CN107159230A - A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing and preparation method thereof - Google Patents
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing and preparation method thereof Download PDFInfo
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- CN107159230A CN107159230A CN201710366757.6A CN201710366757A CN107159230A CN 107159230 A CN107159230 A CN 107159230A CN 201710366757 A CN201710366757 A CN 201710366757A CN 107159230 A CN107159230 A CN 107159230A
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- catalyst
- cobalt
- manganese
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 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 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- 239000011572 manganese Substances 0.000 abstract description 7
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000019391 nitrogen oxide Nutrition 0.000 description 33
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 21
- 229960003753 nitric oxide Drugs 0.000 description 20
- 238000005119 centrifugation Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002521 CoMn Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000013459 approach Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- PAFFVEYJXFIATB-UHFFFAOYSA-N cerium;phosphoric acid Chemical compound [Ce].OP(O)(O)=O PAFFVEYJXFIATB-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
It is used for catalyst of removing low-concentration nitrogen oxide and its preparation method and application under normal temperature the invention discloses a kind of, the catalyst is that the mol ratio of cobalt and manganese in cobalt manganese binary oxide, the catalyst is 1:(0.3~3).The present invention prepares porous nanometer wire cobalt manganese binary oxide by solvent heat and subsequent heat treatment method first from common inorganic manganese salt and cobalt salt as raw material, and using it as catalyst, low-concentration nitrogen oxide is removed for normal temperature.Under the catalyst normal temperature can efficient removal low-concentration nitrogen oxide, concentration can be removed completely for 10ppm NO within initial a few houres at 25 DEG C, reach it is stable after NO is catalytically oxidized to the NO of low concentration2Conversion ratio up to more than 30%.Present invention additionally comprises the method for preparing catalyst that the normal temperature removes nitrogen oxides, the preparation technology that is related to is simple, raw material is inexpensive, production cost is low, environment-friendly, is adapted to popularization and application.
Description
Technical field
The invention belongs to catalytic field, and in particular to a kind of catalysis that low-concentration nitrogen oxide is removed for constant temperature catalyzing
Agent.
Background technology
The NO that mankind's activity is producedxMost (95%) derives from motor vehicle (49%) and coal-fired power plant's (46%).
In recent years, the motor vehicle increased severely for reply, alleviates traffic and solves parking problem, built substantial amounts of roads and tunnels and underground is stopped
Parking lot.In these hemi-closure spaces, the tail gas of vehicular emission can not in time be distributed and accumulated, and cause the nitrogen in these spaces
Oxide concentration may be up to more than ten ppm, and (wherein 90% is NO, and remaining is NO2), far above surrounding air NOxStandard (200ug/
m3, GB3095-2012), greatly endanger the health of drivers and pedestrians.
NO is supercritical gas (Tc=180K) at normal temperatures and pressures, and boiling point and solubility in water are extremely low, it is impossible to only
By alkali liquor absorption or poromerics Adsorption, and NO can be easily removed with both approaches2, therefore NO is oxidized to
NO2, it is then that the effective method of low concentration of NO is removed under normal temperature by absorbing removal.But for low concentration of NO, normal temperature
Lower is difficult to be oxidized as NO2.Research shows that reaction rate is drastically reduced when NO concentration is less than 0.1%；When NO concentration
As little as 20ppm, during no catalysis material, NO oxidation reaction stops substantially.NO chemical property under the conditions of above-mentioned semiclosed region
It is sufficiently stable, it is necessary to which that the catalytic eliminating of low concentration of NO could be realized using efficient catalytic material.
Existing denitration technology is mainly for NOxDischarging source includes the improvement of moving source and stationary source, such as using selectivity
Catalysis reduction (SCR) method at relatively high temperatures (>200 DEG C) with NH3The high concentration discharged for reducing agent to automobile and boiler exhaust gas
NO (hundreds of ppm and more than) is reduced to N2.Obviously, SCR technology is difficult to apply to NO in above-mentioned semiclosed regionsxRemoval.
Chinese patent CN103406122A discloses a kind of low temperature while removing nitrogen oxides in effluent and carbon monoxide
Catalyst, be made up of active component and absorbent charcoal carrier, and active component is cupric oxide or/and cuprous oxide, and active component contains
Amount preferably accounts for the 5~15% of catalyst total amount；The catalyst reaches 97% in 225 DEG C of removal efficiencies for individually removing nitrogen oxides；
94% and 88% are respectively reached in 250 DEG C of removal efficiencies for removing nitrogen oxides and carbon monoxide simultaneously.Chinese patent
CN102441406A discloses a kind of phosphoric acid cerium catalyst, and the wherein mol ratio of cerium and phosphorus is 1:1~1.3, carrier is anatase
Type titanium dioxide, aluminum oxide or ZSM-5 molecular sieve.NO removal efficiency of the catalyst in the range of 200~500 DEG C 90% with
On.
