CN1611454A - Method for photo-oxidative flocculating treatment of organic pollutant waster water - Google Patents
Method for photo-oxidative flocculating treatment of organic pollutant waster water Download PDFInfo
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- CN1611454A CN1611454A CNA2003101026392A CN200310102639A CN1611454A CN 1611454 A CN1611454 A CN 1611454A CN A2003101026392 A CNA2003101026392 A CN A2003101026392A CN 200310102639 A CN200310102639 A CN 200310102639A CN 1611454 A CN1611454 A CN 1611454A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 26
- 230000003311 flocculating effect Effects 0.000 title claims abstract description 12
- 238000011282 treatment Methods 0.000 title claims description 21
- 238000005189 flocculation Methods 0.000 claims abstract description 68
- 230000016615 flocculation Effects 0.000 claims abstract description 65
- 239000002351 wastewater Substances 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 230000003351 photoxidation Effects 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000004062 sedimentation Methods 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 241000628997 Flos Species 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000003657 drainage water Substances 0.000 claims description 2
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 231100000614 poison Toxicity 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 230000007096 poisonous effect Effects 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000007539 photo-oxidation reaction Methods 0.000 abstract 2
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 12
- 239000012467 final product Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011221 initial treatment Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
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- 238000010525 oxidative degradation reaction Methods 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical group 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
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- 239000002975 chemoattractant Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a kind of oxidizing and flocculating synergy technique to resolving poisonous contaminated wastewater with high efficiency and high speed. In light excitation, utilizing a kind of redox characteristic of inorganic and organic compound, great oxidizing property free radical, which generated when having photo oxidation by impressed oxidant, can oxidize and decompose poisonous organic compound with no biodegradation quickly. At the same time, oxidation state of this kind of compound can also hydrolyze quickly and then flocculate, in order to form floccule body with great adsorptivity, so it can extensively adsorb, muffle and precipitate the polluter to settle and separate from the treated water body. Because of contemporaneity and concertedness of photo oxidation and flocculating reaction, adsorption that come out of light-induction oxidization and flocculation can make organic pollutant concentrate to generation source and diffusion rage of the great oxidizing property free radical. So the great oxidizing property free radical and the adsorbed pollutant can have maximal reaction probability, and can achieve oxidizing efficiency by hundredfold or thousandfold. Especially, it adapts to treat poisonous organic contaminated wastewater with high concentration of pollutant and uneasy biological degradation.
Description
Technical field
The present invention relates to a kind of photoxidation flocculation reaction technical field, particularly fast, the photoxidation flocculation coordination technique of advanced treatment height toxicity and the biological organic pollutant that can not degrade.
Background technology
Flocculating settling is that the materialization processing contains insoluble particle thing (SS), heavy metal ion and organic pollutant wastewater method for reducing commonly used, practical flocculation agent is aluminium salt, molysite and the poly-iron that grew up afterwards, poly-aluminium and water miscible high molecular polymer such as polyacrylamide, technological core is that Hydrolysis Reactions of Metal-ions or high molecular polymer form multinuclear hydroxylation precipitation, generation wraps, mixes precipitating action, make tiny insolubles, metal ion or organic pollutant with the flocculation agent sedimentation, reach the effect that pollutent is removed in separation from water body.Therefore flocculating settling can not be removed owing to the coagulation that adopts, adsorb and the mode of wrapping makes the pollutent sedimentation in the effective sedimentation of organic pollutant more weak absorption or strong absorption of polarity or not co-precipitation.In addition, flocculating settling only is the phase transition that pollutent is implemented, and fundamentally pollutent is not carried out oxidation and mineralising is disinfected.
