CN113368892B - FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof - Google Patents
FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof Download PDFInfo
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- 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 113
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000011259 mixed solution Substances 0.000 claims abstract description 118
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910017827 Cu—Fe Inorganic materials 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 14
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 11
- 150000002505 iron Chemical class 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000499 gel Substances 0.000 claims description 40
- 239000002585 base Substances 0.000 claims description 39
- 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 claims description 30
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 27
- 239000004115 Sodium Silicate Substances 0.000 claims description 25
- 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 claims description 25
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 12
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 43
- 238000005303 weighing Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- -1 iron ions Chemical class 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—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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- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/088—Decomposition of a metal salt
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The application relates to the technical field of catalyst preparation, in particular to an FAU type copper-iron composite base cc-SCR molecular sieve catalyst and a preparation method thereof. The preparation method of the FAU type copper-iron composite base cc-SCR molecular sieve catalyst provided by the application comprises the following steps: s101, uniformly mixing a copper salt solution and an iron salt solution to obtain a first mixed solution; s102, adding a silicon source and an aluminum source into a mixed solution of sodium salt and tetrapropyl ammonium hydroxide to obtain a second mixed solution; s103, adding the first mixed solution into the second mixed solution while stirring, and aging to obtain Cu-Fe @ silicon-aluminum gel; s104, drying the Cu-Fe @ silicon-aluminum gel to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst. The molecular sieve catalyst prepared by the preparation method has high copper and iron loading rate and uniform dispersion, improves the catalytic activity of the catalyst, and widens the activity window of the copper-based catalyst.
Description
Technical Field
The application relates to the technical field of catalyst preparation, in particular to an FAU type copper-iron composite base cc-SCR molecular sieve catalyst and a preparation method thereof.
Background
With the strictness of the exhaust emission control of vehicles, china will gradually implement two stages of "nation six a" and "nation six b" of the nation six emission standards. Compared with the national standard five, the emission standard is improved by more than 30%, the nitrogen oxide is reduced by 77%, the particulate matter is reduced by 67%, the limit requirement of PN (particle number) is introduced, the emission durability and OBD related requirements are enhanced, and the emission test requirement of the whole vehicle is introduced, so that the emission standard is fundamentally ensured.
By NH 3 Reduction of NO for reductant selective catalyst x Technique (NH) 3 SCR technology), which is currently the most widely used diesel vehicle exhaust NO x Emission control techniques. SCR (Selective Catalytic Reduction) aims at NO in tail gas emission of diesel vehicles x The treatment principle of the method is that under the action of a catalyst, a reducing agent ammonia or urea is sprayed in to treat NO in the tail gas x Reduction to N 2 And H 2 O, the catalyst has two types of noble metals and non-noble metals, and the treatment process has the advantages of no byproduct, no secondary pollution, simple device structure, high removal efficiency (up to more than 90 percent), reliable operation, convenient maintenance and the like.
Research shows that the copper-based molecular sieve catalyst is used for treating NO in the tail gas of diesel vehicles x The catalyst has high catalytic purification activity, but the preparation process of the existing copper-based catalyst is relatively complicated, a molecular sieve carrier is generally prepared first, and then the catalyst is obtained in an impregnation or ion exchange mode.
Therefore, there is a need for a novel catalyst having a high copper loading rate.
Disclosure of Invention
The embodiment of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which aims to solve the problems of low copper loading rate and easy collapse of a catalyst structure in the related technology.
In a first aspect, the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, uniformly mixing a copper salt solution and a ferric salt solution to obtain a first mixed solution;
step S102, adding a silicon source and an aluminum source into a mixed solution of sodium salt and tetrapropylammonium hydroxide (TPAOH) to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while stirring, and aging to obtain Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In some embodiments, in step S101, the copper salt is selected from one or more of copper sulfate, copper chloride, and copper nitrate.
In some embodiments, in step S101, the iron salt is selected from any one or more of ferric sulfate, ferric chloride, or ferric nitrate.
