CN108745369A - A kind of B doping type double-perovskite catalyst and the preparation method and application thereof - Google Patents
A kind of B doping type double-perovskite catalyst and the preparation method and application thereof Download PDFInfo
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- CN108745369A CN108745369A CN201810459687.3A CN201810459687A CN108745369A CN 108745369 A CN108745369 A CN 108745369A CN 201810459687 A CN201810459687 A CN 201810459687A CN 108745369 A CN108745369 A CN 108745369A
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- salt
- nitrate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 161
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 63
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 32
- 235000010333 potassium nitrate Nutrition 0.000 claims description 28
- 239000004323 potassium nitrate Substances 0.000 claims description 28
- 235000010344 sodium nitrate Nutrition 0.000 claims description 28
- 239000004317 sodium nitrate Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 27
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 21
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 21
- 230000003197 catalytic effect Effects 0.000 claims description 20
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 16
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011833 salt mixture Substances 0.000 claims description 9
- 229940044658 gallium nitrate Drugs 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 10
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 12
- 230000010718 Oxidation Activity Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical group [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005169 Debye-Scherrer Methods 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical group [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical group [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910019016 NaNO3—KNO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical group O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 210000002268 wool Anatomy 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of B doping type double-perovskite catalyst and the preparation method and application thereof, belong to catalyst technical field.The chemical general formula of B doping type double-perovskite catalyst of the present invention is A2B1‑xMxB’O6, wherein A is rare-earth metals La, Ce, Nd or Gd, and B Co, Fe, Ni, Cu, Mn, Mo, Al or Ga, B ' is Co, Fe, Ni, Cu, Mn, Mo, Al or Ga, and M is magnesium-yttrium-transition metal Co, Fe, Ni, Cu, Mn or Mo, and B ≠ B '.The present invention uses molte-salt synthesis, in NaNO3And KNO3Melt the positions the B doping type double-perovskite catalyst A that nanometer regular morphology is prepared in salt system2B1‑xMxB’O6.Nitric oxide catalysis oxidation can be efficiently nitrogen dioxide within the scope of lower temperature and wider temperature by B doping type double-perovskite catalyst, and the method for the present invention is simple for process, and easily operated, cost is relatively low, easily realizes industrialized production.
Description
Technical field
The present invention relates to a kind of B doping type double-perovskite catalyst and the preparation method and application thereof, belong to catalyst skill
Art field.
Background technology
In purifying vehicle exhaust technical aspect, NO is NO by catalysis oxidation2Committed step is served not only as, and with important
Meaning：In LNT (the Lean-burn NOX Trap) stages, NO is oxidized to the NO being stored more easily2；In SCR (Selective
Catalytic Reduction) stage, NO：NO2Ratio be 1:1 catalytic efficiency is optimal；NO in particle trapper DPF2Presence
The initiation temperature of soot can be significantly reduced.The catalyst of catalytic oxidation NO is commonly used mainly using Pt as activated centre
It is supported on A12O3On equal carriers, wherein the load capacity of noble metal is 2% 3%.The higher operating costs of this catalyst, and your gold
Belonging to can occur to reunite and catalytic performance is made to decline in high-temperature catalytic reaction.