Processing for organic pollutant, general and economic method is the long biological degradation of processing cycle at present, the processing of the enterprise wastewater that suitable sanitary sewage of biological degradation and toxicity are less, and contain highly toxic organic compound owing to, become the nondegradable waste water of typical biology to biology poisoning with poison property greatly.For the productivity waste water that a lot of industries such as chemical industry, printing and dyeing, oil refining, process hides etc. are discharged, the pollutents of the overwhelming majority are biological nondegradable toxic organic pollutants, can only handle with controllable high-level oxidation technology (AOT).No matter the AOT technology is that the homogeneous process is (as Fenton, UV/H
2O
2, UV/O
3Deng) still be that the out-phase reaction is (as TiO
2Conductor photocatalysis), all being to use or producing strong oxidizer organic pollutant is carried out oxidative degradation, is mineralization of organic material CO apace
2And water, be the most effective at present oxygenolysis technology, have and eliminate toxic characteristic fully.And the oxygenant that AOT uses all is eco-friendly species, as
OH, H
2O
2, O
3,
1O
2,
OOH/O
2 -And O
2, reacted end product is H
2O, therefore, the AOT technology is the green control techniques of coordinating with ecotope.
The present major part of sophisticated in the world AOT technology can only be used lower concentration and slower oxide treatment, as the light activated TiO of UV
2The conductor photocatalysis technology is utilized Fe
2+/ Fe
3+And mixture catalysis H
2O
2The method of oxidation organic pollutant (Fenton and UV/Fenton reaction) etc.These technology are being removed some organic pollutant especially to containing light concentration organic pollutant (during the waste water of COD＜1000ppm), can show good rate of oxidation and efficient, for example, we are published in U.S.'s " physical chemistry " magazine, 1998,102, the article of 5845-5851 " photoinduction degradation of dye pollutent V, radiation of visible light TiO
2Dispersion system automatic photosensitive oxygenolysis rhodamine B " (T.Wu; G.Liu; J.Zhao, Photoassisted degradation of dye pollutants.V.Self-photosensitizedoxidative transformation of Rhodamine B under visible irradiation in aqueousTiO
2Dispersions, J.Phys.Chem.B, 1998,102,5845-5851) with we article " the iron-phthalocyanine efficient oxidation degradable organic pollutant of excited by visible light " (X.Tao at Germany's " applied chemistry " magazine, W.Ma, T.Zhang, J.Zhao, Efficient oxidative degradation of organicpollutants in the presence of iron terasulfophthalayanine under visibleirradiation, Angew.Chem.Int.Ed., 40,3014 (2001)) and " the resin-carried dipyridyl ironwork of visible light catalytic chemoattractant molecule oxygen effectively degrade organic pollutants in water body " (W.Ma, J.Li, X.Tao, J.He, Y.Xu, J.C.Yu, and J.Zhao.Efficient Degradation of Organic PollutantsUsing Dioxygen Activated by Resin-Exchanged Iron (II) Bipyridine underVisible Irradiation.Angew.Chem.Int.Ed.42,1029. (2003).But to some organic pollutant, when the pollutent initial concentration surpassed 1000ppm, then optical efficiency and rate of oxidation were all very low especially, needed very big light intensity, and the cost of oxygenant also will promote significantly, and AOT just becomes very uneconomic method.
Summary of the invention
The present invention can't reach processing intent separately from traditional materialization flocculation and present high-level oxidation technology AOT just, proposes the new technology-photoxidation flocculation technique of the collaborative coupling of a kind of said two devices.It is a kind of on-the-spot method of making flocculation agent and making the strong oxidizing property living radical that the present invention may be summarized to be, and this process is a concerted reaction, and photoxidation and flocculation are forerunner's dependences each other, are that two in the unit operation play the not process of same-action.The flocculation base of photosensitized oxidation agent oxidation-reduction type is converted into the flocculation agent while of oxidized form, produce the strong oxidizing property free radical, and the adsorption that flocculation produces can focus within strong oxidative free radical generation source and the range of scatter organic pollutant, therefore strong oxidative free radical and flocculation adsorbed contaminants can obtain the maximum probability that reacts, and can reach the oxidation efficiency that hundreds of arrives thousands of times.Simultaneously, because homology free radical transient state reductive absorption base (OH yl), can assist that to wrap up in water miscible organism be poly or mixed aggressiveness, the quilt together sedimentation of base of being flocculated.Therefore, provide effective and economic method in the application facet of handling the higher concentration organic pollutant.
