CN111871456A - Preparation method for synthesizing copper-containing SCR catalyst with CHA structure by one-step method - Google Patents
Preparation method for synthesizing copper-containing SCR catalyst with CHA structure by one-step method Download PDFInfo
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- CN111871456A CN111871456A CN202010844055.6A CN202010844055A CN111871456A CN 111871456 A CN111871456 A CN 111871456A CN 202010844055 A CN202010844055 A CN 202010844055A CN 111871456 A CN111871456 A CN 111871456A
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- 239000010949 copper Substances 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010457 zeolite Substances 0.000 claims abstract description 21
- 239000006255 coating slurry Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000004199 lung function Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/0215—Coating
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a preparation method for synthesizing a copper-containing SCR catalyst with a CHA structure by a one-step method, which comprises the following steps: s1: synthesizing a CHA structure copper-containing zeolite molecular sieve by a hydrothermal synthesis method, wherein S2: separating, drying and calcining the synthesized copper-containing zeolite molecular sieve, wherein S3: preparing the copper-containing zeolite molecular sieve into coating slurry, and performing S4: and coating the slurry on a honeycomb carrier, and drying and roasting to obtain the SCR catalyst. The copper-containing zeolite molecular sieve SCR catalyst with the CHA structure prepared by the invention adopts a one-step synthesis method, so that the Cu base can be uniformly dispersed on the molecular sieve with the CHA structure, and the loading capacity of the Cu base on the CHA molecular sieve is easy to control, thereby being beneficial to improving the activity of the SCR catalyst.
Description
Technical Field
The invention relates to the field of diesel engine tail gas treatment, in particular to a method for treating NO in diesel engine tail gas by using a copper-containing zeolite molecular sieve with a CHA structurexA method for preparing the SCR catalyst.
Technical Field
The diesel engine has been widely used in the fields of power generation, automobiles and ships due to its advantages of high thermal efficiency and low fuel consumption, but nitrogen and oxygen discharged during the operation of the diesel engineCompound (NO)x) Can react with ultraviolet light to generate serious photochemical pollution, and poses certain threat to the environment. At the same time, NOxCan cause the spasm of nerve center of human body, cause respiratory tract infection, and decrease of lung function, and seriously harm human health. In the first-line city of China, more than 40% of NOxIs generated by a diesel engine, thereby improving the utilization of the diesel engine and reducing NOxThe emission of the diesel engine is the problem which is mainly solved by the widely applied diesel engine.
Selective Catalytic Reduction (SCR) technology is NOxOne of the most effective technologies for emission is to treat NO which is widely used in industry at presentxIn an SCR system, the performance of the catalyst is such as to affect the treatment of NOxThe key point of the efficiency is that the copper-based CHA zeolite molecular sieve has a wider temperature window, higher nitrogen selectivity and catalyst activity due to the characteristics of a small pore channel structure, and can meet the requirements of emission regulations on the service life and efficiency of a catalyst, so that the copper-based CHA zeolite molecular sieve becomes the first choice for controlling the emission of nitrogen oxides of a new-generation diesel engine.
The traditional copper-based CHA zeolite molecular sieve usually adopts an ion exchange method and an impregnation method to load an active component Cu on the molecular sieve, but the impregnation method can cause uneven distribution of the active component in a catalyst and can also cause the problem of pore channel blockage of the molecular sieve, and the ion exchange method is difficult to control the load amount to cause the collapse of a molecular sieve framework, thereby influencing the catalytic efficiency of SCR.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects of the background art, the invention discloses a preparation method for synthesizing a copper-containing SCR catalyst with a CHA structure by a one-step method, so that an active component Cu base is uniformly distributed on a molecular sieve with the CHA structure, and the control of the Cu content in the SCR catalyst is facilitated.
