CN112958148A - Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with core-shell structure and synthesis method thereof - Google Patents

Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with core-shell structure and synthesis method thereof Download PDF

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CN112958148A
CN112958148A CN202110170135.2A CN202110170135A CN112958148A CN 112958148 A CN112958148 A CN 112958148A CN 202110170135 A CN202110170135 A CN 202110170135A CN 112958148 A CN112958148 A CN 112958148A
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molecular sieve
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CN112958148B (en
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刘中清
王倩
赵峰
邓兆敬
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China Chemical Equipment Technology Group Co ltd
China Tianchen Engineering Corp
China Chemical Technology Research Institute
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/76—Iron group metals or copper
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    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Abstract

The invention provides a Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with a core-shell structure and a synthesis method thereof. The composite molecular sieve takes a Cu-SSZ-39 molecular sieve as a core and takes a Cu-SSZ-13 molecular sieve as a shell. The invention also provides a synthetic method of the composite molecular sieve. The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure combines the low-temperature activity advantage of Cu-SSZ-13 and the high-temperature activity advantage of Cu-SSZ-39 molecular sieve, and improves the NH activity of a molecular sieve catalyst3Performance in SCR, an extremely wide temperature window capable of covering both low and high temperature regions, and excellent hydrothermal stability.

Description

Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with core-shell structure and synthesis method thereof
Technical Field
The invention relates to a Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with a core-shell structure and a synthesis method thereof, belonging to the technical field of molecular sieve synthesis.
Background
With the increasing strictness of emission regulations, the combination of in-cylinder purification technology and high-efficiency exhaust aftertreatment technology has become the most effective measure for solving the exhaust emission of diesel engines, wherein NH3Selective catalytic reduction (NH)3SCR) technology is currently recognized as one of the most effective methods for reducing NOx emissions from motor vehicles due to its better fuel economy and higher NOx conversion efficiency. Since the national VI emission regulation WHTC test cycle exhaust gas temperature is lower than the national V regulation ETC, this requires a higher activity of the SCR catalyst at low temperatures. On the other hand, a DOC (diesel engine control) system and a DPF (diesel particulate filter) system are generally additionally arranged in front of the SCR system of the diesel engine, and the temperature of tail gas entering the SCR during regeneration of the DPF system can reach 800 ℃ at most. Therefore, it is required that the SCR catalyst has an extremely wide temperature window covering low and high temperature regions, and excellent hydrothermal stability.
Copper ion exchanged SSZ-13 and SSZ-39 molecular sieve catalysts have attracted extensive attention from researchers, showing a wider temperature window and better reactivity in SCR than the vanadium-based catalysts that are currently most widely used. The Hohong Kogym subject group (appl.Catal.B: environ, 2020,264,118511) contrasts the aluminum-rich Cu-SSZ-13 and Cu-SSZ-39 catalysts at NH3Performance in SCR reactions, fresh Cu-SSZ-13 reactivity was found to be significantly higher than fresh Cu-SSZ-39 catalyst at low temperature region below 250 ℃. While Cu-SSZ-39 shows better hydrothermal stability and high-temperature activity, and keeps excellent NH even after being subjected to hydrothermal aging at 850 ℃ for 16 hours3SCR activity, much higher than denitration activity of Cu-SSZ-13 under the same conditions.
However, currently, there is still a lack of NH that is active at both low and high temperatures and has good hydrothermal stability3-an SCR catalyst.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with a core-shell structure and a synthesis method thereof, so as to combine the low temperature activity advantage of Cu-SSZ-13 and the Cu-SSZ-39 moleculeHigh-temperature activity of the sieve, and improvement of NH content of the molecular sieve catalyst3Reactivity and hydrothermal stability in SCR.
In order to achieve the aim, the invention provides a Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with a core-shell structure, wherein the composite molecular sieve takes a Cu-SSZ-39 molecular sieve as a core and takes a Cu-SSZ-13 molecular sieve as a shell.
According to a specific embodiment of the present invention, preferably, in the above composite molecular sieve, the CuO content of the Cu-SSZ-13 molecular sieve is 0.1 wt% to 20 wt%, more preferably 1 wt% to 10 wt%.
According to a specific embodiment of the present invention, preferably, in the above composite molecular sieve, the CuO content of the Cu-SSZ-39 molecular sieve is 0.1 wt% to 20 wt%, more preferably 1 wt% to 10 wt%.
According to a specific embodiment of the present invention, preferably, in the above composite molecular sieve, the Cu-SSZ-39 molecular sieve as the core accounts for 1 wt% to 99 wt%, more preferably 10 wt% to 80 wt%, and further preferably 20 wt% to 50 wt% of the total mass of the composite molecular sieve.
