CN106430759A - Method for treating organic wastewater by catalyzing persulfate through microwave-ultraviolet coupling - Google Patents
Method for treating organic wastewater by catalyzing persulfate through microwave-ultraviolet coupling Download PDFInfo
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- CN106430759A CN106430759A CN201610920449.9A CN201610920449A CN106430759A CN 106430759 A CN106430759 A CN 106430759A CN 201610920449 A CN201610920449 A CN 201610920449A CN 106430759 A CN106430759 A CN 106430759A
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- Prior art keywords
- microwave
- persulfate
- ultraviolet
- organic wastewater
- coupling
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 54
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000010168 coupling process Methods 0.000 title claims abstract description 40
- 230000008878 coupling Effects 0.000 title claims abstract description 39
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 39
- 230000015556 catabolic process Effects 0.000 claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 claims abstract description 40
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 45
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 39
- 229940043267 rhodamine b Drugs 0.000 claims description 39
- 238000004065 wastewater treatment Methods 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 claims description 9
- -1 quinone imides Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000010815 organic waste Substances 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001454 anthracenes Chemical class 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 239000012425 OXONE® Substances 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 2
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000001994 activation Methods 0.000 abstract description 14
- 230000004913 activation Effects 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 239000003344 environmental pollutant Substances 0.000 description 16
- 231100000719 pollutant Toxicity 0.000 description 16
- 238000003918 potentiometric titration Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 9
- 230000005855 radiation Effects 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000004060 quinone imines Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-N sodium;sulfurous acid Chemical compound [Na+].OS(O)=O DWAQJAXMDSEUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating organic wastewater by catalyzing persulfate through microwave-ultraviolet coupling, which comprises the following steps; adding persulfate into organic wastewater, placing the organic wastewater containing persulfate into a container inside a microwave generating device, arranging an ultraviolet light generating device in the container, starting the microwave generating device, exciting the ultraviolet light generating device by microwaves, and degrading the organic wastewater under the action of microwave and ultraviolet light coupling catalytic activation of persulfate. The invention adopts a microwave-ultraviolet light coupling method to catalytically activate persulfate to generate sulfate radicals, forms an oxidation system based on the sulfate radicals, can effectively degrade organic pollutants in wastewater, has no metal ions dissolved out in the catalytic activation process, avoids secondary pollution, has higher degradation efficiency on organic matters in the wastewater under acidic, neutral and alkaline conditions, and realizes the stable treatment of the wastewater under various pH values.
Description
Technical field
The invention belongs to a kind of field of waste water treatment, more particularly to microwave-ultraviolet coupling and catalyzing persulfate process is organic
The method of waste water.
Background technology
At present, China's industrial wastewater pollution phenomenon is serious, and main is water pollution, in national 500 a plurality of trunk rivers
Central, having more than 80% different degrees of pollution to be received because of the discharge of industrial wastewater, flows through national more than 40 big city
River, have more than 90% to be contaminated, with healthy, large effect generated to social environment and the life of resident.Its
In, papermaking and paper products industry total emission volumn account for the largest percentage, and are 39.3 hundred million tons, account for 1/5 of total emission volumn or so, and only secondary has
Chemical raw material and chemical product manufacturing, textile, the production and supply industry of electric power heating power etc., were wherein produced by printing and dyeing enterprise
The impact brought by dyeing waste water produced by journey can not be ignored, due to the raw material that is processed, the kind of product, the technique of processing
With the difference of processing mode, the composition of waste water and qualitative change be also very big, therefore living zone of the presence of dyeing waste water to the mankind
Carry out very big potential safety hazard.
There is the organic polluting water of high toxicity and difficult degradation for those, conventional waste water treatment technology is for example：Physical, change
Learn oxidizing process, chemical electrolysis method, physical-chemical process, bioanalysises etc. to be all difficult to processing requirement is reached, therefore cause quality of water environment
Drastically decline；Further, since the presence of part physical stable chemical nature material so that only using with powerful oxidability
Oxidant, could thorough degradation of contaminant, thus promote the development of high-level oxidation technology.High-level oxidation technology (AOPS) is
Through developing into the mature technology for processing hardly degraded organic substance in drinking water and industrial wastewater etc. because its have organic or
Inorganic pollution is upright to connect mineralising or by aoxidizing the biodegradability for improving sewage, and applied widely, oxidability is strong, reaction
The features such as speed is fast.Traditional AOPS be all with active specy hydroxyl radical free radical (.OH, E0=1.8v-2.7v) carry out pollution degradation
Material.Hydroxyl radical free radical can rapidly and also non-selectivity degraded majority of organic pollutants.But due to.OH is to environmental requirement
Higher, need to carry out oxidation stain thing in acid condition, therefore which receives local material (carbonate, bicarbonate, day in the application
Right Organic substance etc.) impact is larger.
