CN109364943A - A kind of efficient cryogenic denitrating catalyst and its preparation method and application - Google Patents
A kind of efficient cryogenic denitrating catalyst and its preparation method and application Download PDFInfo
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- CN109364943A CN109364943A CN201811515685.8A CN201811515685A CN109364943A CN 109364943 A CN109364943 A CN 109364943A CN 201811515685 A CN201811515685 A CN 201811515685A CN 109364943 A CN109364943 A CN 109364943A
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- denitrating catalyst
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- cryogenic denitrating
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000001376 precipitating effect Effects 0.000 claims abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 229910003286 Ni-Mn Inorganic materials 0.000 claims abstract description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 11
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000004071 soot Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910005798 NiMnO3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- 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
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- 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
- B01J35/613—10-100 m2/g
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- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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Abstract
The present invention discloses a kind of efficient cryogenic denitrating catalyst and its preparation method and application.Using nickel acetate and manganese acetate as raw material, oxalic acid is precipitating reagent, prepares Ni-Mn composite oxide catalysts in 500 DEG C of roastings.Catalyst prepared by the present invention possesses big specific surface area, the Mn of high concentration4+, it is NH3More adsorption sites are provided with NO, the oxidability of catalyst is enhanced, improves the catalytic activity of catalyst.Catalyst conversion rate of NOx at a temperature of 80 DEG C has reached 76%, and conversion rate of NOx has reached 100% at 90 DEG C, and remains high degradation rate at 90 DEG C -250 DEG C.Method for preparing catalyst prepared by the present invention is simple, cost of material is low, has efficient catalytic activity in low temperature, using its at low temperature can efficient degradation NOx, control boiler fired coal, power plant soot, automotive emission nitrogen oxides have important practical application value.
Description
Technical field
The invention belongs to thermocatalytic field of material technology, and in particular to it is a kind of at low temperature can efficient degradation nitrogen oxides
The preparation method and application of composite catalyst.
Background technique
Boiler fired coal, automotive emission nitrogen oxides, photochemical fog, acid rain, Ozone hole and temperature can be caused
The environmental securities such as room effect.Denitration technology becomes the emphasis of people's research, and wherein Dry denitration is paid close attention to by people.Ammonia choosing
Selecting property catalytic reduction of NOx (NH3- SCR) it is one of most common method of current coal-fired flue gas denitration.SCR selective catalytic reduction
It is with NH3(liquefied ammonia or urea decompose) is reducing agent, in O2Under the conditions of existing, under the action of catalyst, selectively and cigarette
NOx reaction in gas, generates nitrogen and water.Industrial most widely used SCR catalyst is mainly with the composite oxygen containing vanadium at present
Based on compound, but its active temperature range is higher (300-400 DEG C), which has the drawback that: operating cost is high, takes up an area face
Product is big, reaction temperature is high, catalyst life is short and toxicity is big.And contain SO in flue gas2, in 180 DEG C of -230 DEG C of temperature ranges,
SO2It is easily reacted with ammonia and is converted into ammonium sulfate, line clogging and equipment is caused to corrode.
Summary of the invention
It is an object of the present invention to provide a kind of efficient cryogenic denitrating catalysts and its preparation method and application.The present invention utilizes low
Warm catalyst and again flue gas technology are, it can be achieved that first desulfurization denitration again, to reduce the obstruction of pipeline.
The technical solution adopted by the present invention is that: a kind of efficient cryogenic denitrating catalyst, the efficient cryogenic denitration catalyst
Agent is Ni-Mn composite oxide catalysts, and preparation method includes the following steps:
1) precipitating reagent aqueous solution is added dropwise to the mixed aqueous solution of nickel acetate and manganese acetate, adjusts the PH of mixed solution
For 5-7, be stirred to react 1-1.5h, be aged 4-5h, filtering takes precipitating, precipitating use respectively deionized water and ethanol washing to PH extremely
7；
2) sediment after step 1) washing is dry at 80 DEG C, obtain Ni-Mn mix powder；
3) by after the grinding of Ni-Mn mix powder obtained by step 2), in Muffle furnace, under air environment, roasting obtains Ni-
Mn composite oxide catalysts.
Further, above-mentioned a kind of efficient cryogenic denitrating catalyst, in step 1), the precipitating reagent be ammonium carbonate or
Oxalic acid.
Further, above-mentioned a kind of efficient cryogenic denitrating catalyst, the precipitating reagent are oxalic acid.
