CN109956502A - Have a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant and the preparation method and application thereof - Google Patents
Have a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant and the preparation method and application thereof Download PDFInfo
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- CN109956502A CN109956502A CN201910160678.9A CN201910160678A CN109956502A CN 109956502 A CN109956502 A CN 109956502A CN 201910160678 A CN201910160678 A CN 201910160678A CN 109956502 A CN109956502 A CN 109956502A
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- 229910001868 water Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 19
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 235000019441 ethanol Nutrition 0.000 claims abstract description 39
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000005416 organic matter Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 37
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 10
- 239000012855 volatile organic compound Substances 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910006364 δ-MnO2 Inorganic materials 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
- B01J23/16—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
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2004/50—Agglomerated particles
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
It has a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant and the preparation method and application thereof the invention discloses a kind of, belongs to catalysis material technical field.Preparation method is by KMnO4Solution is added in chain alcohol, or chain alcohol is added to KMnO4In solution, 6h-48h then is reacted under conditions of 10 DEG C -38 DEG C；It is filtered, will be dried after sediment undergoes washing to get stratiform manganese oxide after the reaction was completed；The carbon atom number of the chain alcohol is less than or equal to 4；It is stirred continuously or shakes in the adition process and reaction process.The chain alcohol is preferably methanol or ethyl alcohol.When the stratiform manganese oxide that the present invention is prepared is applied to the catalysis burning of volatile organic matter, specific surface area with higher has catalytic activity high, and catalytic stability is strong, has many advantages, such as excellent water-resistance and anti-sulfur poisonous performance.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of have a water resisting property aoxidizes with the stratiform of sulfur poisoning-resistant
Manganese and the preparation method and application thereof.
Background technique
Volatile organic contaminant (VOCs) is a major class organic compound of the boiling point at 50~260 DEG C, mainly include aldehyde,
Aromatic hydrocarbons and halogenated hydrocarbons three categories have the potential risks such as high toxicity and " carcinogenic-mutagenesis-teratogenesis " to human body.Currently, absorption,
The kinds of processes such as burning, heat catalytic oxidation, photochemical catalytic oxidation have been applied in VOCs removal.Wherein, low-temperature catalytic oxidation method is
Convert VOCs to harmless CO2And H2The most effective and most economical method of O, and without secondary pollution, thus increasingly by
The concern of people.However, VOCs catalysis, which is reacted, to be carried out under anhydrous equal ideal conditions in most of researchs.In reality
In the industrial application of border, in VOCs gas to be processed often be accompanied by a large amount of vapor and sulfur dioxide gas, vapor and
The active surface sites of the gaseous compound meeting competitive Adsorption of sulfur-bearing on a catalyst, to the VOCs catalytic oxidation activity of catalyst
There is toxic action with a degree of influence, while to catalyst itself, so as to cause catalyst inactivation, reduce catalyst
Service life, increase processing cost and difficulty.Therefore, vapor and sulfur dioxide gas are usually to enter in the prior art
It is dried before catalyst chamber and is handled with lye absorption respectively, but processing increases the workload of additional process in this way.
Summary of the invention
The present invention solves vapor present in volatile organic matter Catalytic processes and sulfur dioxide gas to catalyst
The technical issues of activity reduces.
It is according to the invention in a first aspect, providing a kind of preparation having a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant
Method, by KMnO4Solution is added in chain alcohol or chain alcohol is added to KMnO4In solution, KMnO4Solution adition process
Middle KMnO4Addition speed be more than or equal to 1.58mg/s, the addition speed of chain alcohol is more than or equal to 0.03mL/s；Then 10
6h-48h is reacted under conditions of DEG C -38 DEG C；It is filtered, will be dried after sediment undergoes washing to get tool is arrived after the reaction was completed
There is the stratiform manganese oxide of water-resistance and sulfur poisoning-resistant；The carbon atom number of the chain alcohol is less than or equal to 4；The adition process and
It is stirred continuously or vibrates in reaction process；The KMnO4KMnO in solution4It is (0.67-2) with the ratio between the amount of substance of chain alcohol:
1。
Preferably, the chain alcohol is methanol or ethyl alcohol.