Content of the invention
For the problems referred to above of the prior art, present invention is primarily targeted at provide a kind of microwave-ultraviolet coupling urging
The method for changing organic wastewater treatment through persulfate, defines the oxidation system based on potentiometric titrations, effectively can degrade
Organic pollution in waste water, and under acidic, neutral and alkaline conditions, to the organic matter degradation efficiency in waste water all relatively
High, it is achieved that the stabilized treatment of waste water in the case of multiple pH value.
In order to achieve the above object, the present invention is adopted the following technical scheme that：A kind of microwave-ultraviolet coupling and catalyzing persulfate
The method for processing organic wastewater, comprises the steps：
Persulfate is added in organic wastewater；
In the container that organic wastewater containing persulfate is placed in inside microwave generating apparatus；
Ultraviolet light generating apparatus are set in the container；
The microwave generating apparatus are opened, the ultraviolet light generating apparatus of microwave-excitation, live with ultraviolet light coupling and catalyzing in microwave
Change degradation of organic waste water in the presence of persulfate.
Used as further preferably, the persulfate is selected from sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate., single persulfuric acid
Hydrogen sodium and Potassium Monopersulfate.
As further preferred, comprising Anthraquinones, quinone imides, oxa anthracenes and azo in the organic wastewater
Organic pollution in one or more.
As further, preferably, the organic pollution is selected from reactive brilliant bule, methylene blue, rhodamine B, reactive brilliant red
And methyl orange.
Used as further preferably, in the reaction system, persulfate is 1.25 with the mass ratio of organic pollution：1～
7.5：1.
Used as further preferably, in the reaction system, sodium peroxydisulfate is 100 with the mass ratio of rhodamine B：17.5.
As further, preferably, the microwave generating apparatus include microwave oven, and the ultraviolet generation device includes ultraviolet
Fluorescent tube.
As further, preferably, the ultraviolet light is produced by microwave radiation ultraviolet lamp tube.
As further, preferably, the ultraviolet lamp tube is placed in the reaction system.
Used as further preferably, the microwave irradiation time is 2-60min.
Used as further preferably, the temperature of the reaction system is 10-70 DEG C.
Used as further preferably, the pH value of the reaction system is 3-11.
The invention has the beneficial effects as follows：
(1) present invention is using the method for microwave-ultraviolet coupling, and catalytic activation persulfate produces potentiometric titrations,
The more single activation method of potentiometric titrations conversion ratio is in hgher efficiency, at the same also have hydroxyl radical free radical and super oxygen cloudy in the system from
Other species free radicals such as son, singlet oxygen, form the oxidation system based on potentiometric titrations, and the oxidation system is permissible
Organic substance in effective degradation of organic waste water.And under acidic, neutral and alkaline conditions, the organic pollution in waste water drops
Solution efficiency is all higher, it is achieved that the stabilized treatment of waste water in the case of multiple pH value, it is not necessary to be further appreciated that pH value of waste water, saves
Substantial amounts of processing cost.
(2) present invention is using the method catalytic activation persulfate of microwave and ultraviolet coupling, the activation process no metal from
Son or the utilization of other catalyst, so the dissolution such as metal ion without metal ion or catalyst, will not be in waste water
Extra increase pollutant sources.
(3) in the present invention, ultraviolet light is produced by microwave radiation electrodeless ultraviolet lamp, so without the need for additional energy and power circuit,
Equipment is simple, light source durable energy stable operation more than 80000 hours.
(4) present invention is using microwave and the method catalytic activation persulfate of ultraviolet coupling, oxidation system adaptability itself
Relatively strong, common anion (Cl-、SO4 2-、NO3 -、HCO3 -、HPO4 2-) the treatment effeciency impact of (0-30mmol/L) on pollutant
Less, the presence of anionic part can even improve the treatment effeciency of organic pollution, so answering to polyanionic presence
Miscellaneous treatment of Organic Wastewater efficiency is higher.
