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 PDF

Info

Publication number
CN113368892B
CN113368892B CN202110603514.6A CN202110603514A CN113368892B CN 113368892 B CN113368892 B CN 113368892B CN 202110603514 A CN202110603514 A CN 202110603514A CN 113368892 B CN113368892 B CN 113368892B
Authority
CN
China
Prior art keywords
copper
molecular sieve
aluminum
mixed solution
iron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110603514.6A
Other languages
Chinese (zh)
Other versions
CN113368892A (en
Inventor
姜杨
庞磊
吴章辉
熊洪瑞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongfeng Commercial Vehicle Co Ltd
Original Assignee
Dongfeng Commercial Vehicle Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongfeng Commercial Vehicle Co Ltd filed Critical Dongfeng Commercial Vehicle Co Ltd
Priority to CN202110603514.6A priority Critical patent/CN113368892B/en
Publication of CN113368892A publication Critical patent/CN113368892A/en
Application granted granted Critical
Publication of CN113368892B publication Critical patent/CN113368892B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01D53/74—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
    • 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)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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

FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof
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.
CN202110603514.6A 2021-05-31 2021-05-31 FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof Active CN113368892B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110603514.6A CN113368892B (en) 2021-05-31 2021-05-31 FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110603514.6A CN113368892B (en) 2021-05-31 2021-05-31 FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113368892A CN113368892A (en) 2021-09-10
CN113368892B true CN113368892B (en) 2022-09-06

Family

ID=77575067

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110603514.6A Active CN113368892B (en) 2021-05-31 2021-05-31 FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113368892B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3778484A1 (en) * 2008-05-21 2021-02-17 Basf Se Process for the direct synthesis of cu containing zeolites having cha structure
EP3323785A1 (en) * 2016-11-18 2018-05-23 Umicore AG & Co. KG Crystalline zeolites with eri/cha intergrowth framework type
CN107720776B (en) * 2017-10-23 2020-02-18 中海油天津化工研究设计院有限公司 Synthesis method of sodium-free FAU type molecular sieve
JP7487113B2 (en) * 2018-05-14 2024-05-20 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト Stable small pore zeolite
CN109317188A (en) * 2018-11-14 2019-02-12 福州大学 A kind of preparation method and application of mesoporous FeCu-ZSM-5 molecular sieve

Also Published As

Publication number Publication date
CN113368892A (en) 2021-09-10

Similar Documents

Publication Publication Date Title
CN109985660B (en) Method for synthesizing iron-based molecular sieve catalyst by one-step method and application thereof
CN107362823B (en) Catalytic material for degrading indoor formaldehyde at room temperature and preparation method thereof
JP2022017176A (en) Molecular sieve and manufacturing method thereof
CN111036280A (en) Preparation method of Fe/Cu-SSZ-13 molecular sieve
CN111974444A (en) Preparation method and application of small-pore molecular sieve supported noble metal material prepared by one-pot method
CN112403459B (en) Low-temperature SCR catalyst based on metal phase change microcapsules and preparation method thereof
CN112279266A (en) Cu-SSZ-13@ SSZ-13 core-shell type molecular sieve and preparation method and application thereof
JP2015104682A (en) Catalyst for exhaust gas purification
CN104190464B (en) A kind of Sn bases micro porous molecular sieve NOx SCR catalyst preparation methods
CN108128784A (en) The preparation method of Cu-Ce-La-SSZ-13 molecular sieve catalysts
CN112919494B (en) Preparation method and application of Ce-Cu/SAPO-34 molecular sieve
CN113368892B (en) FAU type copper-iron composite base cc-SCR molecular sieve catalyst and preparation method thereof
CN103534027A (en) Low-temperature oxidation catalyst with particularly marked hydrophobic properties for the oxidation of organic pollutants
CN1915489B (en) Ternary Nano catalyst in use for cellular carrier of full metal, preparation method and coating process
CN113694920B (en) Cordierite-based SCR catalyst and preparation method and application thereof
CN113856744B (en) Atom-doped modified double-shell monolithic hollow catalyst, and preparation method and application thereof
CA1131198A (en) Rare earth-manganese oxidation catalysts and process of producing
CN109894142A (en) A kind of molecular sieve carried CdS-Pt composite photo-catalyst of nanoscale twins MFI and preparation method thereof
CN112774725A (en) Synthesis method of copper-cerium co-doped CNT @ SAPO-34 composite denitration catalyst
CN111250078B (en) MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof
CN113522354A (en) Preparation and application of molecular sieve supported composite metal oxide catalyst
CN110694671A (en) Molecular sieve type SCR denitration catalyst synthesized by using natural diatomite and preparation method thereof
CN114392730B (en) Preparation method of high-dispersion hierarchical pore Ti-based SCR catalyst
US11566340B2 (en) Preparation method of coating material, coating material, catalyst and three-way catalytic converter
CN113952947B (en) Hollow core-shell catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant