CN106238084A - The preparation method and application of visible ray synergy ozone catalytic degradation organic acid catalyst - Google Patents
The preparation method and application of visible ray synergy ozone catalytic degradation organic acid catalyst Download PDFInfo
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- 230000015556 catabolic process Effects 0.000 title claims abstract description 57
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 57
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 53
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 53
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 24
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 14
- 239000011363 dried mixture Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 10
- 239000012498 ultrapure water Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 114
- 235000006408 oxalic acid Nutrition 0.000 claims description 38
- 229910016978 MnOx Inorganic materials 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 6
- 150000004683 dihydrates Chemical class 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002079 cooperative effect Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- PASCVNXEVINGGG-UHFFFAOYSA-N Mollic acid Natural products CC(CCC=C(C)C)C1CCC2(C)C3CCC4C(C)(C(O)CC(O)C45CC35CCC12C)C(=O)O PASCVNXEVINGGG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- OQYYLGRLIXHSOB-UHFFFAOYSA-N ozone phenol Chemical compound [O-][O+]=O.OC1=CC=CC=C1 OQYYLGRLIXHSOB-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides the preparation method of a kind of visible ray synergy ozone catalytic degradation organic acid catalyst, comprise the following steps: step one, weigh manganese acetate and be dissolved in ultra-pure water, after stirring, add tripolycyanamide, obtain mixed solution；Step 2, is heated to mixed solution moisture while stirring and is evaporated and obtains mixture, is dried by mixture, obtains dried mixture；Step 3, calcines after dried mixture step 2 obtained grinding, the mixture after being calcined；Step 4, after the mixture after calcining step 3 obtained grinds, screening obtains catalyst.Use this catalyst to join in organic acid, be passed through ozone and under visible ray illumination condition the organic acid in catalytic degradation industrial wastewater, catalytic degradation efficiency is high, can effectively process the organic acid in industrial wastewater, it is adaptable to industrial applications.
Description
Technical field
The present invention relates to the preparation method and application of a kind of catalytic degradation organic acid catalyst.
Background technology
Being usually present certain density hardly degraded organic substance in industrial wastewater, these materials are through chemistry or biological treatment
After, generally produce the Organic substance of some little molecules, it is difficult to directly mineralising is CO2And H2O.The organic acid of little molecule is typically
Organic product after pollutant chemistry oxidation, its mesoxalic acid is the primary product of phenol ozone degradation.Oxalic acid and ozone molecule
The least (k < 0.04M of reaction rate constant-1s-1), but with OH radical reaction quickly (k ≈ 106M-1s-1).Therefore single
Only ozone oxidation is difficult to completely oxalic acid is converted into CO2With H2O, catalysis ozone has bigger compared to independent ozone oxidation
Degradation effect.
Additionally, ultraviolet catalytic oxidation has good effect in terms of the removal of pollutant, and and ozone oxidation between have
Well synergism.But, ultraviolet light ratio shared by sunlight is the least, and penetration power is the most weak, easily by air
Layer absorbs.Artificial ultraviolet source energy consumption in actual production process is the biggest, it is difficult to large-scale application.Therefore visible light catalytic neck
Territory becomes the focus of research, g-C3N4Chemical property is more stable, forbidden band is narrower, becomes the hot topic of photocatalysis field, g-C3N4Negative
Carry metal-oxide and can optimize g-C further3N4Catalytic effect, improve responsiveness to visible ray, before there is wide development
Scape.With metal oxide-loaded g-C3N4For catalyst, not yet appear in the newspapers at visible ray synergy ozone catalytic degradation water mesoxalic acid
Road.
Summary of the invention
The present invention is carried out for solving the problems referred to above, it is therefore intended that provide a kind of visible ray synergy ozone catalytic degradation
The preparation method and application of organic acid catalyst, carrys out the organic acid in catalytic degradation industrial wastewater effectively.
