CN110127836A - A method of utilizing magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt - Google Patents
A method of utilizing magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt Download PDFInfo
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- CN110127836A CN110127836A CN201910519149.3A CN201910519149A CN110127836A CN 110127836 A CN110127836 A CN 110127836A CN 201910519149 A CN201910519149 A CN 201910519149A CN 110127836 A CN110127836 A CN 110127836A
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- organic wastewater
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- 150000003839 salts Chemical class 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 39
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 13
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000010815 organic waste Substances 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 12
- 229960004643 cupric oxide Drugs 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 239000002086 nanomaterial Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- -1 hydroxyl radical free radical Chemical class 0.000 abstract 1
- 238000003918 potentiometric titration Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 description 10
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- 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 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013319 spin trapping Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/33—Electric or magnetic 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- 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
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of methods using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt, belong to technical field of water pollution control.The magnetic oxygenated copper catalyst activation peroxy-monosulfate of this method using a step facile syntheesis, which generates, has the singlet oxygen of strong oxidizing property as active oxidation kind, so that the hardly degraded organic substance in high salt organic waste water be removed.Compared with the peroxy-monosulfate water treatment technology to generate potentiometric titrations and hydroxyl radical free radical, the singlet oxygen that this method generates is less susceptible to the influence of inorganic salts in water, and catalyst activity is stronger, is more advantageous to the processing of salt-containing organic wastewater.The method that the present invention establishes is suitable for the processing of a variety of salt-containing organic wastewaters, removal organic polluter can be efficiently removed within the scope of wider pH, method for preparing catalyst is simple and convenient to operate, cheap, it is easy to Magneto separate, there is very big application potential in salt-containing organic wastewater process field.
Description
Technical field
The invention belongs to technical field of water pollution control, and in particular to a kind of to be activated using magnetic oxygenated copper (Mag-CuO)
The method of the high salt organic waste water of peroxy-monosulfate (PMS) processing.
Background technique
The discharge of brine waste is generally existing in the industrial production, for example, printing and dyeing, food processing, papermaking, herding, cleaning plus
The industries such as work.In general, the salt content of brine waste is at least 1%, and it is high slat-containing wastewater that salt content, which is higher than 3.5%,.
In these waste water other than the inorganic salts ingredients such as the sodium chloride containing high concentration, sulfate, phosphate, nitrate, there are also a large amount of
Hardly degraded organic substance, such as dyestuff, insecticide, antibiotic, synthetic complexing agent etc., so as to cause traditional biologic treating technique
Huge difficulty is faced with when administering such waste water with materializing strategy technology.
Nearest decades can generate strong oxidative free radical (SO4 ·-And HO·) high-level oxidation technology obtained rapid hair
Exhibition, it is considered to be handle the effective means of persistent organic pollutants.However·OH and SO4 ·-Do not have to most organic pollutants
Selectivity, and it is highly susceptible to the influence of water quality characteristic, when being particularly present a large amount of inorganic salt anionic, to cause free radical
Consumption for no reason, waste medicament.In recent years singlet oxygen (1O2) used extensively as a kind of non-free radical active oxidation kind
Carry out the inactivation of selective removal organic pollutant and pathogenic bacteria.1O2It, can be quick as a kind of medium reactive electrophilic daughter
Electron rich functional group is aoxidized, is optionally removed the lower pollutant of concentration, while less sensitive to the background component in waste water.
Therefore, it utilizes1O2The pollutant removal handled in salt-containing organic wastewater is a kind of effective approach.
Peroxy-monosulfate (PMS) is as a kind of efficient, stable oxidant, and PMS is in addition to the generation of free radical pathway activation
SO4 ·-And HO·In addition, it can also be activated by non-free radical approach, to generate singlet oxygen.Ultrasound, photodissociation, heating, mistake
Degree metal ion and oxide etc. can activate PMS, but most of PMS activation is found by free radical approach
Method based on non-free radical pathway activation PMS is necessary.
Based on this, pass through non-free radical pathway activation PMS's using magnetic oxygenated copper catalyst the invention proposes a kind of
Method, and apply it in treatment of Organic Wastewater with high salt, the difficult drop in high salt organic waste water may be implemented in this way
Solve the efficient removal of organic matter.Catalyst preparation in the invention is simple rapid, easy to industrialized production, and this method organic matter is gone
Except it is high-efficient, easy to operate, be convenient for storage and transportation, Yi Shixian Magneto separate, be suitable for wider pH range, treatment of Organic Wastewater with high salt lead
Domain has huge potentiality and broad application prospect.Before making the present invention, it finds no and utilizes magnetic oxygenated copper product and mistake
The combination of one sulfate handles the report of high salt organic waste water.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide it is a kind of it is new and effective with singlet oxygen be to dominate
The method for aoxidizing organic pollutants with high salt is combined with the magnetic oxygenated copper product of synthesis with peroxy-monosulfate, realizes pollution
The rapidly and efficiently removal of object is rapidly separated recycling with catalyst, possesses broad application prospect.
