CN110860308B - Method for one-step alkali-free solid-phase synthesis of metal molecular sieve catalyst - Google Patents

Method for one-step alkali-free solid-phase synthesis of metal molecular sieve catalyst Download PDF

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CN110860308B
CN110860308B CN201910995540.0A CN201910995540A CN110860308B CN 110860308 B CN110860308 B CN 110860308B CN 201910995540 A CN201910995540 A CN 201910995540A CN 110860308 B CN110860308 B CN 110860308B
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silica
molecular sieve
hydroxide
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zeolite
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CN110860308A (en
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吴勤明
孟祥举
肖丰收
马野
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Jiangsu Lvke New Materials Co.,Ltd.
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Zhejiang University ZJU
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    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/40—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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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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Abstract

The invention relates to a preparation method of a molecular sieve, and aims to provide a method for synthesizing a metal molecular sieve catalyst by a one-step alkali-free metal solid phase method. The method comprises the following steps: adding a silicon-aluminum source, metal hydroxide, an organic amine ligand and a template agent into a mortar, grinding at room temperature, and uniformly mixing; then transferring the mixture into a reaction kettle, adding sodium-free zeolite seed crystals, and carrying out crystallization reaction at 140-180 ℃ for 3-12 days; and directly calcining the reaction product to obtain the molecular sieve catalyst. The whole production process of the invention does not use alkali metal cations such as sodium ions, greatly improves the yield and the kettle utilization rate by a solid phase method, and reduces unnecessary loss in the production process; the product keeps good crystallinity and purity, and has good catalytic reaction activity. The product has larger specific surface area and potential application value to important catalytic reaction. The adopted inorganic raw materials are environment-friendly and have low price, and the method has important significance in the field of actual chemical production.

Description

Method for one-step alkali-free solid-phase synthesis of metal molecular sieve catalyst
Technical Field
The invention belongs to a preparation method of a molecular sieve, and particularly relates to a method for synthesizing SSZ-13, ZSM-5, Beta and EU-1 metal molecular sieve catalysts respectively containing Cu, Ni and Co by a one-step solid-phase alkali-free method.
Background
Zeolites, particularly aluminosilicate zeolites, have been widely used in industrial applications for decades due to their uniform micropore distribution, high thermal and hydrothermal stability, and large surface area. In recent years, metal-exchanged zeolites have received particular attention. For example, Cu intersection has been commercializedUse of exchanged aluminosilicate SSZ-13 zeolites in the treatment of NH3(NH3-SCR) exhibits excellent performance in selective catalytic reduction of NOx; ni exchanged zeolite beta is active for olefin dimerization; co-exchanged ZSM-5 zeolite in N2The catalyst shows good catalytic performance in O decomposition and has good application prospect in industry.
Conventional metal exchanged zeolites require hydrothermal or solid phase synthesis, washing, high temperature direct calcination to remove organic templating agents, ammonium exchange, washing, high temperature direct calcination, metal cation exchange, washing, and high temperature direct calcination to obtain the final catalyst, which produces a large amount of pollution during the catalyst preparation process. In addition, alkali metal cations are inevitably used to balance the molecular sieve framework charge in both hydrothermal and solid phase synthesis.
Therefore, it is necessary to propose a method for synthesizing a metal-containing molecular sieve catalyst to reduce contamination.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for synthesizing a metal molecular sieve catalyst by a one-step alkali-free metal solid phase method.
In order to solve the technical problem, the solution of the invention is as follows:
the method for synthesizing the metal molecular sieve catalyst by the one-step alkali-free solid phase comprises the following steps:
adding a silicon-aluminum source, metal hydroxide, an organic amine ligand and a template agent into a mortar, grinding at room temperature, and uniformly mixing; then transferring the mixture into a reaction kettle, adding sodium-free zeolite seed crystals, and carrying out crystallization reaction at 140-180 ℃ for 3-12 days; directly calcining the reaction product to obtain a molecular sieve catalyst;
the addition amount of each reaction raw material is controlled so that the components and the molar ratio in the reaction system are SiO2∶Al2O3Metal hydroxide, organic amine ligand, template agent and H2O is 1: 0.0042-0.0625: 0.03-0.10: 0.03-0.20: 0.1-0.2: 2.15, and the usage amount of the zeolite seed crystal is 2% of the mass of the silicon-aluminum source; the metal hydroxide is Cu(OH)2Or Ni (OH)2The organic amine ligand is tetraethylenepentamine or diethylenetriamine.