Present invention employs following technical scheme:
The invention provides the preparation method of a kind of visible ray synergy ozone catalytic degradation organic acid catalyst, its feature exists
In, comprise the following steps:
Step one, weighs manganese acetate and is dissolved in ultra-pure water, after stirring 5～10min, adds tripolycyanamide, is mixed
Solution；
Step 2, is heated to mixed solution moisture while stirring and is evaporated and obtains mixture, and mixture is put into temperature is
Dry under conditions of 80～120 DEG C, obtain dried mixture；
Step 3, dried mixture step 2 obtained is forged after grinding under conditions of temperature is 500～600 DEG C
Burn 3～5 hours, the mixture after being calcined；
Step 4, after the mixture after calcining step 3 obtained grinds, screening obtains catalyst.
In the preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of present invention offer, it is also possible to tool
Having such feature: wherein, catalyst is the oxide M nO of manganesexWith graphite type carbon nitride g-C3N4Complex MnOx/g-
C3N4。
In the preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of present invention offer, it is also possible to tool
Have such feature: wherein, in step one, the mass ratio of manganese acetate, ultra-pure water and tripolycyanamide be 1:80～100:5～
10。
In the preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of present invention offer, it is also possible to tool
There is such feature: wherein, the oxide M nO of manganesexThe value of middle X is 1～2.
In the preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of present invention offer, it is also possible to tool
Having such feature: wherein, in step one, manganese acetate is manganese acetate (III) dihydrate.
In the preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of present invention offer, it is also possible to tool
Having such feature: wherein, in step 4, the particle diameter of screening is 100 under Tyler standard screen scale～200 mesh.
It addition, present invention also offers the preparation method system of above-mentioned visible ray synergy ozone catalytic degradation organic acid catalyst
The application in catalytic degradation organic acid of the standby catalyst obtained.
In the above-mentioned catalyst application in catalytic degradation organic acid that the present invention provides, it is also possible to there is such spy
Levy: catalyst and visible ray, ozone cooperative effect carry out catalytic degradation to organic acid.
In the above-mentioned catalyst application in catalytic degradation organic acid that the present invention provides, it is also possible to there is such spy
Levy: catalyst is added to the organic acid soln that concentration is 40～120mg/L, is passed through ozone and under visible ray illumination condition
Organic acid in catalytic degradation water.
In the above-mentioned catalyst application in catalytic degradation organic acid that the present invention provides, it is also possible to there is such spy
Levy: organic acid is oxalic acid, it is seen that the wavelength of light is more than 400nm.
Invention effect and effect
The invention provides the preparation method and application of a kind of visible ray synergy ozone catalytic degradation organic acid catalyst, this
The preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst of invention is by manganese acetate, ultra-pure water and tripolycyanamide
Mixing, be evaporated by heating, dry, grind, calcine and the operation such as screening prepares catalyst MnOx/g-C3N4, preparation method
Simply, it is easy to operation, industrialized production is suitable to.
The application of the visible ray synergy ozone catalytic degradation organic acid catalyst of the present invention is by catalyst MnOx/g-C3N4Add
Enter in organic acid, be passed through ozone and under visible ray illumination condition the organic acid in catalytic degradation industrial wastewater, organic acid enters
Oxidation step is CO2And H2O, catalytic degradation efficiency is high, can effectively process the organic acid in industrial wastewater, it is adaptable to industrialization
Application.
Accompanying drawing explanation
Fig. 1 is the preparation of the visible ray synergy ozone catalytic degradation organic acid catalyst provided according to the embodiment of the present invention one
The catalyst MnO that method preparesx/g-C3N4X-ray diffractogram；And
Fig. 2 is the oxalic acid degradation effect figure during the present invention implements under different condition.
Detailed description of the invention
The system to the visible ray synergy ozone catalytic degradation organic acid catalyst of the present invention below in conjunction with embodiment and accompanying drawing
Preparation Method and application are further described.
