CN109626543A - A kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater - Google Patents
A kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater Download PDFInfo
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- 239000007800 oxidant agent Substances 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 230000003197 catalytic Effects 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 60
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 34
- 230000001590 oxidative Effects 0.000 claims abstract description 17
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- 230000004059 degradation Effects 0.000 claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229910052723 transition metal Inorganic materials 0.000 claims description 24
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000011550 stock solution Substances 0.000 claims description 13
- 229910052803 cobalt Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 11
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 230000000593 degrading Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 210000002356 Skeleton Anatomy 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N Aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 23
- 239000005631 2,4-D Substances 0.000 description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000004435 EPR spectroscopy Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000001187 sodium carbonate Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002195 synergetic Effects 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 2,2-dimethyl-1-oxido-3,4-dihydropyrrol-1-ium Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N Magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl radical Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- AQCHWTWZEMGIFD-UHFFFAOYSA-N Metolazone Chemical compound CC1NC2=CC(Cl)=C(S(N)(=O)=O)C=C2C(=O)N1C1=CC=CC=C1C AQCHWTWZEMGIFD-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910020106 MgCo2O4 Inorganic materials 0.000 description 1
- 229910000949 MnO2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002153 concerted Effects 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen salt Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
Abstract
The invention belongs to high-level oxidation technologies to handle waste water technology field, more particularly, to a kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater.It is process object with organic wastewater, two-phase oxidizer system is constituted with Oxygen in Liquid agent persulfate solution and gaseous oxidizing agent ozone, the degradation of the efficient activation and pollutant of oxidant is realized by support type quaternary hydrotalcites structure catalyst；Since support type quaternary hydrotalcites structure catalyst is for the good catalytic of the two-phase oxidant, the present invention is allowed to reduce actual waste water treatment process, and reaches very high organic matter removal effect.
Description
Technical field
The invention belongs to high-level oxidation technologies to handle waste water technology field, more particularly, to a kind of two-phase oxidant body
It is the method for catalytic oxidation treatment organic wastewater.
Background technique
High-level oxidation technology (AOPs) has because free radical with high performance can degrade persistence organic pollutant
The features such as oxidability is strong, reaction rate is fast, still temperature does not subtract in recent years.But meanwhile it there is also some shortcomings.
During handling complicated organic wastewater, often there is poor processing effect, at high cost etc. in single processing technique
Problem.Some high-level oxidation technologies such as Fenton oxidation method is affected by the pH of waste water, and supercritical Water Oxidation Technology is to temperature
Also there is higher requirement with pressure.Therefore, the various combination of two or more AOPs is considered as that one kind can effectively degrade dirt
Contaminate the method with bright prospects of object.The synergistic effect of multiple tracks technique is generally required in the treatment process of practical organic wastewater
It can effectively degradable organic pollutant.
Based on potentiometric titrations (SO4 ·-) AOPs more and more by the concern of domestic and foreign scholars, cross a sulphur
Sour hydrogen salt (PMS) and persulfate (PS) are activated frequently as oxidant and generate SO4 ·-.Compared with persulfate, PMS is due to it
Structure is asymmetric and is easier to be activated.PMS can pass through heating, ultraviolet light, transition metal, ultrasonic wave, C catalyst and electricity
Chemical process activates.Transition metal (Co, Fe, Cu, Mn), especially heterogeneous state, since it is inexpensive and reusable
Property, superior performance is shown relative to other methods.
Catalytic ozonation belongs to one kind of high-level oxidation technology, since ozone is at low cost, reaction is fast, oxidability
By force, the features such as remaining and without secondary pollution without persistence, application is more and more extensive.Catalytic ozonation is to utilize catalyst
The stronger free radical of oxidability, such as hydroxyl radical free radical, to reach purpose of purifying the water quality are converted by ozone molecule.It can
The metal oxide for being used to catalysis ozone decomposition is mainly some typical transition metal oxides, such as Fe2O3、MnO2、
Co3O4、CuO、TiO2、Al2O3Deng and support type noble heavy metal oxide, such as Ru, Pd.
Strong oxidizing property in view of ozone and reaction are fast, oxidability is strong, remaining and without secondary pollution etc. special without persistence
The advantage of point, catalytic ozonation becomes increasingly conspicuous.Therefore, usually by ozone and hydrogen peroxide, persulfate in industrial application
Equal processing techniques combination is to reach further purpose of purifying the water quality.