Compared with the noble metal catalysts such as Pt, Ru, Pd, perovskite material has cheap, stable structure, catalytic activity
The features such as thermodynamic property is stablized under good and high temperature has good development potentiality in tail gas catalytic purification field.But by
, specific surface area bad in the characteristic of its low temperature ignition is low and complicated component is difficult to deficiency prepared by batch, limits perovskite
The performance of material advantage and actual application.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, the present invention provide a kind of B doping type double-perovskite catalysis
Agent and the preparation method and application thereof, it is A that the chemical general formula of B doping type double-perovskite catalyst of the present invention, which is chemical general formula,2B1- xMxB’O6, wherein 0.1≤x≤0.9, A be rare-earth metals La, Ce, Nd or Gd, B Co, Fe, Ni, Cu, Mn, Mo, Al or
Ga, M are transition elements Co, Fe, Ni, Cu, Mn or Mo, and B ' is Co, Fe, Ni, Cu, Mn, Mo, Al or Ga, and B ≠ B ' ≠ M.B
Nitric oxide efficiently can be catalyzed oxygen by doping type double-perovskite catalyst at a lower temperature and within the scope of wider temperature
Nitrogen dioxide is turned to, it is at low cost, there is good thermal stability, higher catalytic activity can be kept for a long time, hence it is evident that improve
The removal efficiency of nitrogen oxides in vehicle exhaust, at the same molte-salt synthesis prepare double-perovskite catalyst method it is simple, be easy to grasp
Make, is suitble to heavy industrialization application.
The preparation method of the B doping type double-perovskite catalyst, is as follows：
（1）A salt, M salt, B salt and B ' salt are added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A
Salt be rare-earth metals La, Ce, Nd or Gd nitrate, M salt be cobalt nitrate, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate
Or ammonium molybdate, B are cobalt nitrate, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate, aluminum nitrate, gallium nitrate or ammonium molybdate, B ' is nitric acid
Cobalt, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate, aluminum nitrate, gallium nitrate or ammonium molybdate, and B ≠ B ' ≠ M；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 ~ 800 DEG C with the heating rate of 2 ~ 10 DEG C/min and roasts 3 ~ 10h,
Then room temperature is at the uniform velocity cooled to the rate of temperature fall of 2 ~ 3 DEG C/min；
（4）By step（3）Gained product of roasting uses temperature to be washed for 70 ~ 80 DEG C of deionized water for 3 times or more, and then drying is
Obtain B doping type double-perovskite catalyst；
Further, the integral molar quantity of the A salt, M salt, B salt and B ' salt and the ratio of the integral molar quantity of potassium nitrate and sodium nitrate are
1:(20~60)；
Further, the molar ratio of the A salt, B salt, M salt and B ' salt is 2:(1-x):x:1, wherein 0.1≤x≤0.9；
Further, the molar ratio of the potassium nitrate and sodium nitrate is 1:(1~1.5).
The molten salt system of the present invention chooses NaNO3-KNO3Two end number mixing salt system, under standard pressure, NaNO3Fusing point be
308 DEG C, KNO3Fusing point be 344 DEG C, in NaNO3With KNO3Lowest total of the melting point proportioning composition molar fraction NaNO3/(NaNO3
+KNO3) be 47% when lowest total of the melting point be 225 DEG C, i.e., temperature be 225 DEG C when initially form fused salt eutectic, NaNO3-
KNO3Two end number mixing salt system does not dissolve in absolute ethyl alcohol, other metal mixed salt is not interfered to be uniformly mixed in absolute ethyl alcohol；?
Under high-temperature molten salt state, the partial oxidation oxic gas that makes the solid phase synthesis of double-perovskite catalyst be decomposed in fused salt eutectic
It is carried out in atmosphere, is conducive to the formation of metal oxide, after solid phase synthesis, NaNO3-KNO3Two end number mixing salt system group
It is point soluble easily in water, it can quickly remove the fuse salt system component of double-perovskite catalyst.
B doping type double-perovskite catalyst can be used for catalytic oxidation NO, can at a lower temperature and wider temperature
Spend range in efficiently by nitric oxide catalysis oxidation be nitrogen dioxide, the conversion ratio of nitric oxide catalysis oxidation can reach
80% or more, adapt to very much the catalysis oxidation of NO under high temperature；B doping type double-perovskite catalyst have good thermal stability,
Higher catalytic activity can be kept for a long time, hence it is evident that improve the removal efficiency of nitrogen oxides in vehicle exhaust.