Embodiment one prepares MnOx/g-C3N4Catalyst
The preparation method of the catalyst of the visible ray synergy ozone catalytic degradation organic acid that the present embodiment provides, including following
Step:
Step one, weighs manganese acetate (III) dihydrate (C of 0.4g6H13MnO8) and be dissolved in the ultra-pure water of 40ml, stir
After mixing 5min, add 4g tripolycyanamide, obtain mixed solution.
Step 2, is heated to mixed solution moisture while stirring and is evaporated and obtains mixture, and mixture is put into temperature is
The baking oven of 90 DEG C is dried, obtains dried mixture；
Step 3, dried mixture step 2 obtained is put in crucible the horse that temperature is 550 DEG C after grinding
Not calcining 4 hours, the mixture after being calcined in stove (ascending temperature is 10 DEG C/min)；
Step 4, at the screen cloth of 100 mesh (Tyler standard screen scale) after the mixture grinding after calcining step 3 obtained
Lower screening obtains MnOx/g-C3N4Catalyst.
Fig. 1 is the preparation method system of the visible ray synergy ozone catalytic degradation organic acid catalyst provided according to the present embodiment
The MnO obtainedx/g-C3N4X-ray diffractogram.
As it is shown in figure 1, at catalyst MnOx/g-C3N4In, the diffraction maximum in the double angle of diffraction 2 θ=27.6 ° correspond to g-
C3N4002 crystal face, other indicate diffraction maximum belong to JCPDS establishment numbered JCPDS80-
The Mn of 03823O4And Mn2O3, MnO is describedxMain with Mn3O4Form exists.
Embodiment two prepares MnOx/g-C3N4Catalyst
The preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst that the present embodiment provides, including following step
Rapid:
Step one, weighs manganese acetate (III) dihydrate (C of 0.4g6H13MnO8) and the ultra-pure water of molten 32ml in, stirring
After 10min, add 2g tripolycyanamide, obtain mixed solution.
Step 2, is heated to mixed solution moisture while stirring and is evaporated and obtains mixture, mixture is placed in temperature
It is that the baking oven of 80 DEG C is dried, obtains dried mixture.
Step 3, dried mixture step 2 obtained is put in crucible the horse that temperature is 500 DEG C after grinding
Not calcining 3 hours, the mixture after being calcined in stove (ascending temperature is 10 DEG C/min).
Step 4, at the screen cloth of 150 mesh (Tyler standard screen scale) after the mixture grinding after calcining step 3 obtained
Lower screening obtains MnOx/g-C3N4Catalyst.
Embodiment three prepares MnOx/g-C3N4Catalyst
The preparation method of the visible ray synergy ozone catalytic degradation organic acid catalyst that the present embodiment provides, including following step
Rapid:
Step one, weighs manganese acetate (III) dihydrate (C of 0.4g6H13MnO8) and be dissolved in the ultra-pure water of 36ml, stir
After mixing 8min, add 3.2g tripolycyanamide, obtain mixed solution.
Step 2, is heated to mixed solution moisture while stirring and is evaporated and obtains mixture, mixture is placed in temperature
It is that the baking oven of 120 DEG C is dried, obtains dried mixture.
Step 3, dried mixture step 2 obtained is put in crucible at the bar that temperature is 600 DEG C after grinding
Calcining 5 hours, the mixture after being calcined in the Muffle furnace (ascending temperature is 10 DEG C/min) of part.
Step 4, at the screen cloth of 200 mesh (Tyler standard screen scale) after the mixture grinding after calcining step 3 obtained
Lower screening obtains MnOx/g-C3N4Catalyst.
Embodiment four ozone oxidation degraded oxalic acid
Configuration concentration is that the oxalic acid solution of 80mg/L is (additionally, the concentration of oxalic acid solution can also be for 40mg/L and 120mg/
L, choosing optimal concentration is 80mg/L), and make its initial pH=3；Then, under the conditions of lucifuge, being passed through concentration is the smelly of 6mg/L
Oxygen, is that 5min, 10min, 20min, 40min and 60min sample and detect concentration of oxalic acid in the time of being passed through respectively.