However, because ozone belongs to gaseous oxidizing agent, property is unstable in aqueous solution, is extremely easy in decomposition, regardless of being double
Oxygen aqueous systems or persulfate catalytic oxidation system belong to Oxygen in Liquid agent system.Therefore, as long as being related to and ozone
When joint catalysis oxidation, the highest oxidation ability of two-phase oxidant still cannot be effectively played.In practical application, usually will
Ozone is as pretreatment or post-processing process, and strict control reaction condition, and which not only adds processing costs also significantly
Increase operation workload.Therefore, the oxidation of liquid and gas two-phase can be simultaneously effective catalyzed by how searching out a kind of catalyst
Agent system, the technical process for simplifying treatment of Organic Wastewater are extremely urgent.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of two-phase oxidizer systems to be catalyzed oxygen
Change the method for processing organic wastewater, its object is to the hydrotalcite structure quaternary catalytics by using carrying transition metal oxide
Agent, concerted catalysis activate gaseous oxidizing agent ozone and Oxygen in Liquid agent persulfate, are handled by two-phase oxidizer catalytic system
Organic wastewater, since support type quaternary hydrotalcites structure catalyst all has good work for the two-phase oxidizer catalytic system
Change effect, allows the present invention using the simple operational process of one-step method, reaches very high organic matter removal effect, thus solve
Certainly the prior art is related to technical problem complicated for operation, at high cost when waste water treatment by ozone oxidation.
To achieve the above object, according to one aspect of the present invention, a kind of two-phase oxidizer system catalysis oxidation is provided
The method for handling organic wastewater is process object with organic wastewater, with Oxygen in Liquid agent persulfate solution and gaseous oxidizing agent
Ozone constitutes two-phase oxidizer system, and the efficient activation and dirt of oxidant are realized by support type quaternary hydrotalcites structure catalyst
Contaminate the degradation of object；
The quaternary hydrotalcites structure catalyst includes four kinds of metallic elements, and two of them metallic element is to constitute neatly
Rock layers shape basic structure, and surface hydroxyl is provided, promote the absorption to ozone molecule, strengthens the contact of solid-liquid-gas three phase reaction；
Other two kinds of metallic elements are active transition metal element, are turned to carry out electronics with the two-phase oxidizer system
It moves, generates free radicals, the catalytic oxidation treatment organic wastewater in hybrid reaction system.
Preferably, in the hybrid reaction system Oxygen in Liquid agent persulfate be peroxy-monosulfate or peroxydisulfate,
Concentration of the persulfate in the hybrid reaction system is 1~5mmol/L.
Preferably, the concentration of gaseous oxidizing agent ozone is 10~50mg/L in the hybrid reaction system.
Preferably, the support type quaternary hydrotalcites structure catalyst constitutes neatly rock layers using Mg, Al two-spot as skeleton
Shape structure；Concentration of the catalyst in the hybrid reaction system is 0.1~0.5g/L.
Preferably, the transition metal element is Cu, Co or Fe.
Preferably, the quaternary hydrotalcites structure catalyst is CuCoMgAl, and four kinds of metallic elements rubs in the catalyst
You are (0.75~1.5): (0.05~0.15): 15:5 than Cu:Co:Mg:Al；Or the four-way catalyst is FeCoMgAl, it should
The molar ratio Fe:Co:Mg:Al of four kinds of metallic elements is (0.75~1.5): (0.05~0.15): 15:5 in catalyst.
Preferably, the support type quaternary hydrotalcites structure catalyst the preparation method comprises the following steps: with the nitrate of magnesium, aluminium be original
Material has the catalyst precursor of hydrotalcite structure using coprecipitation or hydro-thermal method preparation, then uses coprecipitation or hydro-thermal
The nitrate of two kinds of transition metal in copper, cobalt and iron is carried in the catalyst precursor by method, finally filters mixture
It is dry, in 400~800 DEG C of 5~10h of calcining, obtain the support type quaternary hydrotalcites structure catalyst.
