CN106334552A - MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution - Google Patents
MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution Download PDFInfo
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- CN106334552A CN106334552A CN201610872260.7A CN201610872260A CN106334552A CN 106334552 A CN106334552 A CN 106334552A CN 201610872260 A CN201610872260 A CN 201610872260A CN 106334552 A CN106334552 A CN 106334552A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003912 environmental pollution Methods 0.000 title claims abstract description 7
- 230000002265 prevention Effects 0.000 title abstract description 4
- 229910016978 MnOx Inorganic materials 0.000 title abstract 4
- 239000000243 solution Substances 0.000 claims abstract description 122
- 150000002696 manganese Chemical class 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000013110 organic ligand Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 117
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical class OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 26
- 239000007787 solid Substances 0.000 description 26
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/643—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a MnOx catalyst, a preparation method thereof and application thereof to prevention and control of environmental pollution. The preparation method comprises the following steps: firstly, adding certain organic ligand into a certain organic solvent, so as to obtain an organic ligand solution after the organic ligand is dissolved; secondly, adding manganese salt into an organic solvent, so as to obtain a manganese salt solution after manganese salt is dissolved; thirdly, mixing the organic ligand solution and the manganese salt solution according to a certain volume ratio, so as to obtain a mixed solution; fourthly, heating the mixed solution, so as to obtain a crystallized body; fifthly, drying the crystallized body, and then roasting the crystallized body, so as to obtain the MnOx catalyst. The preparation method is simple in equipment and good in repeatability, has a good industrial application prospect, and the MnOx catalyst obtained has a high-dispersion three-dimensional structure, a specific surface area and a uniform mesoporous structure, can catalyze CO to be completely oxidized in high-temperature and low-temperature stages, can further keep high stability, and is applicable to catalytic reaction to remove CO in atmospheric pollutants.
Description
Technical field
The invention discloses a kind of mnoxCatalyst, its preparation method and the application in preventing and treating environmental pollution, belong to and urge
Change field of material technology.
Background technology
With the fast development of modern industry, transportation, environmental pollution is on the rise, and prevents the pollution of the environment
For being related to the key subjects of national economy.Particularly automobile exhaust pollution becomes one of main source of atmosphere pollution, and co
It is then one of major pollutants in vehicle exhaust, carbon monoxide enters to combine with the hemoglobin in blood of human body and produce
Carbonyl haemoglobin, so that each histocyte anoxic in human body, can lead to death when serious, have certain toxicity.Cause
This purifies to the co causing because of motor-vehicle tail-gas in the motor-driven vehicle passage of the vcehicular tunnel of severe contamination and underground, develops efficient stable
Normal temperature co catalyst have very important significance.
mnoxThe co molecule that mainly comprises the processes of as catalyst reaction adsorbs the bronsted being formed in mn-o first
In the active sites of acid or lewis alkali, further there is selective catalytic reduction reaction in the active specy being formed after absorption.And
There is lewis acidic site in mn-mofs material in its framework, and also can during metal ion mn with organic ligand cooperation
Produce mn-o key, mn can play good catalytic action as variable valency metal in catalytic reaction simultaneously.
Cozzolino etc. synthesizes mn-mof material and uses it for oxidation reaction.
(cozzolino a f,brozek c k,palmer r d,et al.journal of the american
chemical society,2014,136(9):3334-3337.).Xu, r etc. utilize hydro-thermal method and infusion process to synthesize mno2Carrier
And ag/mno2Catalyst, at 126 DEG C, the conversion ratio of co reaches 90% (xu, r；wang,x；wang,d.s；zhou,k.b；li,
y.d.j.catal.2006,237,426-430.).The mno that young-ho lee etc. is synthesized2Oxide catalyst, 300
At DEG C, the conversion ratio of co reaches 90% (young-ho lee, jung-hyun park, chae-ho shin.catalysis
today.2015,265,7-13).S.andreoli et al. has synthesized a kind of mnox, applied in noxIn scr, 200
No at DEG CxConversion ratio reach more than 90% (s.andreoli, f.a.deorsola, c.galletti,
r.pirone.chemical engineering journal.2015,278,174–182).There is in commercial Application its office
Sex-limited.