Fig. 2 is the oxalic acid degradation effect figure during the present invention implements under different condition.
As in figure 2 it is shown, oxalic acid reaches 1.2% at 60min clearance under conditions of this experiment.
Embodiment five MnOx/g-C3N4Catalytic degradation oxalic acid
Configuration concentration is that the oxalic acid solution of 80mg/L is (additionally, the concentration of oxalic acid solution can also be for 40mg/L and 120mg/
And make its initial pH=3 L),；It is subsequently adding the MnO of 0.15g/Lx/g-C3N4Catalyst, under the conditions of lucifuge, is adding respectively
Time is that 5min, 10min, 20min, 40min and 60min sample and detect concentration of oxalic acid.
Result as in figure 2 it is shown, under conditions of this experiment oxalic acid reach 6.6% at 60min clearance.
Embodiment six visible ray (λ > 400nm) illumination degrading oxalic acid
Configuration concentration is that the oxalic acid solution of 80mg/L is (additionally, the concentration of oxalic acid solution can also be for 40mg/L and 120mg/
And make its initial pH=3 L),；Then under visible ray (λ > 400nm) illumination condition, respectively light application time be 5min,
10min, 20min, 40min and 60min sample and detect concentration of oxalic acid.
Result as in figure 2 it is shown, under conditions of this experiment oxalic acid reach 0.9% at 60min clearance.
Embodiment seven MnOx/g-C3N4Catalytic Ozonation oxalic acid
Configuration concentration is that the oxalic acid solution of 80mg/L is (additionally, the concentration of oxalic acid solution can also be for 40mg/L and 120mg/
And make its initial pH=3 L),；It is subsequently adding the MnO of 0.15g/Lx/g-C3N4Catalyst, being passed through concentration under the conditions of lucifuge is
The ozone of 6mg/L, is that 5min, 10min, 20min, 40min and 60min sample and to detect oxalic acid dense in light application time respectively
Degree.
Result as in figure 2 it is shown, under conditions of this experiment oxalic acid reach 86.3% at 60min clearance.
The collaborative lower MnO of embodiment eight visible rayx/g-C3N4Catalytic Ozonation oxalic acid
Configuration concentration is that the oxalic acid solution of 80mg/L is (additionally, the concentration of oxalic acid solution can also be for 40mg/L and 120mg/
And make its initial pH=3 L),；It is subsequently adding the MnO of 0.15g/Lx/g-C3N4Catalyst, irradiates under the xenon lamp of 300W, uses
Optical filter cuts off the light of below wavelength 400nm；Under visible ray (λ > 400nm) illumination condition, being passed through concentration is the smelly of 6mg/L
Oxygen, is that 5min, 10min, 20min, 40min and 60min sample and detect concentration of oxalic acid in the time respectively.
Result as in figure 2 it is shown, under conditions of this experiment oxalic acid reach 91.1% at 60min clearance, ratio implement seven degraded grass
Mollic acid is fast.
The effect of embodiment and effect
Embodiment one to embodiment eight provides the preparation side of a kind of visible ray synergy ozone catalytic degradation Catalyzed by Oxalic Acid agent
Method and application, what embodiment one to embodiment three provided the preparation method of visible ray synergy ozone catalytic degradation Catalyzed by Oxalic Acid agent
By the mixing of manganese acetate, ultra-pure water and tripolycyanamide, it is evaporated by heating, dries, grinds, calcines and the operation system such as screening
Obtain catalyst MnOx/g-C3N4, preparation method is simple, it is easy to operation, is suitable to industrialized production.
The application of the visible ray synergy ozone catalytic degradation Catalyzed by Oxalic Acid agent that embodiment four to embodiment eight provides, will catalysis
Agent MnOx/g-C3N4Join in oxalic acid, be passed through ozone and under visible ray illumination condition the grass in catalytic degradation industrial wastewater
Acid, compared to being individually passed through ozone degradation oxalic acid, being individually added into catalyst MnOx/g-C3N4, individually with visible ray illumination and urge
Agent MnOx/g-C3N4Catalytic Ozonation oxalic acid clearance is high, can the oxalic acid in catalytic degradation industrial wastewater effectively, suitable
For industrial applications.