The invention also provides a method for synthesizing the metal molecular sieve catalyst by the one-step alkali-free solid phase method, which comprises the following steps:
adding a silicon-aluminum source, a cobalt-amine complex (Co-DEPA) and a template agent into a mortar, grinding at room temperature, and uniformly mixing; then transferring the mixture into a reaction kettle, adding sodium-free zeolite seed crystals, and carrying out crystallization reaction at 140-180 ℃ for 3-12 days; directly calcining the reaction product to obtain a molecular sieve catalyst;
the addition amount of each reaction raw material is controlled so that the components and the molar ratio in the reaction system are SiO2∶Al2O3Co-DEPA template agent H2O is 1: 0.0042-0.0625: 0.03-0.10: 0.1-0.2: 2.15, and the usage amount of the zeolite seed crystal is 2% of the mass of the silicon-aluminum source; the cobalt amine complex is a cobalt hydroxide-diethylenetriamine complex.
In the invention, the silicon-aluminum source is silicon-aluminum adhesive with controllable silicon-aluminum ratio.
In the invention, the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or hexamethonium hydroxide.
In the present invention, the sodium-free zeolite seeds are conventional SSZ-13 zeolite, ZSM-5 zeolite, zeolite Beta or EU-1 zeolite.
The mass concentration of the cobalt amine complex (Co-DEPA) in the present invention was 22 wt.%.
In the present invention, the sodium-free zeolite seed crystals are conventional SSZ-13 zeolite, ZSM-5 zeolite, Beta zeolite or EU-1 zeolite, and the crystallization reaction temperatures thereof are 160 ℃, 180 ℃, 140 ℃ and 160 ℃, respectively.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes sodium-free silica-alumina gel with different silica-alumina ratios as a silica-alumina source, takes a cuprammonium, a nickel amine or a cobalt amine complex as an introducing agent of copper, nickel and cobalt, takes N, N, N-trimethyl-1-adamantyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetraethyl ammonium hydroxide and hexamethonium hydroxide as a template agent, and takes sodium-free conventional SSZ-13, ZSM-5, Beta and EU-1 as seed crystals. Compared with the prior art, the whole production process does not use alkali metal cations such as sodium ions, and can greatly improve the yield and the kettle utilization rate by a solid phase method, reduce unnecessary loss in the production process to the maximum extent,
2. the product obtained by the invention keeps good crystallinity and purity, and has good catalytic reaction activity. The product has a large specific surface area and has potential application value for important catalytic reaction.
3. The inorganic raw materials adopted by the invention are environment-friendly and have low price, so the invention has important significance in the field of actual chemical production.
Drawings
FIG. 1: XRD spectrum represented by Cu-SSZ-13.
FIG. 2: nitrogen adsorption isotherm for Cu-SSZ-13 product.
FIG. 3: SEM photograph represented by Cu-SSZ-13.
FIG. 4: XRD spectrum represented by Cu-ZSM-5.
FIG. 5: SEM photograph represented by Cu-ZSM-5.
FIG. 6: the XRD spectrum represented by Cu-Beta.
FIG. 7: Cu-Beta is a typical SEM photograph.
FIG. 8: XRD spectrum represented by Cu-EU-1.
FIG. 9: SEM photograph represented by Cu-EU-1.
FIG. 10: typical XRD patterns are represented by Ni-SSZ-13.
FIG. 11: SEM photograph represented by Ni-SSZ-13.
FIG. 12: XRD spectrum represented by Ni-ZSM-5.
FIG. 13: SEM photograph represented by Ni-ZSM-5.
FIG. 14: and the XRD spectrum represented by Ni-Beta.
FIG. 15: and SEM photograph represented by Ni-Beta.
FIG. 16: XRD spectrum represented by Ni-EU-1.
FIG. 17: SEM photograph represented by Ni-EU-1.
FIG. 18: representative XRD patterns are Co-SSZ-13.
FIG. 19: SEM photograph represented by Co-SSZ-13.
FIG. 20: XRD spectrum represented by Co-ZSM-5.
FIG. 21: SEM photograph represented by Co-ZSM-5.
FIG. 22: Co-Beta is a typical XRD spectrum.
FIG. 23: and a SEM photograph represented by Co-Beta.
FIG. 24: XRD spectrum represented by Co-EU-1.
FIG. 25: SEM photograph represented by Co-EU-1.
Detailed Description
The following describes an implementation of the present invention in detail with reference to specific embodiments.