Content of the invention
The technical problem to be solved in the present invention is to provide one kind to be catalyzed co complete oxidation in low temperature and in two stages of high temperature
While can also keep the mno of high stabilityxCatalyst, and preparation method thereof.
Present invention employs technical scheme below:
The mno that the present invention providesxThe preparation method of catalyst is it is characterised in that comprise the following steps: step one, by one
Determine organic ligand to be added in certain organic solvent with certain mass volume ratio, after dissolving, obtain organic ligand solution；Step 2,
Manganese salt is added in organic solvent with certain mass volume ratio, after dissolving, obtains manganese salt organic solution；Step 3, joins organic
After example mixes according to a certain volume, stirring 0.5-6h obtains mixed solution for liquid solution and manganese salt organic solution；Step 4, will mix
Solution is placed in in teflon-lined reactor, and under conditions of temperature is for 80-200 DEG C, heating 2-12h obtains crystalline substance
Change body；Step 5, after by scrubbed for crystallization body, filtration and being dried 6-24h, then in temperature under conditions of temperature 80-120 DEG C
Reaction atmosphere co, o for 300-800 DEG C2、h2、n2, roasting 2-4 hour in any one or its gaseous mixture in he and ar, obtain
To mnoxCatalyst.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step one, has
Machine part is 1,3,5 benzenetricarboxylic acids, terephthalic acid (TPA), 2,5- dihydric para-phthalic acid, M-phthalic acid, succinic acid, inclined benzene
The mixture of any one or more in tricarboxylic acid and 1,2,3,4- BTCA.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step one, manganese
Salt is manganese nitrate, mncl2·4h2o、mnso4, manganese acetate, mnco3And mn (h2po4)2·4h2Any one in o.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step one and step
In two, organic solvent is methyl alcohol, ethanol, n, n- dimethylformamide and n, any one in n- dimethylacetylamide or many
The mixture planted.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step one, one
Determining mass volume ratio is 0.01955-0.212g organic ligand: 1-5ml organic solvent.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step 2, one
Determining mass volume ratio is 0.5-4g manganese salt: 1-50ml organic solvent.
The mno that the present invention providesxThe preparation method of catalyst, also has a feature in that wherein, in step 3, has
Machine ligand solution is 20:1-25: 1 with the volume ratio of manganese salt organic solution.
The present invention also provides the mno that a kind of above-mentioned preparation method preparesxCatalyst, has the activearm for catalysis
Point it is characterised in that: wherein, active component be mn3o4And mn2o3Mixture.
The mno that the present invention providesxCatalyst, also has a feature in that wherein, mnoxThe molecule of catalyst is cube firefly
Stone structure, mnoxCatalyst is micro- mesoporous structure, and micro- mesoporous aperture is 1.0-3.0nm, mnoxThe specific surface area of catalyst is
10-350m2/g.
A kind of above-mentioned mno of the present invention also offerxCatalyst, preventing and treating environmental pollution in application it is characterised in that: its
In, this catalyst is used for being catalyzed the reaction of the gases such as co, toluene, formaldehyde.
Invention effect and effect
The mno that the present invention providesxThe preparation method of catalyst, is dissolved by a certain percentage using certain organic ligand and manganese salt
Remix after certain organic solution and obtain mixed liquor, after this mixed liquor crystallization is dried, then roasting, just can obtain mnoxCatalysis
Agent, this preparation method, equipment is simple, reproducible, has good prospects for commercial application.
The mno being obtained using above-mentioned preparation methodxCatalyst, molecule is cubic fluorite structure, mnoxThe profile of catalyst is
Micro- mesoporous structure, after testing, micro- mesoporous aperture is 1.0-3.0nm, mnoxThe specific surface area of catalyst is 10-350m2/ g,
It can be seen that this mnoxCatalyst has high dispersive stereochemical structure and a high-specific surface area, homogeneous meso-hole structure, can not only be in high temperature rank
Catalysis co, toluene, formaldehyde complete oxidation in section, and high stability can also be kept, the co in suitable Air Pollution prevention and control, first
Benzene and formaldehyde etc..