The most in an embodiment of the present invention, use the xenon lamp of 300W to irradiate, compare and traditional ultraviolet source irradiation,
Breaking through higher, energy consumption is little, can large-scale application.
Above example is only the basic explanation under present inventive concept, does not limits the invention.And according to the present invention
Any equivalent transformation of being made of technical scheme, belong to protection scope of the present invention.
Claims (10)
1. the preparation method of a visible ray synergy ozone catalytic degradation organic acid catalyst, it is characterised in that include following step
Rapid:
Step one, weighs manganese acetate and is dissolved in ultra-pure water, after stirring 5～10min, adds tripolycyanamide, obtains mixed solution；
Step 2, is heated to described mixed solution moisture while stirring and is evaporated and obtains mixture, described mixture is put into temperature
Degree is dried under conditions of being 80～120 DEG C, obtains dried mixture；
Step 3, dried mixture step 2 obtained calcines 3 after grinding under conditions of temperature is 500～600 DEG C
～5 hours, the mixture after being calcined；
Step 4, after the mixture after calcining step 3 obtained grinds, screening obtains described catalyst.
The preparation method of visible ray synergy ozone catalytic degradation organic acid catalyst the most according to claim 1, its feature
It is:
Wherein, described catalyst is the oxide M nO of manganesexWith graphite type carbon nitride g-C3N4Complex MnOx/g-C3N4。
The preparation method of visible ray synergy ozone catalytic degradation organic acid catalyst the most according to claim 1, its feature
It is:
Wherein, in described step one, the mass ratio of described manganese acetate, described ultra-pure water and described tripolycyanamide be 1:80～
100:5～10.
The preparation method of visible ray synergy ozone catalytic degradation organic acid catalyst the most according to claim 2, its feature
It is:
Wherein, the oxide M nO of described manganesexThe value of middle X is 1～2.
The preparation method of visible ray synergy ozone catalytic degradation organic acid catalyst the most according to claim 1, its feature
It is:
Wherein, in described step one, described manganese acetate is manganese acetate (III) dihydrate.
The most according to claim 1, the preparation method of visible ray synergy ozone catalytic degradation organic acid catalyst, its feature exists
In:
Wherein, in described step 4, the particle diameter of described screening is 100 under Tyler standard screen scale～200 mesh.
7. the preparation of the visible ray synergy ozone catalytic degradation organic acid catalyst as described in any one in claim 1～6
The catalyst that method prepares application in catalytic degradation organic acid.
8. according to the application in catalytic degradation organic acid of the catalyst described in claim 7, it is characterised in that:
Described catalyst and visible ray, ozone cooperative effect carry out catalytic degradation to organic acid.
9. according to the application in catalytic degradation organic acid of the catalyst described in claim 7, it is characterised in that:
Described catalyst is added to the organic acid soln that concentration is 40～120mg/L, is passed through ozone and in visible ray illumination
Under the conditions of organic acid in catalytic degradation water.
10. according to the application in catalytic degradation organic acid of the catalyst described in claim 7, it is characterised in that:
Wherein, described organic acid is oxalic acid, and the wavelength of described visible ray is more than 400nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610538635.6A CN106238084B (en) | 2016-07-11 | 2016-07-11 | The preparation method and application of visible light synergy ozone catalytic degradation organic acid catalyst |
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| CN106861746A (en) * | 2017-03-22 | 2017-06-20 | 北京师范大学 | A kind of carbonitride loads the preparation method of single dispersing oxidation state metal atom catalysis material |
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| CN111889129A (en) * | 2020-07-30 | 2020-11-06 | 大连工业大学 | Preparation of ultrathin porous nano carbon nitride photocatalyst and application of ultrathin porous nano carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of fructose |
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