In some embodiments, in step S102, the silicon source is selected from any one or a mixture of sodium silicate, silica gel, or silicon dioxide.
In some embodiments, in step S102, the aluminum source is selected from any one or more of aluminum sulfate, aluminum nitrate, or aluminum chloride.
In some embodiments, in step S102, the sodium salt is selected from any one or more of sodium chloride, sodium bromide, or sodium sulfate.
In some embodiments, the copper salt is copper nitrate, the iron salt is ferric nitrate, the silicon source is sodium silicate, the aluminum source is aluminum sulfate, and the sodium salt is sodium sulfate.
In some embodiments, the mass ratio of the copper element in the copper salt, the iron element in the iron salt, the silicon element in the silicon source, and the aluminum element in the aluminum source is 2-5: 1-3: 25-70: 3 to 10. In some preferred embodiments, the mass ratio of the copper element in the copper salt, the iron element in the iron salt, the silicon element in the silicon source, and the aluminum element in the aluminum source is 2: 1: 25: 3.
in some embodiments, in step S103, the stirring speed is 1000rpm to 1800 rpm.
In some embodiments, the drying temperature in step S104 is 60 ℃ to 100 ℃.
In some embodiments, in step S104, the temperature of vacuum heating is 450-600 ℃ for 1-4 h.
In a second aspect, the application also provides an FAU type copper-iron composite-based cc-SCR molecular sieve catalyst, which is prepared by the preparation method.
The preparation method provided by the application takes TPAOH as a structure directing agent, and in the crystallization process, the TPAOH isPart of OH - And Na in sodium salt + Activation takes place, these activated Na + And OH - Will cause the T-O-T bond in the amorphous material to dissolve to form soluble T-O (H), soluble T-O (H) and hydrated cation Na + The assembly is converted into a guiding agent T-O, under the action of the guiding agent T-O, silicon salt and aluminum salt can generate hydrolysis and polycondensation reaction in the stirring process to form nanoclusters with different structures, the clusters are adhered to each other to form gel, all materials forming the zeolite structure and doping materials are contained in the original solid phase, the silicon-aluminum gel doped with copper and iron ions is placed in a pressure container, after the temperature and the pressure are raised, liquid in the gel generates phase change to form supercritical fluid, at the moment, a gas-liquid interface disappears, the surface tension does not exist, the porous molecular sieve structure is formed through heating and pressure reduction, and the Cu and Fe nano particles are encapsulated in the porous molecular sieve structure.
The beneficial effect that technical scheme that this application provided brought includes: the preparation method provided by the application does not need to use an organic solvent in the preparation process, and is green and environment-friendly; the molecular sieve catalyst prepared by the preparation method has high copper and iron loading rate and uniform dispersion, improves the catalytic activity of the catalyst, widens the active window of the copper-based catalyst, effectively inhibits the migration of copper and iron ions by encapsulating the copper and iron ions in a pore channel structure of the molecular sieve, and further improves the hydrothermal aging stability of the catalyst.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method for preparing a FAU-type Cu-Fe composite-based cc-SCR molecular sieve catalyst provided in an embodiment of the present application;
FIG. 2 is a scanning electron micrograph and an X-ray diffraction pattern of the molecular sieve powder prepared in example 1;
FIG. 3 is a graph showing the results of activity evaluation of the catalyst obtained in example 1 of the present application and the catalyst obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which can solve the problems of low copper loading rate and easy collapse of a catalyst structure in the related technology.
