catalytic preparation of p-xylene with toluene:
in a molar ratio of 5: dimethyl carbonate and toluene of 1 are used as raw materials, the zeolite molecular sieve doped with the nano Ni fibers prepared in the example 1 is used as a catalyst, the temperature is 220 ℃, the pressure is 0.4MPa, and the mass space velocity is 6h-1The conversion rate of toluene reaches 94.3 percent, and the p-xylene is reactedThe selectivity of the catalyst is up to 96.13 percent.
Example 4
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 25 wt%; mixing zeolite sol gel with solid content of 25wt% and nano Cu fiber in a mass ratio of 15: 0.8, and carrying out vacuum closed reaction for 2.5 hours at the temperature of 60-65 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the zeolite molecular sieve doped with the nano Cu fibers.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Cu fibers prepared by the embodiment is 5.29 Kg/mm; determination of its H by the BET method2O and CO2Adsorption capacity, H at 25 ℃ at a relative humidity of 50%2O adsorption of 49.28%, CO adsorption at 250mmHg column2The adsorption amount was 36.55%.
Catalytic preparation of p-xylene with toluene:
in a molar ratio of 4: dimethyl carbonate and toluene of 1 are used as raw materials, the nano Cu fiber-doped zeolite molecular sieve prepared in example 1 is used as a catalyst, the temperature is 210 ℃, the pressure is 0.2 MPa, and the mass space velocity is 5h-1The conversion rate of toluene reaches 94.3 percent, and the selectivity of p-xylene reaches 97.1 percent.
Example 5
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 25 wt%; mixing zeolite sol gel with solid content of 25wt% and nano Pd fiber in a mass ratio of 18: 1, and carrying out vacuum closed reaction for 2.5 hours at the temperature of 60-65 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the nano Pd fiber doped zeolite molecular sieve.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Pd fibers prepared in the embodiment is 5.20 Kg/mm; determination of its H by the BET method2O and CO2Amount of adsorptionH at 25 ℃ at a relative humidity of 50%2O adsorption of 49.08%, CO adsorption at 250mmHg column2The adsorption amount was 34.16%.
Catalytic preparation of p-xylene with toluene:
according to a molar ratio of 3: dimethyl carbonate and toluene of 1 are used as raw materials, the nano Pd fiber-doped zeolite molecular sieve prepared in example 1 is used as a catalyst, the temperature is 210 ℃, the pressure is 0.2 MPa, and the mass space velocity is 5h-1The conversion rate of toluene reaches 96.3 percent, and the selectivity of p-xylene reaches 98.13 percent.
Example 6
Dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in methanol in the form of colloidal particles to obtain zeolite sol gel with the solid content of 30 wt%; mixing zeolite sol gel with solid content of 30wt% and nano Co-Ag alloy fiber in a mass ratio of 18: 0.3, and carrying out vacuum closed reaction for 2.5 hours at the temperature of 60-65 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an Ar gas protective gas atmosphere with the flow rate of 5ml/min to obtain the zeolite molecular sieve doped with the nano Co-Ag alloy fibers.
And (5) performance measurement and inspection. Tests prove that the strength of the zeolite molecular sieve product doped with the nano Co-Ag alloy fiber prepared by the embodiment is 5.66 Kg/mm; determination of its H by the BET method2O and CO2Adsorption capacity, H at 25 ℃ at a relative humidity of 50%2O adsorption of 49.38%, CO adsorption on 250mmHg column2The adsorption amount was 39.21%.
Catalytic preparation of p-xylene with toluene:
in a molar ratio of 5: dimethyl carbonate and toluene of 1 are used as raw materials, the zeolite molecular sieve doped with the nano Co-Ag alloy fiber prepared in the example 1 is used as a catalyst, the temperature is 210 ℃, the pressure is 0.2 MPa, and the mass space velocity is 6h-1The conversion rate of toluene reaches 98.3%, and the selectivity of p-xylene reaches 94.22%.
Claims (4)
1. A method for synthesizing paraxylene by utilizing molecular sieve catalysis is characterized by comprising the following steps: the method uses dimethyl carbonate and methylBenzene is used as a raw material, a molecular sieve doped with nano metal fibers is used as a catalyst, the temperature is 200-220 ℃, the pressure is 0.1-0.4 MPa, and the mass space velocity is 2-6 h-1The reaction is carried out under the condition that the molar ratio of the raw materials of toluene and dimethyl carbonate is 1: 1-5;
the molecular sieve is prepared by the following method: dispersing zeolite particles with the average particle size of less than or equal to 0.3 mu m in a solvent in the form of colloidal particles to obtain zeolite sol gel with the solid content of 1-30 wt%; mixing the following components in a mass ratio of 12-20: 0.1-1 of zeolite sol gel and nano metal fibers are uniformly mixed, the uniformly mixed liquid is subjected to closed reaction under the vacuum condition, and after the reaction is finished, drying and calcining are carried out to obtain the nano metal fiber doped zeolite molecular sieve, wherein: the nano metal fiber is a nano Cu-Co alloy fiber, a nano Fe-Ag alloy fiber, a nano Ni fiber, a nano Cu fiber, a nano Pd fiber or a nano Co-Ag alloy fiber; the temperature of the closed reaction under the vacuum condition is 60-75 ℃, and the reaction time is 2-4 h.
2. The method for catalytic synthesis of paraxylene by molecular sieve according to claim 1, characterized in that: the pressure is 0.2-0.4 MPa, and the mass airspeed is 4-6 h-1The reaction is carried out under the condition, wherein the molar ratio of the raw materials of toluene to dimethyl carbonate is 1: 3 to 5.
3. The method for catalytic synthesis of paraxylene by molecular sieve according to claim 1, characterized in that: the solvent in the preparation method of the molecular sieve is an alcohol solvent containing 1-3 carbon atoms.
4. The method for catalytic synthesis of paraxylene by molecular sieve according to claim 1, characterized in that: the calcination temperature in the preparation method of the molecular sieve is 400-460 ℃, and the calcination time is 1-5 h.
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