Technological core of the present invention is that the synchronism of photoxidation and flocculation takes place, this synchronism is meant the secondary reactions and the enhanced synergistic effect of photoxidation and flocculation, be that photoxidation is necessary reaction transition of flocculation agent, it simultaneously also is the unique step that produces strong oxidative free radical, and the flocculation reaction of secondary is the combination that belongs to same aglucon with the oxidation unit of original position, the i.e. flocculation agent ionic polymerization of the oxidation of the gain and loss state of the single electron of a hydroxyl and organic pollutant and transition takes place in succession, all be to finish within the diffusion life-span at hydroxyl radical free radical, therefore, the efficient and the speed of two differential responses targets have greatly been strengthened.Simple photoxidation and Flocculating Settling Technology do not belong to this claim.
Realize among the present invention that this technology finished by chemical agent kind and addition sequence and reaction times, thereby the present invention is made up of agent kind and method.
The present invention use to as if the processing of polluted-water, this polluted-water can be the waste water that contains particulate matter, the COD value can be up to below 100000, waste water to special industry, the particularly biological poisonous waste water that can not degrade has excellent adaptability and efficient as waste water such as chemical industry, printing and dyeing, process hides, smeltings.
The present invention is the invention of the agent kind and the mode of adding, and concrete water treating equipment and the device equipment that follows conventional lines gets final product with device.
The organic pollutant waste water that contains that will be cleaned in the present invention is referred to as pending water.
Concrete agent kind, addition sequence, photoxidation and the flucculation process of photoxidation flocculation of the present invention are as follows:
Pending water enters mixing device to be mixed with the solubility reduced form flocculant aqueous solution that is added by mixing tank top, and the concentration of solubility reduced form flocculant aqueous solution is 10
-6-1M and staying water are long-pending than=10
-6: 1-10
-2: 1, after mixing, open ultraviolet/visible (UV/Vis) rayed, stirring down, adding concentration is 10
-6-13M hydrogen peroxide or air (or oxygen) (10
-3～10atm), the concentration ratio of hydrogen peroxide or oxygen and solubility reduced form flocculant aqueous solution is 10
3: 1-1: 10
3Contained organic concentration and kind are relevant in flocculation agent consumption and the waste water, after the solubility reduced form flocculation agent after the hybrid reaction changes into oxidized form, add diluted alkaline solution again, and concentration is 10
-6-10M, stir down, regulating the pH that mixes pending water is 3-9, this section reaction times is very key to the COD clearance, the oxyradical that is the flocculation agent of nascent state and not diffusion all takes place at the same time, can cause very high oxidation conversion efficient and absorption to wrap sedimentation, pollutent and together sedimentation of flocculation agent.If the once oxidation flocculation treatment can not reach desired effect, can be once or twice according to the same again step process of the value of rest COD, until meeting the requirements of water quality standard.For the processing of floss after the flocculation can be divided into multistage sedimentation and traditional inclined tube, the multistage sedimentation of swash plate is as broad as long, after entire reaction is finished, remove the processing of organic pollutant after water flow out from final stage settling vessel upper part discharge port, obtain qualified drainage water.
Main reduced form flocculation agent kind of the present invention can be inorganic metal salt and organic salt, and inorganic salt can be water miscible ferrous salt, cuprous salt, manganous salt and cobalt (II) salt and polyacrylamide, the polyacrylic acid polymeric flocculant.
The concentration of described reduced form flocculation agent kind is relevant with the COD value and the desired COD clearance of pending water, and the general concentration range of using is 10
-6-1M.