(5) microwave itself has heat effect to waste water, and in waste water system, higher temperature is more beneficial for potentiometric titrations
Conversion, waste water treatment efficiency is higher, so the present invention is relatively broad to wastewater temperature subject range.
(6) present invention is also produced to the pollutant in waste water using microwave and ultraviolet while acting on to persulfate
Effect, make organic pollution is easier degraded, so as to improve the treatment effeciency of Organic Pollutants in Wastewater.
Description of the drawings
Fig. 1 shows for the flow process of the method for embodiment of the present invention microwave-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate
It is intended to.
Fig. 2 is for the differential responses time in 1 microwave of the embodiment of the present invention/ultraviolet/sodium peroxydisulfate system to rhodamine B degradation
The schematic diagram of impact.
Fig. 3 is the schematic diagram of impact of the different pH value of 1 reaction system solution of the embodiment of the present invention to rhodamine B degradation.
Fig. 4 is the schematic diagram of impact of the pollutant levels to degradation effect in the embodiment of the present invention 1.
Fig. 5 is the pollutant of 2 microwave of the embodiment of the present invention/ultraviolet/potassium persulfate oxidation system degraded different molecular configuration
Situation schematic diagram.
Fig. 6 is the schematic diagram of impact of the persulfate concentration to rhodamine B degradation in the embodiment of the present invention 2.
Fig. 7 is the schematic diagram of impact of the temperature of reaction system in the embodiment of the present invention 3 to degradation of contaminant.
Specific embodiment
The present invention passes through to provide a kind of method of microwave-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, using micro-
The method of ripple-ultraviolet optical coupling, catalytic activation persulfate produces potentiometric titrations, defines with potentiometric titrations as base
The oxidation system of plinth, organic pollution that can be effectively in degrading waste water, and under acidic, neutral and alkaline conditions, to waste water
In organic matter degradation efficiency all higher, it is achieved that the stabilized treatment of waste water in the case of multiple pH value.Solve prior art
In due to hydroxyl radical free radical higher to environmental requirement, need to carry out the defect of oxidation stain thing in acid condition.
The method of embodiment of the present invention microwave-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, as shown in figure 1, bag
Include following steps：
Step S01:Persulfate is added in organic wastewater；
Step S02:In the container that organic wastewater containing persulfate is placed in inside microwave generating apparatus；
Step S03:Ultraviolet light generating apparatus are set in the container；
Step S04:The microwave generating apparatus are opened, the ultraviolet light generating apparatus of microwave-excitation, in microwave and ultraviolet optocoupler
Close degradation of organic waste water in the presence of catalytic activation persulfate.
In order to be better understood from technique scheme, below in conjunction with Figure of description and specific embodiment to upper
State technical scheme to be described in detail.
Embodiment 1
The method of 1 microwave of the embodiment of the present invention-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, walks including following
Suddenly：
Step S01:Organic wastewater comprising rhodamine B and sodium peroxydisulfate solution are prepared respectively, in having comprising rhodamine B
A certain amount of sodium peroxydisulfate solution is added in the container of machine waste water as reaction system；
The process for preparation of the organic wastewater is as follows：
Accurately weigh 5.000g rhodamine B to be positioned in small beaker, use ultrapure water dissolution, to be dissolved completely after, be transferred to
In 1L volumetric flask, plus appropriate ultra-pure water, then place and be stirred on stirring instrument, to be mixed be uniformly dissolved after, then use ultra-pure water
Dilution is settled to graduation mark, shakes up, and is configured to concentration for 5g L-1Rhodamine B pollutant storing solution；
The process for preparation of the sodium peroxydisulfate solution is as follows：
10.000g sodium peroxydisulfate (Na is accurately weighed2S2O8) be positioned in small beaker, with being transferred to 1L after ultrapure water dissolution
Volumetric flask in, then be settled to scale with ultra-pure water dilution, shake up, be configured to concentration for 10g L-1Sodium peroxydisulfate
(Na2S2O8) storing solution.
Step S02:The container for accommodating the reaction system is placed in microwave oven internal；
Step S03:Ultraviolet lamp tube is placed in the reaction system of microwave oven internal；The ultraviolet light is by microwave radiation
Ultraviolet lamp tube is produced.
Step S04:Microwave oven and ultraviolet lamp tube is opened, microwave catalysis and ultraviolet catalytic are carried out to the reaction system.
