CN112844463A - Preparation method of Ce modified Cu-Fe-SSZ-13 molecular sieve - Google Patents
Preparation method of Ce modified Cu-Fe-SSZ-13 molecular sieve Download PDFInfo
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- CN112844463A CN112844463A CN202110077390.2A CN202110077390A CN112844463A CN 112844463 A CN112844463 A CN 112844463A CN 202110077390 A CN202110077390 A CN 202110077390A CN 112844463 A CN112844463 A CN 112844463A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 88
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000012703 sol-gel precursor Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 13
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MCDIWMIXQGYMLJ-UHFFFAOYSA-N octadecane;hydrate Chemical compound O.CCCCCCCCCCCCCCCCCC MCDIWMIXQGYMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—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
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a Ce modified Cu-Fe-SSZ-13 molecular sieve, in particular to a method for slowly dripping tetraethylenepentamine into a copper sulfate solution under violent stirring, sequentially adding cerium nitrate and ferric nitrate after the reaction is finished, and adding sodium hydroxide after fully and uniformly mixing to prepare a solution A; adding sodium metaaluminate or aluminum sulfate octadecahydrate into the solution A, stirring for 1-2 hours, then adding silica sol, continuing to stir for 2-3 hours, then placing the mixture into a steel reaction kettle with a polytetrafluoroethylene lining, aging for 12-14 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor for 72-96 hours at 120-180 ℃, carrying out solid-liquid separation after crystallization is finished, washing the solid with water until the pH value is neutral, drying, and calcining the solid for 4-8 hours at 500-550 ℃ to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve.
Description
Technical Field
The invention relates to a preparation method of an SSZ-13 molecular sieve catalyst, in particular to a preparation method of a Ce modified Cu-Fe-SSZ-13 molecular sieve, belonging to the field of industrial catalysis.
Background
The nitrogen oxides (NOx) produced by the industrial combustion of automobile exhaust and fossil fuels are useful for ecological systems and humansAnd (4) harming. By NH3Selective Catalytic Reduction (SCR) as a reducing agent is an effective method for removing NO from the exhaust gas of diesel vehicles or coal-fired power plantsXThe technique of (1). V2O5-WO3/TiO2Based SCR catalysts have been commercially used in fixed source denitration processes since the last 70 s, but vanadium based catalysts suffer from some unavoidable problems such as narrow operating temperature range and toxicity of vanadium species. Therefore, it is critical to develop vanadium-free SCR catalysts to remove NOx. And V2O5-WO3/TiO2Compared with the composite metal oxide, the molecular sieve catalyst has better NH3SCR activity, wider operating temperature window, NO removal at high space velocityXThus purifying NO in the exhaust gas of diesel vehiclesXThe field is receiving a great deal of attention. The molecular sieve catalyst mainly comprises Cu-ZSM-5, Cu-SSZ-13, Fe-ZSM-5, Fe-beta and the like, and although the Cu-based molecular sieve catalyst has better low-temperature activity than the Fe-based catalyst, the Cu-based molecular sieve catalyst has hydrothermal stability and SO resistance2The performance remains to be improved, among many catalysts, NH of Cu-SSZ-13 molecular sieve catalysts3The SCR has the most outstanding performance and good application prospect.
The current research shows that the introduction of bimetal into molecular sieve can improve the catalytic activity and stability of catalyst. Fe-based molecular sieve catalyst despite its low temperature NH3The catalytic activity of SCR is not as good as that of Cu-based molecular sieve, but the hydrothermal stability and the sulfur resistance are obviously better than those of Cu-based molecular sieve. CHA-type molecular sieves have smaller pore sizes and are typically Fe with smaller ionic radii2+The salt compound is used as a precursor, and the Fe/CHA or Fe modified Cu/CHA catalyst is prepared by adopting an impregnation or ion exchange method, for example, the Fe/Cu-SSZ-13 catalyst not only has the medium-high temperature denitration activity of the Fe/SSZ-13 catalyst, but also has the low-temperature denitration activity of the Cu-SSZ-13 catalyst, and the high-temperature activity temperature window of the Cu-based molecular sieve catalyst can be widened by the synergistic effect of Fe and Cu. Although Fe/Cu-SSZ-13 molecular sieves have improved low and high temperature properties over Cu-SSZ-13, their hydrothermal stability after aging of low silica to alumina ratio molecular sieves is still less than ideal.
