CN115445654B - Molecular sieve catalyst for purifying ammonia in tail gas of diesel vehicle, preparation method and application - Google Patents
Molecular sieve catalyst for purifying ammonia in tail gas of diesel vehicle, preparation method and application Download PDFInfo
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- CN115445654B CN115445654B CN202211151240.2A CN202211151240A CN115445654B CN 115445654 B CN115445654 B CN 115445654B CN 202211151240 A CN202211151240 A CN 202211151240A CN 115445654 B CN115445654 B CN 115445654B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 114
- 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 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000012266 salt solution Substances 0.000 claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 150000001879 copper Chemical class 0.000 claims abstract description 39
- 150000003057 platinum Chemical class 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 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 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- 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
- B01D53/9436—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a molecular sieve catalyst for purifying ammonia in tail gas of a diesel vehicle, a preparation method and application thereof, comprising the following steps: (1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve; (2) And (3) carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst. The molecular sieve catalyst comprises the active components in percentage by mass: 0.1-0.5% of platinum, 2-4% of copper and the balance of molecular sieve carrier. So as to solve the problem that the ammonia conversion rate and the nitrogen selectivity of the catalyst prepared at present are still lower at low temperature.
Description
Technical Field
The invention relates to the field of tail gas purification of internal combustion engines, in particular to a molecular sieve catalyst for purifying tail gas of diesel vehicles, a preparation method and application thereof, and especially relates to a method for preparing the molecular sieve catalyst for purifying tail gas of diesel vehicles, the prepared catalyst and application thereof.
Background
At present, the quantity of diesel vehicles in China is smaller than that of automobiles, but the emission quantity of nitrogen oxides (NOx) in tail gas of the diesel vehicles far exceeds the total emission quantity of automobiles. Selective catalytic reduction of NO using ammonia in a diesel aftertreatment system x Generating N 2 And H 2 O method for removing NO x However, excessive urea injection still causes ammonia leakage into the atmosphere, causing environmental pollution, and it is important to reduce ammonia emission
The ammonia removal of diesel exhaust is usually carried out by adopting selective catalytic oxidation of ammonia, and the catalyst applied to catalytic oxidation of ammonia mainly comprises a noble metal catalyst, a transition metal catalyst, a composite oxide catalyst and a molecular sieve catalyst. These catalyst materials each have advantages and disadvantages, in which the noble metal catalyst has a high catalytic activity, but N 2 The selectivity is generally poor; transition metal catalyst N 2 The selectivity is better but the temperature window is too high; the catalytic performance of the composite oxide catalyst varies from material to material, and the difference between different materials is obvious; molecular sieve based catalysts are characterized by their own structure to NH 3 Has good catalytic performance, but has poor stability at high temperature. The exhaust temperature of the exhaust gas of the diesel vehicle is about 200-400 ℃, so that the ammonia oxidation catalyst for the exhaust gas of the diesel vehicle must have a wider temperature window and a higher N 2 Selectivity.
The ammonia oxidation catalyst comprises a carrier and a loaded active ingredient, wherein the active ingredient is copper ions and noble metal Pt, the loading amount of the copper ions is 1-5%, the loading amount of the noble metal Pt is 0.1-1%, the loading amount is the mass of the active ingredient accounting for the mass of the ammonia oxidation catalyst, and the carrier is a self-made SSZ-13 molecular sieve. According to the invention, copper ions and noble metal Pt are loaded by the self-made SSZ-13 molecular sieve, and the adsorption capacity of the molecular sieve is enhanced by improving the silicon-aluminum ratio, so that the dispersibility of the noble metal Pt in the molecular sieve can be improved, the catalytic activity of the catalyst is improved, the selectivity of the catalyst is high, and the catalytic capacity is strong. However, the ammonia conversion rate reaches 99% at 250 ℃, and the scheme does not consider the influence of water vapor in tail gas, but the exhaust gas in the practical application process often contains water vapor, which can seriously influence the ammoxidation performance of the catalyst.