Further, above-mentioned a kind of efficient cryogenic denitrating catalyst, in molar ratio, nickel acetate: manganese acetate: precipitating reagent
=2:5:7.
Further, above-mentioned a kind of efficient cryogenic denitrating catalyst, in step 3), in Muffle furnace, under air environment
Roasting, maturing temperature are 500 DEG C, calcining time 4h.
Above-mentioned efficient cryogenic denitrating catalyst is degraded the application in nitrogen oxides at low temperature.
The invention has the following advantages:
1, transition metal is in the prior art due to getting more and more people's extensive concerning with good NO oxidation effectiveness
Ni-Mn composite oxide catalysts opening temperature is not low enough, and active temperature section is narrow.It is urged to improve Ni-Mn composite oxides
The low temperature active of agent, the present invention use oxalic acid as precipitating reagent, are prepared for Ni-Mn composite oxide catalysts, the catalysis of acquisition
Agent has big specific surface area, the Mn of high concentration4+, metal cation sufficiently precipitates, no remnants.
2, preparation process of the present invention is simple, at low cost, reproducible, has a good application prospect.
3, in the present invention, in PH=1-2, oxalic acid cannot ionize oxalic acid completely, mainly with H2C2O4In the presence of being slowly added dropwise
Suitable sal volatile adjusts pH value to 6, ionizes oxalic acid all, all with C2O4 2-Form deposit in the solution, with gold
Belonging to cation combination precipitates it sufficiently.It is stirred solution 1h, then solution is aged 4h.
4, for Ni-Mn composite oxide catalysts of the present invention using oxalic acid as precipitating reagent, the catalyst of preparation possesses big ratio table
Area, the Mn of high concentration4+, it is NH3More adsorption sites are provided with NO, the oxidability of catalyst is enhanced, improves and urge
The catalytic activity of agent.Catalyst conversion rate of NOx at a temperature of 80 DEG C has reached 76%, and conversion rate of NOx reaches at 90 DEG C
100%, and remain high degradation rate at 90 DEG C -250 DEG C.Method for preparing catalyst prepared by the present invention is simple, cost of material
It is low, have efficient catalytic activity in low temperature, using its at low temperature can efficient degradation NOx, control boiler fired coal, power plant combustion
Coal, automotive emission nitrogen oxides have important practical application value.
Detailed description of the invention
Fig. 1 is catalyst XRD diagram prepared by example 1.
Fig. 2 is catalyst SEM figure prepared by example 1.
Fig. 3 is catalyst XRD diagram prepared by example 2.
Fig. 4 is catalyst SEM figure prepared by example 2.
Fig. 5 is the specific surface area of catalyst contrast table of different precipitating reagents preparation.
Fig. 6 is the catalyst degradation NO activity comparison diagram of different precipitating reagents preparation.
Specific embodiment
1 ammonium carbonate of embodiment is the efficient cryogenic denitrating catalyst of precipitating reagent preparation
(1) the preparation method is as follows:
1. measuring 0.994g (0.004mol) nickel acetate, 2.45g (0.01mol) manganese acetate is transferred in 200ml beaker, adds
Enter 80ml deionized water, stirs evenly to obtain nickel acetate and manganese acetate mixed aqueous solution.Measure 2.2g (0.014mol) ammonium carbonate in
In 50ml beaker, 20ml deionized water is added, obtains ammonium carbonate solution.
2. ammonium carbonate solution is added dropwise in nickel acetate and manganese acetate mixed aqueous solution with rubber head dropper, stirring is mixed
Solution 1h to be closed, then solution is aged 4h, is filtered, precipitating is taken, precipitating uses deionized water and ethanol washing three times respectively, until PH is 7,
Remove other impurities ion.
3. the dry 12h at 80 DEG C of the sediment after step 2 is washed, obtains Ni-Mn mix powder.
4. after the grinding of step 3 gained Ni-Mn mix powder, in Muffle furnace, under air environment, 500 DEG C of roasting 4h,
Obtain Ni-Mn composite oxide catalysts.
(2) it detects
Fig. 1 is that the XRD diagram for the efficient cryogenic denitrating catalyst that ammonium carbonate is precipitating reagent preparation occurs different as seen from Figure 1
Diffraction maximum, correspond respectively to Mn3O4、MnNi2O4、NiO。
Fig. 2 is the SEM figure for the efficient cryogenic denitrating catalyst that ammonium carbonate is precipitating reagent preparation, from Figure 2 it can be seen that catalyst is in
Now typical chondritic.