Preferably, the temperature of the drying is less than or equal to 100 DEG C.
Preferably, the cleaning is to be cleaned with deionized water.
Preferably, the drying is forced air drying or vacuum drying.
It is another aspect of this invention to provide that providing the layer having a water resisting property with sulfur poisoning-resistant that the method is prepared
Shape manganese oxide, which is characterized in that the specific surface area of layered manganese oxide is 160m2/g-210m2/g；Layered manganese oxide is
Monoclinic system, and layered manganese oxide is δ crystal form.
It is another aspect of this invention to provide that providing described have a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant for waving
The application of hair property catalytic organism burning.
Preferably, the volatile organic matter is toluene, formaldehyde or chlorobenzene.
Preferably, water vapour or sulfur dioxide are mixed in the volatile organic matter.
Preferably, concentration and sulfur dioxide concentration in combustion system of the volatile organic matter in combustion system
The ratio between be more than or equal to 3；The mass fraction that the quality of the vapor accounts for combustion system is less than or equal to 1.6%.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
(1) in catalyst of transition metal oxide, Lacking oxygen is active in volatile organic matter (VOCs) catalysis oxidation
The absorption of oxygen and resolvation site play a leading role in the complete oxidation of VOCs.The monoclinic system layer being prepared in the present invention
Shape manganese oxide, the disadvantage high compared to the manganese oxide catalyst initiation temperature of existing precipitation method synthesis, redox of the present invention
The stratiform manganese oxide catalyst of method preparation has large specific surface area, specific surface area 160m2/g-210m2/ g has higher oxygen
The advantages that vacancy concentration, and initiation temperature is low, water-resistance and good sulfur poisoning-resistant.
(2) application of the monoclinic system stratiform manganese oxide prepared by the present invention as volatile organic compounds by catalytic combustion, has
Catalytic activity is high, and catalytic stability is strong, water-resistance and the good feature of sulfur poisoning-resistant.Existed using catalyst prepared by the present invention
300ppm toluene gas, 1.6wt%H2O exists, O220% and residue of volume of gas are accounted for by N2Test-strips as Balance Air
Under part: T50=172 DEG C, T90=195 DEG C.Compared in anhydrous conditions, the temperature that toluene is converted completely wants low 40 DEG C, 200
DEG C Toluene conversion ratio can be stably maintained at 95% or so, and the conversion ratio duration is 42h.In 300ppm toluene gas
Body, 100 or 50 or 10ppm SO2, 20 volume ratio O2And N2Under the conditions of Balance Air, sulfur dioxide in reaction gas is found
When gas concentration is 100ppm or less, catalyst reaction activity is not impacted substantially.
(3) this method preparation method does not use any surfactant, and the use of Template-free method does not generate secondary pollution,
It is environmentally protective.The present invention carries out at room temperature, is not necessarily to water bath with thermostatic control, and without ice bath, preparation process is simple, operation letter
Just.For the present invention using chain alcohol as raw material, the carbon atom number of chain alcohol is less than or equal to 4, preferably using methanol or ethyl alcohol as raw material,
In the reducing substances under equal quality, methanol or ethyl alcohol contain the hydroxyl that more molal quantitys are easily oxidized, so that potassium permanganate
Redox reaction is easier to carry out between this kind of substance, obtains more target product stratiform manganese oxide, and methanol and second
Alcohol is low in cost, is easy to obtain.
(4) KMnO in the present invention4Solution is added to KMnO during chain alcohol4Addition speed be more than or equal to 1.58mg/s,
Chain alcohol is added to KMnO4Speed is more than or equal to 0.03mL/s in solution, and constantly stirs in adition process and reaction process
It mixes or vibrates.When rate of addition is too slow, the manganese oxide for reacting generation can directly reunite, and the XRD spectrum of obtained product is without crystalline substance
Face diffraction maximum occurs, and illustrates that manganese oxide does not have layer structure.KMnO is added in the present invention4The process of solution or chain alcohol and anti-
It answers process to be stirred continuously and shake, makes KMnO4It is come into full contact with chain alcohol, to obtain stratiform manganese oxide.The present invention is preferably
Dry temperature is less than or equal to 100 DEG C, when drying temperature is excessively high, if dried long-time, and the stratiform of obtained manganese oxide
Structure can be destroyed, and can cause the burning of chain alcohol.