Brief description
Fig. 1 is the mno in the embodiment of the present invention 1xThe mno that the preparation method of catalyst is obtainedxThe x-ray diffraction of catalyst
Figure；
Fig. 2 is the mno in the embodiment of the present invention 1xCatalyst oxidation co activity figure；
Fig. 3 is the mno in the embodiment of the present invention 1xCatalyst is in the co catalytic oxidation effect figure of high temperature section；
Fig. 4 is the mno in the embodiment of the present invention 1xThe sem figure of catalyst；
Fig. 5 is the mno in the embodiment of the present invention 1xThe h of catalyst2Tpr schemes.
Specific embodiment
The present invention is expanded on further below in conjunction with specific embodiment.For used concrete grammar in embodiment or material
Material, those skilled in the art on the basis of the technology of the present invention thinking, can carry out the replacement choosing of routine according to existing technology
Select, be not limited solely to the concrete record of the embodiment of the present invention.
Experimental technique used in following embodiments if no special instructions, is conventional method；The material that used,
Reagent etc., if no special instructions, all commercially obtains.
Embodiment 1
The mno that the present embodiment providesxThe preparation method of catalyst, comprises the following steps:
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
1h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids the condition for 300-800 DEG C for the temperature conditionss (atmosphere volume ratio 1%co, 20%
o2, 79%he) under roasting 2h, obtain mnoxCatalyst.
Fig. 1 is the mno in the embodiment of the present invention 1xThe mno that the preparation method of catalyst is obtainedxThe x-ray diffraction of catalyst
Figure.
As shown in figure 1, mnox catalyst the angle of diffraction 2 θ=17.838 °, 28.824 °, 32.404 °, 36.231 °,
38.144 °, 58.821 ° when have mn3o4Significantly diffraction maximum；Have at 2 θ=23.084 °, 32.863 °, 38.206 °, 55.241 °
mn2o3Significantly diffraction maximum.
Fig. 2 is the mno in the embodiment of the present invention 1xThe co of catalyst.Abscissa is relative pressure (p/p0), ordinate is to inhale
Acceptor amasss (cm3g-1).
As shown in Fig. 2 pre-process synthesized mnox out through different temperatures, apply it to co catalysis oxidation
In, show that the activity through 700 DEG C of pretreatments is best, 800 DEG C of activity is worst.
Fig. 3 is the mno in the embodiment of the present invention 1xCatalyst is in the co catalytic oxidation effect figure of high temperature section.Abscissa is temperature
Degree (DEG C), ordinate is the temperature (DEG C) that conversion ratio is during a hundred per cent.
As shown in figure 3, can intuitively find out very much, when conversion ratio is 100%, the minimum temperature of conversion temperature 245
Temperature spot corresponding to DEG C is 700 DEG C, illustrates that the sample activity of 700 DEG C of pretreatments is best.
Fig. 4 is the mno in the embodiment of the present invention 1xThe sem figure of catalyst.
As shown in figure 4, the mno by the reversion of mofs materialxCatalyst, its pattern is irregular cube.
Fig. 5 is the mno in the embodiment of the present invention 1xThe h of catalyst2Tpr schemes.Abscissa is temperature (DEG C), and ordinate is
Signal strength signal intensity (a u).
As shown in figure 5, between 400 DEG C -500 DEG C of temperature, occurring in that characteristic peak.It is mainly mn3+It is transformed to mn2+
Variation of valence.
Embodiment 2
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 7h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 100 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 30%o2,
70%ar) roasting 1h, obtains mnoxCatalyst.
Embodiment 3
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
3.25h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 140 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 160 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%ar) and roasting 4h, obtain mnoxCatalyst.