Fig. 1 is a schematic flow chart of a preparation method of a FAU type copper-iron composite based cc-SCR molecular sieve catalyst provided in an embodiment of the present application, and referring to fig. 1, the preparation method of the molecular sieve catalyst comprises the following steps:
step S101, uniformly mixing a copper salt solution and an iron salt solution to obtain a first mixed solution; the copper salt is selected from one or more of copper sulfate, copper chloride or copper nitrate; the ferric salt is selected from one or a mixture of ferric sulfate, ferric chloride or ferric nitrate;
step S102, adding a silicon source and an aluminum source into a mixed solution of sodium salt and tetrapropyl ammonium hydroxide (TPAOH) to obtain a second mixed solution; the silicon source is selected from one or a mixture of more of sodium silicate, silica gel or silicon dioxide; the aluminum source is selected from any one or a mixture of aluminum sulfate, aluminum nitrate or aluminum chloride; the sodium salt is selected from one or more of sodium chloride, sodium bromide or sodium sulfate; the mass ratio of copper element in the copper salt, iron element in the iron salt, silicon element in the silicon source and aluminum element in the aluminum source is 2-5: 1-3: 25-70: 3 to 10.
Step S103, adding the first mixed solution into the second mixed solution while stirring at the speed of 1000-1800 rpm, and aging at room temperature for 2-8 h to obtain white uniform Cu-Fe @ silicon-aluminum gel;
step S104, drying the Cu-Fe @ silicon-aluminum gel at 60-100 ℃ for 6-12 h to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 450-600 ℃ for 1-4 h to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst, wherein the loading rate of Cu is 1-6%, and the loading rate of Fe is 1-4%.
Tetrapropylammonium hydroxide of the formula C 12 H 29 NO, CAS number 4499-86-9.
Silica gel is a high-activity adsorption material, belongs to an amorphous substance, and has a chemical molecular formula of mSiO 2 ·nH 2 O, non-toxic and tasteless, stable chemical property, high adsorption performance, good thermal stability and higher mechanical strength.
The preparation method provided by the application takes TPAOH as a structure directing agent, and in the crystallization process, part of OH is contained - And Na in sodium salt + Activation takes place, these activated Na + And OH - Will cause the T-O-T bond in the amorphous material to dissolve to form soluble T-O (H), soluble T-O (H) and hydrated cation Na + The assembly is converted into a guiding agent T-O, under the action of the guiding agent T-O, silicon salt and aluminum salt can undergo hydrolysis and polycondensation reactions in the stirring process to form nanoclusters with different structures, the nanoclusters are adhered to each other to form gel, all materials forming a zeolite structure and doping materials are contained in an original solid phase, the silicon-aluminum gel doped with copper and iron ions is placed in a pressure container, after heating and pressure boosting, liquid in the gel undergoes phase change to form supercritical fluid, at the moment, a gas-liquid interface disappears, surface tension does not exist, and a porous molecular sieve structure is formed by heating and pressure reducing, and Cu and Fe nano particles are packaged in the porous molecular sieve structure.
The preparation method provided by the application does not need to use an organic solvent in the preparation process, and is green and environment-friendly; the molecular sieve catalyst prepared by the preparation method has high copper and iron loading rate and uniform dispersion, improves the catalytic activity of the catalyst, widens the activity window of the copper-based catalyst, effectively inhibits the migration of copper and iron ions by encapsulating the copper and iron ions in a molecular sieve pore structure, and further improves the hydrothermal aging stability of the catalyst.
The FAU type copper-iron composite based cc-SCR molecular sieve catalyst and the preparation method thereof provided by the present application are explained in detail below with reference to examples and comparative examples.
Example 1:
the embodiment 1 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution and an iron nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1200rpm, stirring for 3 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 2 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 80 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 500 ℃ for 1 hour to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 1, the ratio of copper element: iron element: silicon element: aluminum element 2: 1: 25: 3, weighing copper nitrate, ferric nitrate, sodium silicate and aluminum sulfate.
Referring to fig. 2, fig. 2a is a scanning electron micrograph of the molecular sieve powder obtained in example 1, and fig. 2b is an X-ray diffraction pattern of the molecular sieve powder obtained in example 1, and it can be seen from fig. 2 that the molecular sieve obtained in example 1 is FAU type.