The technical scheme is as follows: the preparation method for synthesizing the copper-containing SCR catalyst with the CHA structure by the one-step method comprises the following steps:
s1: synthesis of copper-containing zeolite molecular sieve with CHA structure by hydrothermal synthesis method
Selecting a silicon source, an aluminum source, a copper source, a phosphorus source and a structure directing agent, putting the silicon source, the aluminum source, the copper source, the phosphorus source and the structure directing agent into water according to a certain proportion, stirring for 2-4 hours, transferring the suspension into a reaction kettle, carrying out hydrothermal crystallization at the temperature of 100-200 ℃, and cooling at the speed of 25-35 ℃/h after the reaction time is 20-30 hours;
s2: separating, washing, drying and calcining the synthesized copper-containing zeolite molecular sieve
Collecting the solid in the suspension obtained from S1 by filtration or centrifugation, washing for 3 times by using a detergent, then placing in an oven to be dried for 2-6 hours at the temperature of 100-650 ℃, and then calcining for 8-10 hours at the temperature of 500-650 ℃ in a muffle furnace;
s3: preparing copper-containing zeolite molecular sieve into coating slurry
Uniformly dispersing the copper-containing zeolite molecular sieve calcined in S2 in an inorganic adhesive, then adding a thickening agent and an organic adhesive, and stirring for 2 hours to obtain uniformly mixed coating slurry;
s4: coating the slurry on a honeycomb carrier, drying and roasting
The coating slurry obtained in S3 was adhered to a honeycomb carrier, and then dried at 120 ℃ for 2-4 hours and then calcined in a muffle furnace at 900 ℃ for 2-8 hours at 500-.
Further, the silicon source in S1 may be selected from one or more of silicate, silica, silicic acid, and tetraalkoxysilane; the aluminum source can be one or more of aluminum hydroxide and aluminum triisopropoxide, the phosphorus source can be one or more of phosphoric acid and ammonium phosphate, the copper source can be one or more of copper oxide, copper acetate and copper fluoride, and the structure directing agent can be one of morpholine, tetraethyl ammonium hydroxide, piperidine and tetraethyl ammonium chloride.
Further, the mass ratio of each element in S1 is 0.1-0.25 Si: 0.5 Al: 0.4-0.475P: 0.06-0.13 Cu: 0-50H2O: 2-3 structure directing agent, wherein Si +4P ═ 2.
Further, the detergent described in S2 is water and ethanol in a ratio of 1: 0.1-2 ratio of the mixture.
Further, the inorganic adhesive of S3 uses one or more of a silica sol, an alumina sol, a titania sol, and a phosphate solution, the thickener is one of diatomaceous earth and silica gel, and the organic adhesive is one or more of cellulose ether, polyvinyl alcohol, and polyvinyl acetate emulsion.
Further, the slurry is coated on the honeycomb substrate in a manner of wetting, spraying or rinsing in S4.
Has the advantages that: the invention adopts a one-step method to synthesize the SCR catalyst containing copper, so that the active component Cu base is uniformly distributed on the molecular sieve with the CHA structure, and the Cu content in the SCR catalyst is favorably controlled. Compared with the traditional impregnation method and the ion exchange method, the method disclosed by the invention has the advantages that the problems of uneven distribution of an active component Cu on the catalyst, blockage of molecular sieve pore channels, collapse of a molecular sieve framework and the like are avoided, and the catalytic activity of the SCR is effectively ensured.
Detailed Description
The technical solution of the present invention will be further described with reference to the following examples.
Example 1:
a preparation method for synthesizing a copper-containing SCR catalyst with a CHA structure in a one-step method comprises the following steps:
s1: synthesis of copper-containing zeolite molecular sieve with CHA structure by hydrothermal synthesis method
Selecting 150g of phosphoric acid to be mixed with 900g of deionized water, stirring for 5 minutes, then adding 5g of copper oxide, adding 111g of aluminum oxide after dissolving, stirring for 30 minutes at room temperature, adding 198g of morpholine, stirring for 80 minutes to reduce the temperature to the room temperature, adding 74g of silicon dioxide, stirring for 10 minutes to obtain uniformly dispersed suspension, transferring the suspension into a 2.5L reaction kettle, heating for 72 hours at 170 ℃, and cooling to the room temperature at the speed of 30 ℃/h;
s2: separating, washing, drying and calcining the synthesized copper-containing zeolite molecular sieve
Collecting the solid in the suspension obtained in the S1 by filtration or centrifugation, washing the solid for 3 times by using 1:3 water and ethanol, then placing the solid in an oven to be dried for 4 hours at 120 ℃, and then calcining the solid for 8 hours at 600 ℃ in a muffle furnace to obtain 172g of off-white powder;
s3: preparing copper-containing zeolite molecular sieve into coating slurry
Mixing and stirring the copper-containing zeolite molecular sieve calcined in S2 and alumina sol according to the proportion of 1:5 for 45 minutes, then adding 5 w.t.thousandth of cellulose ether and silica gel, and stirring for 2 hours to obtain uniformly mixed coating slurry;
s4: coating the slurry on a honeycomb carrier, drying and roasting
The coating slurry obtained in S3 was adhered in a wet manner to a honeycomb carrier, and after drying at 120 ℃ for 2 hours, it was calcined at 600 ℃ for 6 hours in a muffle furnace.