Example 1: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-SSZ-13 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, and uniformly grinding the materials at room temperature, wherein the components and the molar ratio of the mixture are SiO2:Al2O3:Cu(OH)2Tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, H2O is 1:0.0042:0.04:0.04:0.2:2.15, the amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 3 days at the temperature of 160 ℃, and the product is directly calcined, thus obtaining the Cu-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
FIG. 1 is an XRD spectrum of a sample, from which it can be seen that the product has a typical molecular sieve structure of SSZ-13 zeolite and the sample has a high degree of crystallinity.
Fig. 2 is a nitrogen adsorption desorption isotherm of a sample, from which it can be seen that the sample has a typical microporous adsorption curve and has a high specific surface area.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a sample. As can be seen from the scanning electron micrograph, the sample has a typical spherical shape.
Example 2: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-SSZ-13 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, and uniformly grinding the materials at room temperature, wherein the components and the molar ratio of the mixture are SiO2:Al2O3:Cu(OH)2Tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, H2O is 1:0.0625:0.03:0.03:0.1:2.15, the amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 6 days at the temperature of 160 ℃, and the product is directly calcined, thus obtaining the Cu-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 3: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-SSZ-13 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, and uniformly grinding the materials at room temperature, wherein the components and the molar ratio of the mixture are SiO2:Al2O3:Cu(OH)2The preparation method comprises the following steps of preparing tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, H2O, wherein the weight ratio of the tetraethylenepentamine to the H2O is 1:0.017:0.10:0.20:0.15:2.15, the using amount of zeolite seed crystals is 2% of the mass fraction of silica-alumina gel, transferring the mixture into a reaction kettle, crystallizing for 12 days at the temperature of 160 ℃, and directly calcining the product to obtain the Cu-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 4: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-ZSM-5 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:TPAOH:H2O is 1:0.0042:0.03:0.03:0.15:2.15, the amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 4 days at the temperature of 180 ℃, and the product is directly calcined, thus obtaining the Cu-ZSM-5 molecular sieve catalyst.
Example 5: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-ZSM-5 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:TPAOH:H2O is 1:0.045:0.04:0.04:0.2:2.15, the use amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 3 days at the temperature of 180 ℃, and the product is directly calcined, thus obtaining the Cu-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
FIG. 4 is an XRD spectrum of a sample, from which it can be seen that the product has a typical ZSM-5 zeolite molecular sieve structure and the sample has a high degree of crystallinity.
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 6: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-ZSM-5 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:TPAOH:H2O is 1:0.0625:0.10:0.20:0.1:2.15, the amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 12 days at the temperature of 180 ℃, and the product is directly calcined, thus obtaining the Cu-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 7: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-Beta molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Cu(OH)2:TEPA:TEAOH:H2O is 1:0.037:0.04:0.04:0.2:2.15, the amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 4 days at the temperature of 140 ℃, and the product is directly calcined to obtain the Cu-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample of figure 6 shows that the product has a typical zeolite Beta molecular sieve structure, and the sample has high crystallinity.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 8: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-Beta molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Cu(OH)2:TEPA:TEAOH:H2O is 1:0.0062:0.03:0.03:0.1:2.15, the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred to a reaction kettle, the mixture is crystallized for 3 days at the temperature of 140 ℃, and the product is directly calcined, thus obtaining the Cu-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 9: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-Beta molecular sieve
Placing copper hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, and uniformly grinding the materials at room temperatureThe reaction raw materials are added in such an amount that the components and the molar ratio of the components in the mixture before the mixture is charged into the reaction vessel are SiO2:Al2O3:Cu(OH)2:TEPA:TEAOH:H2O is 1:0.0625:0.10:0.20:0.15:2.15, the amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle, the mixture is crystallized for 12 days at the temperature of 140 ℃, and the product is directly calcined, thus obtaining the Cu-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 10: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-EU-1 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:HMOH:H2O is 1:0.0042:0.04:0.04:0.2:2.15, the amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 6 days at the temperature of 160 ℃, and the product is directly calcined, thus obtaining the Cu-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample of figure 8 shows that the product has a typical EU-1 zeolite molecular sieve structure, and the sample has high crystallinity.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 11: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-EU-1 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:HMOH:H2O is 1:0.033:0.03:0.03:0.15:2.15, the amount of zeolite seed crystals is 2% by mass of the silica-alumina gel, and the mixture is then transferred to a mixerAnd (3) moving the mixture into a reaction kettle, crystallizing the mixture for 3 days at the temperature of 160 ℃, and directly calcining the product to obtain the Cu-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 12: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Cu-EU-1 molecular sieve
Placing copper hydroxide, tetraethylenepentamine, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Cu(OH)2:TEPA:HMOH:H2O is 1:0.0625:0.10:0.20:0.1:2.15, the amount of the zeolite seed crystals is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle, the mixture is crystallized for 12 days at the temperature of 160 ℃, and the product is directly calcined, thus obtaining the Cu-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 13: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-SSZ-13 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is to ensure that the components in the mixture before being filled into a reaction kettle and the molar ratio are SiO2:Al2O3:Ni(OH)2:DETA:TMAdaOH:H2O is 1:0.0042:0.10:0.20:0.15:2.15, the amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel, then the mixture is transferred into a reaction kettle and crystallized for 12 days at the temperature of 160 ℃, and the product is directly calcined, thus obtaining the Ni-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 14: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-SSZ-13 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica alumina gel with controllable silica alumina ratio into a mortar, and grinding the materials at room temperatureThe reaction materials are added uniformly in such an amount that the components and the molar ratio of the reaction materials in the mixture before the mixture is charged into the reaction vessel are SiO2:Al2O3:Ni(OH)2:DETA:TMAdaOH:H2O is 1:0.033:0.04:0.08:0.2:2.15, and the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 6 days at 160 ℃, and directly calcining the product to obtain the Ni-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample of fig. 10 shows that the product has a typical molecular sieve structure of SSZ-13 zeolite, and the sample has high crystallinity.
FIG. 11 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 15: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-SSZ-13 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is to ensure that the components in the mixture before being filled into a reaction kettle and the molar ratio are SiO2:Al2O3:Ni(OH)2:DETA:TMAdaOH:H2O is 1:0.0625:0.03:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 160 ℃, and directly calcining the product to obtain the Ni-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 16: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-ZSM-5 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Ni(OH)2:DETA:TPAOH:H2O is 1:0.0042:0.10:0.20:0.15:215, the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 180 ℃, and directly calcining the product to obtain the Ni-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 17: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-ZSM-5 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Ni(OH)2:DETA:TPAOH:H2O is 1:0.033:0.04:0.08:0.2:2.15, and the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 180 ℃, and directly calcining the product to obtain the Ni-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample of fig. 12 shows that the product has a typical ZSM-5 zeolite molecular sieve structure, and the sample has a high degree of crystallinity.
FIG. 13 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 18: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-ZSM-5 molecular sieve
Putting fresh nickel hydroxide, tetraethylenepentamine, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio are SiO2:Al2O3:Ni(OH)2:DETA:TPAOH:H2O is 1:0.0625:0.03:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 4 days at 180 ℃, and directly calcining the product to obtain the Ni-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 19: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-Beta molecular sieve
Placing fresh nickel hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.0042:0.10:0.20:0.15:2.15, and the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 140 ℃, and directly calcining the product to obtain the Ni-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 20: compared with the method of synthesizing the Ni-Beta molecular sieve which can directly use the catalytic reaction by a one-step method solid phase alkali-free metal cation
Placing fresh nickel hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.045:0.04:0.08:0.2:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 4 days at 140 ℃, and directly calcining the product to obtain the Ni-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample of figure 14 shows that the product has a typical zeolite Beta molecular sieve structure, and the sample has high crystallinity.
FIG. 15 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 21: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-Beta molecular sieve
Fresh nickel hydroxide, tetraethylenepentamine, tetraethylammonium hydroxide and silicon controlled aluminum ratioThe silica-alumina gel is put in a mortar, the materials are uniformly ground at room temperature, and the addition amount of each reaction raw material is that the components and the molar ratio in the mixture before being put into a reaction kettle are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.0625:0.03:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 140 ℃, and directly calcining the product to obtain the Ni-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 22: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-EU-1 molecular sieve
Placing fresh nickel hydroxide, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the above materials uniformly at room temperature, wherein the addition amount of each reaction raw material is such that the components and molar ratio in the mixture before charging into a reaction kettle are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.0042:0.04:0.08:0.2:2.15, and the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 6 days at 160 ℃, and directly calcining the product to obtain the Ni-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the sample shown in figure 16 shows that the product has a typical EU-1 zeolite molecular sieve structure, and the sample has high crystallinity.