Chinese patent document CN110180583A (application number): 201910573377.9) discloses a Cu-Fe-Ce-based molecular sieve material, a preparation method thereof and a catalyst; the method adopts Fe2+As active centre, but the invention uses Fe3+The method adopts a one-step method to synthesize the Cu-Fe-Ce-SSZ-13 molecular sieve, avoids using an expensive template agent, and has great improvement on the aspects of cost, easy realization in industry and the like.
Chinese patent document CN108128784A (application number: 201711459925.2) provides a preparation method of a Cu-Ce-La-SSZ-13 molecular sieve catalyst; the method selects the La modified Cu-Ce-SSZ-13 molecular sieve to improve the stability of Ce in the SSZ-13 molecular sieve, and the Ce is introduced to modify the Cu-Fe-SSZ-13 molecular sieve, so that the high temperature window of the Cu-Fe-SSZ-13 molecular sieve is maintained, and the catalytic activity and the hydrothermal stability are greatly improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a Ce modified Cu-Fe-SSZ-13 molecular sieve
The technical scheme provided by the invention can improve the damage degree of the framework of the low-silica-alumina ratio molecular sieve sample in the hydrothermal aging process, improve the framework stability of the molecular sieve product and improve the catalytic activity.
According to the invention, a one-step synthesis method is used for selecting Ce ions to modify the Fe/Cu-SSZ-13 catalyst, so that the expensive template is avoided, the cost is greatly reduced, the framework stability of the obtained Cu-Fe-Ce-SSZ-13 molecular sieve is better, and the hydrothermal stability and the catalytic activity are improved.
The technical scheme of the invention is as follows:
a Cu-Fe-Ce-SSZ-13 molecular sieve catalyst comprises a first active component, a second active component and a third active component;
the first active component is a Cu species;
the second active component is a Fe species;
the third active component is a Ce species.
According to the invention, the Cu content in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is preferably 1.5-4 wt%;
the content of Fe in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 2-5 wt%;
the content of Ce in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 0.1-1.5 wt%;
the mol ratio of silicon dioxide to aluminum oxide in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 9-16.
According to the invention, the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst has the total specific surface area of 600m2More than g.
The preparation method of the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst comprises the following steps:
(1) copper sulfate (CuSO) under vigorous stirring4) Slowly dripping Tetraethylenepentamine (TEPA) into the solution, and sequentially adding cerium nitrate (Ce (NO))3·6H2O) and iron nitrate (Fe ((NO)3) Fully and uniformly mixing, and then adding sodium hydroxide to prepare solution A;
(2) adding sodium metaaluminate or aluminum sulfate octadecahydrate into the solution A obtained in the step (1), stirring for 1-2 hours, then adding silica sol, further stirring for 2-3 hours, then placing the mixture into a steel reaction kettle with a polytetrafluoroethylene lining, aging for 12-14 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor for 72-96 hours at 120-180 ℃, carrying out solid-liquid separation after crystallization is finished, washing the solid with water until the pH value is neutral, drying, and calcining the solid for 4-8 hours at 500-550 ℃ to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve.
According to the invention, the preparation method comprises the following steps:
(1) according to the parts by weight, 3.9 parts of CuSO4·5H2Dissolving O in 15 parts of deionized water, stirring uniformly, dropwise adding 14.88 parts of Tetraethylenepentamine (TEPA), stirring for 1 hour, and adding 1.0 part of Ce (NO)3·6H2O and 3.6 parts Fe (NO)3Fully and uniformly mixing, and then adding 10.4 parts of NaOH to prepare solution A;
(2) adding 5.6 parts of NaAlO into the solution A prepared in the step (1)2(41.0％Al2O3) Stirring for 1 hour, adding 60.0 parts of silica sol (b)31.5％SiO2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 72 hours, carrying out centrifugal separation after crystallization is finished, washing with water until the pH value is 7, drying, and calcining the solid at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is applied to the removal of NOx in the tail gas of a diesel vehicle.
The invention has the advantages of
1. The Cu-Fe-Ce-SSZ-13 molecular sieve can improve the damage degree of the framework of a molecular sieve sample with a low silica-alumina ratio in the hydrothermal aging process and improve the framework stability of a molecular sieve product.