For example, CN101966451A discloses a nano cerium pick solid solution-based catalyst for catalytic purification of ammonia gas in actual industrial tail gas, wherein a carrier is nano cerium pick solid solution, and active components are copper, silver, manganese, iron and the like. The catalyst can reach 100 percent of ammonia conversion rate at 280 ℃ and does not examine H in the mixed gas in practical application 2 Influence of O.
CN114146705a discloses a high water-resistant low-temperature nano oxide catalyst for purifying automobile exhaust, the catalyst comprises an acid-treated nano oxide carrier (alumina, titania, etc.), acidic metal (niobium, tungsten, vanadium, etc.) and metallic silver, and the ammonia conversion rate of the catalyst is less than 100% at 200 ℃.
The defects of the catalyst are mainly that: (1) The catalyst has insufficient low-temperature activity and low ammonia conversion rate at 200-250 ℃; (2) The nitrogen selectivity of the catalyst is low, and the byproduct pollution is serious; (3) The effect of water vapor in the actual tail gas is not considered, and the water vapor can reduce the catalytic activity of the ammoxidation reaction.
Therefore, developing a catalyst with high water resistance, high catalytic activity, low temperature window, and high nitrogen selectivity faces a great challenge.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a diesel vehicle tail gas ammonia purification molecular sieve catalyst, a preparation method and application thereof, so as to solve the problem that the ammonia conversion rate and the nitrogen selectivity of the catalyst prepared at present are still lower at low temperature.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a molecular sieve catalyst for purifying ammonia in tail gas of a diesel vehicle, which comprises the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) And (3) carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst.
According to the preparation method provided by the invention, copper is firstly exchanged into sites of the molecular sieve by an ion exchange method, and copper ions exist in ionic states at cationic sites of the molecular sieve. After stirring and centrifuging the platinum salt solution and the copper-containing molecular sieve, uniformly dispersing platinum on the copper-containing molecular sieve, and roasting at high temperature, wherein the platinum exists in the form of metal nano small particles to cooperate with copper components to form a bimetallic catalyst of metal platinum and ionic copper, so that the metals cooperate with each other, and the requirements of low-temperature performance and high nitrogen selectivity of diesel exhaust ammonia treatment are met.
In the invention, the low temperature is lower than other high temperature conditions in the operation of the tail gas of the diesel vehicle.
As a preferred embodiment of the present invention, the copper salt used in the copper salt solution of the preparing step (1) includes 1 or at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate, preferably copper nitrate;
preferably, the ammonia-type molecular sieve of step (1) comprises 1 or a combination of at least 2 of a ZSM-5 molecular sieve, an SSZ-13 molecular sieve, or a Y molecular sieve;
preferably, the molar ratio of silicon to aluminum atoms of the ammonia-type molecular sieve in the step (1) is (3-20): 1, for example, it may be 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
As a preferred embodiment of the present invention, the molar concentration of the copper element in the copper salt solution in the step (1) is 0.01 to 1mol/L, for example, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, etc., but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the solid to liquid ratio g/mL of the ammonia-type molecular sieve and copper salt solution in step (1) is 1 (50-100), and may be, for example, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, or 1:100, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the first mixing and stirring in the step (1) is 20 to 80 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the time of the first mixing and stirring in the step (1) is 2-8h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h, 7.8h or 8h, etc., but not limited to the recited values, other non-recited values in the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the first firing in the step (1) is 400 to 650 ℃, for example, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, or the like, but the temperature is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the first calcination in step (1) is performed for 3-8 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours, 7 hours, 7.2 hours, 7.4 hours, 7.6 hours, 7.8 hours, or 8 hours, etc., but the present invention is not limited to the above values, and other non-listed values in the range are equally applicable.
As a preferred technical scheme of the invention, the mass ratio of the supported copper molecular sieve to the platinum element in the platinum salt solution in the step (2) is 1 (0.01-0.05), for example, 1:0.01, 1:0.012, 1:0.014, 1:0.016, 1:0.018, 1:0.02, 1:0.022, 1:0.024, 1:0.026, 1:0.028, 1:0.03, 1:0.032, 1:0.034, 1:0.036, 1:0.038, 1:0.04, 1:0.042, 1:0.044, 1:0.046, 1:0.048 or 1:0.005, etc., but the invention is not limited to the listed values, and other non-listed values are equally applicable in the range.