The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure can combine the low-temperature activity advantage of Cu-SSZ-13 and the high-temperature activity advantage of the Cu-SSZ-39 molecular sieve, and improve the activity of a molecular sieve catalyst in NH3Reaction performance in SCR and hydrothermal stability.
According to a specific embodiment of the invention, the SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure generally has a specific surface area of 500m2/g。
The invention also provides a synthesis method of the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure, which specifically comprises the following steps:
the first synthesis method comprises the following steps: adding a certain amount of SSZ-13 synthetic gel into the SSZ-39 synthetic gel after crystallization for a period of time, stirring uniformly, continuing crystallization to prepare a composite molecular sieve with SSZ-13 on the crystal surface and SSZ-39 inside the crystal, and then preparing a Cu-SSZ-39@ Cu-SSZ-13 molecular sieve through ion exchange;
or:
and a second synthesis method comprises the following steps: mixing and crystallizing a Cu-SSZ-39 molecular sieve serving as a nuclear layer material and SSZ-13 molecular sieve synthetic gel for preparing a shell layer material to prepare an SSZ-39@ SSZ-13 molecular sieve, and then preparing the Cu-SSZ-39@ Cu-SSZ-13 molecular sieve by ion exchange.
According to a specific embodiment of the present invention, preferably, the first synthesis method comprises the following specific steps:
mixing a silicon source, an aluminum source, an alkali source, an organic template agent a and water, and aging for 0.1h-100h at room temperature to 100 ℃ to obtain synthetic gel A (namely the gel for synthesizing the SSZ-39 molecular sieve); the Y-type molecular sieve is used as a silicon source and an aluminum source, or the Y-type molecular sieve is used as an aluminum source and a part of silicon source, and a silicon-containing compound is used as a second silicon source;
mixing a silicon source, an aluminum source, an alkali source, an organic template agent B and water, and aging for 0.1h-100h at room temperature to 100 ℃ to obtain synthetic gel B (namely the gel for synthesizing the SSZ-13 molecular sieve);
crystallizing the synthesized gel A in an autoclave at 120-200 ℃ for 0.1-70 h;
adding the synthetic gel B into the high-pressure kettle, and continuously crystallizing for 0.1-70 h at the temperature of 120-200 ℃;
and cooling, filtering, washing, drying and roasting to obtain the Na-type SSZ-39@ SSZ-13 molecular sieve, and performing ammonium ion exchange and Cu ion exchange to obtain the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure.
According to a specific embodiment of the present invention, preferably, the second synthesis method comprises the following specific steps:
mixing a silicon source, an aluminum source, an alkali source, an organic template agent B and water, and aging for 0.1-100 h at room temperature to 100 ℃ to obtain a synthetic gel B;
adding an SSZ-39 molecular sieve into the synthetic gel B, and continuously crystallizing for 0.1-100 h at the temperature of 120-200 ℃;
and cooling, filtering, washing, drying and roasting to obtain the Na-type SSZ-39@ SSZ-13 molecular sieve, and performing ammonium ion exchange and Cu ion exchange to obtain the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure.
In the specific embodiment of the invention, compared with the synthesis method I in which the synthesis gel A is added into the synthesis gel B for crystallization, the synthesis method II in which the SSZ-39 molecular sieve crystal grains are directly added into the synthesis gel B can shorten the crystallization time. In some embodiments, SSZ-39 molecular sieve is added into the synthetic gel B and crystallized at the temperature of 120-200 ℃, and the crystallization time can be shortened to 0.1-50 h.
According to the specific embodiment of the invention, preferably, in the first synthesis method and the second synthesis method, the calcination temperature before obtaining the Na-type SSZ-39@ SSZ-13 molecular sieve is 400-700 ℃, and the calcination time is 2-10 h; more preferably, the roasting temperature is 450-600 ℃, and the roasting time is 2-6 h.
According to a specific embodiment of the present invention, preferably, in the first synthesis method, the Y-type molecular sieve comprises USY molecular sieve, NaY molecular sieve and NH4One or a combination of two or more of the Y molecular sieves.
According to the specific embodiment of the present invention, preferably, in the first synthesis method, the second silicon source used for synthesizing gel a includes one or a combination of two or more of silicate, tetraethoxysilane, precipitated silica, silica sol and the like, and more preferably, silica sol.
According to a specific embodiment of the present invention, in the first and second synthesis methods, the silicon source used for synthesizing gel B preferably includes one or a combination of two or more of silicate, tetraethoxysilane, precipitated silica, silica sol, and the like, and more preferably silica sol.