Described oxygenant can be H
2O
2, air (or oxygen), potassium permanganate, sodium chlorate and clorox the aqueous solution, the working concentration scope is 10
-6-13M.
The concentration ratio of described oxygenant and solubility reduced form flocculation agent is 10
3: 1-1: 10
3
Light source of the present invention can be UV-light and visible light artificial light, also can be to utilize sunlight.
Adding of the present invention and reaction sequence are to add solubility reduced form flocculant aqueous solution earlier, and rayed and stirring add aqueous oxidizing agent solution down then.
Stirring operation of the present invention is necessary, and the mixing speed scope is at 0.1-10000 commentaries on classics/min
Basic solution of the present invention is meant basic solutions such as sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash; Described basic solution concentration can be 10
-6-10M.
Described basic solution is regulated the pH of photoxidation system to 2-12.
Reaction times of the present invention is meant phototransformation reaction times and flocculation reaction time, and be convergence time the pitch time between the two.
The phototransformation reaction times of the present invention is that the reduced form flocculation agent kind more than 95% is oxidized to reaction times of oxidation state from going back ortho states, and generally the scope of using is 0.1-5 hour.
Described flocculation time is the time of the oxidation state flocculation ion hydrolysis flocculation more than 95%, the generally speed decision that should add the time by diluted alkaline, and practical scope is 0.01-5 hour.
Convergence time of the present invention is that photoxidation begins to the interval that adds before the dilute alkaline soln, and this interval is to oxidation and flocculate that very big influence, use range are arranged is 0.1-5 hour.
The repeatedly photoxidation flocculation treatment that can not meet the requirements of the same steps as of being expert at for photoxidation flocculation treatment of the present invention, number of processes according to water quality condition with relevant to water quality requirement, repeat same step and be meant that operation is identical, dosage can be adjusted, and generally is to reduce dosage step by step.
Flocculating settling of the present invention is meant bulk and the sedimentation of shape throw out soon that this technology obtains, and its settling process is identical with general sedimentation.
The preparation and the process for preparation of photoxidation of the present invention flocculation institute consumption agent solution are
(1) preparation of reduced form inorganic flocculating agent kind solution
Prepare dilute hydrochloric acid, nitric acid or the sulphuric acid soln of 0.1～0.5mol/L earlier, the solid-to-liquid ratio according to 10～200 grams per liters adds corresponding soluble salt then, and stirring and dissolving gets final product.The best matching while using of this class solution is placed on for a long time in the air hydrolysis may take place.Described water-soluble salt is water miscible divalent iron salt, water miscible manganous salt, water miscible cuprous salt, water miscible divalent cobalt.
(2) preparation of flocculating polymer agent solution
Selected organic compounds containing nitrogen is dissolved in the ratio that 1 gram/1-50 rises earlier, and the need vigorous stirring could be molten entirely during dissolving, has only complete moltenly just can be effective.Described water-soluble polymer flocculation agent can be a polyacrylamide, polyacrylic acid.
The purposes of photoxidation flocculation technique of the present invention:
Photoxidation flocculation technique of the present invention is mainly used in trade effluent, factory effluents such as the chemical industry of serious pollution, printing and dyeing, papermaking, process hides, refining of petroleum particularly also can be suitable for the photoxidation flocculation treatment of organic pollutant in city domestic sewage and surface water and the tap water.
Description of drawings
Specify the effect of photoxidation flocculation treatment high-concentration waste water of the present invention below in conjunction with accompanying drawing:
Fig. 1 flocculates, directly flocculates for photoxidation and the effect of direct sunshine oxide treatment wastewater from chemical industry compares.
Fig. 2 is for also having added the polyacrylamide of 100ppm in operating except direct flocculation.