It can be seen that, although at present both at home and abroad it has been reported that low temperature catalyst removal efficiency it is higher, the temperature of catalyst is much
Higher than normal temperature condition, and the concentration of nitrogen oxides is far above concentration in air, can not possibly be applied to closing or semiclosed completely
In space in gas nitrogen oxides removing.
The content of the invention
The purpose of the present invention is in view of the deficienciess of the prior art, a kind of activity of offer is high, stability is good, normal temperature condition
Down can efficient removal is semiclosed or catalyst of low-concentration nitrogen oxide in closed area, the catalyst can be at normal temperatures
Efficient removal low-concentration nitrogen oxide, has its NO removal efficiency within initial a few houres to be up to 100%；The preparation method being related to simultaneously
Simply, production cost is low, and repetitive rate is high, with important actual application value.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, it is the porous cobalt and manganese oxide of nanometer wire
(CoMnxOy), wherein the mol ratio of cobalt element and manganese element is 1:(0.3~3).
In such scheme, the concentration of the low-concentration nitrogen oxide is 10~20ppm.
In such scheme, the normal temperature condition is 15~35 DEG C.
In such scheme, the length of the porous cobalt and manganese oxide of nanometer wire is 10~100 μm, a diameter of 10~
50nm, specific surface area is 100~120m2/ g, containing meso-hole structure, mesoporous pore size is 3~5nm.
A kind of preparation method of above-mentioned catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, including following step
Suddenly：Using solvent heat and the subsequent heat treatment method synthesis porous cobalt and manganese oxide of nanometer wire, following steps are specifically included：By nothing
Then gained mixed solution is placed in solvent thermal reaction by machine manganese salt, cobalt salt and nitrilotriacetic acid stirring and dissolving in aqueous isopropanol
In kettle, heating carries out solvent thermal reaction, then naturally cools to normal temperature, washing and filtering obtains pink product, finally done
Dry, roasting, produces the catalyst that low-concentration nitrogen oxide is removed for normal temperature.
In such scheme, the inorganic manganese salt is manganese chloride or manganese nitrate；Inorganic cobalt salt is cobalt chloride or cobalt nitrate.
In such scheme, the mol ratio of cobalt element, manganese element and nitrilotriacetic acid is 1 in the mixed solution:(0.3~3):
(1.0~1.5).
It is preferred that, the mol ratio of cobalt element and manganese element is 1 in the mixed solution:(0.5~2).
In such scheme, the concentration of isopropanol is 50~75wt% in the aqueous isopropanol.
In such scheme, the temperature of the solvent thermal reaction is 180~200 DEG C, and the time is 12~24h.
In such scheme, the reagent used is washed for deionized water and ethanol, and alternately washing is until gained filtrate is in neutrality.
In such scheme, the drying temperature is 60~80 DEG C, and the time is 12~18h, air atmosphere.
In such scheme, the sintering temperature be 300~450 DEG C, the time be 0.5~2h, heating rate be 1~3 DEG C/
min。
It is relatively low (with Gas phase Smoke that catalyst described in such scheme is mainly used in nitrous oxides concentration in semiclosed or closed area
Than), and temperature is the purification of nitrogen oxides (predominantly NO) under normal temperature occasion.
In such scheme, purified gained NO2Using alkali liquor absorption or the further removal of poromerics absorption.
The present invention principle be：The present invention uses common inorganic cobalt salt to prepare cobalt manganese binary oxygen with manganese salt for raw material first
Compound catalyst, low concentration of NO is removed for normal temperature：Ternary compound can be formed using hexa-coordinate metallic cobalt, manganese with nitrilotriacetic acid
Thing, under the shielding action of isopropanol, the macromolecular chain self assembly formed generates the nano wire of high-sequential, then by water
Heat and thermally decompose to yield the porous cobalt and manganese oxide of nanometer wire, wherein cobalt, manganese ion synergy, and formed it is special one-dimensional
Nanometer wire mesoporous porous structure, with higher specific surface area and hole, makes gained binary oxide have bigger absorption
With oxidation NO active sites, its catalytic oxidation of low-concentration NO under normal temperature condition ability can be effectively improved.
Beneficial effects of the present invention are：
1) catalyst of the present invention is first from the cobalt manganese binary prepared using common inorganic cobalt salt and manganese salt as raw material
Oxide is catalyst, low concentration of NO is removed for normal temperature, with initiative.