Preferably, the platinum salt used in the platinum salt solution of step (2) comprises 1 or a combination of at least 2 of platinum tetrammine nitrate, chloroplatinic acid, platinum chloride or ammonium chloroplatinate, preferably platinum tetrammine nitrate.
In a preferred embodiment of the present invention, the temperature of the second mixing and stirring in the step (2) is 20 to 40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or the like, but the present invention is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the second mixing and stirring time in step (2) is 0.5-3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h or 3h, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the rotational speed of the centrifugation in the step (2) is 3000-8000r/min, for example, 3000r/min, 3500r/min, 4000r/min, 4500r/min, 5000r/min, 5500r/min, 6000r/min, 6500r/min, 7000r/min, 7500r/min or 8000r/min, etc., but not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the temperature of the second firing in the step (2) is 400 to 650 ℃, for example, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second calcination in step (2) is performed for 3-7 hours, for example, but not limited to, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours, or 7 hours, and the like, and other non-enumerated values are equally applicable in this range.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst;
preparing a copper salt used in the copper salt solution in the step (1) to comprise 1 or at least 2 combinations of copper chloride, copper sulfate, copper nitrate or copper acetate, wherein the molar concentration of copper element in the copper salt solution is 0.01-1mol/L, the ammonia type molecular sieve comprises 1 or at least 2 combinations of ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve, the molar ratio of silicon to aluminum is (3-20) to 1, the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and the copper salt solution is 1 (50-100), the temperature of the first mixing and stirring is 20-80 ℃, the time of the first mixing and stirring is 2-8h, the temperature of the first roasting is 400-650 ℃, and the time of the first roasting is 3-8h;
the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution is 1 (0.01-0.05), the platinum salt used in the platinum salt solution comprises 1 or at least 2 of tetramine platinum nitrate, chloroplatinic acid, platinum chloride or ammonium chloroplatinate, the temperature of the second mixing and stirring is 20-40 ℃, the time of the second mixing and stirring is 0.5-3h, the rotating speed of the centrifugal treatment is 3000-8000r/min, the temperature of the second roasting is 400-650 ℃, and the time of the second roasting is 3-7h.
In a second aspect, the present invention provides a molecular sieve catalyst obtained by the preparation method according to the first aspect, wherein the molecular sieve catalyst comprises active components in percentage by mass: 0.1-0.5% of platinum, 2-4% of copper and the balance of molecular sieve carrier.
In a second aspect, the invention provides a use of the molecular sieve obtained by the preparation method according to the first aspect, wherein the use comprises the step of adopting the molecular sieve catalyst to carry out conversion treatment on ammonia in tail gas of a diesel vehicle;
the temperature of the conversion treatment is 175-400 ℃;
the ammonia concentration in the tail gas of the diesel vehicle is 50-600ppm;
the water content of the diesel vehicle tail gas is 5-10% by volume.
In the invention, the total flow of the gas in purification can be 400-600mL/min, and the airspeed is 100000-300000h -1 。
Compared with the prior art, the invention has the following beneficial effects:
(1) Because the ammonia oxidation catalyst is generally placed in the final link of the tail gas post-treatment of the diesel vehicle, the working temperature is relatively low, and the catalyst prepared by the invention can still have higher activity at the low temperature of 200 ℃, thereby meeting the requirement of completely purifying the ammonia in the tail gas at the low temperature. The reason for the high activity at low temperature is that noble metal platinum is distributed on the molecular sieve in the form of small nano particles, so that the atomic utilization rate is higher and the activity is stronger.
(2) After the tail gas of diesel vehicle is treated by ammonia oxidation catalyst, it is discharged into atmosphere, in order to protect environment and reduce pollutant concentration in tail gas discharge, the invention introduces copper into catalyst, and is favorable for reducing by-product nitrogen oxide produced by platinum in ammonia oxidation reaction, so that the nitrogen selectivity in whole temperature range (200-400 deg.C) is maintained at 80% -94%, and compared with nitrogen selectivity of other invention, it is higher, and can effectively reduce pollutant discharge.
