CN109364913A - Catalyst for catalyzing and oxidizing VOCs (volatile organic compounds) by ultraviolet light self-excited ozone and preparation method and application thereof - Google Patents
Catalyst for catalyzing and oxidizing VOCs (volatile organic compounds) by ultraviolet light self-excited ozone and preparation method and application thereof Download PDFInfo
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 59
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 title abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- 238000006555 catalytic reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- QGBLCIBATKETJC-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;manganese(2+) Chemical compound [Mn+2].O1B([O-])OB2OB([O-])OB1O2 QGBLCIBATKETJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000001291 vacuum drying Methods 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 238000002791 soaking Methods 0.000 abstract 2
- 238000009835 boiling Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 20
- 239000007789 gas Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01D53/007—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 by irradiation
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/869—Multiple step processes
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01D2251/104—Ozone
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- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B01D2259/804—UV light
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Abstract
A catalyst for catalyzing and oxidizing VOCs by ultraviolet light self-excited ozone and its preparation method and application, taking alkali-free and wax-free glass fiber, boiling with nitric acid solution, cleaning with deionized water to neutral, and drying; taking tetrabutyl titanate as a precursor, and mixing the tetrabutyl titanate with absolute ethyl alcohol to obtain a solution A; dissolving deionized water, zirconium oxychloride and acetic acid in ethanol, and stirring to obtain a solution B; uniformly stirring the solution A, adding the solution B, and stirring to obtain a light yellow precursor C; soaking the glass fiber in the faint yellow precursor C, drying, aging at room temperature, drying in a vacuum drying oven in vacuum, calcining in a muffle furnace, and naturally cooling to room temperature to obtain the Zr-Ti loaded glass fiber; mixing manganese nitrate, ethanol, acetic acid and deionized water to obtain a solution D; soaking the Zr-Ti loaded glass fiber into the solution D, aging, drying and roasting to obtain the catalyst for catalyzing and oxidizing VOCs by the cooperation of the ultraviolet light self-excited ozone.
Description
Technical field
The invention belongs to environmental catalysis and VOCs process field, and in particular to a kind of ultraviolet light self-excitation ozone cooperative catalysis
Aoxidize VOCs catalyst and its preparation method and application more particularly to a kind of Mn-Zr-TiO2/ GF catalytic ozonation is compound to urge
The preparation and application of agent.
Background technique
China is industrial power, and national number of the enterprise and total cumulative output value of industry constantly rise.However, in economic flourishing hair
While exhibition, brought problem of environmental pollution, especially industrial waste gas pollution problem is also on the rise, the problem serious prestige
Coerce the health of resident.Currently, VOCs improvement has drawn attention and has been brought into schedule, the extensive concern by government and people.
Most common for VOCs is the methods of catalysis burning, but these methods do not conform to for handling low concentration Wind Volume VOCs
It is suitable.For the VOCs of low concentration Wind Volume, using photocatalysis technology, photocatalysis oxidation technique has quick and high efficient reaction, to dirt
Contaminate object complete decomposition and advantages of environment protection.But traditional loaded catalyst still have active particulate sizes poor controllability,
The problems such as active component is easy to reunite, the efficiency of light energy utilization is low.Presently, there are the technologies of ozone and photocatalysis combination degradation VOCs, still
Used is the ozone being exogenously introduced, and increases the cost of processing, and largely introduces this by-product of ozone in the product
Object limits the application of the technology industrially.So that photocatalysis and ozone catalytic is organically coupled and handles industry
On organic exhaust gas become limit its environment protection field development key.Pass through Mn-Zr-TiO at present with ozone cooperative is ultraviolet2It urges
Agent handles VOCs there is not yet report.
Summary of the invention
The technical issues of solution: presently, there are ozone and photocatalysis combination degradation VOCs technology, but used is outer
Source introduce ozone, increase the cost of processing, and largely introduce this by-product of ozone in the product, this ozone and
Photocatalysis simply piles up superposition and limits the application of the technology industrially.The present invention provides a kind of ultraviolet light self-excitation ozone association
It, can be while photocatalytic degradation organic exhaust gas in system with catalysis oxidation VOCs catalyst and its preparation method and application
Spontaneous generation ozone, and in composite catalyst under the action of ozone catalytic module can catalysis ozone to organic exhaust gas into
Row is degraded again, the ozone of endogenous spontaneous generation is taken full advantage of, by ultraviolet photolysis, ozone oxidation and the organic coupling of photochemical catalytic oxidation
It is combined, can adequately be degraded to organic matter.