Preferably, the method for the two-phase oxidizer system catalytic oxidation treatment organic wastewater includes the following steps:
(1) use ozone generator, streams of ozone is passed through with the rate Xiang Shuizhong of 5~10g/h, be passed through the time be 3~
20min obtains the ozone stock solution that concentration is 10~50mg/L；
(2) the ozone stock solution obtained containing the organic wastewater that organic concentration is 100~200ppm with step (1) is pressed
Mixed according to 0.2~2:1 of volume ratio, a certain amount of catalyst and persulfate be added, obtains hybrid reaction system, sealing,
It is reacted under the conditions of being protected from light, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system is 0.1~0.5g/L, the persulfate
Concentration in the hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
Preferably, the method for the two-phase oxidizer system catalytic oxidation treatment organic wastewater includes the following steps:
(1) organic wastewater is mixed in the container that bottom is equipped with gas distributor with the catalyst, it is anti-obtains mixing
Answer system；The concentration of the organic waste Organic substance in water is 20~100ppm；
(2) ozone generator is used, the streams of ozone that rate is 2~5g/h is continued by step (1) container bottom
It is passed through, is sufficiently reacted with mixed liquor in the container, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system is 0.1~0.5g/L, the persulfate
Concentration in the hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention processing organic wastewater is two-phase oxidizer catalytic oxidation system, using carrying transition metal oxide
Hydrotalcite structure four-way catalyst, not only have the advantages that hydrotalcite material stability is good, leaching rate is low etc., there are also more table
Face hydroxyl, large specific surface area are conducive to stablize the ozone in liquid-phase system by adsorbing in conjunction with ozone, make its oxidation efficiency
It improves, with two-phase oxidant electronics transfer can occur for the transition metal of load simultaneously, to improve the catalysis oxidation efficiency.
(2) the catalyst carrying transition metal oxide that the present invention uses, activity is strong, further increases catalytic efficiency.
(3) two-phase oxidizer system is used, there are a variety of free radicals for reaction process, can not only effectively improve organic pollutant
Degradation rate, can also be effectively reduced water quality parameter bring influence.
Detailed description of the invention
Fig. 1 is the catalytic mechanism figure of CuCoMgAl catalyst；
Fig. 2 is electron paramagnetic resonance (EPR) energy spectrum diagram that lower reaction solution is added in radical scavenger DMPO；
Fig. 3 is electron paramagnetic resonance (EPR) energy spectrum diagram that lower reaction solution is added in radical scavenger TEMP；
Fig. 4 is the XRD spectra before and after CuCoMgAl catalyst reaction.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of method of two-phase oxidizer catalytic oxidation processes organic wastewater provided by the invention is processing with organic wastewater
Object is constituted two-phase oxidizer system with Oxygen in Liquid agent persulfate solution and gaseous oxidizing agent ozone, passes through support type four
First hydrotalcite structure catalyst realizes the degradation of the efficient activation and pollutant of oxidant.The quaternary hydrotalcites structure catalyst
Including four kinds of metallic elements, two of them metallic element provides surface hydroxyl to constitute hydrotalcite stratiform basic structure, promotees
Into the absorption to ozone molecule, strengthen the contact of solid-liquid-gas three phase reaction；Other two kinds of metallic elements are active transition
Metallic element is generated free radicals, is catalyzed in hybrid reaction system to carry out electronics transfer with the two-phase oxidizer system
Oxidation processes organic wastewater.
In some preferred embodiments, support type quaternary hydrotalcites structure catalyst of the present invention using Mg, Al two-spot as skeleton,
It constitutes stable hydrotalcite layered structure and surface hydroxyl is provided, using two-spot active transition metal as modification, aoxidized with two-phase
Agent ozone and persulfate carry out electronics transfer, generate free radicals.
Transition metal element can be two kinds in Cu, Co and Fe.In preferred embodiment, the carrying transition metal oxidation
The hydrotalcite-like compound four-way catalyst of object is formed using the two-spot in active transition metal Cu, Co or Fe as modification
CuCoMgAl catalyst or FeCoMgAl catalyst with hydrotalcite-like compound.
In some embodiments, the support type quaternary hydrotalcites structure catalyst the preparation method comprises the following steps: with the nitric acid of Mg, Al
Salt is raw material, has the catalyst precursor of hydrotalcite structure using coprecipitation or hydro-thermal method preparation, then use coprecipitation
Or the nitrate of the transition metal such as copper, cobalt or iron, cobalt is carried in the catalyst precursor by hydro-thermal method, finally by mixture mistake
It is filtered dry dry, in 400~800 DEG C of 5~10h of calcining, obtains the support type quaternary hydrotalcites structure catalyst.