The microwave oven output power is set as 460w or so, and the microwave irradiation time is 0-60min.
In order to obtain the effect of microwave ultraviolet coupling and catalyzing sodium peroxydisulfate degradable organic pollutant, embodiment 1 is carried out
Following series of experiments is proved：
Test 1：Impact of the different time of microwave/ultraviolet coupling and catalyzing to rhodamine B degradation
Using the process method step rhodamine B degradation of embodiment 1, the initial concentration of rhodamine B in the reaction system
For 40mg/L and sodium peroxydisulfate initial concentration be 200mg/L, in 1 processing procedure of embodiment, every 2min, 5min,
10min, 20min, 30min, 40min, 60min timing sampling 2.00ml, and with 2ml 0.5mol L-1Sodium sulfite
(Na2S2O3) solution be quenched react for absorbance measure.The degraded situation of pollutant rhodamine B is as shown in Figure 2.C is reaction
During rhodamine B concentration value, C0Concentration value for rhodamine B in primary response system.
1 graphical results of above-mentioned test show：1 microwave of the present embodiment/ultraviolet/sodium peroxydisulfate system (MW/UV+PS) is to Luo Dan
The degradation effect of bright B is projected, in 60min, it is possible to almost 100% rhodamine B degradation.This is because the presence of microwave
Reaction activity is reduced, is accelerated reaction rate and selectivity is enhanced, ultraviolet therefore, it is possible to couple in the shorter time
Photoactivation persulfate produces more potentiometric titrations, reaches the effect of fast degradation rhodamine B.
Test 2：Impact of the different pH value of reaction system solution to rhodamine B degradation
Using the process method step rhodamine B degradation of embodiment 1, the initial concentration of rhodamine B in the reaction system
It is 200mg/L for the initial concentration of 40mg/L and sodium peroxydisulfate, the low-concentration sulfuric acid after the dilution and low-concentration hydrogen oxidation
Sodium adjusts the original ph of reaction system, makes every secondary response pH be close to 3,5,7,9 and 11 respectively.Different pH value are dropped to rhodamine B
The impact of solution is as shown in Figure 3.
2 graphical results of above-mentioned test show：In acid condition, 60min almost can be corresponding with 100% rhodamine B degradation
Alkalescence condition under pH=10.96 when, the degradation rate of 60min rhodamine B also reaches 80%, the increasing being on the one hand because with pH
Plus potentiometric titrations start to decompose and are transformed into hydroxyl radical free radical；On the other hand, as potentiometric titrations are in acid condition
Under more stable, in system main active specy be potentiometric titrations.But pH value is to this between pH value 3.03 to 9.03
The impact of system rhodamine B degradation is little, and when pH is 9.03 to 10.96, degradation efficiency has somewhat declined, but general effect
70% or so can be also reached, the test 2 confirms that 1 microwave of embodiment/ultraviolet/sodium peroxydisulfate oxidation system adapts to relatively to pH scope
Extensively, in acidity to all there is better effects between alkalescence.
Test 3：Impact of the pollutant levels to degradation effect
Degraded using the process method step of embodiment 1, test 3 is provided with the L from 35 to 60mg-1The concentration of rhodamine B
Gradient, measures the change of 60min time internal absorbance.The initial concentration of sodium peroxydisulfate is=200mg/L, T=28 ± 1.5 DEG C,
Experimental result is as shown in Figure 4.
Shown in Fig. 4 test result indicate that, rhodamine B concentration is higher, and degradation rate reduces therewith, is primarily due to necessarily dense
The persulfate of degree is limited to the degradation rate of rhodamine B, after rhodamine B concentration increases, the SO4- that persulfate is produced
Concentration seem less, so as to degradation rate reduce.But generally speaking, 200mg L-1Sodium peroxydisulfate is to 35mg L-1Rhodamine
B degradation effect is optimal, and during 60min, percent of decolourization reaches 99%.
Embodiment 2
The method of 2 microwave of the embodiment of the present invention-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, walks including following
Suddenly：
Step S01:Organic wastewater comprising pollutant and potassium persulfate solution are prepared respectively, comprising the organic of pollutant
A certain amount of potassium persulfate solution is added in the container of waste water as reaction system；
The process for preparation similar embodiment 1 of the organic wastewater and the potassium persulfate solution, repeats no more.