Technical solution: a kind of preparation method of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, preparation step
It is rapid as follows: (1) it takes alkali-free without wax glass fibre, with nitric acid solution 1~2h of brew, then is washed with deionized water to neutral drying,
It is spare；(2) using butyl titanate as presoma, it is mixed with dehydrated alcohol, it is spare to obtain solution A, the butyl titanate with
The molar ratio of dehydrated alcohol is 1:(50~200)；(3) ionized water, ZrOCl are removed2·8H2O and CH3COOH is dissolved in CH3CH2OH
In, stir to get that solution B is spare, zirconium oxychloride: glacial acetic acid: deionized water: the molar ratio of dehydrated alcohol is (1~5): (10~
50):31:49；(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, standby
With；(5) will through step (1), treated dries after glass fibre impregnates in faint yellow presoma C, and be aged in room temperature,
It is dried in vacuo in vacuum oven, the 400-700 DEG C of high-temperature calcination in Muffle furnace, cooled to room temperature obtains Zr-Ti load
Glass fibre, it is spare；(6) mixed nitrate manganese, CH3CH2OH、CH3COOH and deionized water, four molar ratios are (1~50):
(50~200): (10~50): 150, solution D is obtained, is stirred spare；(7) glass fibers for loading Zr-Ti made from step (5)
Dimension is impregnated into solution D, is roasted after room temperature ageing, drying to get a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation is arrived
VOCs catalyst (Mn-Zr-TiO2/GF)。
Preferably, specification of the alkali-free without wax glass fibre used in step (1) is 60-200g/m2。
Preferably, the volumetric concentration of nitric acid solution used in step (1) is 10%.
Preferably, the digestion time is 12-24 hours.
Preferably, step (7) drying temperature is 80 DEG C, and maturing temperature is 550 DEG C, and calcining time is 3 hours.
Preferably, metal salt described in step (6) be manganese salt, molysite, cobalt salt, aluminium salt, cerium salt, magnesium salts or nickel salt, it is described
Manganate is manganese nitrate, manganese sulfate, manganese acetate, manganese borate or manganese carbonate, Mn2+And Ti2+Molar ratio be 0.5%~20%.
Ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst made from the above method.
Application of the above-mentioned catalyst in VOCs processing.
Ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst produced by the present invention has following performance:
(1) UVC and VUV due to wavelength it is short, photon energy with higher can be opened under the action of UVC and VUV
The lower C-S of bond energy in VOCs, C-N etc. realize the photodissociation of moieties in this VOCs, achieve the purpose that deodorization.
(2) VUV of wavelength 185nm photon energy with higher, though it is unable to the higher substance of bond energy in photodissociation VOCs,
It is active specy-hydroxyl radical free radical that energy photocatalytic water generates Strong oxdiative, hydroxyl radical free radical has strong oxidizing property, can aoxidize
VOCs。
(3) ultraviolet lighting is mapped to Mn-Zr-TiO2On/GF composite catalyst, TiO can be excited2In the valence band of upper low-lying level
In electron transition to the conduction band of high level.Hole is generated in valence band, and there is strong oxidizing property, organic matter can be played well
Removal effect.185nm ultraviolet light can excite oxygen to generate ozone in the process, and ozone has stronger oxidation susceptibility.It is smelly
Mechanism of action there are two types of oxygen oxidation VOCs is current, first is that ozone direct oxidation VOCs, second is that the middle substance such as water of ozone and environment
It reacts and generates the hydroxyl radical free radical of strong oxidizing property, realize the oxidation to VOCs, further eliminate VOCs.
(4) conventional Ti O2Catalyst is compound due to photo-generated carrier, reduces its catalytic efficiency.Zr ranges titanium subgroup
Element, valence electron structure (n-1) d2ns2It is identical with Ti, and Zr4+Ionic radius and Ti4+It is close, so Zr4+It can enter
Easily cause surface defect in TiO2 lattice, is conducive to improve catalysis material active site.
(5) the features such as glass fibre has large specific surface area, and translucency is high, at low cost, it is excellent to can be used as photochemical catalyst
Carrier.It will modified TiO2Load can overcome powder-type TiO on the glass fibers2It is low to the efficiency of light energy utilization, be difficult to recycle separation again
Using and to the slow disadvantage of rate of contaminant degradation.
(6) present invention joint utilizes the multiple-effect of the catalytic oxidation activity of ultraviolet catalytic degradation of contaminant and ozone,
Efficiently using the light degradation of vacuum UV lamp, photocatalysis, catalytic ozonation synergistic effect, especially with endogenous ozone
Further organic exhaust gas is aoxidized, on the one hand realizes the efficient process of organic exhaust gas, is on the other hand turned waste into wealth sufficiently
Endogenous ozone is utilized, and reduces its concentration in the product of gas, photocatalysis and ozone catalytic are organically coupled.