The purpose of the present invention is achieved through the following technical solutions:
A method of using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt, with the oxidation of nanometer four three
Iron powder and acetic acid copper solution are raw material, so that ferroso-ferric oxide is integrated to cupric oxide nano on piece, shape using a step coprecipitation
At having magnetic cupric oxide nano catalysis material, magnetic oxygenated copper and peroxy-monosulfate are added in high salt organic waste water,
The fast degradation that organic matter can be achieved is reacted under room temperature.
Specifically comprise the following steps:
1) nano ferriferrous oxide powder (commercially available, 20nm) and copper acetate are pressed iron: copper molar ratio is 1: (5-15)
It is added in 200mL deionized water, and 0.01-0.1mL 1- mercapto glycerol is added as dispersing agent, stir simultaneously ultrasound 30min shape
At finely dispersed solution；
2) to the sodium hydroxide solution (4mol/L) of 50mL is added dropwise in 1) as precipitating reagent, and continue stirring 1 hour,
It is then allowed to stand aging in 2 hours；
3) in 2) obtain it is solids-conditioned after, then separated with permanent magnet and use dehydrated alcohol and distillation
After water is cleaned multiple times, not higher than drying in 80 DEG C of baking ovens, magnetic oxygenated copper nanometer sheet material can be obtained.
4) magnetic Nano copper oxide material and peroxy-monosulfate are added to the with high salt organic of pollutant to be removed when using
In waste water, sufficiently reacted, it can be with oxidation removal organic pollutant.
In the above method, the catalyst is the bielement nano that the load of cupric oxide nano on piece has ferriferrous oxide nano sphere
Compound.
In the above method, the catalyst is with excellent Magneto separate and peroxy-monosulfate activation capacity.
In the above method, the preparation method of the magnetic oxygenated copper catalyst is simple one-step synthesis.
In the above method, the activation of catalyst peroxy-monosulfate mainly passes through the non-free radical way for generating singlet oxygen
Diameter.
In the above method, the method has good organic matter removal effect to salt-free and salt-containing organic wastewater.
In the above method, the usage amount of catalyst is 0.1-0.6g/L in the method, and the concentration of peroxy-monosulfate is 1-
8mM。
In the above method, the pH value of the high salt organic waste water is 3-9.
The magnetic oxygenated copper product makes copper oxide in conjunction with ferroso-ferric oxide, forms heterojunction structure, strengthens electronics
Transmitting, while the stability of copper oxide is enhanced, reduce the dissolution of copper ion, while catalyst being made to be easy to Magneto separate, is catalyzed
The surface hydroxylation effect of agent and Fe-Cu catalytic oxidation-reduction circulation promote peroxy-monosulfate to generate more by non-free radical approach
More singlet oxygen, to improve the degradation efficiency of organic pollutant.
The advantages and effects of the present invention are:
1. the magnetic oxygenated copper product stability of synthesis is strong, re-usability is good, and catalytic activity is high, is easy to Magneto separate.
2. synthetic route is simple, it can be achieved that large-scale production, technological operation is simple, meet production actual needs.
3. magnetic oxygenated copper product can efficiently activate peroxy-monosulfate in broader pH range (3-9).
4. this method realizes the degradation of organic pollutant so that singlet oxygen is leading non-free radical approach, not vulnerable to water
Matter characteristic influences, the processing suitable for high salt organic waste water.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture that material is prepared in the present invention, display cupric oxide nano piece and ferriferrous oxide nano
Grain is combined togather, and forms heterojunction structure.
Fig. 2 is that the X-ray diffractogram testimonial material group of material is prepared in the present invention as copper oxide and ferroso-ferric oxide.
Fig. 3 is Magneto separate picture in the H-M curve and aqueous solution of the magnetic oxygenated copper product prepared in the present invention.
Fig. 4 is to be demonstrated using the electron paramagnetic resonance spectrum (EPR) figure of 2,2,6,6- tetramethyl piperidine spin trapping singlet oxygens
Magnetic oxygenated copper product activation peroxy-monosulfate generates singlet oxygen in the present invention.
Fig. 5 is using method of the invention to containing 0.2M Na2SO4It is the rhodamine B (RhB) that has respectively in waste water, sub-
3 kinds of organic pollutant removal situations comparison such as methyl blue (MB), Atrazine (ATZ), it was demonstrated that this method is to organic pollutant
Efficient removal.
Fig. 6 is using method of the invention to containing 0.2M Na2SO4With the place of 0.1mM acid orange 7 waste water from dyestuff with high salt
Reason.