Embodiment
1, certain chemical plant M waste water photoxidation flocculation treatment result
This waste water quality index:
pH＝5.55；
Total insoluble substance (SS) 510ppm;
Total organic carbon (TOC)=937.45ppm, wherein principal pollutant matter is drawn back powder (sodium butylnaphthalenesulfonate), aniline, oil of mirbane and vinyl cyanide etc.;
Chemical oxygen demand (COD)=2886ppm;
Each treatment capacity 1000ml;
The reduced form flocculation agent is incorporated as 5g/ time among Fig. 1, oxygenant H
2O
2(30%) add-on is 1ml/ time; Directly flocculation adds solid ferric polysulfate 5g/ time; Directly the UV photoxidation is decomposed and is added H
2O
2(30%) is 1ml/ time.Order be first dissolving flocculation agent, then under the irradiation of UV-light, stirs and adds oxygenant, continues to stir photoresponse 1.5-2 hour, and adjust pH is more than 9, make whole iron sedimentations or filtration after, water outlet enters oxidizing, flocculating next time.
2, certain butyronitrile workshop, chemical plant waste water photoxidation flocculation treatment result
This waste water quality index:
pH＝8.05；
Total insoluble substance (SS) 681ppm;
Draw back powder=734ppm, vinyl cyanide=38ppm;
Total organic carbon (TOC)=1650ppm;
Chemical oxygen demand (COD)=6553ppm;
Each treatment capacity 1000ml.
3, certain chemical plant ethylene unit waste lye waste water photoxidation flocculation treatment result
This waste water quality index:
pH＞14；
COD＝48367ppm；
Total insoluble substance (SS) 230ppm;
Each treatment capacity 2000ml;
Table 1 is photoxidation flocculation treatment ethylene unit high density (48367ppm) waste lye waste water effect
| Number of times | The reduced form flocculation agent | Oxygenant H 2O 2(30％) | Rest COD ppm | COD velocity of variation (%) |
| ????1 | ????70g | ????1.0ml | ?2650.6ppm | ????94.5 |
| ????2 | ????1.5g | ????0.5ml | ?1636.2ppm | ????96.6 |
| ????3 | ????1.5g | ????0.5ml | ?644.2ppm | ????98.7 |
4, certain dyes the chemical plant and contains toxicity nitrobenzene waste water photoxidation flocculation treatment result
This waste water quality index:
pH＝13.15；
TOC＝133.8ppm；
COD＝330.5ppm；
Total insoluble substance (SS) 80ppm;
Each treatment capacity 2000ml.
Table 2 is photoxidation flocculation treatment toxicity oil of mirbane lower concentration (COD:330.5ppm) waste water effect
| Flocculant addition | ??H 2O 2??(30％) | Pollutent oxidation is in time eliminated | |||
| ????1(h) | ????2(h) | ????3(h) | |||
| 0.05g | (0.3ml gradation) | TOC clearance (%) | ????17.1 | ????46.2 | ????70.7 |
| COD clearance (%) | ????47.9 | ????63.5 | ????81.2 | ||
| 0.05g | (0.6ml gradation) | TOC clearance (%) | ????64.3 | ????83.5 | ????92.5 |
| COD clearance (%) | ????72.8 | ????87.8 | ????96.8 | ||
With ferrous sulfate (FeSO
47H
2O) 5 grams join the 2000ml waste water solution (COD2800ppm SS:521ppm), stir and (40 changes/min) after the dissolving, add the H of 1mol/L under the UV rayed
2O
2Solution 20ml, adition process continues 15min, continue to stir that (40 change/min) rayed 1.5 hours down, after adjusting stirring velocity and be～5 commentariess on classics/min, add dilute alkaline soln and regulate about pH to 8, it is complete that iron is flocculated, standing sedimentation.Inclining then, supernatant liquor be water outlet, measures COD value and whether reach requirement, surpasses desired value, needs the capable again primary treatment of the same manner, gets final product until reaching requirement.