The beneficial effects of the invention are as follows：
（1）The method of the present invention, as mixed melting salt, is roasted in mixed melting salt and is mixed up to B using potassium nitrate and sodium nitrate
Miscellaneous type double-perovskite catalyst A2B1-xMxB’O6, preparation method is simple, easily operated, is suitble to heavy industrialization application；
（2）B doping type double-perovskite catalyst of the present invention is double-perovskite type structure, and stable structure is not easy phase transformation, thus has
There are excellent thermal stability, long lifespan that can keep higher catalytic activity for a long time；
（3）B doping type double-perovskite catalyst of the present invention can be used for catalytic oxidation NO, can be at a lower temperature and wider
Within the temperature range of efficiently by nitric oxide catalysis oxidation be nitrogen dioxide, have good thermal stability, can protect for a long time
Hold higher catalytic activity, hence it is evident that improve the removal efficiency of nitrogen oxides in vehicle exhaust.
Description of the drawings
Fig. 1 is the La that embodiment 1 is adulterated2Co0.75Cu0.25MnO6The XRD spectrum of double-perovskite catalyst；
Fig. 2 is the conversion ratio-temperature variation curve for the double-perovskite catalyst oxidization of nitric oxide that embodiment 1 ~ 3 is adulterated.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1：B doping type double-perovskite catalyst of the present embodiment are La2Co0.75Cu0.25MnO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is lanthanum nitrate）, M salt（M salt is cobalt nitrate）, B salt（B salt is copper nitrate）And B ' salt（B ' salt is nitric acid
Manganese）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Lanthanum nitrate）, B salt（Copper nitrate）,M
Salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Molar ratio be 2:0.25:0.75:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Lanthanum nitrate）, B salt（Copper nitrate）, M salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:30；The molar ratio of potassium nitrate and sodium nitrate is 1:1；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 700 DEG C with the heating rate of 2 DEG C/min and roasts 6h, then with 2 DEG C/
The rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 3 steps for 80 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type La2Co0.75Cu0.25MnO6Double-perovskite catalyst；
The positions the B doping type La of the present embodiment2Co0.75Cu0.25MnO6The XRD spectrum of double-perovskite catalyst is as shown in Figure 1, from Fig. 1
It is found that the La of pure phase2Co0.75Cu0.25MnO6Spectrogram, 2 θ be 23 °, 32 °, 40 °, 47 °, 52 °, 58 °, 68 ° and 78 ° at go out
The characteristic diffraction peak of perovskite structure is showed, not the appearance of dephasign peak, it was demonstrated that it is compound to form single-phase rare earth double-perovskite
Metal oxide structures.According to Debye Scherrer formula (Debye-Scherrer equation), the flat of nanotube sample can be calculated
The expression of equal crystallite dimension, Debye Scherrer formula is：D=k λ/(β cos θ), wherein k are Scherrer constant, and numerical value is
0.89, λ is the wavelength of incident X-rays, and β is the full width at half maximum (FWHM) of diffraction maximum, and θ is the angle of diffraction；It is calculated
La2Co0.75Cu0.25MnO6The average grain size of double-perovskite catalyst is 18nm；
The positions the B doping type La of the present embodiment2Co0.75Cu0.25MnO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is carried out in homemade columned reactor, wherein a diameter of 6 mm of columned reactor, length is 550 mm, will
The positions the B doping type La of 500mg2Co0.75Cu0.25MnO6Double-perovskite catalyst is placed in reactor center position, and silica wool is used at both ends
It clogs；Before carrying out catalysis reaction, by catalyst in 10%O2/N2（500mL/min）It is 300 DEG C steady that temperature is warming up under atmosphere
Determine 1h, it is 100 DEG C that temperature is then cooled under identical atmosphere, and after temperature stabilization, it is 500 mL/min's to be passed through total flow