Such as specifically: 5-20mmol magnesium nitrate, 2-10mmol aluminum nitrate are dissolved completely in shape in 250ml deionized water
At mixed nitrate solution, 15-50mM sodium carbonate is dissolved in 250ml deionized water, sodium carbonate liquor is put into 60-80 DEG C of perseverance
It is stirred in warm magnetic stirring apparatus, meanwhile, mixed nitrate solution is instilled in sodium carbonate liquor dropwise in 60min, was titrated
Journey remains pH=10 ± 0.02 in sodium carbonate liquor or so (adjusting pH 2M NaOH solution), after dripping off, gained is suspended
Liquid stands aging for 24 hours at room temperature, and then, cleaning precipitating repeatedly with deionized water makes pH close to neutrality, and filtered filter residue is put
Enter crucible, be put into 80 DEG C of oven drying 12h or more, obtaining solid powder is LDH structure catalyst presoma.Again with same side
Transition metal is carried on LDH structure catalyst presoma by method using the nitrate of 0-2mmol transition metal as raw material.It will most
The solid obtained afterwards is crushed into powder, and is put into 300-600 DEG C of Muffle furnace calcining 5-8h.
In some embodiments, in hybrid reaction system persulfate be peroxy-monosulfate (PMS) or peroxydisulfate (PS),
Concentration of the persulfate in hybrid reaction system is 1~5mmol/L.
In some embodiments, the concentration of ozone is 10~50mg/L in the hybrid reaction system.
In some embodiments, the quaternary hydrotalcites structure catalyst is CuCoMgAl, four kinds of metal members in the catalyst
The molar ratio Cu:Co:Mg:Al of element is (0.75~1.5): (0.05~0.15): 15:5；Or the four-way catalyst is
FeCoMgAl, the molar ratio Fe:Co:Mg:Al of four kinds of metallic elements is (0.75~1.5): (0.05~0.15) in the catalyst:
15:5。
In some embodiments, the method for processing organic wastewater of the present invention includes the following steps:
(1) use ozone generator, streams of ozone is passed through with the rate Xiang Shuizhong of 5~10g/h, be passed through the time be 3~
20min obtains the ozone stock solution that concentration is 10~50mg/L；
(2) the ozone stock solution that the pollutant stock solution that organic concentration is 100~200ppm is obtained with step (1) is pressed
Mixed according to 0.2~2:1 of volume ratio, a certain amount of catalyst and persulfate be added, obtains hybrid reaction system, sealing,
It is reacted under the conditions of being protected from light, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system is 0.1~0.5g/L, the persulfate
Concentration in the hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
In some embodiments, the method for processing organic wastewater of the present invention includes the following steps:
(1) organic pollutant stock solution is mixed in the container that bottom is equipped with gas distributor with the catalyst, is obtained
To hybrid reaction system；The concentration of organic matter is 20~100ppm in the organic pollutant stock solution；
(2) ozone generator is used, the streams of ozone that rate is 2~5g/h is continued by step (1) container bottom
It is passed through, is sufficiently reacted with mixed liquor in the container, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system is 0.1~0.5g/L, the persulfate
Concentration in the hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
The present invention contains in the two-phase catalytic oxidation treatment organic wastewater system of ozone and persulfate, and catalyst is by class water
Talcum (LDH) structure loads the transition metal oxide with greater activity as skeleton.LDH structure catalyst itself has
Stablize, the advantages such as leaching rate is low, while with persulfate electronics transfer can occur for the stronger transition metal of surface-active, generate strong
The potentiometric titrations of oxidisability.Ozone is because of its selective oxidizing and unstability, and utilization rate is low in the treatment of waste water, ozone
Waste is big.The catalyst surface hydroxyl is conducive to the ozone molecule in adsorbent solution, plays the role of stable ozone, so as to
Promote that electronics transfer occurs between transition metal oxide and ozone, generates the hydroxyl radical free radical without selective oxidizing, while EPR
It is demonstrated experimentally that also there is singlet oxygen generation in reaction process.Under the synergistic effect of a variety of free radicals, can effectively it enhance to having
The degradation capability of machine waste water, while improving the utilization efficiency to ozone.
The following are embodiments:
Embodiment 1
Take ozone stock solution (13.5 ± 0.5mg/L) 12mL prepared in brown sealed glass jars, addition configures
2,4-D stock solution (100ppm) 8mL, be added catalyst 3mg, PMS 2mM, allow the mixed liquor at 25 DEG C constant temperature stir, instead
Answer 60min.Different catalysts are as shown in table 1 to the degradation efficiency of 2,4-D.The ozone stock solution uses ozone generator, with
The rate Xiang Shuizhong of 8g/h is passed through streams of ozone, and being passed through the time is 8~10min, obtains the ozone that concentration is 13.5 ± 0.5mg/L
Stock solution.