2. The invention relates to a preparation method of a Cu-Fe-Ce-SSZ-13 molecular sieve, which adopts cheap copper sulfate, tetraethylammonium penta-acetate, ferric nitrate, cerium nitrate, sodium metaaluminate and silica sol as raw materials, has simple preparation process and low cost, and is a high-performance diesel vehicle tail gas NOx removal catalyst.
3. The invention uses a Fe-containing alloy3+The Cu-Fe-Ce-SSZ-13 molecular sieve is prepared from the substances, and the action performance of the prepared molecular sieve is superior to that of the molecular sieve containing Fe2+The Cu-Fe-Ce-SSZ-13 molecular sieve prepared from the material.
Detailed Description
The invention will be further elucidated with reference to the following specific examples, without the scope of the invention being limited thereto.
In the following, the raw materials in the examples of the present invention were all purchased from commercial sources, unless otherwise specified.
The analytical methods involved in the examples of the invention are as follows:
the samples were analyzed for silica to alumina ratio using a Japanese ZSX Primus II X-ray fluorescence spectrometer.
The samples were analyzed for Ce content using an Agilent Varian 715-ES model plasma emission spectrometer.
The pore structure of the samples was analyzed using an ASAP2460 surface area and porosity analyzer from mack, usa.
Example 1
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D0 comprises the following steps:
(1) 2.7g of CuSO4·5H2Dissolving O in 15mL of deionized water, uniformly stirring, dropwise adding 14.88g of Tetraethylenepentamine (TEPA), and continuously stirring for 1 hour; then 0.6g of Ce (NO) was added3·6H2O and 4.8g Fe (NO)3The resulting solution was sufficiently dissolved in 33.78g of water, and 10.4g of NaOH was added thereto to prepare solution A.
(2) Adding 5.6g of NaAlO into the solution A prepared in the step (1)2(41.0% Al by mass fraction)2O3) After stirring for 1 hour, 60.0g of silica sol (31.5% by mass of SiO) was added2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 72 hours, carrying out centrifugal separation after crystallization is finished, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 3.12 percent, 4.83 percent and 0.87 percent according to mass fraction, and SiO2/Al2O3Is 11.83.
Comparative example 1
A method for preparing Ce-free Cu-Fe-SSZ-13 molecular sieve B1, comprising the following steps:
(1) 2.7g of CuSO4·5H2O in 15ml of deionized water, 14.88g of Tetraethylenepentamine (TEPA) were added dropwise after stirring, stirring was continued for 1 hour, and then 4.8g of Fe (NO)3The resulting solution was sufficiently dissolved in 33.78g of water, and 10.4g of NaOH was added thereto to prepare solution A.
(2) Adding 5.6g of NaAlO into the solution A prepared in the step (2)2(41.0% Al by mass fraction)2O3) After stirring for 1 hour, 60.0g of silica sol (31.5% by mass of SiO) was added2) Stirring for 2-3 hr, loading into steel reactor with polytetrafluoroethylene lining, aging for 12 hr, performing hydrothermal reaction at 160 deg.C for 72 hr, crystallizing, and centrifugingAnd washing the catalyst with water until the pH value is 7, drying the catalyst and calcining the catalyst at 550 ℃ for 8h to obtain the Cu-Fe-SSZ-13 molecular sieve catalyst.
The contents of Cu and Fe in the molecular sieve catalyst are respectively 3.06 percent and 4.75 percent by mass fraction, and SiO2/Al2O3Is 11.72.
Example 2
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D1 comprises the following steps:
(3) 3.9g of CuSO4·5H2Dissolving O in 15ml deionized water, stirring, adding 14.88g Tetraethylenepentamine (TEPA) dropwise, stirring for 1 hr, adding 1.0g Ce (NO)3·6H2O and 3.6g Fe (NO)3After mixing well, 10.4g of NaOH is added to prepare solution A.
(4) Adding 5.6g of NaAlO into the solution A prepared in the step (1)2(41.0% Al by mass fraction)2O3) After stirring for 1 hour, 60.0g of silica sol (31.5% by mass of SiO) was added2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 72 hours, carrying out centrifugal separation after crystallization is finished, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 3.76 percent, 2.87 percent and 1.23 percent according to mass fraction, and SiO2/Al2O3Is 12.14.