Fig. 5 is the specific surface area of catalyst contrast table of different precipitating reagents preparation.As seen from Figure 5, ammonium carbonate is precipitating reagent system
The specific surface of standby efficient cryogenic denitrating catalyst is only 53.25m2g-1。
2 oxalic acid of embodiment is the efficient cryogenic denitrating catalyst of precipitating reagent preparation
(1) the preparation method is as follows:
1. measuring 0.994g (0.004mol) nickel acetate, 2.45g (0.01mol) manganese acetate is transferred in 200ml beaker, adds
Enter 80ml deionized water, stirs evenly to obtain nickel acetate and manganese acetate mixed aqueous solution.Measure 1.76g (0.014mol) oxalic acid in
In 50ml beaker, 20ml deionized water is added, obtains oxalic acid aqueous solution.
2. after oxalic acid aqueous solution is added dropwise in nickel acetate and manganese acetate mixed aqueous solution with rubber head dropper, being added dropwise suitable
The ammonium carbonate solution of amount, the pH for adjusting mixed solution is 6, is stirred solution 1h, then mixed solution is aged 4h, makes metal
Cationic sufficiently precipitating, filtering take precipitating, and precipitating uses deionized water and ethanol washing three times respectively, until PH is 7, remove other
Foreign ion.
Because oxalic acid is in PH=1-2, oxalic acid cannot ionize completely, mainly with H2C2O4In the presence of suitable carbonic acid is slowly added dropwise
Ammonium salt solution adjusts pH value to 6, ionizes oxalic acid all, all with C2O4 2-Form deposit in the solution, with metal cation knot
Conjunction precipitates it sufficiently.
3. the dry 12h at 80 DEG C of the sediment after step 2 is washed, obtains Ni-Mn mix powder.
4. after the grinding of step 3 gained Ni-Mn mix powder, in Muffle furnace, under air environment, 500 DEG C of roasting 4h,
Obtain Ni-Mn composite oxide catalysts.
(2) it detects
Fig. 3 is that the XRD diagram for the efficient cryogenic denitrating catalyst that oxalic acid is precipitating reagent preparation occurs different as seen from Figure 3
Diffraction maximum corresponds respectively to NiMnO3、MnNi2O4、NiO。
Fig. 4 is the SEM figure for the efficient cryogenic denitrating catalyst that oxalic acid is precipitating reagent preparation, from fig. 4, it can be seen that catalyst is presented
Typical chondritic.
Fig. 5 is the specific surface area of catalyst contrast table of different precipitating reagents preparation.As seen from Figure 5, oxalic acid is precipitating reagent preparation
Efficient cryogenic denitrating catalyst possess big specific surface, specific surface area 103.30m2g-1。
The application of 3 efficient cryogenic denitrating catalyst of embodiment
The Ni-Mn composite oxide catalysts of Examples 1 and 2 preparation are subjected to thermocatalytic degradation NO active testing.
(1) method is as follows:
Simulated flue gas: NO (500ppm), NH3(500ppm), O2(5%), N2For the mixed gas of Balance Air.
Catalyst activity test carries out in the tubular fixed-bed reactor continuously flowed, internal diameter 16mm, using dynamic
Distribution, is passed through normal temperature and pressure Imitating flue gas, and total flow 260mL/min, air speed GHSV are 51000h-1.Use flue gas analysis
O in instrument (German Testo 350) on-line checking unstripped gas and tail gas2, NO content.
It measures 200mg efficient cryogenic denitrating catalyst to be put into tubular fixed-bed reactor, is passed through the simulated flue gas of preparation
Mixed gas, begun to warm up when gas content reaches desired value, reaction temperature control at 20 DEG C -260 DEG C, every 20 DEG C protect
Warm 20min is re-recorded to gas values stabilization.NO conversion ratio calculation formula: NO conversion ratio (%)=(NO goes out into-NO)/NO into
× 100%.As a result as shown in fig. 6, the NO conversion ratio when reaction temperature reaches 90 DEG C reaches using oxalic acid as the catalyst of precipitating reagent
100%, and temperature window is 90 DEG C -240 DEG C, and the conversion ratio at 90 DEG C is 80% using ammonium carbonate as the catalyst of precipitating reagent
Left and right, 110 DEG C just reach 100% conversion ratio.It embodies and is existed with the Ni-Mn composite oxide catalysts of oxalic acid precipitation agent preparation
The high degradation rate of low temperature.