Step S02:The container for accommodating the reaction system is placed in microwave furnace bottom；
Step S03:Ultraviolet lamp tube is placed in the reaction system of microwave oven internal；The ultraviolet light is by microwave radiation
Ultraviolet lamp tube is produced.
Step S04:Microwave oven and ultraviolet lamp tube is opened, microwave catalysis and ultraviolet catalytic are carried out to the reaction system.
The microwave oven output power is set as 700w or so, and the microwave irradiation time is 0-60min.
In order to obtain the effect of microwave ultraviolet coupling and catalyzing potassium peroxydisulfate degradable organic pollutant, embodiment 2 is carried out
Following series of experiments is proved：
Test 4：The situation of the pollutant of 2 microwave of embodiment/ultraviolet/potassium persulfate oxidation system degraded different molecular configuration
In step S01, reactive brilliant bule with anthraquinone ring, the methylene blue of quinone imines structure, oxa anthracenes are chosen
The reactive brilliant red and methyl orange of rhodamine B and azo is used as simulating pollution thing, and potassium peroxydisulfate initial concentration is 200mg/L,
± 1.5 DEG C of above-mentioned five kinds of pollutant initial concentration 20mg/L, T=33, sample time is inconsistent, other operating conditions such as embodiment
1, degradation effect result is as shown in Figure 5.
As shown in figure 5, the rate of contaminant degradation of different molecular configuration has differences, reactive brilliant red is in 3.5min percent of decolourization
96% is just reached, overall description, this experimental system is degraded all effective to multiple pollutant.
Test 5：Impact of the persulfate concentration to rhodamine B degradation
Using the process method step rhodamine B degradation of embodiment 1,50 are added to arrive 500mg L-1The concentration of sodium peroxydisulfate
Gradient, measures the change of 60min time internal absorbance, and the initial concentration of rhodamine B is ± 1.5 DEG C of 40mg/L, T=28.Add
The impact that the sodium peroxydisulfate of variable concentrations is degraded to rhodamine B is as shown in Figure 6.
As can be seen from Figure 6, sodium peroxydisulfate concentration is higher, and rhodamine B degradation rate is bigger, because sodium peroxydisulfate is in microwave coupling
Close under ultraviolet catalytic, the SO of generation4 -Increase with sodium peroxydisulfate concentration and increase, therefore oxidation efficiency also can increase therewith.Real
When testing 60min, the poor 50mg L of effect-1Sodium peroxydisulfate has 74.6% to rhodamine B percent of decolourization, and effect is best
500mg·L-1Sodium peroxydisulfate has 99.1% to rhodamine B percent of decolourization, but which is also only than 300mg L-1Sodium peroxydisulfate is to rhodamine
B percent of decolourization 98.7% has more 0.4%, and 300mg L is described-1Sodium peroxydisulfate degraded 40mg L-1Rhodamine B has been nearly in full
And state, as sodium peroxydisulfate concentration increases, rhodamine B degradation rate is increased more and more little.
Embodiment 3
The method of 3 microwave of the embodiment of the present invention-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, walks including following
Suddenly：
Step S01:Organic wastewater comprising reactive brilliant red and Ammonium Persulfate 98.5 solution are prepared respectively, comprising rhodamine B
A certain amount of Ammonium Persulfate 98.5 solution is added in the container of organic wastewater as reaction system；
The organic wastewater and the process for preparation similar embodiment 1 of the Ammonium Persulfate 98.5 solution, repeat no more.
Step S02:The container for accommodating the reaction system is placed in microwave furnace bottom；
Step S03:Ultraviolet lamp tube is placed in the reaction system of microwave oven internal；The ultraviolet light is by microwave radiation
Ultraviolet lamp tube is produced.
Step S04:Microwave oven and ultraviolet lamp tube is opened, microwave catalysis and ultraviolet catalytic are carried out to the reaction system.
The microwave oven output power is set as 600w or so, and the microwave irradiation time is 0-60min.
In order to obtain the effect of microwave ultraviolet coupling and catalyzing potassium peroxydisulfate degradable organic pollutant, embodiment 3 is carried out
Following series of experiments is proved：
Test 6：Impact of the reaction temperature to degradation of contaminant
Degraded using the process method step of embodiment 3, the concentration of the initial Ammonium persulfate. of reaction system is 200mg/L, just
The concentration of beginning reactive brilliant red is 40mg/L, is to investigate the impact that temperature is degraded to reactive brilliant red, and this test 6 is selected at 28-68 DEG C
Temperature range carry out.Result of the test is as shown in Figure 7.