2) preparation method of the present invention is simple, and using solvent-thermal method and subsequent heat treatment, many of nanometer wire are made
Pore catalyst, with larger specific surface area, is conducive to improving the normal temperature activity of catalyst.
3) catalyst activity of the present invention is high, is 4000~20000h in air speed-1In the range of to NO initial removal efficiency
Up to 100%, NO catalysis oxidation rate is up to more than 30% during stable state.
4) catalyst of the present invention be applied to semiclosed or closed area in (roads and tunnels, underground parking etc.), often
The removal of low concentration nitrogen oxides under the conditions of temperature.
Brief description of the drawings
Fig. 1 is the gained MnCo of the embodiment of the present invention 12O4SEM figure.
Fig. 2 is the gained MnCo of the embodiment of the present invention 12O4To NO catalytic eliminating effect of the initial concentration for 20ppm at 25 DEG C
Figure.
Embodiment
Further the present invention will be described with reference to the accompanying drawings and examples, but present disclosure is not limited solely to
The following examples.
In following examples, the method for testing of the catalyst normal temperature removing NO effects is as follows：By gained catalyst fines
Tabletting, grinding, sieving are carried out, 0.10~0.30g of product of 30~60 mesh is weighed, the quartz ampoule that caliber is 6mm is inserted, filling is high
Spend for 15~45mm.Low-concentration nitrogen oxide is by NO Standard Gases, O2、N2Three kinds of gases are formulated, and are controlled by mass flowmenter
Its flow is made and adjusts, gaseous mixture total flow is 200~400SCCM, and NO concentration is adjusted to 10~30ppm, O2Concentration is
Concentration in 21vol%, simulated air, it is 15~35 DEG C that the temperature during catalytic eliminating is controlled by water-bath；Nitrogen oxides
Concentration is measured using chemoluminescence method nitrogen-oxide analyzer,.
Embodiment 1
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, its preparation method comprises the following steps：
1) the chloride hydrate manganese (MnCl of 4mmol (0.7917g) four are weighed2·4H2O), the chloride hydrates of 8mmol (1.9034g) six
Cobalt (CoCl2·6H2O) (mol ratio of cobalt and manganese is 2:1) with 4.7mmol (0.9g) nitrilotriacetic acid, three is dissolved in isopropanol
In solution (10ml deionized waters and 30ml isopropanols), strong agitation is configured to uniform mixed solution in 30 minutes；
2) by step 2) gained mixed solution be transferred in ptfe autoclave, in hydro-thermal reaction 12h at 180 DEG C,
Question response kettle is naturally cooled to after normal temperature, by gained sediment respectively with deionized water and absolute ethyl alcohol alternately washing and repeatedly from
The heart separates (centrifugal rotational speed is 6000rpm, each centrifugation time 5min), until filtrate is in neutrality, will be obtained after washing and centrifugation
Pink precipitate at 60 DEG C under air atmosphere dry 12h；
3) by step 2) dry after products therefrom be placed in Muffle furnace, with 1 DEG C/min speed be heated to 300 DEG C roasting
2h, produces catalyst (the cobalt and manganese oxide MnCo that low-concentration nitrogen oxide is removed for constant temperature catalyzing2O4)。
Gained MnCo of the invention2O4Scanning electron microscope (SEM) photograph see in Fig. 1, figure that visible products therefrom is porous nano wire, nanometer
Linear diameter is 20~50nm, long 10~100 μm.Its BET specific surface area is calculated for 112m according to N2 adsorption/desorption curve2/ g, is adopted
It is mainly concentrate on 4nm mesoporous that its aperture is calculated with BJH models.
By MnCo obtained by the present embodiment2O4Carry out normal temperature removing NO measure of merit, wherein MnCo2O4Consumption be 0.20g,
Packed height is 25mm, and NO concentration is 10ppm, and gaseous mixture total flow is 300SCCM, and temperature control is 25 DEG C.The present embodiment
Gained MnCo2O4Catalytic eliminating test result see visible high to the removal efficiency of nitrogen oxides in initial 3 hours in Fig. 2, figure
Up to 100%, when reaching stable state, NO catalysis oxidations are NO2Conversion ratio be more than 30%.