Table 1 can be seen that the LDH structure catalyst density of surface hydroxyl of carrying transition metal oxide is high, reaction efficiency
It is remarkably reinforced.As can be seen from the table, the LDH catalyst for having loaded Cu, Co oxide obviously increases the removal efficiency of organic matter
By force.The LDH structure catalyst being made of MgAl considerably increases the density of surface hydroxyl of catalyst.And loaded transition metal it
Although rear catalyst density of surface hydroxyl reduces, have more strongly active transition metal oxide promote catalyst with
Electronics transfer between ozone and persulfate, to improve the reaction rate of system.CuCoMgAl catalyst has simultaneously
Two kinds of stronger transition metal of activity, and have relatively high density of surface hydroxyl and biggish specific surface area, promote with
The contact and reaction of two-phase oxidant, so having reached maximum removal rate.
Degradation efficiency of 1 different catalysts of table to 2,4-D
The catalytic mechanism of CuCoMgAl catalyst is as shown in Figure 1, be made of houghite (LDH) base Mg, Al in embodiment 1
This structure loads transition metal oxide Cu, the Co with greater activity.LDH structure catalyst is due to its density of surface hydroxyl
It is larger, be conducive to adsorb ozone, play the role of stable ozone, so as to promote that electronics transfer occurs between Cu, Co and ozone,
Generate OH and1O2.With persulfate electronics transfer can occur for Cu, Co simultaneously, generate the SO of strong oxidizing property4 ·-.In a variety of freedom
Under the synergistic effect of base, 2,4-D can quickly and effectively be decomposed.
Embodiment 2
Using CuCoMgAl, FeCoMgAl catalyst of different transition metal ratios as heterogeneous catalysis, implemented
Experiment described in example 1, reaction time 60min.Degradation efficiency such as table 2 institute of the different transition metal ratio catalyst to 2,4-D
Show.
Degradation efficiency of the different transition metal ratio catalyst of table 2 to 2,4-D
Table 2 can be seen that different transition metal ratios have a significant effect to the catalytic efficiency of catalyst, but relative to implementation
Ternary and binary catalyst in example 1 all have better catalytic efficiency.Illustrate transition metal in the catalytic activity of catalyst
Occupy important function, and four-way catalyst has better catalytic action relative to ternary and binary catalyst.
Embodiment 3
On the basis of embodiment 1, change the concentration of Oxygen in Liquid agent PMS and gaseous oxidizing agent ozone respectively, be added real
Apply CuCoMgAl the catalyst 3mg, reaction time 60min in example 1.Degradation efficiency such as table 3 of the various concentration oxidant to 2,4-D
It is shown.
Degradation efficiency of the 3 various concentration oxidant of table to 2,4-D
Table 3 can be seen that the concentration of oxidant has a significant effect to the degradation efficiency of 2,4-D, but in PMS concentration in 1.5mM
More than, ozone concentration can reach good treatment effect in 11mg/L or more, greatly reduce reaction cost.
Embodiment 4
Taking concentration is 50ppm reaction substrate 20mL in the following glass tube equipped with silica distributor, is added and implements
CuCoMgAl catalyst 3mg, PMS 3mM in example 1.Using ozone generator, with the rate of 2g/h by ozone under glass tube
Side is continually fed into, and reacts 40min.CuCoMgAl catalyst is as shown in table 4 to different degradation of substrates efficiencies.
4 CuCoMgAl catalyst of table is to different degradation of substrates efficiency
Table 4 is it can be seen that the catalyst system has good degradation effect to different pollutants.
Embodiment 5
On the basis of embodiment 4, carries out electron paramagnetic resonance test experience (EPR), exist to detect in reaction process
Free radical.Electron paramagnetic resonance (EPR) is can directly to prove technology existing for free radical, using DMPO radical scavenger
Capture OH and SO4 ·-, experimental result as shown in Fig. 2, ◆ andRespectively indicate OH and SO4 ·-, peak intensity 1:2:2:1,
For the characteristic peak of OH, the lesser peak of intensity between OH characteristic peak is SO4 ·-Characteristic peak.Using TEMP free radical capture
Agent captures1O2, experimental result as shown in figure 3, peak intensity be 1:1:1, be1O2Characteristic peak.Fig. 2 and Fig. 3 can be seen that the reaction
There is OH, SO in the process4 ·-、1O2A variety of free radicals.
Embodiment 6
XRD test experience is carried out to the CuCoMgAl catalyst of reaction front and back in embodiment 1.XRD spectra is as shown in Figure 4.