Result of the test shows, the rising of temperature has obvious facilitation to the degraded of reactive brilliant red.When temperature reaches 68
DEG C, reactive brilliant red is just substantially completely degraded in 20min, and percent of decolourization is up to 99.4%, and when temperature only has 28 DEG C, experiment proceeds to
60min, percent of decolourization also has 98.6%.It can thus be seen that temperature to react carrying out have significant facilitation, mainly because
For the SO that persulfate is produced4 -, in the presence of the rising of temperature, higher thermal activation energy, it is more easily broken off O -- O bond,
So that reaction process is substantially accelerated.
Embodiment 4
The method of 4 microwave of the embodiment of the present invention-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, walks including following
Suddenly：
Step S01:Organic wastewater comprising reactive brilliant bule and monopersulfate sodium solution are prepared respectively, gorgeous comprising activity
A certain amount of monopersulfate sodium solution is added as reaction system in the container of blue organic wastewater；Single described in reaction system
Hydrogen persulfate na concn is 200mg L-1Sodium peroxydisulfate, the concentration of the reactive brilliant bule is 40mg L-1.
The organic wastewater and the process for preparation similar embodiment 1 of the monopersulfate sodium solution, repeat no more.
Step S02:The container for accommodating the reaction system is placed in microwave furnace bottom；
Step S03:Ultraviolet lamp tube is placed in the reaction system of microwave oven internal；The ultraviolet light is by microwave radiation
Ultraviolet lamp tube is produced.
Step S04:Microwave oven and ultraviolet lamp tube is opened, microwave catalysis and ultraviolet catalytic are carried out to the reaction system.
The microwave oven output power is set as 650w or so, and the microwave irradiation time is 0-60min.
In processing procedure, timing sampling determines reactive brilliant bule absorbance, as a result shows, in 4 reaction system of the embodiment of the present invention
The degradation effect of reactive brilliant bule is projected.
The embodiment of the present application 1-4 can control the temperature of reaction system solution by water-bath or other thermostats；Separately
Outward, in order to confirm the effect of microwave-ultraviolet coupling and catalyzing, need to exclude the effect of the promotion degraded that the elevated factor of temperature is brought
When, reaction system for example can be made temperature will not to raise because of the heating of microwave radiation by outer heating/cooling device, so as to come
The factor that individually consideration microwave-ultraviolet coupling and catalyzing is activated.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
(1) present invention is using the method for microwave-ultraviolet coupling, and catalytic activation persulfate produces potentiometric titrations,
The more single activation method of potentiometric titrations conversion ratio is in hgher efficiency, at the same also have hydroxyl radical free radical and super oxygen cloudy in the system from
Other species free radicals such as son, singlet oxygen, form the oxidation system based on potentiometric titrations, and the oxidation system is permissible
Organic substance in effective degradation of organic waste water.And under acidic, neutral and alkaline conditions, the organic pollution in waste water drops
Solution efficiency is all higher, it is achieved that the stabilized treatment of waste water in the case of multiple pH value, it is not necessary to be further appreciated that pH value of waste water, saves
Substantial amounts of processing cost.
(2) present invention is using the method catalytic activation persulfate of microwave and ultraviolet coupling, the activation process no metal from
Son or the utilization of other catalyst, so the dissolution such as metal ion without metal ion or catalyst, will not be in waste water
Extra increase pollutant sources.
(3) in the present invention, ultraviolet light is produced by microwave radiation electrodeless ultraviolet lamp, so without the need for additional energy and power circuit,
Equipment is simple, light source durable energy stable operation more than 80000 hours.
(4) present invention is using microwave and the method catalytic activation persulfate of ultraviolet coupling, oxidation system adaptability itself
Relatively strong, common anion (Cl-、SO4 2-、NO3 -、HCO3 -、HPO4 2-) the treatment effeciency impact of (0-30mmol/L) on pollutant
Less, the presence of anionic part can even improve the treatment effeciency of organic pollution, so answering to polyanionic presence
Miscellaneous treatment of Organic Wastewater efficiency is higher.
(5) microwave itself has heat effect to waste water, and in waste water system, higher temperature is more beneficial for potentiometric titrations
Conversion, waste water treatment efficiency is higher, so the present invention is relatively broad to wastewater temperature subject range.