FIG. 17 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 23: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-EU-1 molecular sieve
Placing fresh nickel hydroxide, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the above materials uniformly at room temperature, wherein the addition amount of each reaction raw material is such that the components and molar ratio in the mixture before charging into a reaction kettle are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.019:0.10:0.20:0.15:2.15, zeoliteThe usage amount of the seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 160 ℃, and directly calcining the product to obtain the Ni-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 24: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Ni-EU-1 molecular sieve
Placing fresh nickel hydroxide, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, grinding the above materials uniformly at room temperature, wherein the addition amount of each reaction raw material is such that the components and molar ratio in the mixture before charging into a reaction kettle are SiO2:Al2O3:Ni(OH)2:DETA:TEAOH:H2O is 1:0.0625:0.03:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 160 ℃, and directly calcining the product to obtain the Ni-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 25: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-SSZ-13 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is such that the components and the molar ratio in the mixture before being put into a reaction kettle are SiO2:Al2O3:Co-DETA:TMAdaOH:H2O is 1:0.0042:0.10:0.15:2.15, and the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 160 ℃, and directly calcining the product to obtain the Co-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 26: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-SSZ-13 molecular sieve
The cobalt hydroxide-diethylenetriamine complex solution, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and the silicon-aluminum ratio can be controlledPlacing the silica-alumina gel in a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components and the molar ratio in the mixture before the mixture is put into a reaction kettle are SiO2:Al2O3:Co-DETA:TMAdaOH:H2O is 1:0.033:0.04:0.2:2.15, and the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 6 days at 160 ℃, and directly calcining the product to obtain the Co-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
The XRD spectrum of the product in figure 18 shows that the product has a typical SSZ-13 zeolite molecular sieve structure, and the sample has high crystallinity.
FIG. 19 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 27: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-SSZ-13 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, N, N, N-trimethyl-1-adamantyl ammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, grinding the materials uniformly at room temperature, wherein the addition amount of each reaction raw material is such that the components and the molar ratio in the mixture before being put into a reaction kettle are SiO2:Al2O3:Co-DETA:TMAdaOH:H2O is 1:0.0625:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 160 ℃, and directly calcining the product to obtain the Co-SSZ-13 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 28: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-ZSM-5 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is to ensure that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:TPAOH:H2O is 1:0.0042:0.10:0.152.15, wherein the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 180 ℃, and directly calcining the product to obtain the Co-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 29: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-ZSM-5 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is to ensure that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:TPAOH:H2O is 1:0.019:0.04:0.2:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 180 ℃, and directly calcining the product to obtain the Co-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
FIG. 20 is an XRD spectrum of a sample, from which it can be seen that the product has a typical ZSM-5 zeolite molecular sieve structure and the sample has a high degree of crystallinity.
FIG. 21 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 30: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-ZSM-5 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetrapropylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is to ensure that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:TPAOH:H2O is 1:0.0625:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 4 days at 180 ℃, and directly calcining the product to obtain the Co-ZSM-5 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 31: one-step solid-phase alkali-free cation synthesis method for directly catalyzing reaction of Co-Beta molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Co-DETA:TEAOH:H2O is 1:0.0042:0.10:0.15:2.15, and the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 12 days at 140 ℃, and directly calcining the product to obtain the Co-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 32: one-step solid-phase alkali-free cation synthesis method for directly catalyzing reaction of Co-Beta molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is that the components in the mixture before being put into a reaction kettle and the molar ratio of the components are SiO2:Al2O3:Co-DETA:TEAOH:H2O is 1:0.033:0.04:0.2:2.15, and the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 4 days at 140 ℃, and directly calcining the product to obtain the Co-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
FIG. 22 is an XRD spectrum of a sample, from which it can be seen that the product has a typical zeolite Beta molecular sieve structure and the sample has a very high degree of crystallinity.
FIG. 23 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 33: one-step solid-phase alkali-free cation synthesis method for directly catalyzing reaction of Co-Beta molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, tetraethylammonium hydroxide and silica-alumina gel with controllable silica-alumina ratio in a mortar, and placing the above materials at room temperatureThe materials are uniformly ground, and the addition amount of each reaction raw material is such that the components and the molar ratio of the components in the mixture before the mixture is put into a reaction kettle are SiO2:Al2O3:Co-DETA:TEAOH:H2O is 1:0.0625:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 140 ℃, and directly calcining the product to obtain the Co-Beta molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 34: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-EU-1 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is such that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:HMOH:H2O is 1:0.0042:0.04:0.2:2.15, and the usage amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 6 days at 160 ℃, and directly calcining the product to obtain the Co-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
FIG. 24 is an XRD spectrum of a sample, from which it can be seen that the product has a typical zeolite Beta molecular sieve structure and the sample has a very high degree of crystallinity.