Comparative example 1:
the Cu-ZSM-5 molecular sieve catalyst prepared in the comparative example 1 of the application comprises the following preparation processes: weighing 300g H-ZSM-5 powder, calcining at 550 ℃ for 4h, and then cooling to room temperature; adding H-ZSM-5 powder into a copper nitrate solution, rotationally drying the powder at 80 ℃ to be powdery, and calcining the powder at 550 ℃ for 2 hours to obtain the Cu-ZSM-5 molecular sieve catalyst, wherein the mass ratio of copper ions in the copper nitrate solution to the H-ZSM-5 powder is 2: 25.
The catalysts prepared in example 1 and comparative example 1 were subjected to activity evaluation by the following method: weighing 50g of FAU type copper-iron composite base cc-SCR molecular sieve catalyst prepared in the embodiment 1, adding the FAU type copper-iron composite base cc-SCR molecular sieve catalyst into 150mL of deionized water, and mixing to obtain slurry A; weighing 50g of the Cu-ZSM-5 molecular sieve catalyst prepared in the comparative example 1, adding the catalyst into 150mL of deionized water, and mixing to obtain slurry B; respectively coating the slurry A and the slurry B on a hole number of 400 cells/in 2 Sample A and sample B were obtained on a cordierite honeycomb ceramic substrate having a volume of 0.18L, and the coating amounts of slurry A and slurry B were 220 g.L -1 Then, respectively drying the sample A and the sample B at 100 ℃ for 2h, then roasting at 500 ℃ for 2h to obtain a copper-based catalyst A and a copper-based catalyst B, respectively putting the copper-based catalyst A and the copper-based catalyst B into a fixed bed activity evaluation device for simulation test, wherein the simulated tail gas comprises 1000ppm NO and 1100ppm NH 3 、5％O 2 And 10% of H 2 O, the reaction space velocity is 30000h -1 。
The test results are shown in fig. 3, in which cc-SCR fresh represents the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst prepared in example 1, cc-SCR aging represents the hydrothermal aging of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst prepared in example 1 at 700 ℃ for 12 hours, comparative-aging represents the hydrothermal aging of the catalyst prepared in comparative example 1 at 700 ℃ for 12 hours, and comparative-fresh represents the catalyst prepared in comparative example 1, and it can be seen from fig. 3 that the catalyst prepared in example 1 has superior hydrothermal stability to the catalyst prepared in comparative example 1.
Example 2:
the embodiment 2 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution and a ferric chloride solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silica gel and aluminum nitrate into a mixed solution of sodium chloride and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1300rpm, stirring for 2 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 3 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 65 ℃ for 7h to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 550 ℃ for 1.5h to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 2, the ratio of copper element: iron element: silicon element: aluminum element 3: 2: 30: 4, weighing copper nitrate, ferric chloride, silica gel and aluminum nitrate according to the mass ratio.
Example 3:
the embodiment 3 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper sulfate solution and a ferric sulfate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1500rpm, stirring for 3.5 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 5 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel for 8 hours at 85 ℃ to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder for 1 hour at 600 ℃ to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 3, as copper element: iron element: silicon element: aluminum element 2.5: 1.5: 32: weighing copper sulfate, ferric sulfate, sodium silicate and aluminum sulfate according to the mass ratio of 3.5.
Example 4:
the embodiment 4 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper chloride solution and a ferric chloride solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silicon dioxide and aluminum nitrate into a mixed solution of sodium bromide and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1600rpm, stirring for 5 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 4 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel for 8 hours at 75 ℃ to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder for 2.5 hours at 520 ℃ to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 4, the ratio of copper element: iron element: silicon element: aluminum element 3.5: 2.5: 43: 4.5 weighing copper chloride, ferric chloride, silicon dioxide and aluminum nitrate according to the mass ratio.