Drawings
FIG. 1 is a graph showing the ammonia conversion and nitrogen selectivity of the ammoxidation reaction in practical example 1 of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a diesel vehicle tail gas ammonia purifying molecular sieve catalyst, which comprises the following active components in percentage by mass: 0.5% of platinum, 3% of copper and the balance of molecular sieve carrier;
the preparation method comprises the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst;
preparing copper salt used in the copper salt solution in the step (1) into copper nitrate, wherein the molar concentration of copper element in the copper salt solution is 0.1mol/L, the ammonia type molecular sieve is SSZ-13 molecular sieve, the molar ratio of silicon atoms to aluminum atoms is 9:1, the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and the copper salt solution is 1:100, the temperature of the first mixing and stirring is 40 ℃, the time of the first mixing and stirring is 5h, the temperature of the first roasting is 600 ℃, and the time of the first roasting is 6h;
the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution is 1:0.05, the platinum salt used in the platinum salt solution is platinum tetramine nitrate, the temperature of the second mixing and stirring is 25 ℃, the time of the second mixing and stirring is 3h, the rotating speed of the centrifugal treatment is 8000r/min, the temperature of the second roasting is 550 ℃, and the time of the second roasting is 3h.
Example 2
The embodiment provides a diesel vehicle tail gas ammonia purifying molecular sieve catalyst, which comprises the following active components in percentage by mass: 0.42% of platinum, 4% of copper and the balance of molecular sieve carrier;
the preparation method comprises the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst;
preparing copper salt used in the copper salt solution in the step (1) into copper nitrate, wherein the molar concentration of copper element in the copper salt solution is 0.5mol/L, the ammonia type molecular sieve is SSZ-13 molecular sieve, the molar ratio of silicon atoms to aluminum atoms is 9:1, the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and the copper salt solution is 1:100, the temperature of the first mixing and stirring is 40 ℃, the time of the first mixing and stirring is 5h, the temperature of the first roasting is 600 ℃, and the time of the first roasting is 6h; repeating the steps twice to obtain the 4.0% copper molecular sieve;
the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution is 1:0.04, the platinum salt used in the platinum salt solution is platinum tetramine nitrate, the temperature of the second mixing and stirring is 25 ℃, the time of the second mixing and stirring is 3h, the rotating speed of the centrifugal treatment is 8000r/min, the temperature of the second roasting is 550 ℃, and the time of the second roasting is 3h.
Example 3
The embodiment provides a diesel vehicle tail gas ammonia purifying molecular sieve catalyst, which comprises the following active components in percentage by mass: 0.39% of platinum, 4% of copper and the balance of molecular sieve carrier;
the preparation method comprises the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst;
preparing copper salt used in the copper salt solution in the step (1) into copper nitrate, wherein the molar concentration of copper element in the copper salt solution is 0.1mol/L, the ammonia type molecular sieve is SSZ-13 molecular sieve, the molar ratio of silicon atoms to aluminum atoms is 12:1, the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and the copper salt solution is 1:80, the temperature of the first mixing and stirring is 50 ℃, the time of the first mixing and stirring is 4 hours, the temperature of the first roasting is 500 ℃, and the time of the first roasting is 8 hours; repeating the steps twice to obtain the 4.0% copper molecular sieve;
the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution in the step (2) is 1:0.02, the platinum salt used in the platinum salt solution is tetramine platinum nitrate, the temperature of the second mixing and stirring is 30 ℃, the time of the second mixing and stirring is 3h, the rotating speed of the centrifugal treatment is 8000r/min, the temperature of the second roasting is 550 ℃, and the time of the second roasting is 3h.