Contain 500 ppm NO, 10%O2N2Balance Air, air speed (GHSV) are 30000 h-1；Stablize 30 at being 150 DEG C in temperature ~
60min is until NO concentration at the outlet no longer changes；Under identical atmosphere, catalyst is risen into temperature with the heating rate of 10 DEG C/min
Degree is 450 DEG C, after initial concentration measures, adjusts temperature controller setting value, reactor is made to reach required test temperature, test temperature
Ranging from 150 DEG C ~ 400 DEG C, a test point is taken every 25 DEG C, is respectively kept for 15 minutes in each test point, is exported NOX（NO,
NO2）Concentration is analyzed by 42i-HL type high concentration nitrogen oxide analyzers；B doping type La2Co0.75Cu0.25MnO6Double-perovskite is urged
Agent catalysis NO is oxidized to NO2Conversion ratio as shown in Fig. 2, as can be seen from Figure 2, B doping type La2Co0.75Cu0.25MnO6Double calcium titaniums
The maximum conversion of mine catalyst is 83%, and the temperature corresponding to maximum conversion is 290 DEG C, and the double-perovskite catalyst is to NO
Catalytic oxidation performance comply fully with thermodynamical equilibrium, i.e., NO is oxidized to NO under thermodynamical equilibrium2Conversion ratio reach maximum value
After, with the raising of temperature, conversion ratio continuously decreases, therefore there are maximum conversions.
Embodiment 2：B doping type double-perovskite catalyst of the present embodiment are La2Ga0.1Co0.9MnO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is lanthanum nitrate）, M salt（M salt is cobalt nitrate）, B salt（B salt is gallium nitrate）And B ' salt（B ' salt is nitric acid
Manganese）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Lanthanum nitrate）, B salt（Gallium nitrate）,M
Salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Molar ratio be 2:0.9:0.1:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Lanthanum nitrate）, B salt（Gallium nitrate）, M salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.1；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 800 DEG C with the heating rate of 3 DEG C/min and roasts 5h, then with 2.5
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 5 steps for 70 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type La2Ga0.1Co0.9MnO6Double-perovskite catalyst；
The positions the B doping type La of the present embodiment2Ga0.1Co0.9MnO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is same as Example 1, B doping type La2Ga0.1Co0.9MnO6The catalysis NO of double-perovskite catalyst is oxidized to NO2Conversion ratio
As shown in Fig. 2, as can be seen from Figure 2, B doping type La2Ga0.1Co0.9MnO6The maximum conversion of double-perovskite catalyst is 84%, most
Temperature corresponding to high conversion is 310 DEG C.
Embodiment 3：B doping type double-perovskite catalyst of the present embodiment are La2Co0.5Fe0.5MnO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is lanthanum nitrate）, M salt（M salt is ferric nitrate）, B salt（B salt is cobalt nitrate）And B ' salt（B ' salt is nitric acid
Manganese）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Lanthanum nitrate）, M salt（Ferric nitrate）,B
Salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Molar ratio be 2:0.25:0.75:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Lanthanum nitrate）, M salt（Ferric nitrate）, B salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.2；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 DEG C with the heating rate of 5 DEG C/min and roasts 10h, then with 3
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 8 steps for 75 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type La2Co0.5Fe0.5MnO6Double-perovskite catalyst；
The positions the B doping type La of the present embodiment2Co0.5Fe0.5MnO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is same as Example 1, B doping type La2Co0.5Fe0.5MnO6Double-perovskite catalyst NO is oxidized to NO2Conversion ratio such as
Shown in Fig. 2, as can be seen from Figure 2, B doping type La2Co0.5Fe0.5MnO6The maximum conversion of double-perovskite catalyst is 86%, highest
Temperature corresponding to conversion ratio is 315 DEG C.