Example 5:
the embodiment 5 provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper sulfate solution and a ferric nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum chloride into a mixed solution of sodium chloride and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1300rpm, stirring for 4.5 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 6 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel for 7 hours at 70 ℃ to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder for 2 hours at 550 ℃ to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 5, the ratio of copper element: iron element: silicon element: aluminum element 4: 2.8: 35: 4, weighing copper sulfate, ferric nitrate, sodium silicate and aluminum chloride according to the mass ratio.
Example 6:
the embodiment 6 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper sulfate solution and a ferric sulfate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silicon dioxide and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1400rpm, stirring for 3.5 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and aging for 6 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 80 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 500 ℃ for 1 hour to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 6, as copper element: iron element: silicon element: aluminum element 2: 1: 25: 3, weighing copper sulfate, ferric sulfate, silicon dioxide and aluminum sulfate according to the mass ratio.
Example 7:
the application embodiment 7 provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a copper chloride solution and an iron nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1500rpm, stirring for 3 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 2 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 90 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 500 ℃ for 1 hour to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 7, the ratio of copper element: iron element: silicon element: aluminum element 3: 2: 45: 5, weighing copper nitrate, copper chloride, ferric nitrate, sodium silicate and aluminum sulfate.
Example 8:
the embodiment 8 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, an iron nitrate solution and ferric chloride uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum nitrate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1600rpm, stirring for 4 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 3 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 65 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 580 ℃ for 3 hours to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 8, as the copper element: iron element: silicon element: aluminum element 4.5: 1.5: 43: 6, weighing copper nitrate, ferric chloride, sodium silicate and aluminum nitrate according to the mass ratio.
Example 9:
the embodiment 9 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper sulfate solution, a copper nitrate solution and a ferric nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1500rpm, stirring for 3 hours to enable the first mixed solution to be centrifugally dispersed into the second mixed solution, and then aging for 2 hours at room temperature to obtain white and uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 80 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 540 ℃ for 2 hours to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 9, the ratio of copper element: iron element: silicon element: aluminum element 4: 2: 35: weighing copper sulfate, copper nitrate, ferric nitrate, sodium silicate and aluminum sulfate according to the mass ratio of 7.
Example 10:
the embodiment 10 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a ferric nitrate solution and a ferric sulfate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silica gel, sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1400rpm, stirring for 3 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 2 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 95 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 560 ℃ for 2 hours to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 10, the ratio of copper element: iron element: silicon element: aluminum element 3: 2: 25: 3, weighing copper nitrate, ferric sulfate, silica gel, sodium silicate and aluminum sulfate.
Example 11:
the embodiment 11 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a copper chloride solution and an iron nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate, sodium bromide and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotation speed of 1300rpm, stirring for 3 hours to enable the first mixed solution to be centrifugally dispersed into the second mixed solution, and then aging for 2 hours at room temperature to obtain white and uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 80 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 570 ℃ for 2 hours to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 11, the ratio of copper element: iron element: silicon element: aluminum element 2: 2: 55: 6, weighing copper nitrate, copper chloride, ferric nitrate, sodium silicate and aluminum sulfate.
Example 12:
the embodiment 12 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a copper chloride solution, an iron nitrate solution and an iron sulfate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silicon dioxide, sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate, sodium chloride and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1500rpm, stirring for 5 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 3 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 75 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 500 ℃ for 1 hour to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 12, the ratio of copper element: iron element: silicon element: aluminum element 3: 2: 65: weighing copper nitrate, copper chloride, ferric nitrate, ferric sulfate, silicon dioxide, sodium silicate and aluminum sulfate according to the mass ratio of 8.
Example 13:
the embodiment 13 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a copper chloride solution, a copper sulfate solution, an iron chloride solution and an iron nitrate solution uniformly according to a certain proportion to obtain a first mixed solution;
step S102, adding silica gel, silicon dioxide and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at the rotating speed of 1600rpm, stirring for 4 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 2 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 95 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 550 ℃ for 1 hour to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 13, the ratio of copper element: iron element: silicon element: aluminum element 2: 2.5: 56: weighing copper nitrate, copper chloride, copper sulfate, ferric chloride, ferric nitrate, silica gel, silicon dioxide and aluminum sulfate according to the mass ratio of 7.5.