Embodiment 2
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, its preparation method comprises the following steps：
1) the chloride hydrate manganese (MnCl of 8mmol tetra- are weighed2·4H2O), 4mmol cobalt chloride hexahydrates (CoCl2·6H2O) (cobalt
Mol ratio with manganese is 1:2) and 4.0mmol nitrilotriacetic acids, three is dissolved in aqueous isopropanol (10ml deionized waters and
30ml isopropanols), strong agitation is configured to uniform mixed solution in 30 minutes；
2) by step 2) gained mixed solution be transferred in ptfe autoclave, in hydro-thermal reaction 24h at 200 DEG C,
Question response kettle is naturally cooled to after normal temperature, by gained sediment respectively with deionized water and absolute ethyl alcohol alternately washing and repeatedly from
The heart separates (centrifugal rotational speed is 6000rpm, each centrifugation time 5min), until filtrate is in neutrality, will be obtained after washing and centrifugation
Pink precipitate at 70 DEG C under air atmosphere dry 24h；
3) by step 2) dry after products therefrom be placed in Muffle furnace, with 2 DEG C/min speed be heated to 300 DEG C roasting
1h, produces catalyst (the cobalt and manganese oxide MnCo that low-concentration nitrogen oxide is removed for constant temperature catalyzing2O4)。
By MnCo obtained by the present embodiment2O4Carry out normal temperature removing NO measure of merit, wherein MnCo2O4Consumption be 0.10g,
Packed height is 12mm, and NO concentration is 20ppm, and gaseous mixture total flow is 200SCCM.CoMn obtained by the present embodiment2O4At 20 DEG C
When start to reach 100% to the removal efficiency of nitrogen oxides in 2.5 hours, be 32% to NO conversion rate of oxidation when reaching stable state.
Embodiment 3
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, its preparation method comprises the following steps：
1) weighing the nitric hydrate manganese of 6mmol tetra-, 6mmol cabaltous nitrate hexahydrates, (mol ratio of cobalt and manganese is 1:1) and
7.2mmol nitrilotriacetic acids, (20ml deionized waters and 60ml isopropanols), strong agitation 30 are dissolved in aqueous isopropanol by three
Minute is configured to uniform mixed solution；
2) by step 2) gained mixed solution be transferred in ptfe autoclave, in hydro-thermal reaction 18h at 190 DEG C,
Question response kettle is naturally cooled to after normal temperature, by gained sediment respectively with deionized water and absolute ethyl alcohol alternately washing and repeatedly from
The heart separates (centrifugal rotational speed is 6000rpm, each centrifugation time 5min), until filtrate is in neutrality, will be obtained after washing and centrifugation
Pink precipitate at 60 DEG C under air atmosphere dry 12h；
3) by step 2) dry after products therefrom be placed in Muffle furnace, with 3 DEG C/min speed be heated to 350 DEG C roasting
0.5h, produces catalyst (the cobalt and manganese oxide MnCoO that low-concentration nitrogen oxide is removed for constant temperature catalyzing4)。
By MnCoO obtained by the present embodiment4Carry out normal temperature removing NO measure of merit, wherein MnCoO4Consumption be 0.2g, filling
Highly it is 25mm, NO concentration is 20ppm, and gaseous mixture total flow is 400SCCM.MnCoO obtained by the present embodiment4In 30 DEG C of beginnings
1.8 hours in the removal efficiency of nitrogen oxides up to 100%, up to stable state after NO conversion rate of oxidation be 25%.
Embodiment 4
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, its preparation method comprises the following steps：
1) the chloride hydrate manganese (MnCl of 9mmol tetra- are weighed2·4H2O), 3mmol cobalt chloride hexahydrates (CoCl2·6H2O) (cobalt
Mol ratio with manganese is 1:3) and 4.5mmol nitrilotriacetic acids, three is dissolved in aqueous isopropanol (10ml deionized waters and
30ml isopropanols), strong agitation is configured to uniform mixed solution in 30 minutes；
2) by step 2) gained mixed solution be transferred in ptfe autoclave, in hydro-thermal reaction 24h at 200 DEG C,
Question response kettle is naturally cooled to after normal temperature, by gained sediment respectively with deionized water and absolute ethyl alcohol alternately washing and repeatedly from
The heart separates (centrifugal rotational speed is 6000rpm, each centrifugation time 5min), until filtrate is in neutrality, will be obtained after washing and centrifugation
Pink precipitate at 60 DEG C under air atmosphere dry 12h；
3) by step 2) dry after products therefrom be placed in Muffle furnace, with 1 DEG C/min speed be heated to 400 DEG C roasting
1h, produces catalyst (the cobalt and manganese oxide MnCo that low-concentration nitrogen oxide is removed for constant temperature catalyzing2O4)。
By CoMn obtained by the present embodiment3O4Carry out normal temperature removing NO measure of merit, wherein CoMn3O4Consumption be 0.10g,
Packed height is 12mm, and NO concentration is 10ppm, and gaseous mixture total flow is 400SCCM, and temperature is 15 DEG C.Obtained by the present embodiment
CoMn3O4Catalytic eliminating test result be time of complete removing nitrogen oxides be 2 hours, be to NO conversion ratio during stable state
22%.