The utility model has the advantages that a kind of 1, preparation process of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst of the present invention
Simply, at low cost, it is easy to large-scale industrial production, selects glass fibre as carrier, while there is the energy of O3 catalytic oxidation
Power, VOCs removal effect are good；2, the present invention uses sol-gel technique, and a variety of efficient metal oxides are passed through gel process
It is supported on fiberglass surfacing, roasting can form nanoscale catalytic active layer in fiberglass surfacing under the high temperature conditions, urge
Change active layer large specific surface area, catalytic performance is better than ozone catalyst catalyst that infusion process is prepared while can add
The fast reaction mechanism mechanism of reaction shortens the ozone oxidation time；3, this catalyst stability is good, long service life, catalytic performance after recycling repeatedly
Still remain unchanged.Catalyst of the present invention can act synergistically photodissociation, photocatalysis, free-radical oxidation, catalytic ozonation
In VOCs, have the characteristics that efficiently quick；4, catalyst of the present invention can have photodissociation, photocatalysis, catalytic ozonation
Machine, which is coupled, acts synergistically on VOCs, has the characteristics that efficiently quick.
Detailed description of the invention
Fig. 1 is the toluene removal efficiency chart of embodiment 1.
Fig. 2 is the toluene removal efficiency chart of embodiment 2.
Specific embodiment:
A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst pair of the present invention is inquired into conjunction with specific example
The catalytic effect of VOCs, however, the present invention is not limited thereto.
Embodiment 1
A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, preparation method are as follows:
(1) 80-120g/m is taken2Alkali-free is without wax glass fibre, with nitric acid solution 1~2h of brew of volume ratio 10%, then uses
Deionized water, which is cleaned to neutrality, dries, spare；
(2) using butyl titanate as presoma, it is mixed with dehydrated alcohol, obtains solution A, wherein butyl titanate and nothing
The molar ratio of water-ethanol is 1:50, spare；
(3) a certain amount of deionized water, ZrOCl are taken2·8H2O and CH3COOH is dissolved in CH3CH2In OH, stir to get molten
Liquid B, wherein zirconium oxychloride: glacial acetic acid: deionized water: dehydrated alcohol molar ratio is 1:10:31:49, spare；
(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, spare；
(5) will treated glass fibre dipping-drying-dipping in faint yellow presoma C, realization loads three times.It is negative
It is aged 12h in room temperature after load, is dried in vacuo 2h in a vacuum drying oven, 500 DEG C of high-temperature calcination 2h, natural cooling in Muffle furnace
Glass fibre (the Zr-TiO of Zr-Ti load is obtained to room temperature2/ GF), it is spare；
(6) a certain amount of pure Mn (NO of analysis is taken3)2·4H2O is added to CH3CH2OH、CH3In COOH and deionized water, four
Person's molar ratio are as follows: 1:55:10:150 obtains solution D, stirs spare；
(7) by step (5) ready Zr-TiO2/ GF is impregnated into solution D, ageing 12h, 80 DEG C of drying, 550 DEG C of roastings
3h is burnt to get a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst (Mn-Zr-TiO is arrived2/GF)。
Above-mentioned ozone/ultraviolet light composite catalytic oxidation VOCs catalyst is used for the VOCs that auto manufacturing gives off, with
Toluene is probed into as probe, and reaction carries out in the static glass reactor of 30*30*110mm, and 2.5g catalyst is taken to be placed in
In reactor, the initial concentration of toluene is 300mg/m3.Ultraviolet lamp 185/254nm, power 150W.Experiment at room temperature (25 ± 2
DEG C) under carry out, every 1h sample detection, experimental result is as shown in the figure.