Detailed description of the invention
Fig. 1 shows the stratiform oxidation manganese material XRD spectrum prepared in the embodiment of the present invention 1.
The SEM and TEM that Fig. 2 (a) and Fig. 2 (b) shows the stratiform oxidation manganese material prepared in the embodiment of the present invention 3 shine
Piece.
Fig. 3 (a) and Fig. 3 (b) shows stratiform oxidation manganese material nitrogen adsorption desorption and the hole of the preparation of the embodiment of the present invention 4
Diameter is distributed map.
Fig. 4 shows the stratiform oxidation manganese material toluene catalytically sulfur resistance test chart of the preparation of the embodiment of the present invention 5.
Fig. 5 shows the stratiform oxidation manganese material toluene catalytically water vapor performance test figure of the preparation of the embodiment of the present invention 6.
Fig. 6 shows the stratiform oxidation manganese material toluene catalytically stability test chart of the preparation of the embodiment of the present invention 6.
Fig. 7 is to obtain the XRD spectrum of product in comparative example 1.
Fig. 8 is to obtain the XRD spectrum of product in comparative example 2.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
The molar ratio of potassium permanganate and ethyl alcohol is 2:3, by KMnO4Solution is added in ethanol solution in the case where keeping stirring,
The KMnO4KMnO in solution4Rate of addition be 1.58mg/s.Above-mentioned mixed solution stirs for 24 hours at 10 DEG C.Then it will give birth to
At precipitating filtering, be washed with deionized, obtain stratiform manganese oxide catalyst after 80 DEG C of dryings of air blast.What the present embodiment obtained
The XRD of stratiform manganese oxide catalyst is as shown in Figure 1, as shown in Figure 1,12.5 °, 25 °, 36.5 ° and 65.5 ° of position is right respectively
It should be in δ-MnO2The crystal face (001) (002) (- 111) (- 312) of (JCPDS 80-1098).Wherein, what (001) crystal face occurred spreads out
It penetrates peak to illustrate the manganese oxide there are layer structures, belongs to monoclinic system.
Embodiment 2
The molar ratio of potassium permanganate and methanol is 1:1, by KMnO4Solution is added in ethanol solution in the case where keeping stirring,
The KMnO4KMnO in solution4Rate of addition be 4.74mg/s.Above-mentioned mixed solution stirs 48h at 15 DEG C.Then it will give birth to
At precipitating filtering, be washed with deionized, obtain stratiform manganese oxide catalyst after 80 DEG C of dryings of air blast.
Embodiment 3
The molar ratio of potassium permanganate and ethyl alcohol is 2:3, and it is molten that ethanol solution is quickly poured into potassium permanganate in the case where keeping stirring
In liquid.Above-mentioned mixed solution stirs for 24 hours at 10 DEG C.Then the precipitating of generation is filtered, is washed with deionized, 60 DEG C of air blast
Stratiform manganese oxide catalyst is obtained after drying.SEM and the TEM figure for the stratiform manganese oxide catalyst that the present embodiment obtains are respectively as schemed
Shown in 2 (a) and Fig. 2 (b).By Fig. 2 (a), it is found that, which is to be assembled into more tools at random by tiny nanometer sheet
There is the aggregate of lamellar structure.By Fig. 2 (b) it is found that nanometer sheet rough surface is irregular, illustrate that there are a large amount of surfaces on its surface
Defect and Lacking oxygen.