Example 3
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D2 comprises the following steps:
(1) 6.3g of CuSO4·5H2Dissolving O in 50ml deionized water, stirring, adding 36.7g Tetraethylenepentamine (TEPA) dropwise, stirring for 1 hr, adding 1.5g Ce (NO)3·6H2O and 9.0gFe (NO)3The resultant solution was thoroughly dissolved in 178.53g of water, and 25.38g of NaOH was added thereto to prepare solution A.
(2) Adding 51.9g of octadecane hydrate into the solution A prepared in the step (1)Aluminum sulfate, stirring for 1 hour, and adding 60g of solid silica gel (98% SiO by mass)2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 96 hours, after crystallization, carrying out centrifugal separation, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 2.12 percent, 2.76 percent and 0.48 percent, and SiO2/Al2O3Is 10.14.
Example 4
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D3 comprises the following steps:
(1) 7.8g of CuSO4·5H2Dissolving O in 50ml deionized water, stirring, adding 36.7g Tetraethylenepentamine (TEPA) dropwise, stirring for 1 hr, adding 4.8g Ce (NO)3·6H2O and 11.7g Fe (NO)3A solution A was prepared by dissolving the above components in 178.53g of water, and adding 25.38g of NaOH thereto.
(2) To the solution A obtained in the step (1), 51.9g of aluminum sulfate octadecahydrate was added, and after stirring for 1 hour, 60g of solid silica gel (98% SiO by mass) was added2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 96 hours, after crystallization, carrying out centrifugal separation, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 2.57 percent, 3.43 percent and 1.53 percent, and SiO2/Al2O3Is 9.93.
Example 5
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D4 comprises the following steps:
(1) 7.8g of CuSO4·5H2Dissolving O in 50ml deionized water, stirring, adding 36.7g Tetraethylenepentamine (TEPA) dropwise, stirring for 1 hr, and adding4.8g Ce (NO)3·6H2O and 11.7g Fe (NO)3After mixing well, 22.5g NaOH was added to prepare solution A.
(2) Adding 14.1g of NaAlO to the solution A prepared in the step (1)2(41.0% Al by mass fraction)2O3) After stirring for 1 hour, 60g of solid silica gel (98% SiO by mass) were added2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 96 hours, after crystallization, carrying out centrifugal separation, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 2.12 percent, 3.21 percent and 1.42 percent, and SiO2/Al2O3Is 15.23.
Example 6
A preparation method of Cu-Fe-Ce-SSZ-13 molecular sieve D5 comprises the following steps:
(1) 6.9g of CuSO4·5H2Dissolving O in 50ml deionized water, stirring, adding 36.7g Tetraethylenepentamine (TEPA) dropwise, stirring for 1 hr, adding 3.8g Ce (NO)3·6H2O and 9.9gFe (NO)3After mixing well, 22.5g NaOH was added to prepare solution A.
(2) Adding 14.1g of NaAlO to the solution A prepared in the step (1)2(41.0% Al by mass fraction)2O3) After stirring for 1 hour, 60g of solid silica gel (98% SiO by mass) were added2) And then stirring for 2-3 hours, putting the mixture into a polytetrafluoroethylene-lined steel reaction kettle, aging for 12 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor at 160 ℃ for 96 hours, after crystallization, carrying out centrifugal separation, washing with water until the pH value is 7, drying, and calcining at 550 ℃ for 8 hours to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
The contents of Cu, Fe and Ce in the molecular sieve catalyst are respectively 1.82 percent, 2.81 percent and 0.82 percent, and SiO2/Al2O3Is 15.14.
Effect example 1
The pore structures of the molecular sieve catalysts D0, D1, D2 and B1 and the corresponding aged molecular sieves D0, D1, D2 and B1 were analyzed, and before the test, the molecular sieves were subjected to vacuum pretreatment for 10 hours on a degassing station at a temperature of 300 ℃, an adsorption temperature of-196 ℃ and an adsorption temperature of N12For adsorbate, the BET (Brunauer-Emmett-Teller) method is adopted to calculate the total specific surface area, and the t-plot method is adopted to calculate the micropore specific surface area; the aging conditions of the sample are 800 ℃, 10% of water vapor and 16 h; the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the Cu-Fe-Ce-SSZ-13 molecular sieve provided by the invention can improve the damage degree of the framework of a low-silica-alumina ratio molecular sieve sample in the hydrothermal aging process, and improve the framework stability of a molecular sieve product; the invention relates to a preparation method of a Cu-Fe-Ce-SSZ-13 molecular sieve, which adopts cheap copper sulfate, tetraethylammonium penta-acetate, ferric nitrate, cerium nitrate, sodium metaaluminate and silica sol as raw materials, has simple preparation process and low cost, and is a high-performance diesel vehicle tail gas NOx removal catalyst.