Embodiment 2
A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, preparation method are as follows:
(1) 80-120g/m is taken2Alkali-free is without wax glass fibre, with nitric acid solution 1~2h of brew of volume ratio 10%, then uses
Deionized water, which is cleaned to neutrality, dries, spare；
(2) to analyze pure butyl titanate as presoma, it is mixed with dehydrated alcohol, obtains solution A, wherein four fourth of metatitanic acid
The molar ratio of ester and dehydrated alcohol is 1.1:50, spare；
(3) a certain amount of deionized water, ZrOCl are taken2·8H2O and CH3COOH is dissolved in CH3CH2In OH, stir to get molten
Liquid B, wherein zirconium oxychloride: glacial acetic acid: deionized water: dehydrated alcohol molar ratio is 1:20:31:49, spare；
(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, spare；
(5) will treated glass fibre dipping-drying-dipping in faint yellow presoma C, realization loads three times.It is negative
It is aged 12h in room temperature after load, is dried in vacuo 2h in a vacuum drying oven, 500 DEG C of high-temperature calcination 2h, natural cooling in Muffle furnace
The glass fibre of Zr-Ti load is obtained to room temperature, it is spare；
(6) a certain amount of pure Mn (NO of analysis is taken3)2·4H2O is added to CH3CH2OH、CH3It is obtained in COOH and deionized water
Solution D stirs spare wherein four molar ratios are 3:50:10:150；
(7) by step (5) ready Zr-TiO2/ GF is impregnated into solution D, ageing 12h, 80 DEG C of drying, 550 DEG C of roastings
3h is burnt to get a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst (Mn-Zr-TiO is arrived2/GF)。
Above-mentioned ozone/ultraviolet light composite catalytic oxidation VOCs catalyst is used for the VOCs that auto manufacturing gives off, with
Toluene is probed into as probe, and reaction carries out in the static glass reactor of 30*30*110mm, and 2.5g catalyst is taken to be placed in
In reactor, the initial concentration of toluene is 300mg/m3.Ultraviolet lamp 185/254nm, power 150W.Experiment at room temperature (25 ± 2
DEG C) under carry out, every 1h sample detection, experimental result is as shown in the figure.
Embodiment 3
A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, preparation method are as follows:
(1) 80-120g/m is taken2Alkali-free is without wax glass fibre, with nitric acid solution 1~2h of brew of volume ratio 10%, then uses
Deionized water, which is cleaned to neutrality, dries, spare；
(2) to analyze pure butyl titanate as presoma, it is mixed with dehydrated alcohol, obtains solution A, wherein four fourth of metatitanic acid
The molar ratio of ester and dehydrated alcohol is 1:50, spare；
(3) a certain amount of deionized water, ZrOCl are taken2·8H2O and CH3COOH is dissolved in CH3CH2In OH, stir to get molten
Liquid B, wherein zirconium oxychloride: glacial acetic acid: deionized water: the molar ratio of dehydrated alcohol is 1:15:31:49, spare；
(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, spare；
(5) will treated glass fibre dipping-drying-dipping in faint yellow presoma C, realization loads three times.It is negative
It is aged 12h in room temperature after load, is dried in vacuo 2h in a vacuum drying oven, 500 DEG C of high-temperature calcination 2h, natural cooling in Muffle furnace
The glass fibre of Zr-Ti load is obtained to room temperature, it is spare；
(6) a certain amount of pure Mn (NO of analysis is taken3)2·4H2O is added to CH3CH2OH、CH3It is obtained in COOH and deionized water
Solution D stirs spare wherein four molar ratios are 1:100:10:150；
(7) by step (5) ready Zr-TiO2/ GF is impregnated into solution D, ageing 12h, 80 DEG C of drying, 550 DEG C of roastings
3h is burnt to get a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst (Mn-Zr-TiO is arrived2/GF)。
Above-mentioned ozone/ultraviolet light composite catalytic oxidation VOCs catalyst is used for the VOCs that auto manufacturing gives off, with
Toluene is probed into as probe, and reaction carries out dynamic experiment in the stainless steel reactor of 600*800*1110mm, takes 0.5m2
It three layers of catalyst, is placed in reactor, the initial concentration of toluene is 160mg/m3.Ultraviolet lamp 185/254nm, power 300W, wind
Measure 2500m3/h.It tests and is carried out under (25 ± 2 DEG C) at room temperature, detected in dynamic experiment, practical inlet gas concentration 160mg/m3,
Tail gas concentration is 8mg/m after processing3, removal rate 95%.