Specific embodiment
Embodiment 1
It weighs 9.0815g copper acetate and 1.1577g nano ferriferrous oxide is dissolved in 200mL deionized water, be stirred continuously,
And 0.1mL 1- mercapto glycerol is added as dispersing agent, ultrasonic 30min forms finely dispersed solution；The case where being kept stirring
The lower sodium hydroxide solution (4mol/L) for instilling 50mL dropwise to the above solution forms brown suspension, and continues stirring 1 hour,
It is then allowed to stand aging in 2 hours and forms black solid precipitating；Then it is separated with permanent magnet and uses dehydrated alcohol and distilled water
After being cleaned multiple times, not higher than drying in 80 DEG C of baking ovens, magnetic oxygenated copper nanometer sheet is obtained.By the permonosulphuric acid of 2mM when use
Salt is added to containing 0.1mM acid orange 7 and 0.2M Na2SO4Waste water from dyestuff with high salt in, adjust pH to neutrality, add 0.1g/
The magnetic oxygenated copper product of L, keeps being stirred continuously, and acid orange 7 degradation rate in 30min reaches 95.81%, as shown in Figure 6.
Embodiment 2
By the peroxy-monosulfate of 2mM be added separately to the methylene blue of 0.1mM, the rhodamine B of 0.1mM and 0.09mM Ah
Te Lajin (0.2M Na with high salt2SO4) in organic wastewater, adjust pH to neutrality, add the magnetic oxygenated copper product of 0.1g/L, protect
It holds and is stirred continuously, the degradation rate of methylene blue, rhodamine B and Atrazine after 30min is respectively 74.57%, 100% He
100%, as shown in figure 5, the method in the present invention shows the efficient removal ability to Some Organic Pollutants.
Embodiment 3
The high salt dyestuff that the peroxy-monosulfate of 2mM is added to the acid orange 7 containing 0.1mM and various concentration inorganic salts is given up
In water, the magnetic oxygenated copper of 0.1g/L is added, keeps being stirred continuously, degradation rate and degradation rate of the acid orange 7 in 30min
Constant such as following table, no matter in single salt or a variety of mixed salts, the method for the present invention is to the removal rate of acid orange 7 80%
More than, show that this method is suitable for the removal of plurality of inorganic salt wastewater through organic matter.
Embodiment 4
It is repeatedly washed after used magnetic oxygenated copper is collected with deionized water and dehydrated alcohol, and is dried at 80 DEG C
It is recycled again, the peroxy-monosulfate of 2mM is added to containing 0.1mM acid orange 7 and 0.2M Na2SO4High salt dyestuff it is useless
In water, adjust pH to neutrality, add the magnetic oxygenated copper product after the recovery of 0.1g/L, keep being stirred continuously, by 4 times this
After the recycling of sample, the degradation rate of acid orange 7 is still up to 94.58%, it was demonstrated that the magnetic oxygenated copper product tool in the invention
There are good stability and Recycling.
One of the above description is merely a specific embodiment, and those skilled in the art can be by using for reference in this paper
To hold, the appropriate links such as process route that change are realized, although method of the invention is described by preferred embodiment, phase
Closing technical staff obviously can be modified or reconfigure to method described herein not departing from the content of present invention and range,
To realize final result.In particular, it should be pointed out that anyone skilled in the art disclosed herein technology
In range, it should all be encompassed within protection scope without the variation and replacement of inventive concept.
Claims (9)
1. a kind of method using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt, it is characterised in that: to receive
Rice ferroferric oxide powder and acetic acid copper solution are raw material, so that ferroso-ferric oxide is integrated to copper oxide using a step coprecipitation and receive
Rice on piece, forms and has magnetic cupric oxide nano catalysis material, and magnetic oxygenated copper and peroxy-monosulfate, which are added to, with high salt to be had
In machine waste water, the fast degradation that organic matter can be achieved is reacted under room temperature.
2. according to claim 1, which is characterized in that magnetic oxygenated copper nano material the preparation method comprises the following steps:
1) nano ferriferrous oxide powder (commercially available, 20nm) and copper acetate are pressed iron: copper molar ratio is 1: (5-15) is added
Into 200mL deionized water, and 0.01-0.1mL 1- mercapto glycerol is added as dispersing agent, stirs and ultrasound 30min is formed and divided
Dissipate uniform solution；
2) to the sodium hydroxide solution (4mol/L) of 50mL is added dropwise in 1) as precipitating reagent, and continue stirring 1 hour, then
Stand aging in 2 hours；
3) in 2) obtain it is solids-conditioned after, then separated and used dehydrated alcohol and distilled water more with permanent magnet
After secondary cleaning, not higher than drying in 80 DEG C of baking ovens, magnetic oxygenated copper nanometer sheet can be obtained.
3. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the catalyst is that the load of cupric oxide nano on piece has the bielement nano of ferriferrous oxide nano sphere compound
Object.
4. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the catalyst is with excellent Magneto separate and peroxy-monosulfate activation capacity.
5. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the preparation method of the magnetic oxygenated copper catalyst is simple one-step synthesis.
6. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the activation of catalyst peroxy-monosulfate mainly passes through the non-free radical approach for generating singlet oxygen.
7. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the method has good organic matter removal effect to salt-free and salt-containing organic wastewater.
8. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the usage amount of catalyst is 0.1-0.6g/L in the method, and the concentration of peroxy-monosulfate is 1-8mM.
9. a kind of side using magnetic oxygenated member permonosulphuric acid salt treatment organic wastewater with high salt according to claim 1
Method, it is characterized in that: the pH value of the high salt organic waste water is 3-9.
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