According to the specific embodiment of the present invention, preferably, in the above-mentioned first and second synthesis methods, the aluminum source used for synthesizing the gel B includes one or a combination of two or more of aluminum hydroxide, pseudoboehmite, aluminum isopropoxide, sodium metaaluminate and the like, and more preferably, sodium metaaluminate and aluminum isopropoxide.
According to a specific embodiment of the present invention, preferably, in the above-mentioned first and second synthesis methods, the alkali source used for synthesizing gel a and gel B includes sodium hydroxide and/or potassium hydroxide.
According to a specific embodiment of the present invention, preferably, in the above first synthesis method, the organic template a comprises N, N-dimethyl-3, 5-dimethylpiperidine ion, N-diethyl-2, 6-dimethylpiperidine ion, 2, 6-dimethyl-5-azoniaspiro- [4.5] -decane ion, N-diethyl-2-ethylpiperidine ion, N-ethyl-N-propyl-2, 6-dimethylpiperidine ion, N-methyl-N-ethyl-2-ethylpiperidine ion, 2, 5-dimethyl-N, N-diethylpyrrole ion, N-dimethyl-N, 6-dimethylpiperidine ion, N-ethyl-2-ethylpiperidine ion, N-methyl-N-ethyl-2-ethylpiperidine ion, 2, 5-dimethyl-, 2, 6-dimethyl-N, N-dimethylpiperidinium ion, 3, 5-dimethyl-N, N-dimethylpiperidinium ion, 2-ethyl-N, N-dimethylpiperidinium ion, one or a combination of two or more of salts and/or bases of 2,2,6, 6-tetramethyl-N-methyl-N-ethylpiperidinium ion, N-cyclooctyl-pyridinium ion, 2,6, 6-tetramethyl-N, N-dimethylpiperidinium ion and N, N-dimethyl-N, N-bicyclononane ion, and the like, and more preferably one or a combination of two or more of salts and/or bases of N, N-diethyl-2, 6-dimethylpiperidinium ion and/or 3, 5-dimethyl-N, N-dimethylpiperidinium ion.
According to a specific embodiment of the present invention, preferably, in the above first and second synthesis methods, the organic template b includes one or a combination of two or more of salts and/or bases of N, N-trimethyl-1-adamantylammonium ion, benzyltrimethylammonium ion, N-dimethylethylcyclohexylammonium bromide ion, tetraethylammonium hydroxide ion, choline chloride ion, and Cu-tetraethylenepentamine ion.
According to a specific embodiment of the present invention, in the second synthesis method, the SSZ-39 molecular sieve is generally powder, and the particle size of the SSZ-39 molecular sieve is preferably 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm, and still more preferably 0.7 μm to 1.5 μm.
According to a specific embodiment of the present invention, in the second synthesis method, the SSZ-39 molecular sieve can be prepared by any method. The cation in the SSZ-39 molecular sieve may include Na+、H+、NH4 +、Cu2+One or a combination of two or more of (1).
According to a specific embodiment of the present invention, preferably, in the above synthesis method one and synthesis method two, the chemical compositions of the synthesis gel a and the synthesis gel B respectively satisfy the following molar ratio ranges:
SiO2/Al2O3＝5-180，OH-/SiO2＝0.1-1，H2O/SiO2＝3-80，R/SiO20.01-0.5; wherein R represents an organic template.
According to the specific embodiment of the invention, the silicon-aluminum ratio of the synthetic gel A is generally different from that of the synthetic gel B, so that the distribution conditions of aluminum in a nuclear layer and a shell layer in the SSZ-39@ Cu-SSZ-13 composite molecular sieve are different, and the aggregation of Cu centers is slowed down, thereby changing the hydrothermal stability of the molecular sieve and improving the activity of the molecular sieve at low temperature and high temperature.
According to a specific embodiment of the present invention, preferably, in the above-mentioned first synthesis method, when the synthetic gel B is added to the autoclave, the mass ratio of the synthetic gel B to the synthetic gel a is 0.01 to 5, more preferably 0.05 to 2, and further preferably 0.1 to 1.
According to a specific embodiment of the present invention, preferably, in the above synthesis method two, when the SSZ-39 molecular sieve is added to the synthesis gel B, the mass ratio of the SSZ-13 molecular sieve to the synthesis gel B is 0.001 to 0.2, preferably 0.005 to 0.2, more preferably 0.01 to 0.1.