The diffraction maximum occurred at 2 θ=11 °, 22 °, 34 °, 39 °, 46 °, 60 ° is the characteristic peak of LDH, is occurred at 2 θ=43 ° and 62 °
Diffraction maximum be corresponding oxide may be MgO, CoO, Co3O4And MgCo2O4.Fig. 4 can be seen that reaction front and back CuCoMgAl
The XRD spectra of catalyst is substantially similar, illustrates that the catalyst is with good stability.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater, which is characterized in that with organic wastewater be place
Object is managed, two-phase oxidizer system is constituted with Oxygen in Liquid agent persulfate solution and gaseous oxidizing agent ozone, passes through support type
Quaternary hydrotalcites structure catalyst realizes the activation of oxidant and the degradation of pollutant；
The quaternary hydrotalcites structure catalyst includes four kinds of metallic elements, and two of them metallic element is to constitute neatly rock layers
Shape structure, and surface hydroxyl is provided, promote the absorption to ozone molecule, strengthens the contact of solid-liquid-gas three phase reaction；Other two kinds
Metallic element is active transition metal element, to carry out electronics transfer with the two-phase oxidizer system, is produced from
By base, the catalytic oxidation treatment organic wastewater in hybrid reaction system.
2. the method as described in claim 1, which is characterized in that Oxygen in Liquid agent persulfate is in the hybrid reaction system
Peroxy-monosulfate or peroxydisulfate, concentration of the persulfate in the hybrid reaction system are 1~5mmol/L.
3. the method as described in claim 1, which is characterized in that the concentration of gaseous oxidizing agent ozone in the hybrid reaction system
For 10~50mg/L.
4. the method as described in claim 1, which is characterized in that the support type quaternary hydrotalcites structure catalyst is with Mg, Al
Two-spot constitutes hydrotalcite layered structure as skeleton；Concentration of the catalyst in the hybrid reaction system be 0.1~
0.5g/L。
5. the method as described in claim 1, which is characterized in that the transition metal element is Cu, Co or Fe.
6. method as claimed in claim 5, which is characterized in that the quaternary hydrotalcites structure catalyst is CuCoMgAl, should
The molar ratio Cu:Co:Mg:Al of four kinds of metallic elements is (0.75~1.5): (0.05~0.15): 15:5 in catalyst；Or it is described
Four-way catalyst is FeCoMgAl, and the molar ratio Fe:Co:Mg:Al of four kinds of metallic elements is (0.75~1.5) in the catalyst:
(0.05~0.15): 15:5.
7. the method as described in claim 1, which is characterized in that the preparation side of the support type quaternary hydrotalcites structure catalyst
Method are as follows: using magnesium, aluminium nitrate as raw material, using coprecipitation or hydro-thermal method preparation have hydrotalcite structure complex catalyst precursor
Body, then before the nitrate of two kinds of transition metal in copper, cobalt and iron is carried on the catalyst using coprecipitation or hydro-thermal method
It drives in body, mixture filtration drying is finally obtained into the support type quaternary hydrotalcites knot in 400~800 DEG C of 5~10h of calcining
Structure catalyst.
8. the method as described in claim 1, which comprises the steps of:
(1) ozone generator is used, streams of ozone is passed through with the rate Xiang Shuizhong of 5~10g/h, being passed through the time is 3~20min,
Obtain the ozone stock solution that concentration is 10~50mg/L；
(2) by the ozone stock solution obtained containing the organic wastewater and step (1) that organic concentration is 100~200ppm according to body
Product is mixed than 0.2~2:1, and a certain amount of catalyst and persulfate is added, obtains hybrid reaction system, is sealing, is being protected from light
Under the conditions of reacted, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system be 0.1~0.5g/L, the persulfate in institute
Stating the concentration in hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
9. the method as described in claim 1, which comprises the steps of:
(1) organic wastewater is mixed in the container that bottom is equipped with gas distributor with the catalyst, obtains hybrid reaction body
System；The concentration of the organic waste Organic substance in water is 20~100ppm；
(2) ozone generator is used, the streams of ozone that rate is 2~5g/h is continued to be passed through by step (1) described container bottom,
It is sufficiently reacted with mixed liquor in the container, the organic matter in the pollutant of degrading；
Wherein, concentration of the catalyst in the hybrid reaction system be 0.1~0.5g/L, the persulfate in institute
Stating the concentration in hybrid reaction system is 1~5mmol/L；Reaction time is 0.2~1h.
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