Embodiment 4
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 150ml, weighs 1.995 1,3,5- benzene three
Formic acid adds in above-mentioned 150ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；(59.6∶1)
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 10ml, weighs 3g mn (no3)2·4h2O adds
Enter in above-mentioned 10ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；(2.6∶1)
Step 3, more above-mentioned 150ml organic ligand solution is mixed with above-mentioned 10ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 6h at 120 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%n2) roasting 2h, obtain mnoxCatalyst.
Embodiment 5
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
6h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 80 DEG C, heats 12h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 15h at 100 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 100%n2) roasting
Burn 2.5h, obtain mnoxCatalyst.
Embodiment 6
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 200 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 24h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 7
Step one, is placed in 200ml beaker with the ethanol solution that graduated cylinder measures 100ml, weighs 1.995g 1,3,5- benzene three
Formic acid adds in above-mentioned 100ml ethanol solution, 35 DEG C of agitating heating in water-bath, until 1,3,5- benzenetricarboxylic acids are completely molten
Solution, obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the ethanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (no3)2·4h2O adds
Enter in above-mentioned 5ml ethanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 130 DEG C, heats 2.5h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 12h at 120 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2.5h, obtain mnoxCatalyst.
Embodiment 8
Step one, measures the n of 100ml, n- dimethylformamide (dmf) solution is placed in 200ml beaker, weighs with graduated cylinder
1.995g 1,3,5- benzenetricarboxylic acid adds above-mentioned 100ml n, in n- dimethylformamide (dmf) solution, 35 DEG C in water-bath
Agitating heating, until 1,3,5- benzenetricarboxylic acids are completely dissolved, obtains being formed transparent with machine ligand solution；
Step 2, measures the n of 5ml, n- dimethylformamide (dmf) solution is placed in 50ml beaker, weighs with graduated cylinder
2.5g mncl2·4h2O adds above-mentioned 5ml n, in n- dimethylformamide (dmf) solution, stirs to being completely dissolved, obtains manganese
Salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 9
Step one, measures the n of 100ml, n- dimethylacetylamide (dma) solution is placed in 200ml beaker, weighs with graduated cylinder
1.995g 1,3,5- benzenetricarboxylic acid adds above-mentioned 100ml n, in n- dimethylacetylamide (dma) solution, 35 DEG C in water-bath
Agitating heating, until 1,3,5- benzenetricarboxylic acids are completely dissolved, obtains being formed transparent with machine ligand solution；
Step 2, measures the n of 5ml, n- dimethylacetylamide (dma) solution is placed in 50ml beaker, weighs with graduated cylinder
2.5g manganese acetate adds above-mentioned 5ml n, in n- dimethylacetylamide (dma), stirs to being completely dissolved, obtains manganese salt organic molten
Liquid；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 10
Step one, measures the n of 200ml, n- dimethylacetylamide (dma) solution is placed in 200ml beaker, weighs with graduated cylinder
2.10g1,2,3,4- BTCAs add above-mentioned 220ml n, in n- dimethylacetylamide (dma) solution, 35 in water-bath
DEG C agitating heating, until 1,2,3,4- BTCAs are completely dissolved, obtains being formed transparent with machine ligand solution；
Step 2, measures the n of 20ml, n- dimethylacetylamide (dma) solution is placed in 50ml beaker, weighs with graduated cylinder
2.5g mn(no3)2·4h2O adds above-mentioned 20ml n, in n- dimethylacetylamide (dma), stirs to being completely dissolved, obtains manganese
Salt organic solution；
Step 3, more above-mentioned 220ml organic ligand solution is mixed with above-mentioned 20ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 11
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 200ml, weighs 1.995g terephthalic acid (TPA)
Add in above-mentioned 200ml methanol solution, 35 DEG C of agitating heating in water-bath, until terephthalic acid (TPA) is completely dissolved, obtain shape
Become transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 8ml, weighs the addition of 2.5g manganese sulfate above-mentioned