According to a specific embodiment of the present invention, preferably, in the above synthesis method one and synthesis method two, the ammonium ion exchange is performed according to the following steps:
na type SSZ-39@ SSZ-13 molecular sieve and NH4NO3Ion exchanging the solution (with a molar concentration of preferably 0.01M-2M, more preferably 0.1M) twice at 50-95 deg.C (preferably 80 deg.C) for 5-20h to obtain NH4Type SSZ-39@ SSZ-13 molecular sieves.
According to the embodiment of the present invention, drying, calcination, etc. may be further performed after each ammonium ion exchange. The drying temperature can be controlled to be 100-120 ℃, and the drying time is generally more than 10 h. The roasting temperature can be controlled to be 400-700 ℃ (preferably 450-600 ℃), and the roasting time can be controlled to be 2-10 h (preferably 2-6 h).
According to a specific embodiment of the present invention, preferably, in the above synthesis method one and synthesis method two, the Cu ion exchange is performed according to the following steps:
NH obtained by ion exchange of ammonium4And carrying out ion exchange on the type SSZ-39@ SSZ-13 molecular sieve and a Cu salt solution for 1h-24h to obtain the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve.
According to a specific embodiment of the present invention, preferably, in the above-mentioned first and second synthesis methods, the molar concentration of the Cu salt solution used for Cu ion exchange is 0.1M to 0.2M.
According to a specific embodiment of the present invention, preferably, in the first synthesis method and the second synthesis method, the Cu salt used for Cu ion exchange includes one or a combination of two or more of copper nitrate, copper sulfate, copper carbonate, copper oxide, copper hydroxide, copper acetate, copper phosphate, and the like.
According to the specific embodiment of the invention, drying, roasting and the like can also be carried out after each Cu ion exchange. The drying temperature can be controlled to be 100-120 ℃, and the drying time is generally more than 10 h. The roasting temperature can be controlled to be 400-700 ℃ (preferably 450-600 ℃), and the roasting time can be controlled to be 2-10 h (preferably 2-6 h).
The invention also provides the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure in NH3-use in an SCR reaction.
The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure combines the low-temperature activity advantage of Cu-SSZ-13 and the high-temperature activity advantage of Cu-SSZ-39 molecular sieve, and improves the NH activity of a molecular sieve catalyst3Performance in SCR, an extremely wide temperature window capable of covering both low and high temperature regions, and excellent hydrothermal stability.
Drawings
Fig. 1-6 are XRD patterns of the molecular sieves prepared in examples 1-6, respectively.
Fig. 7-8 are XRD patterns of the molecular sieves prepared in comparative examples 1-2, respectively.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel a:
an aqueous solution of 25 wt% N, N-dimethyl-3, 5-dimethylpiperidine hydroxide (SDA as an organic template), pure water, sodium hydroxide, and NH4The Y molecular sieve and silica sol (silica content 40%) were thoroughly mixed to give a synthetic gel a of the starting composition (molar ratio) having the following composition, and aged at room temperature for 10 h:
SiO2/Al2O3＝55
hereinafter referred to as SDA/SiO2＝0.13
H2O/SiO2＝20
OH/SiO2＝0.58。
2) Preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH, as an organic template) at a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and silica sol (silica content 40%) were thoroughly mixed to obtain a synthetic gel B having a raw material composition (molar ratio) of the following composition, and aged at room temperature for 10 hours:
SiO2/Al2O3＝20
SDA/SiO2＝0.12
H2O/SiO2＝20
OH/SiO2＝0.18。
3) and (3) putting the synthesized gel A into an autoclave, and heating to 160 ℃ under a stirring state to crystallize for 50 hours.
4) Adding the synthetic gel B with the mass 2 times of that of the synthetic gel A into the autoclave in the step 3), and continuously crystallizing for 60 hours at 170 ℃ under the stirring state.
5) Stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 1. As can be seen from FIG. 1, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves, and the diffraction peak intensity is high, indicating that the molecular sieve has high crystallinity. N is a radical of2The measurement result of a physical adsorption instrument shows that the specific surface area of the molecular sieve is 540m2/g。
Example 2
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel a:
an aqueous solution of N, N-dimethyl-3, 5-dimethylpiperidine hydroxide with a concentration of 25 wt%, pure water, sodium hydroxide, USY molecular sieve (silica to alumina ratio 12) and water glass (silica content 20%) were thoroughly mixed to give a synthetic gel a of a raw material composition (molar ratio) having the following composition, and aged at 50 ℃ for 100 hours:
SiO2/Al2O3＝180
SDA/SiO2＝0.25
H2O/SiO2＝80
OH/SiO2＝0.98。
2) preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) having a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel B of a raw material composition (molar ratio) having the following composition, and aged at 100 ℃ for 0.1 h:
SiO2/Al2O3＝60
SDA/SiO2＝0.12
H2O/SiO2＝50
OH/SiO2＝0.30。
3) and (3) putting the synthesized gel A into an autoclave, and heating to 170 ℃ under stirring for crystallization for 50 h.