30% manganese sulfate solution is joined in the waste water that contains vinyl cyanide that 2000ml COD is 2500ppm, under the UV rayed, add the H of 1mol/L
2O
2Solution 40ml, adition process continues 30min, and adjusting stirring velocity then is that 2-3 commentaries on classics/min adds 0.1% polyacrylamide (molecular weight is greater than 9,000,000) solution 0.1ml, adjusts the pH value of aqueous systems to 8-9 with dilute alkaline soln under the rayed, continue to stir photoresponse 1 hour, standing sedimentation gets final product.
With the inferior cobalt (CoSO of sulfuric acid
47H
2O) 25g joins the aqueous solution that contains the solubility organic pollutant (COD～20000ppm, SS:390ppm) among the 2000ml, stirring and dissolving adds 27% H under the UV rayed
2O
22ml continues photoresponse 2 hours altogether, and adjusting stirring velocity is 2-3 commentaries on classics/min.Add 0.1% polyacrylamide (molecular weight is greater than 9,000,000) solution 0.1ml then, simultaneously with the pH of dilute alkaline soln regulator solution to 7-9, flocculating settling leaves standstill or filters and gets final product.
Embodiment 4
Copperas solution 0.5mol/L 30ml is joined the 2000ml waste water solution, make the liquid layer thickness of solution in container, after the stirring and dissolving, add the H of 1mol/L at 2-3cm
2O
2Solution 20ml, adition process continues 15min, utilizes sunlight reaction 1.5 hours under continuing to stir, and adjusts stirring velocity then and is＜5 commentaries on classics/min, adds dilute alkaline soln and regulates about pH to 8, makes the iron flocculation fully, and standing sedimentation gets final product.Inclining then, supernatant liquor be water outlet, measures COD value and whether reach requirement, surpasses desired value, needs the capable again primary treatment of the same manner, gets final product until reaching requirement.
Embodiment 5
With ferrous sulfate (FeSO
47H
2O) 5 grams join the 2000ml waste water solution, after the stirring and dissolving, add the H of 1mol/L under the UV rayed simultaneously respectively
2O
2Solution 20ml and dilute alkaline soln are regulated about pH to 8, and this adition process continues 15min, and adjusting stirring velocity is that＜5 commentaries on classics/min continue to stir rayed 1.5 hours, makes the iron flocculation fully, standing sedimentation.Inclining then, supernatant liquor be water outlet, measures COD value and whether reach requirement, surpasses desired value, needs the capable again primary treatment of the same manner, gets final product until reaching requirement.
Embodiment 6
With ferrous sulfate (FeSO
47H
2O) 5 grams join the 2000ml waste water solution, stir and (40 change/min) after the dissolving, add the H of 1mol/L
2O
2Solution 20ml, adition process continues 15min, continues to stir reaction down 1.5 hours, after the adjustment stirring velocity is～5 commentaries on classics/min, adds dilute alkaline soln and regulates about pH to 8, makes the iron flocculation fully, standing sedimentation.
Embodiment 7
With ferrous sulfate (FeSO
47H
2O) 5 grams join the 2000ml waste water solution, after the stirring and dissolving, the sodium chlorate solution 20ml that adds 1mol/L under the UV rayed, adition process continues 15min, continue stirring (40 changes/min) rayed 1.5 hours down, after adjusting stirring velocity and be～5 commentariess on classics/min, about adding dilute alkaline soln adjusting pH to 8, make the iron flocculation fully, standing sedimentation.Inclining then, supernatant liquor be water outlet, measures COD value and whether reach requirement, surpasses desired value, needs the capable again primary treatment of the same manner, gets final product until reaching requirement.
Reference examples 1
With ferrous sulfate (FeSO
47H
2O) 5 grams join the 2000ml waste water solution, stir (40 change/min) after the dissolving, UV rayed stirring reaction 1.5 hours after adjusting stirring velocity and be～5 commentariess on classics/min, adds dilute alkaline soln and regulates about pH to 8, and it is complete that iron is flocculated, standing sedimentation.