In 5ml methyl alcohol, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 200ml organic ligand solution is mixed with above-mentioned 8ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；(25∶1)
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 140 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 120 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 12
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 110ml, weighs 1.995g 2,5- dihydroxy
Terephthalic acid (TPA) adds in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until 2,5- dihydroxy is to benzene two
Formic acid is completely dissolved, and obtains being formed transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5gmnco3Add above-mentioned 5ml
In methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 110ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；(22∶1)
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Embodiment 13
Step one, is placed in 200ml beaker with the methanol solution that graduated cylinder measures 100ml, weighs 1.995g trimellitic acid
Add in above-mentioned 100ml methanol solution, 35 DEG C of agitating heating in water-bath, until trimellitic acid is completely dissolved, obtain shape
Become transparent with machine ligand solution；
Step 2, is placed in 50ml beaker with the methanol solution that graduated cylinder measures 5ml, weighs 2.5g mn (h2po4)2·4h2o
Add in above-mentioned 5ml methanol solution, stir to being completely dissolved, obtain manganese salt organic solution；
Step 3, more above-mentioned 100ml organic ligand solution is mixed with above-mentioned 5ml manganese salt organic solution, continue stirring anti-
0.5h is answered to obtain mixed solution；
Step 4, above-mentioned mixed solution is placed in in teflon-lined reactor, seals, put into baking oven
In, under conditions of temperature is 120 DEG C, heats 2h, obtain crystallization body；
Step 5, by scrubbed for above-mentioned crystallization body, filtration and is dried 8h at 80 DEG C, obtains solids；
Step 6, by above-mentioned solids under conditions of temperature conditionss are for 300-800 DEG C (atmosphere volume ratio 1%co, 20%
o2, 79%he) and roasting 2h, obtain mnoxCatalyst.
Catalyst activity evaluation experimental
The mno that 1-13 prepares will be implementedxCatalyst is carried out instead respectively in fixed bed continuously flows differential reactor
Should, the internal diameter of differential reactor is the glass u-shaped pipe of 4mm, and the loadings of catalyst are 200mg, the unstripped gas of each embodiment
Constituent (volume ratio) respectively as shown in table 2.Gas flow rate is 30ml/min, in continuous flowing differential reactor,
Under different pretreatment temperatures, after reaction 20min, in product gas, co is through being furnished with thermal conductivity cell detector gc-2060 gas-chromatography
Instrument on-line analysis, finally obtains co conversion ratio, and co conversion ratio represents mnoxThe reactivity of catalyst, finally gives table 1 below
Performance with table 2.
Table 1 mnoxThe performance indications of catalyst
| Embodiment | Specific surface area (m2/g) | Aperture (nm) |
| Example 1 | 58.5 | 3.0 |
| Example 2 | 205 | 1.690 |
| Example 3 | 184 | 1.692 |
| Example 4 | 108 | 1.429 |
| Example 5 | 350 | 1.430 |
| Example 6 | 307 | 2.189 |
| Example 7 | 10 | 2.101 |
| Example 8 | 134 | 1.0 |
| Example 9 | 89.9 | 2.112 |
| Example 10 | 105 | 1.565 |
| Example 11 | 57.7 | 1.868 |
Table 2 mnoxThe catalytic performance of catalyst
Embodiment effect and effect
The mno that embodiment 1-11 providesxThe preparation method of catalyst, using certain organic ligand and manganese salt by a certain percentage
Remix after being dissolved in certain organic solvent and obtain mixed liquor, after this mixed liquor crystallization h is dried, then roasting, just can obtain
mnoxCatalyst, preparation technology and equipment are simple, reproducible, have good prospects for commercial application.
The mno being obtained using above-mentioned preparation methodxCatalyst, active component is mn3o4And mn2o3Mixture, molecule
For cube structure, mnoxCatalyst is micro- mesoporous structure, and after testing, micro- mesoporous aperture is 1.0-3.0nm, mnoxCatalysis
The specific surface area of agent is 10-350m2/ g is it is seen that this mnoxCatalyst has high dispersive stereochemical structure and high-specific surface area, homogeneous
Meso-hole structure, can not only be catalyzed co, toluene, formaldehyde complete oxidation in hot stage, and can also keep high stability, suitably
Co in Air Pollution prevention and control, toluene, formaldehyde.