Embodiment 4
The molar ratio of potassium permanganate and methanol is 1:1, by KMnO4Solution is added rapidly to the methanol solution under keeping stirring
In.Above-mentioned mixed solution stirs for 24 hours at 18 DEG C.Then the precipitating of generation is filtered, is washed with deionized, 80 DEG C of vacuum are dry
Stratiform manganese oxide catalyst, the N for the stratiform manganese oxide catalyst that the present embodiment obtains are obtained after dry2Adsorption desorption curve and aperture point
Butut is respectively as shown in Fig. 3 (a) and Fig. 3 (b).By Fig. 3 (a) it is found that the specific surface for the stratiform manganese oxide that the implementation method obtains
Product is 160m2/g.It by Fig. 3 (b) it is found that catalyst surface pore size distribution range is wide, is stacked up by tiny nanometer sheet
Porous structure.
Embodiment 5
The molar ratio of potassium permanganate and ethyl alcohol is 2:3, by KMnO4Solution is added in ethanol solution in the case where keeping stirring,
The KMnO4KMnO in solution4Rate of addition be 1.58mg/s.20 DEG C of above-mentioned mixed solution stirrings are for 24 hours.Then by generation
Precipitating filtering, is washed with deionized, and obtains stratiform manganese oxide catalyst after 70 DEG C of vacuum drying.And in catalyst reaction device
Catalyst performance is tested, test condition is 300ppm toluene gas, 100 or 50 or 10ppm SO2, 20 volume ratio O2And N2
As Balance Air, concentration of the toluene in combustion system is SO respectively23 times, 6 times and 30 times of concentration in combustion system.
The anti-sulfur poisonous performance figure of the stratiform manganese oxide catalyst that the present embodiment obtains as shown in figure 4, in entrance reaction gas titanium dioxide
When sulphur concentration is 100ppm, the catalytic activity of this kind of catalyst is not substantially reduced, and it is good that this illustrates that the stratiform manganese oxide has
Sulfur poisoning-resistant.
Embodiment 6
The molar ratio of potassium permanganate and ethyl alcohol is 2:3, by KMnO4Solution is added rapidly to the ethanol solution under keeping stirring
In.10 DEG C of stirring 12h of above-mentioned mixed solution.Then the precipitating of generation is filtered, is washed with deionized, after 60 DEG C of dryings of vacuum
Obtain stratiform manganese oxide catalyst.And catalyst performance is tested in catalyst reaction device, test condition is respectively 300ppm first
Benzene gas, 20 volume ratio O2, N2As Balance Air, 0 or 1.13wt%H2O.The stratiform manganese oxide catalyst that the present embodiment obtains
Water repelling property figure and catalytic stability figure difference it is as shown in Figure 5 and Figure 6.As shown in Figure 5, it is seen that catalyst is in moisture content
Under conditions of 1.6wt% than it is anhydrous it is existing under the conditions of, conversion temperature when toluene conversion reaches 100% is reduced close to 40
DEG C, catalytic activity greatly improves.As can be seen from Figure 6, when catalyst moisture content 1.6wt%, catalytic temperature are fixed on 200 DEG C,
Its toluene conversion maintains 95% or so and is 42 hours.These results suggest that this kind of layered catalyst has good resist
It is aqueous and to be catalyzed thermal stability.
Embodiment 7
The molar ratio of potassium permanganate and ethyl alcohol is 2:3, and ethanol solution is added in the case where not failure of oscillation is swung with the speed of 0.03mL/s
Enter to KMnO4In solution.Above-mentioned mixed solution stirs for 24 hours at 10 DEG C.Then the precipitating of generation is filtered, is washed with deionized water
It washs, obtains stratiform manganese oxide catalyst after 60 DEG C of forced air dryings.
Comparative example 1
The preparation method is the same as that of Example 1 in this comparative example, only KMnO4KMnO in solution4Rate of addition be 0.5mg/s, obtain
To product XRD diagram as shown in fig. 7, it is known that the XRD spectrum of product obtained in this comparative example is without crystal face from Fig. 7
Diffraction maximum occurs, and illustrates that manganese oxide does not have layer structure.