Embodiment 5
A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, its preparation method comprises the following steps：
1) the chloride hydrate manganese (MnCl of 3mmol tetra- are weighed2·4H2O), 9mmol cobalt chloride hexahydrates (CoCl2·6H2O) (cobalt
Mol ratio with manganese is 3:1) and 9.0mmol nitrilotriacetic acids, three is dissolved in aqueous isopropanol (20ml deionized waters and
60ml isopropanols), strong agitation is configured to uniform mixed solution in 30 minutes；
2) by step 2) gained mixed solution be transferred in ptfe autoclave, in hydro-thermal reaction 18h at 200 DEG C,
Question response kettle is naturally cooled to after normal temperature, by gained sediment respectively with deionized water and absolute ethyl alcohol alternately washing and repeatedly from
The heart separates (centrifugal rotational speed is 6000rpm, each centrifugation time 5min), until filtrate is in neutrality, will be obtained after washing and centrifugation
Pink precipitate at 70 DEG C under air atmosphere dry 18h；
3) by step 2) dry after products therefrom be placed in Muffle furnace, with 2 DEG C/min speed be heated to 400 DEG C roasting
0.5h, produces catalyst (the cobalt and manganese oxide MnCo that low-concentration nitrogen oxide is removed for constant temperature catalyzing2O4)。
By MnCo obtained by the present embodiment3O4Carry out normal temperature removing NO measure of merit, wherein MnCo3O4Consumption be 0.10g,
Packed height is 12mm, and NO concentration is 20ppm, and gaseous mixture total flow is 200SCCM, and temperature is 35 DEG C.Obtained by the present embodiment
MnCo3O4Catalytic eliminating test result be time of complete removing nitrogen oxides be 1.5 hours.
It the foregoing is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, make some modifications and variations, these belong to the protection model of the present invention
Enclose.
Claims (10)
1. a kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing, it is characterised in that the catalyst is nanometer
The porous cobalt and manganese oxide of wire, the wherein mol ratio of cobalt element and manganese element are 1:(0.3~3).
2. catalyst according to claim 1, it is characterised in that the concentration of the low-concentration nitrogen oxide is 10~
20ppm。
3. catalyst according to claim 1, it is characterised in that the length of the porous cobalt and manganese oxide of nanometer wire is
10~100 μm, a diameter of 10~50nm, specific surface area is 100~120m2/ g, containing meso-hole structure, mesoporous pore size is 3~
5nm。
4. it is used for the preparation method that constant temperature catalyzing removes the catalyst of low-concentration nitrogen oxide described in any one of claims 1 to 3,
Characterized in that, synthesizing the porous cobalt and manganese oxide of nanometer wire using solvent heat and subsequent heat treatment method, specifically include as follows
Step：By inorganic manganese salt, cobalt salt and nitrilotriacetic acid stirring and dissolving in aqueous isopropanol, then by gained mixed solution heat into
Normal temperature is naturally cooled to after row solvent thermal reaction, washing and filtering obtains pink product, is then dried, is calcined, and produces institute
State the catalyst that low-concentration nitrogen oxide is removed for normal temperature.
5. preparation method according to claim 4, it is characterised in that the inorganic manganese salt is manganese chloride or manganese nitrate；Nothing
Machine cobalt salt is cobalt chloride or cobalt nitrate.
6. preparation method according to claim 4, it is characterised in that cobalt element, manganese element and ammonia in the mixed solution
The mol ratio of triacetic acid is 1:(0.3~3):(1.0~1.5).
7. preparation method according to claim 4, it is characterised in that the temperature of the solvent thermal reaction is 180~200
DEG C, the time is 12~24h.
8. preparation method according to claim 4, it is characterised in that wash the reagent used for deionized water and ethanol,
Alternately washing is until gained filtrate is in neutrality.
9. preparation method according to claim 4, it is characterised in that the drying temperature is 60~80 DEG C, and the time is 12
~18h.
10. preparation method according to claim 4, it is characterised in that the sintering temperature is 300~450 DEG C, the time is
0.5~2h.
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| CN110871074A (en) * | 2018-08-29 | 2020-03-10 | 天津大学 | Porous nanosheet-based NiCo2O4Nanotube for high efficiency catalytic elimination of soot |
| CN111992222A (en) * | 2020-08-26 | 2020-11-27 | 华东理工大学 | Cobalt-manganese hydrated oxide for normal-temperature removal of low-concentration nitrogen oxide and preparation method thereof |
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