Application example 1
The molecular sieve catalyst of the embodiment 1 is adopted to carry out conversion treatment on the tail gas of the simulated diesel vehicle;
the transformation process is carried out by performing temperature gradient experiment at 150deg.C, 175 deg.C, 200 deg.C, 225 deg.C, 250 deg.C, 275 deg.C, 300 deg.C, 325 deg.C, 350 deg.C, 375 deg.C and 400 deg.C with constant airspeed of 200000h -1 ；
The ammonia concentration in the tail gas of the diesel vehicle is 550ppm;
the water content of the tail gas of the diesel vehicle is 5 percent by volume, and the flow rate is 500mL/min;
the indexes of the gas before and after purification at 200 ℃ are shown in Table 1, and other results are shown in FIG. 1.
Application example 2
The molecular sieve catalyst of the embodiment 2 is adopted to carry out conversion treatment on the tail gas of the simulated diesel vehicle;
the temperature of the conversion treatment is 200 ℃ and the airspeed is 200000h -1 ；
The ammonia concentration in the tail gas of the diesel vehicle is 550ppm;
the water content of the tail gas of the diesel vehicle is 5% by volume, and the flow rate is 500mL/min.
The indexes of the gas before and after purification are shown in Table 1.
Application example 3
The molecular sieve catalyst of the embodiment 2 is adopted to carry out conversion treatment on the tail gas of the simulated diesel vehicle;
the temperature of the conversion treatment is 300 ℃ and the airspeed is 200000h -1 ；
The ammonia concentration in the tail gas of the diesel vehicle is 550ppm;
the water content of the tail gas of the diesel vehicle is 5 percent by volume, and the flow rate is 500mL/min;
the indexes of the gas before and after purification are shown in Table 1.
Application example 4
The molecular sieve catalyst of the embodiment 3 is adopted to carry out conversion treatment on the tail gas of the simulated diesel vehicle;
the temperature of the conversion treatment is 200 ℃ and the airspeed is 200000h -1 ；
The ammonia concentration in the tail gas of the diesel vehicle is 550ppm;
the water content of the tail gas of the diesel vehicle is 5% by volume, and the flow rate is 500mL/min.
The indexes of the gas before and after purification are shown in Table 1.
Application example 5
The molecular sieve catalyst of the embodiment 3 is adopted to carry out conversion treatment on the tail gas of the simulated diesel vehicle;
the temperature of the conversion treatment is 300 ℃ and the airspeed is 200000h -1 ；
The ammonia concentration in the tail gas of the diesel vehicle is 550ppm;
the water content of the tail gas of the diesel vehicle is 5% by volume, and the flow rate is 500mL/min.
The indexes of the gas before and after purification are shown in Table 1.
TABLE 1
As can be seen from the results of the above application examples, the preparation method provided by the invention firstly exchanges copper into sites of the molecular sieve by an ion exchange method, and copper ions exist in ionic states at cationic sites of the molecular sieve. After stirring and centrifuging the platinum salt solution and the copper-containing molecular sieve, uniformly dispersing platinum on the copper-containing molecular sieve, and roasting at high temperature, wherein the platinum exists on the copper component in the form of metal nano small particles to form a bimetallic catalyst of metal platinum and ionic copper, so that the metals are synergistic, and the requirements of low temperature and high nitrogen selectivity of diesel exhaust ammonia treatment are met.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (16)
1. The preparation method of the molecular sieve catalyst for ammonia oxidation of diesel vehicle tail gas is characterized by comprising the following steps:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve; the ammonia type molecular sieve is an SSZ-13 molecular sieve; the temperature of the first roasting is 400-650 ℃;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain a molecular sieve catalyst for ammonia oxidation of ammonia with the water content of 5-10% by volume, wherein the nitrogen selectivity in the ammonia oxidation is 80-94%;
the temperature of the second roasting is 400-650 ℃;
wherein the molar concentration of copper element in the copper salt solution is 0.01-1mol/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1 (50-100); the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution is 1 (0.01-0.05).
2. The method of claim 1, wherein the copper salt used to prepare the copper salt solution of step (1) comprises 1 or a combination of at least 2 of copper chloride, copper sulfate, copper nitrate, or copper acetate.