Embodiment 4
A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, preparation method are as follows:
(1) 80-120g/m is taken2Alkali-free is without wax glass fibre, with nitric acid solution 1~2h of brew of volume ratio 10%, then uses
Deionized water, which is cleaned to neutrality, dries, spare；
(2) to analyze pure butyl titanate as presoma, it is mixed with dehydrated alcohol, obtains solution Sol A, wherein metatitanic acid
The molar ratio of four butyl esters and dehydrated alcohol is 1.2:50, spare；
(3) a certain amount of deionized water, ZrOCl are taken2·8H2O and CH3COOH is dissolved in CH3CH2In OH, stir to get molten
Liquid B, wherein zirconium oxychloride: glacial acetic acid: deionized water: dehydrated alcohol=1:20:31:49, it is spare；
(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, spare；
(5) will treated glass fibre dipping-drying-dipping in faint yellow presoma C, realization loads three times.It is negative
It is aged 12h in room temperature after load, is dried in vacuo 2h in a vacuum drying oven, 500 DEG C of high-temperature calcination 2h, natural cooling in Muffle furnace
The glass fibre of Zr-Ti load is obtained to room temperature, it is spare；
(6) a certain amount of pure Mn (NO of analysis is taken3)2·4H2O is added to CH3CH2OH、CH3It is obtained in COOH and deionized water
Solution D stirs spare wherein four molar ratios are 2:50:10:150；
(7) by step (5) ready Zr-TiO2/ GF is impregnated into solution D, ageing 12h, 80 DEG C of drying, 550 DEG C of roastings
3h is burnt to get a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst (Mn-Zr-TiO is arrived2/GF)。
Above-mentioned ozone/ultraviolet light composite catalytic oxidation VOCs catalyst is used for the VOCs that auto manufacturing gives off, with
Toluene is probed into as probe, and reaction carries out dynamic experiment in the stainless steel reactor of 600*800*1110mm, takes 0.5m2
It three layers of catalyst, is placed in reactor, the initial concentration of toluene is 136mg/m3.Ultraviolet lamp 185/254nm, power 450W, wind
Measure 2500m3/h.It tests and is carried out under (25 ± 2 DEG C) at room temperature, detected in dynamic experiment, practical inlet gas concentration 136mg/m3,
Tail gas concentration is 8mg/m after processing3, removal rate 94%.
Schematically the invention and embodiments thereof are described above, actual technical solution is not limited to
In this.So if those of ordinary skill in the art are inspired by it, in the case where not departing from this creation objective, without wound
The property made designs embodiment similar with the technical solution, should belong to the protection scope of this patent.
Claims (8)
1. a kind of preparation method of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst, it is characterised in that preparation step
It is as follows: (1) it takes alkali-free without wax glass fibre, with nitric acid solution 1 ~ 2h of brew, then is washed with deionized water to neutrality and dries, it is standby
With；(2) using butyl titanate as presoma, it is mixed with dehydrated alcohol, it is spare to obtain solution A, the butyl titanate and nothing
The molar ratio of water-ethanol is 1:(50 ~ 200)；(3) ionized water, ZrOCl are removed2·8H2O and CH3COOH is dissolved in CH3CH2In OH,
Stir to get that solution B is spare, zirconium oxychloride: glacial acetic acid: deionized water: the molar ratio of dehydrated alcohol is (1 ~ 5): (10 ~ 50):
31:49；(4) by solution A, 34:31 is stirred by volume with solution B after mixing evenly, obtains faint yellow presoma C, spare；(5)
Will through step (1), treated dries after glass fibre impregnates in faint yellow presoma C, and be aged in room temperature, it is dry in vacuum
It is dried in vacuo in dry case, the 400-700 DEG C of high-temperature calcination in Muffle furnace, cooled to room temperature obtains the glass of Zr-Ti load
Fiber, it is spare；(6) mixed nitrate manganese, CH3CH2OH、CH3COOH and deionized water, four molar ratios are (1 ~ 50): (50 ~
200): (10 ~ 50): 150, solution D is obtained, is stirred spare；(7) by the glass fiber impregnated of the load of Zr-Ti made from step (5)
Into solution D, roasting is catalyzed after room temperature ageing, drying to get to a kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs
Agent (Mn-Zr-TiO2/ GF).
2. a kind of preparation side of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst according to claim 1
Method, it is characterised in that: specification of the alkali-free without wax glass fibre is 60-200g/m used in step (1)2。
3. a kind of preparation side of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst according to claim 1
Method, it is characterised in that: the volumetric concentration of nitric acid solution used in step (1) is 10%.
4. a kind of preparation side of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst according to claim 1
Method, it is characterised in that: the digestion time is 12-24 hours.
5. a kind of preparation side of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst according to claim 1
Method, it is characterised in that: step (7) drying temperature is 80 DEG C, and maturing temperature is 550 DEG C, and calcining time is 3 hours.
6. a kind of preparation side of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst according to claim 1
Method, it is characterised in that: metal salt described in step (6) is manganese salt, molysite, cobalt salt, aluminium salt, cerium salt, magnesium salts or nickel salt, the manganese
Hydrochlorate is manganese nitrate, manganese sulfate, manganese acetate, manganese borate or manganese carbonate, Mn2+And Ti2+Molar ratio be 0.5% ~ 20%.
7. ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst made from any the method for claim 1-6.
8. application of the catalyst described in claim 7 in VOCs processing.
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| CN114177565A (en) * | 2021-11-30 | 2022-03-15 | 内蒙古中泰汇金环保科技有限公司 | Wet oxidation treatment method for low-content organic waste salt |
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