4) Adding the synthetic gel B with the mass 2 times of that of the synthetic gel A into the autoclave in the step 3), and continuously crystallizing for 30 hours at 190 ℃ under the stirring state.
5) Stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 2. As can be seen from FIG. 2, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves, and the diffraction peak intensity is high, indicating that the molecular sieve has high crystallinity. N is a radical of2The measurement result of a physical adsorption instrument shows that the specific surface area of the molecular sieve is 556m2/g。
Example 3
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel a:
an aqueous solution of N, N-dimethyl-3, 5-dimethylpiperidine hydroxide with a concentration of 25 wt%, pure water, sodium hydroxide, USY molecular sieve (silica to alumina ratio 12) and water glass (silica content 20%) were thoroughly mixed to give a synthetic gel a of a raw material composition (molar ratio) having the following composition, and aged at 70 ℃ for 0.5 h:
SiO2/Al2O3＝40
SDA/SiO2＝0.08
H2O/SiO2＝15
OH/SiO2＝0.45。
2) preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) having a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel B of a raw material composition (molar ratio) having the following composition, and aged at 80 ℃ for 15 hours:
SiO2/Al2O3＝120
SDA/SiO2＝0.12
H2O/SiO2＝20
OH/SiO2＝0.18。
3) putting the synthesized gel A into a high-pressure kettle, heating to 150 ℃ under stirring, and crystallizing for 40 hours;
4) adding the synthetic gel B with the mass of 0.1 time of that of the synthetic gel A into the high-pressure kettle in the step 3), and continuously crystallizing for 70 hours at 180 ℃ under the stirring state;
5) stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 3. As can be seen from FIG. 3, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves and has high diffraction peak intensity, indicating that the molecular sieves have high crystallinity. N is a radical of2The result of the physical adsorption instrument shows that the specific surface area of the molecular sieve is 537m2/g。
Example 4
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) having a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel B of a raw material composition (molar ratio) having the following composition, and aged at 40 ℃ for 100 hours:
SiO2/Al2O3＝40
SDA/SiO2＝0.12
H2O/SiO2＝20
OH/SiO2＝0.55。
2) adding the synthetic gel B and a commercial SSZ-39 molecular sieve (the ratio of silicon to aluminum is 18) with the mass being 0.1 time of that of the synthetic gel B into an autoclave, and crystallizing for 40 hours at 160 ℃ under the stirring state.
3) Stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 4. As can be seen from FIG. 4, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves and has high diffraction peak intensity, indicating that the molecular sieves have high crystallinity. N is a radical of2The result of physical adsorption shows that the specific surface area of the molecular sieve is 521m2/g。
Example 5
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) having a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel B of a raw material composition (molar ratio) having the following composition, and aged at 80 ℃ for 10 hours:
SiO2/Al2O3＝20
SDA/SiO2＝0.08
H2O/SiO2＝10
OH/SiO2＝0.15。
2) adding the synthesized gel B and a commercial SSZ-39 molecular sieve (the silica-alumina ratio is 25) with the mass being 0.1 time of that of the synthesized gel B into an autoclave, and crystallizing for 70 hours at 190 ℃ under the stirring state.
3) Stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 5. As can be seen from FIG. 5, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves and has high diffraction peak intensity, indicating that the molecular sieves have high crystallinity. N is a radical of2The result of physical adsorption measurement shows that the specific surface area of the molecular sieve is 553m2/g。
Example 6
The embodiment provides a Na-type SSZ-39@ SSZ-13 molecular sieve with a core-shell structure, and the synthesis method comprises the following steps:
1) preparation of synthetic gel B:
an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) having a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel B of a raw material composition (molar ratio) having the following composition, and aged at 60 ℃ for 5 hours:
SiO2/Al2O3＝140
SDA/SiO2＝0.15
H2O/SiO2＝50
OH/SiO2＝0.32。
2) adding the synthesized gel B and a commercial SSZ-39 molecular sieve (the silica-alumina ratio is 50) with the mass being 0.05 times of that of the synthesized gel B into an autoclave, and crystallizing for 90 hours at 140 ℃ under the stirring state;
3) stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39@ SSZ-13 molecular sieve.
The XRD pattern of the SSZ-39@ SSZ-13 molecular sieve sample prepared in this example is shown in FIG. 6. As can be seen from FIG. 6, the molecular sieve sample has both SSZ-13 and SSZ-39 molecular sieves and has high diffraction peak intensity, indicating that the molecular sieves have high crystallinity. N is a radical of2The measurement result of a physical adsorption instrument shows that the specific surface area of the molecular sieve is 527m2/g。
Comparative example 1
The comparative example provides a Na-type SSZ-13 molecular sieve, and the synthesis method comprises the following steps:
1) an aqueous solution of N, N-trimethylamantadine ammonium hydroxide (TMADAOH) at a concentration of 25 wt%, pure water, sodium hydroxide, sodium metaaluminate and white carbon black (white carbon black content 99%) were thoroughly mixed to obtain a synthetic gel of a raw material composition (molar ratio) having the following composition, and aged at 60 ℃ for 5 hours:
SiO2/Al2O3＝25
SDA/SiO2＝0.15
H2O/SiO2＝30
OH/SiO2＝0.25。
2) adding the synthesized gel into a high-pressure kettle, and crystallizing for 70 hours at 170 ℃ under the stirring state;
3) stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na-type SSZ-13 molecular sieve.
XRD testing was performed on the SSZ-13 molecular sieve sample prepared in this comparative example, and the spectrum results are shown in FIG. 7. As can be seen in fig. 7, the diffraction peak intensity of this sample is high, indicating that the molecular sieve crystallinity is high. N is a radical of2The measurement result of a physical adsorption instrument shows that the specific surface area of the molecular sieve is 520m2/g。
Comparative example 2
The comparative example provides a Na-type SSZ-39 molecular sieve, the synthesis method of which comprises the following steps:
1) an aqueous solution of N, N-dimethyl-3, 5-dimethylpiperidine hydroxide with a concentration of 25 wt%, pure water, sodium hydroxide, USY molecular sieve (silica to alumina ratio 7) and water glass (silica content 20%) were thoroughly mixed to give a synthetic gel of a raw material composition (molar ratio) having the following composition, and aged at 80 ℃ for 5 hours:
SiO2/Al2O3＝40
SDA/SiO2＝0.08
H2O/SiO2＝15
OH/SiO2＝0.45
2) adding the synthesized gel into a high-pressure kettle, and crystallizing for 60 hours at 160 ℃ under the stirring state;
3) stopping crystallization, cooling to below 60 ℃, filtering, washing, drying a solid sample, and roasting at 550 ℃ for 8 hours to obtain the Na type SSZ-39 molecular sieve.
SSZ-39 molecular sieve sample prepared for this comparative exampleThe product was subjected to XRD measurement, and the spectrum results are shown in FIG. 8. As can be seen in fig. 8, the diffraction peak intensity of this sample is high, indicating that the molecular sieve crystallinity is high. N is a radical of2The result of physical adsorption shows that the specific surface area of the molecular sieve is 545m2/g。
Test example 1
This test example provides NH for samples of the SSZ-39@ SSZ-13 composite molecular sieves prepared in examples 1-63-SCR reaction performance test, the specific test method comprising:
ammonium exchange of molecular sieve: the SSZ-39@ SSZ-13 composite molecular sieves prepared in examples 1-6, the SSZ-13 molecular sieve prepared in comparative example 1 and the SSZ-39 molecular sieve prepared in comparative example 2 were mixed together as ammonium nitrate: molecular sieve: water (mass ratio) 1: 1: 10, adjusting the pH value to 8-8.5 by ammonia water, exchanging for 1h at 90 ℃ in a stirring state, filtering, washing, drying, and roasting for 2h at 550 ℃. Repeating the above process for 3 times until Na in the molecular sieve2The O content is less than 0.1 mass%.
Loading molecular sieve copper: cu (NO) with 5% of CuO loading corresponding to molecular sieve3)2Dissolving in 50 times of water, adding ammonium exchanged molecular sieve while stirring, adjusting pH to 8-8.5 with ammonia water, filtering, washing, oven drying, and calcining at 550 deg.C for 2 h.
The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieves prepared in examples 1 to 6, which were subjected to ammonium exchange and Cu loading, the Cu-SSZ-13 molecular sieve prepared in comparative example 1 and the Cu-SSZ-39 molecular sieve prepared in comparative example 2 were separately subjected to tablet forming, pulverization, sieving, and blending in a 10% H ratio2After hydrothermal aging for 100h at 650 ℃ in an O + 90% air atmosphere, 0.5g of a 40-60 mesh sample is taken and used for NH3-SCR reaction, wherein the composition of the reaction mixture is: 1000ppmNO, 1100ppmNH3、10Vol％O2、10Vol％H2O，N2As balance gas, the volume space velocity is 120000h-1And the reaction temperature is 200-600 ℃, and a Nicolet infrared gas analyzer is used for detecting the concentration of NOx in the tail gas on line. The test results are shown in table 1.