Embodiment 4：B doping type double-perovskite catalyst of the present embodiment are La2Mn0.25Al0.75CoO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is lanthanum nitrate）, M salt（M salt is manganese nitrate）, B salt（B salt is aluminum nitrate）And B ' salt（B ' salt is nitric acid
Cobalt）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Lanthanum nitrate）, M salt（Ferric nitrate）,B
Salt（Cobalt nitrate）And B ' salt（Manganese nitrate）Molar ratio be 2:0.25:0.75:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Lanthanum nitrate）, B salt（Manganese nitrate）, M salt（Aluminum nitrate）And B ' salt（Cobalt nitrate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.2；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 DEG C with the heating rate of 5 DEG C/min and roasts 10h, then with 3
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 8 steps for 75 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type La2Mn0.25Al0.75CoO6Double-perovskite catalyst；
The positions the B doping type La of the present embodiment2Mn0.25Al0.75CoO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is same as Example 1, B doping type La2Mn0.25Al0.75CoO6The maximum conversion of double-perovskite catalyst is 81%, and highest turns
Temperature corresponding to rate is 330 DEG C.
Embodiment 5：B doping type double-perovskite catalyst of the present embodiment are Ce2Mn0.25Fe0.75MoO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is cerous nitrate）, M salt（M salt is manganese nitrate）, B salt（B salt is ferric nitrate）And B ' salt（B ' salt is molybdic acid
Ammonium）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Cerous nitrate）, M salt（Manganese nitrate）,B
Salt（Ferric nitrate）And B ' salt（Ammonium molybdate）Molar ratio be 2:0.25:0.75:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Cerous nitrate）, M salt（Manganese nitrate）, B salt（Ferric nitrate）And B ' salt（Ammonium molybdate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.2；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 DEG C with the heating rate of 5 DEG C/min and roasts 10h, then with 3
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 8 steps for 75 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type Ce2Mn0.25Fe0.75MoO6Double-perovskite catalyst；
The positions the B doping type Ce of the present embodiment2Mn0.25Fe0.75MoO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is same as Example 1, B doping type Ce2Mn0.25Fe0.75MoO6The maximum conversion of double-perovskite catalyst is 83%, and highest turns
Temperature corresponding to rate is 298 DEG C.
Embodiment 6：B doping type double-perovskite catalyst of the present embodiment are Nd2Co0.9Ni0.1MnO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is neodymium nitrate）, M salt（M salt is cobalt nitrate）, B salt（B salt is nickel nitrate）And B ' salt（B ' salt is nitric acid
Manganese）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Neodymium nitrate）, M salt（Cobalt nitrate）,B
Salt（Nickel nitrate）And B ' salt（Manganese nitrate）Molar ratio be 2:0.9:0.1:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Neodymium nitrate）, M salt（Cobalt nitrate）, B salt（Nickel nitrate）And B ' salt（Manganese nitrate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.2；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 DEG C with the heating rate of 5 DEG C/min and roasts 10h, then with 3
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 8 steps for 75 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type Nd2Co0.9Ni0.1MnO6Double-perovskite catalyst；
The positions the B doping type Nd of the present embodiment2Co0.9Ni0.1MnO6The NO catalytic oxidation activity evaluation experimentals of double-perovskite catalyst
It is same as Example 1, B doping type Nd2Co0.9Ni0.1MnO6The maximum conversion of double-perovskite catalyst is 82%, highest conversion
Temperature corresponding to rate is 305 DEG C.