Example 2:
the other starting components and process parameters were unchanged and the hydrothermal time was 60 hours, giving 168g of pale yellow powder.
Example 3:
the other raw material components and the process parameters were unchanged, and the hydrothermal time was 40 hours, yielding 188g of light blue powder.
Example 4:
the other raw material components and process parameters were unchanged and the hydrothermal time was 20 hours, yielding 168g of grey powder.
Claims (6)
1. A preparation method for synthesizing a copper-containing SCR catalyst with a CHA structure by a one-step method is characterized by comprising the following steps:
s1: synthesis of copper-containing zeolite molecular sieve with CHA structure by hydrothermal synthesis method
Selecting a silicon source, an aluminum source, a copper source, a phosphorus source and a structure directing agent, putting the silicon source, the aluminum source, the copper source, the phosphorus source and the structure directing agent into water according to a certain proportion, stirring for 2-4 hours, transferring the suspension into a reaction kettle, carrying out hydrothermal crystallization at the temperature of 100-200 ℃, forming a copper-containing zeolite molecular sieve after the reaction time is 20-80 hours, and cooling at the speed of 25-35 ℃/h;
s2: separating, washing, drying and calcining the synthesized copper-containing zeolite molecular sieve
Collecting the solid in the suspension obtained from S1 by filtration or centrifugation, washing for several times by using a detergent, placing in an oven for drying at 150 ℃ for 2-6 hours at 100 ℃ and then calcining for 8-10 hours at 650 ℃ in a muffle furnace;
s3: preparing copper-containing zeolite molecular sieve into coating slurry
Dispersing the copper-containing zeolite molecular sieve calcined in S2 in an inorganic adhesive, adding a thickening agent and an organic adhesive, and stirring for 2 hours to obtain uniformly mixed coating slurry;
s4: coating the slurry on a honeycomb carrier, drying and roasting
The coating slurry obtained in S3 was adhered to a honeycomb carrier, and then dried at 120 ℃ for 2-4 hours and then calcined in a muffle furnace at 900 ℃ for 2-8 hours at 500-.
2. The method of claim 1 for the one-step synthesis of a copper-containing SCR catalyst with CHA structure, characterized in that: the silicon source in S1 is one or more of silicate, silicon dioxide, silicic acid and tetraalkoxysilane; the aluminum source is one or more of aluminum hydroxide and aluminum triisopropoxide; the phosphorus source is one or more of phosphoric acid and ammonium phosphate; the copper source is one or more of copper oxide, copper acetate and copper fluoride; the structure directing agent is selected from one of morpholine, tetraethyl ammonium hydroxide, piperidine and tetraethyl ammonium chloride.
3. The method of claim 1 for the one-step synthesis of a copper-containing SCR catalyst with CHA structure, characterized in that: the mass ratio of each element in S1 is 0.1-0.25 Si: 0.5 Al: 0.4-0.475P: 0.06-0.13 Cu: 0-50H2O: 2-3 structure directing agent, wherein Si +4P ═ 2.
4. The method of claim 1 for the one-step synthesis of a copper-containing SCR catalyst with CHA structure, characterized in that: the detergent in S2 is water and ethanol, and the volume ratio of the water to the ethanol is 1: 0.1-2 ratio of the mixture.
5. The method of claim 1 for the one-step synthesis of a copper-containing SCR catalyst with CHA structure, characterized in that: the inorganic adhesive of S3 is one or more of silica sol, alumina sol, titanium dioxide sol and phosphate solution; the thickening agent is one of diatomite and silica gel; the organic adhesive is one or more of cellulose ether, polyvinyl alcohol and polyvinyl acetate emulsion.
6. The method of claim 1 for the one-step synthesis of a copper-containing SCR catalyst with CHA structure, characterized in that: the slurry is applied to the honeycomb carrier by dipping, spraying or rinsing in S4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010844055.6A CN111871456A (en) | 2020-08-20 | 2020-08-20 | Preparation method for synthesizing copper-containing SCR catalyst with CHA structure by one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010844055.6A CN111871456A (en) | 2020-08-20 | 2020-08-20 | Preparation method for synthesizing copper-containing SCR catalyst with CHA structure by one-step method |
Publications (1)
| Publication Number | Publication Date |
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