NOxThe conversion is defined as:
Figure BDA0002937162270000121
TABLE 1
200 ℃ NOx conversion 550 ℃ NOx conversion
Example 1 94％ 89％
Example 2 97％ 88％
Example 3 98％ 89％
Example 4 95％ 86％
Example 5 96％ 93％
Example 6 95％ 90％
Comparative example 1 92％ 81％
Comparative example 2 93％ 80％
As can be seen from Table 1, the Cu-SSZ-13@ Cu-SSZ-39 composite molecular sieves with core-shell structures prepared in examples 1-6 of the invention have higher DeNOx activity, and the DeNOx activity of the composite molecular sieves provided by the invention is higher than that of the Cu-SSZ-13 and Cu-SSZ-39 prepared in comparative examples 1 and 2 under the conditions of low temperature (200 ℃) and high temperature (600 ℃). The main reason is that the ratio of silicon to aluminum in the core layer and the shell layer of the Cu-SSZ-13@ Cu-SSZ-39 composite molecular sieve is different, so that the aluminum distribution at different positions in the framework of the composite molecular sieve is different, and the low-temperature activity of the composite molecular sieve is obviously improved compared with that of the SSZ-13 molecular sieve alone. Similarly, the change in the distribution of aluminum in the composite molecular sieve can also slow down the aggregation of the Cu active centers, thereby obviously improving the high-temperature activity of the composite molecular sieve compared with that of SSZ-39 alone.

Claims (10)

1. The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve has a core-shell structure, wherein the Cu-SSZ-39 molecular sieve is used as a core of the composite molecular sieve, and the Cu-SSZ-13 molecular sieve is used as a shell of the composite molecular sieve.
2. The composite molecular sieve of claim 1, wherein the Cu-SSZ-13 molecular sieve has a CuO content of 0.1 wt% to 20 wt%, preferably 1 wt% to 10 wt%;
the CuO content of the Cu-SSZ-39 molecular sieve is 0.1-20 wt%, preferably 1-10 wt%.
3. The composite molecular sieve of claim 1 or 2, wherein the Cu-SSZ-39 molecular sieve as the core comprises from 1 wt% to 99 wt%, preferably from 10 wt% to 80 wt%, more preferably from 20 wt% to 50 wt% of the total mass of the composite molecular sieve.
4. A synthesis method of the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve having a core-shell structure as claimed in any one of claims 1 to 3, wherein the synthesis method comprises:
mixing a silicon source, an aluminum source, an alkali source, an organic template agent a and water, and aging for 0.1-100 h at room temperature to 100 ℃ to obtain a synthetic gel A; the Y-type molecular sieve is used as a silicon source and an aluminum source, or the Y-type molecular sieve is used as an aluminum source and a part of silicon source, and a silicon-containing compound is used as a second silicon source;
mixing a silicon source, an aluminum source, an alkali source, an organic template agent B and water, and aging for 0.1-100 h at room temperature to 100 ℃ to obtain a synthetic gel B;
crystallizing the synthesized gel A in an autoclave at 120-200 ℃ for 0.1-70 h;
adding the synthetic gel B into the high-pressure kettle, and continuously crystallizing for 0.1-70 h at the temperature of 120-200 ℃;
obtaining a Na-type SSZ-39@ SSZ-13 molecular sieve by cooling, filtering, washing, drying and roasting, and obtaining the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure by ammonium ion exchange and Cu ion exchange;
or:
mixing a silicon source, an aluminum source, an alkali source, an organic template agent B and water, and aging for 0.1-100 h at room temperature to 100 ℃ to obtain a synthetic gel B;
adding an SSZ-39 molecular sieve into the synthetic gel B, and continuously crystallizing for 0.1-100 h at the temperature of 120-200 ℃;
and cooling, filtering, washing, drying and roasting to obtain the Na-type SSZ-39@ SSZ-13 molecular sieve, and performing ammonium ion exchange and Cu ion exchange to obtain the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with the core-shell structure.