Embodiment 7：B doping type double-perovskite catalyst of the present embodiment are Gd1.75Co0.1Fe0.9MoO6；
The preparation method of B doping type double-perovskite catalyst, is as follows：
（1）By A salt（A salt is gadolinium nitrate）, M salt（M salt is cobalt nitrate）, B salt（B salt is ferric nitrate）And B ' salt（B ' salt is molybdic acid
Ammonium）It is added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A salt（Gadolinium nitrate）, M salt（Cobalt nitrate）,B
Salt（Ferric nitrate）And B ' salt（Ammonium molybdate）Molar ratio be 2:0.25:0.75:1；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；Wherein A salt（Gadolinium nitrate）, M salt（Cobalt nitrate）, B salt（Ferric nitrate）And B ' salt（Ammonium molybdate）Integral molar quantity and potassium nitrate
Ratio with the integral molar quantity of sodium nitrate is 1:20；The molar ratio of potassium nitrate and sodium nitrate is 1:1.2；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 DEG C with the heating rate of 5 DEG C/min and roasts 10h, then with 3
DEG C/rate of temperature fall of min is at the uniform velocity cooled to room temperature；
（4）Temperature is used to wash 8 steps for 75 DEG C of deionized water（3）Then gained product of roasting is drying to obtain B doping
Type Gd1.75Co0.1Fe0.9MoO6Double-perovskite catalyst；
The positions the B doping type Gd of the present embodiment1.75Co0.1Fe0.9MoO6The NO catalytic oxidation activities evaluation of double-perovskite catalyst is real
Test same as Example 1, B doping type Gd1.75Co0.1Fe0.9MoO6The maximum conversion of double-perovskite catalyst is 85%, highest
Temperature corresponding to conversion ratio is 323 DEG C.
The specific implementation mode of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Go out various change.
Claims (6)
1. a kind of B doping type double-perovskite catalyst, it is characterised in that：Chemical general formula is A2B1-xMxB’O6, wherein 0.1≤x
≤ 0.9, A be rare-earth metals La, Ce, Nd or Gd, B Co, Fe, Ni, Cu, Mn, Mo, Al or Ga, M be transition elements Co,
Fe, Ni, Cu, Mn or Mo, B ' are Co, Fe, Ni, Cu, Mn, Mo, Al or Ga, and B ≠ B ' ≠ M.
2. the preparation method of B described in claim 1 doping type double-perovskite catalyst, which is characterized in that be as follows：
（1）A salt, M salt, B salt and B ' salt are added in absolute ethyl alcohol and is ground to dissolving and obtains ethyl alcohol metal salt solution, wherein A
Salt be rare-earth metals La, Ce, Nd or Gd nitrate, M salt be cobalt nitrate, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate
Or ammonium molybdate, B are cobalt nitrate, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate, aluminum nitrate, gallium nitrate or ammonium molybdate, B ' is nitric acid
Cobalt, ferric nitrate, nickel nitrate, copper nitrate, manganese nitrate, aluminum nitrate, gallium nitrate or ammonium molybdate, and B ≠ B ' ≠ M；
（2）In step（1）Gained ethyl alcohol metal salt solution, potassium nitrate and sodium nitrate are uniformly mixed, and drying and volatilizing ethyl alcohol is mixed
Close salt；
（3）Step（2）Gained salt-mixture is at the uniform velocity warming up to 400 ~ 800 DEG C with the heating rate of 2 ~ 10 DEG C/min and roasts 3 ~ 10h,
Then room temperature is at the uniform velocity cooled to the rate of temperature fall of 2 ~ 3 DEG C/min；
（4）By step（3）Gained product of roasting uses temperature to be washed for 70 ~ 80 DEG C of deionized water for 3 times or more, and then drying is
Obtain B doping type double-perovskite catalyst.
3. the preparation method of B doping type double-perovskite catalyst according to claim 2, it is characterised in that：A salt, M salt, B
The integral molar quantity of salt and B ' salt is 1 with the ratio of potassium nitrate and the integral molar quantity of sodium nitrate:(20~60).
4. the preparation method of B doping type double-perovskite catalyst according to claim 2, it is characterised in that：A salt, B salt, M
The molar ratio of salt and B ' salt is 2:(1-x):x:1, wherein 0.1≤x≤0.9.
5. the preparation method of B doping type double-perovskite catalyst according to claim 2, it is characterised in that：Potassium nitrate with
The molar ratio of sodium nitrate is 1:(1~1.5).
6. application of B described in the claim 1 doping type double-perovskite catalyst in catalytic oxidation NO.
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