Claims (6)
1. a kind of efficient cryogenic denitrating catalyst, which is characterized in that the efficient cryogenic denitrating catalyst is Ni-Mn composite oxygen
Compound catalyst, preparation method include the following steps:
1) precipitating reagent aqueous solution is added dropwise in the mixed aqueous solution of nickel acetate and manganese acetate, the PH for adjusting mixed solution is
5-7, is stirred to react 1-1.5h, is aged 4-5h, filtering, takes precipitating, and precipitating is respectively 7 with deionized water and ethanol washing to PH；
2) it will be deposited in drying at 80 DEG C after step 1) washing, obtains Ni-Mn mix powder；
3) by after the grinding of Ni-Mn mix powder obtained by step 2), in Muffle furnace, under air environment, it is multiple to obtain Ni-Mn for roasting
Close oxide catalyst.
2. a kind of efficient cryogenic denitrating catalyst according to claim 1, which is characterized in that in step 1), described is heavy
Shallow lake agent is ammonium carbonate or oxalic acid.
3. a kind of efficient cryogenic denitrating catalyst according to claim 2, which is characterized in that the precipitating reagent is grass
Acid.
4. a kind of efficient cryogenic denitrating catalyst according to claim 1,2 or 3, which is characterized in that in molar ratio, acetic acid
Nickel: manganese acetate: precipitating reagent=2:5:7.
5. a kind of efficient cryogenic denitrating catalyst according to claim 1, which is characterized in that in step 3), in Muffle furnace
In, it is roasted under air environment, maturing temperature is 500 DEG C, calcining time 4h.
Application 6. efficient cryogenic denitrating catalyst described in claim 1 is degraded at low temperature in nitrogen oxides.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847807A (en) * | 2019-03-21 | 2019-06-07 | 青岛大学 | Denitration filtrate and preparation method thereof based on corona treatment and in situ deposition method |
| CN109876824A (en) * | 2019-04-03 | 2019-06-14 | 四川大学 | A kind of MnO2- NiO activated coke low-temperature denitration catalyst and preparation method thereof |
| CN110586124A (en) * | 2019-09-04 | 2019-12-20 | 南京大学 | Preparation and application of FeMn oxide low-temperature denitration catalyst with ultrahigh specific surface area |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130144085A1 (en) * | 2011-12-02 | 2013-06-06 | Paulette Hazin | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
| CN105944713A (en) * | 2016-05-09 | 2016-09-21 | 清华大学 | Denitration catalyst containing tungsten-tin-manganese-cerium composite oxide as well as preparation and application of denitration catalyst |
| WO2016181407A1 (en) * | 2015-05-08 | 2016-11-17 | Viridis Chemicals Private Limited | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes |
| CN106179323A (en) * | 2016-07-01 | 2016-12-07 | 中国科学院城市环境研究所 | A kind of vanadium tungsten titanium oxide catalyst and its production and use |
| CN108704650A (en) * | 2018-06-22 | 2018-10-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application |
-
2018
- 2018-12-12 CN CN201811515685.8A patent/CN109364943A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130144085A1 (en) * | 2011-12-02 | 2013-06-06 | Paulette Hazin | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
| WO2016181407A1 (en) * | 2015-05-08 | 2016-11-17 | Viridis Chemicals Private Limited | Additive composition for mixed metal oxide catalysts and its use in hydrocarbon conversion processes |
| CN105944713A (en) * | 2016-05-09 | 2016-09-21 | 清华大学 | Denitration catalyst containing tungsten-tin-manganese-cerium composite oxide as well as preparation and application of denitration catalyst |
| CN106179323A (en) * | 2016-07-01 | 2016-12-07 | 中国科学院城市环境研究所 | A kind of vanadium tungsten titanium oxide catalyst and its production and use |
| CN108704650A (en) * | 2018-06-22 | 2018-10-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847807A (en) * | 2019-03-21 | 2019-06-07 | 青岛大学 | Denitration filtrate and preparation method thereof based on corona treatment and in situ deposition method |
| CN109847807B (en) * | 2019-03-21 | 2022-04-08 | 青岛大学 | Denitration filter material based on plasma treatment and in-situ deposition method and preparation method thereof |
| CN109876824A (en) * | 2019-04-03 | 2019-06-14 | 四川大学 | A kind of MnO2- NiO activated coke low-temperature denitration catalyst and preparation method thereof |
| CN110586124A (en) * | 2019-09-04 | 2019-12-20 | 南京大学 | Preparation and application of FeMn oxide low-temperature denitration catalyst with ultrahigh specific surface area |
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Application publication date: 20190222 |