Reference examples 2
With Tai-Ace S 150 (Al
3(SO
4)
318H
2O) 5 grams join the 2000ml waste water solution, after the stirring and dissolving, add the H of 1mol/L under the UV rayed
2O
2Solution 20ml, adition process continues 15min, continue to stir and (40 to change/min) rayed 1.5 hours down, after adjusting stirring velocity and be～5 commentariess on classics/min, about adding dilute alkaline soln adjusting pH to 8, to make aluminum flocculation complete, standing sedimentation.
Reference examples 3
Stir down, the UV rayed adds the H of 1mol/L simultaneously
2O
2Solution 20ml is to the 2000ml waste water solution, and this adition process continues 15min, continues then to stir rayed 1.5 hours, standing sedimentation.
Claims (9)
1, a kind of method of photoxidation flocculation treatment organic pollutant wastewater, constitute by photoxidation and original position flocculating settling are collaborative, oxidized dose of oxidation under UV-light/visible light-inducing of water miscible reduced form flocculation agent, become the core ion of facile hydrolysis flocculation, produce the free radical and the water soluble contaminants reaction of strong oxidizing property simultaneously; Flocculation process is to be core with the oxidized form metal ion, forms multinuclear aggregate generation sedimentation under the effect of hydroxyl precipitation agent; The steps include:
Pending water enters mixing device to be mixed with solubility reduced form flocculant aqueous solution, and the concentration of flocculant aqueous solution is 10
-6-1M and staying water are long-pending than=10
-6: 1-10
-2: 1, after mixing, ultraviolet irradiation 0.1-2 hour, stirring down, adding concentration is 10
-6-13M oxygenant, the concentration ratio of oxygenant and solubility reduced form flocculant aqueous solution is 10
3: 1-1: 10
3, react after 0.1-5 hour that to add concentration be 10
-6-10M basic solution, regulating the pH that mixes pending water is 2-10, stirs standing sedimentation or filtration 0.01-5 hour;
Described solubility reduced form flocculation agent is inorganic salt flocculation agent or organic salt flocculation agent, and wherein: inorganic salt are that water-soluble ferrous salt, cuprous salt, manganous salt are or/and cobalt (II) salt; Organic salt is that polyacrylamide is or/and polyacrylic acid;
Described oxygenant is H
2O
2, air, oxygen, potassium permanganate, sodium chlorate be or/and the aqueous solution of clorox.
2, method according to claim 1 is characterized in that, the clear liquid after standing sedimentation or the filtration can be handled once or several by the same step of claim 1 again.
3, method according to claim 1, it is characterized in that, adopt inclined tube, the multistage sedimentation of swash plate for the floss after the flocculation, after entire reaction is finished, water flows out from final stage settling vessel upper part discharge port after removing the processing of organic pollutant, obtains qualified drainage water.
4, method according to claim 1 is characterized in that, described inorganic salt are that water miscible divalent iron salt, water miscible manganous salt, water miscible cuprous salt are or/and water miscible divalent cobalt.
5, method according to claim 1, it is characterized in that, the preparation of described reduced form inorganic flocculating agent: prepare dilute hydrochloric acid, nitric acid or the sulphuric acid soln of 0.1～0.5mol/L earlier, the solid-to-liquid ratio according to 10～200 grams per liters adds corresponding soluble salt, stirring and dissolving then.
6, method according to claim 1 is characterized in that, the preparation of described organic-flocculation agent solution: organic compounds containing nitrogen is under agitation dissolved in the ratio that 1 gram/1-50 rises.
7, method according to claim 1 is characterized in that, the mixing speed of described photoxidation and flocculation process is 1-100 commentaries on classics/min, and mixing speed is 1-10 commentaries on classics/min when adding alkaline solution.
8, method according to claim 1 is characterized in that, described basic solution is that sodium hydroxide, potassium hydroxide, calcium hydroxide are or/and the yellow soda ash basic solution.
9, method according to claim 1 is characterized in that, described light source is UV-light/visible light artificial light or sunlight.
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