Comparative example 2
The preparation method is the same as that of Example 1 in this comparative example, and only manganese oxide drying temperature is 120 DEG C, the XRD of obtained product
Figure is as shown in figure 8, it is known that the XRD spectrum of product obtained in this comparative example newly occurs belonging to Mn from Fig. 83O4Spread out
Peak (JCPDS 24-0734) is penetrated, illustrates that the crystal structure of manganese oxide has occurred and that change.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method having a water resisting property with the stratiform manganese oxide of sulfur poisoning-resistant, which is characterized in that by KMnO4Solution adds
Enter into chain alcohol or chain alcohol is added to KMnO4In solution, KMnO4KMnO in solution adition process4Addition speed it is big
In being equal to 1.58mg/s, the addition speed of chain alcohol is more than or equal to 0.03mL/s；Then it is reacted under conditions of 10 DEG C -38 DEG C
6h-48h；It is filtered, will be dried after sediment undergoes washing to get to having a water resisting property and sulfur poisoning-resistant after the reaction was completed
Stratiform manganese oxide；The carbon atom number of the chain alcohol is less than or equal to 4；Be stirred continuously in the adition process and reaction process or
Oscillation；The KMnO4KMnO in solution4It is (0.67-2) with the ratio between the amount of substance of chain alcohol: 1.
2. the preparation method having a water resisting property as described in claim 1 with the stratiform manganese oxide of sulfur poisoning-resistant, which is characterized in that
The chain alcohol is methanol or ethyl alcohol.
3. the preparation method having a water resisting property as described in claim 1 with the stratiform manganese oxide of sulfur poisoning-resistant, which is characterized in that
The temperature of the drying is less than or equal to 100 DEG C.
4. the preparation method having a water resisting property as described in claim 1 with the stratiform manganese oxide of sulfur poisoning-resistant, which is characterized in that
The cleaning is to be cleaned with deionized water.
5. the preparation method having a water resisting property as described in claim 1 with the stratiform manganese oxide of sulfur poisoning-resistant, which is characterized in that
The drying is forced air drying or vacuum drying.
6. the stratiform manganese oxide that any the method for claim 1-5 was prepared have a water resisting property with sulfur poisoning-resistant, special
Sign is that the specific surface area of layered manganese oxide is 160m2/g-210m2/g；Layered manganese oxide is monoclinic system, and institute
Stating stratiform manganese oxide is δ crystal form.
7. being had a water resisting property described in claim 6 with the stratiform manganese oxide of sulfur poisoning-resistant for volatile organic compounds by catalytic combustion
Using.
8. the use as claimed in claim 7, which is characterized in that the volatile organic matter is toluene, formaldehyde or chlorobenzene.
9. the use as claimed in claim 7, which is characterized in that be mixed with water vapour or titanium dioxide in the volatile organic matter
Sulphur.
10. application as claimed in claim 9, which is characterized in that concentration of the volatile organic matter in combustion system with
The ratio between the concentration of sulfur dioxide in combustion system is more than or equal to 3；The quality of the vapor accounts for the mass fraction of combustion system
Less than or equal to 1.6%.
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| CN110732323A (en) * | 2019-10-24 | 2020-01-31 | 黑龙江科技大学 | α -MnO for catalyzing oxidation of volatile organic compounds2Process for preparing catalyst |
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| CN111215067A (en) * | 2020-03-20 | 2020-06-02 | 北京工业大学 | Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst |
| CN111686754A (en) * | 2020-07-07 | 2020-09-22 | 四川大学 | Non-noble metal catalyst for catalytic combustion of volatile organic compounds and preparation method thereof |
| CN114433073A (en) * | 2021-12-29 | 2022-05-06 | 广东省科学院化工研究所 | Manganese-based catalyst and preparation method and application thereof |
| CN115957621A (en) * | 2023-01-30 | 2023-04-14 | 昆明理工大学 | Application of manganese oxide in catalytic decomposition of mixed mercaptan |
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| CN114433073A (en) * | 2021-12-29 | 2022-05-06 | 广东省科学院化工研究所 | Manganese-based catalyst and preparation method and application thereof |
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