3. The method of claim 2, wherein the copper salt used in the copper salt solution of step (1) is copper nitrate.
4. The process according to claim 1, wherein the ammonia-type molecular sieve in step (1) has a molar ratio of silicon to aluminum atoms of (3 to 20): 1.
5. The method of claim 1, wherein the temperature of the first mixing agitation in step (1) is 20-80 ℃.
6. The method of claim 1, wherein the first mixing and stirring in step (1) is for a period of time ranging from 2 to 8 hours.
7. The method of claim 1, wherein the first firing in step (1) is for a period of 3 to 8 hours.
8. The method of claim 1, wherein the platinum salt used in the platinum salt solution of step (2) comprises 1 or a combination of at least 2 of platinum tetrammine nitrate, chloroplatinic acid, platinum chloride, or ammonium chloroplatinate.
9. The method of claim 8, wherein the platinum salt used in the platinum salt solution in step (2) is platinum tetrammine nitrate.
10. The method of claim 1, wherein the second mixing temperature in step (2) is 20-40 ℃.
11. The method of claim 1, wherein the second mixing and stirring in step (2) is performed for a period of 0.5 to 3 hours.
12. The method according to claim 1, wherein the rotational speed of the centrifugal treatment in the step (2) is 3000 to 8000r/min.
13. The method of claim 1, wherein the second firing in step (2) is for a period of 3 to 7 hours.
14. The preparation method according to any one of claims 1 to 13, characterized in that the preparation method comprises the steps of:
(1) Carrying out first mixing and stirring on an ammonia molecular sieve and a copper salt solution by adopting an ion exchange method, and then carrying out solid-liquid separation, first drying and first roasting in sequence to obtain a copper-loaded molecular sieve;
(2) Carrying out second mixing and stirring on the loaded copper molecular sieve and the platinum salt solution obtained in the step (1), and then carrying out centrifugal treatment, second drying and second roasting in sequence to obtain the molecular sieve catalyst;
preparing a copper salt used in the copper salt solution in the step (1), wherein the copper salt comprises 1 or at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate, the molar concentration of copper element in the copper salt solution is 0.01-1mol/L, the ammonia type molecular sieve is SSZ-13 molecular sieve, the molar ratio of silicon to aluminum is (3-20): 1, the solid-liquid ratio g/mL of the ammonia type molecular sieve and the copper salt solution is 1 (50-100), the temperature of the first mixing and stirring is 20-80 ℃, the time of the first mixing and stirring is 2-8h, the temperature of the first roasting is 400-650 ℃, and the time of the first roasting is 3-8h;
the mass ratio of the loaded copper molecular sieve to the platinum element in the platinum salt solution is 1 (0.01-0.05), the platinum salt used in the platinum salt solution comprises 1 or at least 2 of tetramine platinum nitrate, chloroplatinic acid, platinum chloride or ammonium chloroplatinate, the temperature of the second mixing and stirring is 20-40 ℃, the time of the second mixing and stirring is 0.5-3h, the rotating speed of the centrifugal treatment is 3000-8000r/min, the temperature of the second roasting is 400-650 ℃, and the time of the second roasting is 3-7h.
15. A molecular sieve catalyst obtainable by the process of any one of claims 1 to 14, wherein the molecular sieve catalyst comprises, in mass percent: 0.1-0.5% of platinum, 2-4% of copper and the balance of molecular sieve carrier.
16. Use of the molecular sieve catalyst obtained by the process according to any one of claims 1 to 14, wherein the use comprises a conversion treatment of ammonia in diesel vehicle exhaust with the molecular sieve catalyst;
the temperature of the conversion treatment is 175-400 ℃;
the ammonia concentration in the tail gas of the diesel vehicle is 50-600ppm;
the water content of the diesel vehicle tail gas is 5-10% by volume.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004774A1 (en) * | 2005-07-06 | 2007-01-11 | Heesung Catalysts Corporation | An oxidation catalyst for nh3 and an apparatus for treating slipped or scrippedd nh3 |
| CN101417237A (en) * | 2008-11-27 | 2009-04-29 | 中国科学院生态环境研究中心 | PtX-Fe-ZSM-5 molecular sieve catalyst for ammine selective catalytic oxidation |
| EP2308596A1 (en) * | 2009-10-07 | 2011-04-13 | Ford Global Technologies, LLC | Cu/zeolite SCR catalyst for NOx reduction in exhaust gases and manufacture method thereof |
| CN102271810A (en) * | 2008-11-03 | 2011-12-07 | 巴斯夫公司 | Bimetallic catalysts for selective ammonia oxidation |
| CN102946996A (en) * | 2009-12-18 | 2013-02-27 | 巴斯夫公司 | Process for preparation of copper containing molecular sieves with the cha structure, catalysts, systems and methods |
| CN104368380A (en) * | 2014-10-08 | 2015-02-25 | 宁波高新区永石科技有限公司 | Catalyst for catalytic reduction denitration of diesel vehicle tail gas and preparation method thereof |
| CN107115888A (en) * | 2017-05-27 | 2017-09-01 | 中国科学院生态环境研究中心 | A kind of preparation method and its usage of the catalyst of Cu SSZ 13 |
| CN107847861A (en) * | 2015-06-18 | 2018-03-27 | 庄信万丰股份有限公司 | Design in SCR system positioned at the first NH_3 leakage catalyst |
| CN109174173A (en) * | 2018-09-30 | 2019-01-11 | 中自环保科技股份有限公司 | A kind of molecular sieve SCR catalyst preparation method and its catalyst of preparation |
| CN109414684A (en) * | 2016-03-08 | 2019-03-01 | 巴斯夫公司 | Show reduced N2The Ion exchange-Size exclusion catalyst of O discharge |
| CN109647500A (en) * | 2019-01-17 | 2019-04-19 | 广州市威格林环保科技有限公司 | A kind of ammoxidation catalyst and preparation method thereof for end gas purification system for internal combustion |
| CN110075907A (en) * | 2019-05-08 | 2019-08-02 | 中自环保科技股份有限公司 | A kind of ammoxidation catalyst and preparation method thereof for diesel car tail gas refining |
| WO2020073667A1 (en) * | 2018-10-08 | 2020-04-16 | 中自环保科技股份有限公司 | Integrated catalyst system for stoichiometric-burn natural gas vehicles and preparation method therefor |
| CN111408401A (en) * | 2020-04-02 | 2020-07-14 | 济南大学 | Preparation method of Cu-SSZ-13 with wide temperature window, obtained product and application |
| CN112076803A (en) * | 2020-09-16 | 2020-12-15 | 包头稀土研究院 | Ammonia oxidation catalyst, preparation method and application |
| CN113413910A (en) * | 2021-06-14 | 2021-09-21 | 山东迅达化工集团有限公司 | NH (hydrogen sulfide)3-SCO catalyst and its use in purification treatment of ammonia-containing gas streams |
| CN113996333A (en) * | 2021-11-26 | 2022-02-01 | 中触媒新材料股份有限公司 | SSZ-13 molecular sieve for selective catalytic reduction of NOx and synthesis method and application thereof |
| CN114272951A (en) * | 2021-12-22 | 2022-04-05 | 济南大学 | Method for improving hydrothermal stability of Cu-SSZ-13 molecular sieve, obtained product and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100765413B1 (en) * | 2005-07-06 | 2007-10-09 | 희성촉매 주식회사 | An oxidation catalyst for NH3 and an apparatus for treating slipped or scrippedd NH3 |
| CN105251359A (en) * | 2007-02-27 | 2016-01-20 | 巴斯夫公司 | Bifunctional catalysts for selective ammonia oxidation |
-
2022