In addition, in embodiment 1-11, organic solvent is methyl alcohol, ethanol, n, n- dimethylformamide and n, n- dimethyl
Acetamide, as the organic solvent of the present invention, can also be the arbitrarily multiple combination in them；
In addition, in embodiment 1-11, organic ligand is 1,3,5 benzenetricarboxylic acids, terephthalic acid (TPA), 2,5- dihydroxy to benzene two
Formic acid, trimellitic acid and 1,2,3,4- BTCAs, as the organic ligand of the present invention, can also be M-phthalic acid
Or the arbitrarily multiple combination in succinic acid or above-mentioned various material.
Claims (10)
1. a kind of mnoxThe preparation method of catalyst is it is characterised in that comprise the following steps:
Step one, certain organic ligand is added in certain organic solvent with certain mass volume ratio, obtains organic after dissolving
Ligand solution；
Step 2, manganese salt is added in described organic solvent with certain mass volume ratio, obtains manganese salt organic solution after dissolving；
Step 3, described organic ligand solution and described manganese salt organic solution after example mixes according to a certain volume, are stirred 0.5-
6h obtains mixed solution；
Step 4, described mixed solution is placed in in teflon-lined reactor, is 80-200 DEG C in temperature
Under the conditions of heating 2-12h obtain crystallization body；
Step 5, after by scrubbed for described crystallization body, filtration and being dried 6-24h, then in temperature under conditions of temperature 80-120 DEG C
Spend reaction atmosphere co, the o for 300-800 DEG C2、h2、n2, roasting 2-4 hour in any one or its gaseous mixture in he and ar,
Obtain described mnoxCatalyst.
2. preparation method according to claim 1 it is characterised in that:
Wherein, in step one, described organic ligand is 1,3,5 benzenetricarboxylic acids, terephthalic acid (TPA), 2,5- dihydroxy terephthaldehyde
The mixing of any one or more in acid, M-phthalic acid, succinic acid, trimellitic acid and 1,2,3,4- BTCA
Thing.
3. preparation method according to claim 1 it is characterised in that:
Wherein, in described step one, described manganese salt is manganese nitrate, mncl2·4h2o、mnso4, manganese acetate, mnco3And mn
(h2po4)2·4h2Any one in o.
4. preparation method according to claim 1 it is characterised in that:
Wherein, in described step one with described step 2, described organic solvent is methyl alcohol, ethanol, n, n- dimethylformamide
And n, the mixture of any one or more in n- dimethylacetylamide.
5. preparation method according to claim 1 it is characterised in that:
Wherein, in described step one, described organic solvent is 39: 1-79: 1 with the mass ratio of organic ligand.
6. preparation method according to claim 1 it is characterised in that:
Wherein, in described step 2, the mass ratio of described organic solvent and manganese salt is 1.586:1-6.344: 1.
7. preparation method according to claim 1 it is characterised in that:
Wherein, in described step 3, described organic ligand solution is 20:1-25 with the volume ratio of described manganese salt organic solution:
1.
8. the mno that a kind of preparation method as claim 1 to 7 any one obtainsxCatalyst, has the activity for catalysis
Component it is characterised in that:
Wherein, described active component is mn3o4And mn2o3Mixture.
9. mno according to claim 8xCatalyst it is characterised in that:
Wherein, described mnoxThe molecule of catalyst is cube structure,
Described mnoxCatalyst is micro- mesoporous structure,
Described micro- mesoporous aperture is 1.0-3.0nm,
Described mnoxThe specific surface area of catalyst is 10-350m2/g.
10. a kind of mno as described in claim 9xCatalyst preventing and treating environmental pollution in application it is characterised in that:
Wherein, this catalyst is used for being catalyzed the reaction of the gases such as co, toluene, formaldehyde.
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| CN114950409A (en) * | 2022-05-10 | 2022-08-30 | 中国地质大学（武汉） | Manganese-based catalytic material and preparation method and application thereof |
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| CN115555018B (en) * | 2022-10-18 | 2024-02-20 | 华南理工大学 | Catalyst for low-temperature ozone catalytic oxidation of VOCs and preparation method thereof |
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