(6) present invention is also produced to the pollutant in waste water using microwave and ultraviolet while acting on to persulfate
Effect, make organic pollution is easier degraded, so as to improve the treatment effeciency of Organic Pollutants in Wastewater.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation
Property concept, then can make other change and modification to these embodiments.So, claims are intended to be construed to include excellent
Select embodiment and fall into being had altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out the essence of various changes and modification without deviating from the present invention to the present invention
God and scope.So, if these modifications of the present invention and modification belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising these changes and modification.
Claims (9)
1. the method for a kind of microwave-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, it is characterised in that：Methods described bag
Include：
Persulfate is added in organic wastewater；
In the container that organic wastewater containing persulfate is placed in inside microwave generating apparatus；
Ultraviolet light generating apparatus are set in the container；
The microwave generating apparatus are opened, the ultraviolet light generating apparatus of microwave-excitation, activated with ultraviolet light coupling and catalyzing in microwave
Degradation of organic waste water in the presence of sulfate.
2. the method for microwave according to claim 1-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The persulfate is selected from sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate., monopersulfate sodium and Potassium Monopersulfate.
3. the method for microwave according to claim 1-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：One kind in organic pollution comprising Anthraquinones, quinone imides, oxa anthracenes and azo in the organic wastewater or
Multiple.
4. the method for microwave according to claim 3-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The organic pollution is selected from reactive brilliant bule, methylene blue, rhodamine B, reactive brilliant red and methyl orange.
5. the method for microwave according to claim 3-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：In the reaction system, persulfate is 1.25 with the mass ratio of organic pollution：1～7.5：1.
6. the method for microwave according to claim 1-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The microwave generating apparatus include microwave oven, and the ultraviolet generation device includes ultraviolet lamp tube；The ultraviolet light is by microwave spoke
Penetrate ultraviolet lamp tube generation.
7. the method for microwave according to claim 6-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The microwave irradiation time is 2-60min.
8. the method for microwave according to claim 1-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The temperature of the reaction system is 10-70 DEG C.
9. the method for microwave according to claim 1-ultraviolet coupling and catalyzing organic wastewater treatment through persulfate, its feature exists
In：The pH value of the reaction system is 3-11.
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| CN107410353A (en) * | 2017-06-27 | 2017-12-01 | 山东普锐医用科技有限公司 | Hospital Sewage Treatment Potassium Monopersulfate composite disinfectant |
| CN109319879A (en) * | 2018-10-15 | 2019-02-12 | 江苏理工学院 | A method of activation persulfuric acid hydrogen salt degradation Organic substance in water |
| CN110282695A (en) * | 2019-07-31 | 2019-09-27 | 上海应用技术大学 | A kind of method that ultraviolet/chlorine group technology removes phenylurea analog herbicide isoproturon in water removal |
| CN110523358A (en) * | 2019-08-28 | 2019-12-03 | 清华大学 | A kind of method of ultraviolet coupling peroxy-monosulfate removal tributyl phosphate |
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| CN112939164A (en) * | 2021-03-15 | 2021-06-11 | 广西大学 | Novel disinfection method for marine aquaculture water body |
| CN113666451A (en) * | 2021-07-28 | 2021-11-19 | 浙江工业大学 | Method for efficiently degrading micro-pollutant saccharin in water by activating persulfate |
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| CN107410353A (en) * | 2017-06-27 | 2017-12-01 | 山东普锐医用科技有限公司 | Hospital Sewage Treatment Potassium Monopersulfate composite disinfectant |
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| CN110282695A (en) * | 2019-07-31 | 2019-09-27 | 上海应用技术大学 | A kind of method that ultraviolet/chlorine group technology removes phenylurea analog herbicide isoproturon in water removal |
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| CN111533210A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Method for treating dye wastewater by using UV (ultraviolet) to heat and activate persulfate |
| CN112939164A (en) * | 2021-03-15 | 2021-06-11 | 广西大学 | Novel disinfection method for marine aquaculture water body |
| CN112939164B (en) * | 2021-03-15 | 2022-05-24 | 广西大学 | Method for disinfecting marine aquaculture water |
| CN113666451A (en) * | 2021-07-28 | 2021-11-19 | 浙江工业大学 | Method for efficiently degrading micro-pollutant saccharin in water by activating persulfate |
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