FIG. 25 is a Scanning Electron Microscope (SEM) photograph of a sample.
Example 35: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-EU-1 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is such that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:HMOH:H2O is 1:0.033:0.10:0.15:2.15, and the using amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. Then subjecting the mixture toAnd transferring the mixture into a reaction kettle, crystallizing for 12 days at 160 ℃, and directly calcining the product to obtain the Co-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Example 36: one-step solid-phase alkali-free cation synthesis method for directly using catalytic reaction Co-EU-1 molecular sieve
Placing cobalt hydroxide-diethylenetriamine complex solution, hexamethonium hydroxide and silica-alumina gel with controllable silica-alumina ratio into a mortar, uniformly grinding the materials at room temperature, wherein the addition amount of each reaction raw material is such that the components in the mixture before being placed into a reaction kettle and the molar ratio are SiO2:Al2O3:Co-DETA:HMOH:H2O is 1:0.0625:0.03:0.1:2.15, and the use amount of the zeolite seed crystal is 2 percent of the mass fraction of the silica-alumina gel. And then transferring the mixture into a reaction kettle, crystallizing for 3 days at 160 ℃, and directly calcining the product to obtain the Co-EU-1 molecular sieve catalyst. Wherein the silica-alumina source is from silica-alumina gel.
Although the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the technical scope of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (3)

1. A method for synthesizing a metal molecular sieve catalyst by a one-step alkali-free solid phase is characterized by comprising the following steps:
adding a silicon-aluminum source, metal hydroxide, an organic amine ligand and a template agent into a mortar, grinding at room temperature, and uniformly mixing; then transferring the mixture into a reaction kettle, adding sodium-free zeolite seed crystals, and carrying out crystallization reaction at 140-180 ℃ for 3-12 days; directly calcining the reaction product to obtain a molecular sieve catalyst;
the addition amount of each reaction raw material is controlled so that the components and the molar ratio in the reaction system are SiO2：Al2O3: metal hydroxide: organic amine ligand: template agent: h2O = 1: 0.0042-0.0625: 0.03-0.10: 0.03-0.20: 0.1-0.2: 2.15, the using amount of the zeolite seed crystal is 2 percent of the mass of the silicon-aluminum source; the metal hydroxide is Cu (OH)2Or Ni (OH)2The organic amine ligand is tetraethylenepentamine or diethylenetriamine;
the silicon-aluminum source is silicon-aluminum adhesive with controllable silicon-aluminum ratio; the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or hexamethonium hydroxide; the sodium-free zeolite seed crystal is conventional SSZ-13 zeolite, ZSM-5 zeolite, Beta zeolite or EU-1 zeolite, wherein the crystallization reaction temperatures of the molecular sieve catalyst obtained by adding the corresponding sodium-free zeolite seed crystal are 160 ℃, 180 ℃, 140 ℃ and 160 ℃.
2. A method for synthesizing a metal molecular sieve catalyst by a one-step alkali-free solid phase is characterized by comprising the following steps:
adding a silicon-aluminum source, a cobalt-amine complex and a template agent into a mortar, grinding at room temperature, and uniformly mixing; then transferring the mixture into a reaction kettle, adding sodium-free zeolite seed crystals, and carrying out crystallization reaction at 140-180 ℃ for 3-12 days; directly calcining the reaction product to obtain a molecular sieve catalyst;
the addition amount of each reaction raw material is controlled so that the components and the molar ratio in the reaction system are SiO2：Al2O3: cobalt amine complex: template agent: h2O = 1: 0.0042-0.0625: 0.03-0.10: 0.1-0.2: 2.15, the using amount of the zeolite seed crystal is 2 percent of the mass of the silicon-aluminum source; the cobalt amine complex is a cobalt hydroxide-diethylenetriamine complex;
the silicon-aluminum source is silicon-aluminum adhesive with controllable silicon-aluminum ratio; the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or hexamethonium hydroxide; the sodium-free zeolite seed crystal is conventional SSZ-13 zeolite, ZSM-5 zeolite, Beta zeolite or EU-1 zeolite, wherein the crystallization reaction temperatures of the molecular sieve catalyst obtained by adding the corresponding sodium-free zeolite seed crystal are 160 ℃, 180 ℃, 140 ℃ and 160 ℃.
3. The method of claim 2, wherein the cobalt amine complex has a mass concentration of 22 wt.%.
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