Claims (6)
1. The Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is characterized by comprising a first active component, a second active component and a third active component;
the first active component is a Cu species;
the second active component is a Fe species;
the third active component is a Ce species.
2. The molecular sieve catalyst of claim 1, wherein the molecular sieve catalyst has a Cu content of 1.5 to 4 wt%;
the content of Fe in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 2-5 wt%;
the content of Ce in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 0.1-1.5 wt%;
the mol ratio of silicon dioxide to aluminum oxide in the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst is 9-16.
3. The molecular sieve catalyst of claim 2, wherein the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst has a total specific surface area of 600m2More than g.
4. A process for the preparation of a molecular sieve catalyst according to any of claims 1 to 3, comprising the steps of:
(1) copper sulfate (CuSO) under vigorous stirring4) Slowly dripping Tetraethylenepentamine (TEPA) into the solution, and sequentially adding cerium nitrate (Ce (NO))3·6H2O) and iron nitrate (Fe ((NO)3) Fully and uniformly mixing, and then adding sodium hydroxide to prepare solution A;
(2) adding sodium metaaluminate or aluminum sulfate octadecahydrate into the solution A obtained in the step (1), stirring for 1-2 hours, then adding silica sol, further stirring for 2-3 hours, then placing the mixture into a steel reaction kettle with a polytetrafluoroethylene lining, aging for 12-14 hours, carrying out homogeneous hydrothermal reaction on the obtained sol-gel precursor for 72-96 hours at 120-180 ℃, carrying out solid-liquid separation after crystallization is finished, washing the solid with water until the pH value is neutral, drying, and calcining the solid for 4-8 hours at 500-550 ℃ to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve.
5. The method of claim 4, comprising the steps of:
(1) according to the parts by weight, 3.9 parts of CuSO4·5H2Dissolving O in 15 parts of deionized water, stirring uniformly, dropwise adding 14.88 parts of Tetraethylenepentamine (TEPA), stirring for 1 hour, and adding 1.0 part of Ce (NO)3·6H2O and 3.6 parts Fe (NO)3Fully and uniformly mixing, and then adding 10.4 parts of NaOH to prepare solution A;
(2) adding 5.6 parts of NaAlO into the solution A prepared in the step (1)2(41.0％Al2O3) After stirring for 1 hour, 60.0 parts of silica sol (31.5% SiO) was added2) Stirring for 2-3 hr, and filling the polytetrafluoroethylene liningAging the obtained sol-gel precursor for 12h in the steel reaction kettle, performing homogeneous hydrothermal reaction on the obtained sol-gel precursor for 72h at 160 ℃, after crystallization is finished, performing centrifugal separation, washing with water until the pH value is 7, drying, and calcining the solid for 8h at 550 ℃ to obtain the Cu-Fe-Ce-SSZ-13 molecular sieve catalyst.
6. Use of the molecular sieve catalyst of any of claims 1 to 3 for diesel vehicle exhaust NOx removal.
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| EP3205402A1 (en) * | 2016-02-12 | 2017-08-16 | Hyundai Motor Company | Catalyst and method for preparing catalyst |
| CN108452841A (en) * | 2018-02-07 | 2018-08-28 | 浙江大学 | A kind of preparation method for the SSZ-13 molecular sieve catalysts that Cu and Fe is modified altogether |
| CN110180583A (en) * | 2019-06-18 | 2019-08-30 | 安徽艾可蓝环保股份有限公司 | Based molecular sieve material of cerium containing copper and iron and preparation method thereof and catalyst |
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| EP3205402A1 (en) * | 2016-02-12 | 2017-08-16 | Hyundai Motor Company | Catalyst and method for preparing catalyst |
| CN108452841A (en) * | 2018-02-07 | 2018-08-28 | 浙江大学 | A kind of preparation method for the SSZ-13 molecular sieve catalysts that Cu and Fe is modified altogether |
| CN110180583A (en) * | 2019-06-18 | 2019-08-30 | 安徽艾可蓝环保股份有限公司 | Based molecular sieve material of cerium containing copper and iron and preparation method thereof and catalyst |
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