- 2022-09-21 CN CN202211151240.2A patent/CN115445654B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004774A1 (en) * | 2005-07-06 | 2007-01-11 | Heesung Catalysts Corporation | An oxidation catalyst for nh3 and an apparatus for treating slipped or scrippedd nh3 |
| CN102271810A (en) * | 2008-11-03 | 2011-12-07 | 巴斯夫公司 | Bimetallic catalysts for selective ammonia oxidation |
| CN101417237A (en) * | 2008-11-27 | 2009-04-29 | 中国科学院生态环境研究中心 | PtX-Fe-ZSM-5 molecular sieve catalyst for ammine selective catalytic oxidation |
| EP2308596A1 (en) * | 2009-10-07 | 2011-04-13 | Ford Global Technologies, LLC | Cu/zeolite SCR catalyst for NOx reduction in exhaust gases and manufacture method thereof |
| CN102946996A (en) * | 2009-12-18 | 2013-02-27 | 巴斯夫公司 | Process for preparation of copper containing molecular sieves with the cha structure, catalysts, systems and methods |
| CN104368380A (en) * | 2014-10-08 | 2015-02-25 | 宁波高新区永石科技有限公司 | Catalyst for catalytic reduction denitration of diesel vehicle tail gas and preparation method thereof |
| CN107847861A (en) * | 2015-06-18 | 2018-03-27 | 庄信万丰股份有限公司 | Design in SCR system positioned at the first NH_3 leakage catalyst |
| CN109414684A (en) * | 2016-03-08 | 2019-03-01 | 巴斯夫公司 | Show reduced N2The Ion exchange-Size exclusion catalyst of O discharge |
| CN107115888A (en) * | 2017-05-27 | 2017-09-01 | 中国科学院生态环境研究中心 | A kind of preparation method and its usage of the catalyst of Cu SSZ 13 |
| CN109174173A (en) * | 2018-09-30 | 2019-01-11 | 中自环保科技股份有限公司 | A kind of molecular sieve SCR catalyst preparation method and its catalyst of preparation |
| WO2020073667A1 (en) * | 2018-10-08 | 2020-04-16 | 中自环保科技股份有限公司 | Integrated catalyst system for stoichiometric-burn natural gas vehicles and preparation method therefor |
| CN109647500A (en) * | 2019-01-17 | 2019-04-19 | 广州市威格林环保科技有限公司 | A kind of ammoxidation catalyst and preparation method thereof for end gas purification system for internal combustion |
| CN110075907A (en) * | 2019-05-08 | 2019-08-02 | 中自环保科技股份有限公司 | A kind of ammoxidation catalyst and preparation method thereof for diesel car tail gas refining |
| CN111408401A (en) * | 2020-04-02 | 2020-07-14 | 济南大学 | Preparation method of Cu-SSZ-13 with wide temperature window, obtained product and application |
| CN112076803A (en) * | 2020-09-16 | 2020-12-15 | 包头稀土研究院 | Ammonia oxidation catalyst, preparation method and application |
| CN113413910A (en) * | 2021-06-14 | 2021-09-21 | 山东迅达化工集团有限公司 | NH (hydrogen sulfide)3-SCO catalyst and its use in purification treatment of ammonia-containing gas streams |
| CN113996333A (en) * | 2021-11-26 | 2022-02-01 | 中触媒新材料股份有限公司 | SSZ-13 molecular sieve for selective catalytic reduction of NOx and synthesis method and application thereof |
| CN114272951A (en) * | 2021-12-22 | 2022-04-05 | 济南大学 | Method for improving hydrothermal stability of Cu-SSZ-13 molecular sieve, obtained product and application |
Non-Patent Citations (4)
| Title |
|---|
| Chemical deactivation of Cu-SSZ-13 ammonia selective catalyticreduction (NH3-SCR) systems;I.systemsI. Lezcano-Gonzalez et al.;《Applied Catalysis B：Environmental》;第154-155卷;339-349 * |
| Oxidation of ammonia to nitrogen over Pt/Fe/ZSM5 catalyst: Influence of catalyst support on the low temperature activity;Min-Sung Kim et al.;《Journal of Hazardous Materials》;153-160 * |
| Progress on Selective Catalytic Ammonia Oxidation (NH3-SCO) over Cu Containing Zeolite-Based Catalysts;Magdalena Jabłońska;ChemCatChem(第12期);4490–4500 * |
| SAPO-34 分子筛负载铜氨氧化催化剂的制备;袁梦琦等;《第十一届全国环境催化与环境材料学术会议》;全文 * |
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