5. The method of synthesis of claim 4, wherein:
the second silicon source used for preparing the synthetic gel A comprises one or the combination of more than two of silicate, tetraethoxysilane, deposited silicon dioxide and silica sol, and the silica sol is preferably selected;
preferably, the silicon source used for preparing the synthesis gel B comprises one or a combination of more than two of silicate, tetraethoxysilane, precipitated silica and silica sol, and the silica sol is preferred;
preferably, the aluminum source used for preparing the synthesis gel B comprises one or a combination of more than two of aluminum hydroxide, pseudo-boehmite, aluminum isopropoxide and sodium metaaluminate, preferably sodium metaaluminate and aluminum isopropoxide;
preferably, the alkaline source used to prepare synthesis gel a and synthesis gel B comprises sodium hydroxide and/or potassium hydroxide;
preferably, the organic template a includes N, N-dimethyl-3, 5-dimethylpiperidinium ion, N-diethyl-2, 6-dimethylpiperidinium ion, 2, 6-dimethyl-5-azoniaspiro- [4.5] -decane ion, N-diethyl-2-ethylpiperidinium ion, N-ethyl-N-propyl-2, 6-dimethylpiperidinium ion, N-methyl-N-ethyl-2-ethylpiperidinium ion, 2, 5-dimethyl-N, N-diethylpyrrole ion, 2, 6-dimethyl-N, N-dimethylpiperidinium ion, N-diethylpiperidine ion, N-, 3, 5-dimethyl-N, N-dimethylpiperidinium ion, 2-ethyl-N, N-dimethylpiperidinium ion, 2,6, 6-tetramethyl-N-methyl-N-ethylpiperidinium ion, one or a combination of two or more of salts and/or bases of N-cyclooctyl-pyridinium ion, 2,6, 6-tetramethyl-N, N-dimethylpiperidinium ion and N, N-dimethyl-N, N-bicyclononane ion, more preferably one or a combination of two or more of salts and/or bases of N, N-diethyl-2, 6-dimethylpiperidinium ion and/or 3, 5-dimethyl-N, N-dimethylpiperidinium ion;
preferably, the organic template agent b comprises one or a combination of more than two of salts and/or bases of N, N, N-trimethyl-1-adamantylammonium ion, benzyltrimethylammonium ion, N, N, N-dimethylethylcyclohexylammonium bromide ion, tetraethylammonium hydroxide ion, choline chloride ion and Cu-tetraethylenepentamine ion;
preferably, the SSZ-39 molecular sieve has a particle size of 0.1 to 10 μm, more preferably 0.5 to 5 μm, and still more preferably 0.7 to 1.5 μm;
preferably, the cation in the SSZ-39 molecular sieve comprises Na+、H+、NH4 +、Cu2+One or a combination of two or more of (1).
6. The synthesis method according to claim 4 or 5, wherein the chemical compositions of the synthesis gel A and the synthesis gel B respectively satisfy the following molar ratio ranges:
SiO2/Al2O3＝5-180，OH-/SiO2＝0.1-1，H2O/SiO2＝3-80，R/SiO2＝0.01-0.5；
wherein R represents an organic template.
7. The synthesis method according to claim 4 or 5, wherein the roasting temperature is 400-700 ℃, and the roasting time is 2-10 h; preferably, the roasting temperature is 450-600 ℃, and the roasting time is 2-6 h;
when the synthetic gel B is added into the autoclave, the mass ratio of the synthetic gel B to the synthetic gel A is 0.01-5, preferably 0.05-2, and more preferably 0.1-1;
when the SSZ-39 molecular sieve is added to the synthesis gel B, the mass ratio of the SSZ-13 molecular sieve to the synthesis gel B is 0.001-0.2, preferably 0.005-0.2, more preferably 0.01-0.1.
8. The synthesis method according to claim 4, wherein the ammonium ion exchange is carried out according to the following steps:
na type SSZ-39@ SSZ-13 molecular sieve and NH4NO3Ion exchange is carried out on the solution twice at the temperature of 50-95 ℃ for 5-20h each time, thus obtaining NH4Type SSZ-39@ SSZ-13 molecular sieve;
wherein, the NH4NO3The molar concentration of the solution is preferably 0.01M-2M, more preferably 0.1M; the temperature of the ion exchange is preferably 80 ℃.
9. The synthesis method according to claim 4 or 8, wherein the Cu ion exchange is carried out according to the following steps:
NH obtained by ion exchange of ammonium4Carrying out ion exchange on the type SSZ-39@ SSZ-13 molecular sieve and a Cu salt solution for 1h-24h to obtain the Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve;
preferably, the molar concentration of the Cu salt solution is 0.1M to 0.2M;
preferably, the Cu salt includes one or a combination of two or more of copper nitrate, copper sulfate, copper carbonate, copper oxide, copper hydroxide, copper acetate, and copper phosphate.
10. The Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve having a core-shell structure as set forth in any one of claims 1 to 3 in NH3-use in SCR.
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