Example 14:
the embodiment 14 of the application provides a preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst, which comprises the following steps:
step S101, mixing and stirring a copper nitrate solution, a ferric chloride solution and a ferric sulfate solution according to a certain proportion to obtain a first mixed solution;
step S102, adding sodium silicate and aluminum sulfate into a mixed solution of sodium sulfate and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
step S103, adding the first mixed solution into the second mixed solution while magnetically stirring at a rotating speed of 1700rpm, stirring for 3 hours, centrifugally dispersing the first mixed solution into the second mixed solution, and then aging for 6.5 hours at room temperature to obtain white uniform Cu-Fe @ silicon-aluminum gel;
and S104, drying the Cu-Fe @ silicon-aluminum gel at 80 ℃ for 6 hours to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder at 540 ℃ for 1.5 hours to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
In example 14, the ratio of copper element: iron element: silicon element: aluminum element 2: 2.5: 70: 4, weighing copper nitrate, ferric chloride, ferric sulfate, sodium silicate and aluminum sulfate.
In the description of the present specification, reference to the description of "one embodiment/mode", "some embodiments/modes", "example", "specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the present application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
It is noted that, in the present application, relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. In this application, "plurality" means at least two, e.g., two, three, etc., unless specifically stated otherwise.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of an FAU type copper-iron composite base cc-SCR molecular sieve catalyst is characterized by comprising the following steps:
s101, uniformly mixing a copper salt solution and a ferric salt solution to obtain a first mixed solution;
s102, adding a silicon source and an aluminum source into a mixed solution of sodium salt and tetrapropyl ammonium hydroxide to obtain a second mixed solution;
s103, adding the first mixed solution into the second mixed solution while stirring, and aging to obtain Cu-Fe @ silicon-aluminum gel;
s104, drying the Cu-Fe @ silicon-aluminum gel to obtain molecular sieve powder, and then carrying out vacuum heating treatment on the molecular sieve powder to obtain the FAU type copper-iron composite base cc-SCR molecular sieve catalyst.
2. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein in step S101, the copper salt is selected from one or more of copper sulfate, copper chloride or copper nitrate; the ferric salt is selected from one or more of ferric sulfate, ferric chloride or ferric nitrate.
3. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein in step S102, the silicon source is selected from any one or a mixture of sodium silicate, silica gel or silicon dioxide; the aluminum source is selected from any one or a mixture of aluminum sulfate, aluminum nitrate or aluminum chloride; the sodium salt is selected from one or more of sodium chloride, sodium bromide or sodium sulfate.
4. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein the copper salt is copper nitrate, the iron salt is ferric nitrate, the silicon source is sodium silicate, the aluminum source is aluminum sulfate, and the sodium salt is sodium sulfate.
5. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein the mass ratio of copper element in copper salt, iron element in iron salt, silicon element in silicon source and aluminum element in aluminum source is 2-5: 1-3: 25-70: 3 to 10.
6. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein the mass ratio of the copper element in the copper salt, the iron element in the iron salt, the silicon element in the silicon source, and the aluminum element in the aluminum source is 2: 1: 25: 3.
7. the method for preparing a FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as recited in claim 1, wherein the stirring speed in step S103 is 1000rpm to 1800 rpm.
8. The method for preparing a FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein the drying temperature in step S104 is 60 ℃ to 100 ℃.
9. The preparation method of the FAU-type copper-iron composite-based cc-SCR molecular sieve catalyst as claimed in claim 1, wherein the vacuum heating temperature is 450-600 ℃ for 1-4 h in step S104.
10. An FAU type copper-iron composite based cc-SCR molecular sieve catalyst, characterized in that it is prepared by the preparation method of any one of claims 1 to 9.
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