CN106365366B - The preprocess method of one kind 2,4-D acid synthesis technology waste water - Google Patents
The preprocess method of one kind 2,4-D acid synthesis technology waste water Download PDFInfo
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- CN106365366B CN106365366B CN201610795264.XA CN201610795264A CN106365366B CN 106365366 B CN106365366 B CN 106365366B CN 201610795264 A CN201610795264 A CN 201610795264A CN 106365366 B CN106365366 B CN 106365366B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000005516 engineering process Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000012530 fluid Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005273 aeration Methods 0.000 claims abstract description 10
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 47
- 230000003647 oxidation Effects 0.000 abstract description 45
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 25
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 229960004275 glycolic acid Drugs 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 isopropyl ester Chemical class 0.000 description 5
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 4
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- KHZWIIFEFQBNKL-UHFFFAOYSA-N 2-(2,6-dichlorophenoxy)acetic acid Chemical compound OC(=O)COC1=C(Cl)C=CC=C1Cl KHZWIIFEFQBNKL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UQMRAFJOBWOFNS-UHFFFAOYSA-N butyl 2-(2,4-dichlorophenoxy)acetate Chemical compound CCCCOC(=O)COC1=CC=C(Cl)C=C1Cl UQMRAFJOBWOFNS-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- 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
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses the preprocess methods of one kind 2,4-D acid synthesis technology waste water, comprising: (1) pH value of 2,4-D acid synthesis technology waste water is adjusted to 5~9, H is added2O2, in mass, H2O2Additional amount be the 0.1~10% of wastewater quality, reaction temperature is 20~70 DEG C, and using immobilized AlCl_3 catalyst, the mass space velocity of 2,4-D acid synthesis technology wastewater treatments is 0.5~5h‑1, the pH value of system is maintained at 5~9 in reaction process, after processing treatment fluid I；(2) H is added into treatment fluid I2O2, in mass, H2O2Additional amount be treatment fluid I mass 1~20%, the pH value of system is maintained at 5~9,20~50 DEG C of 1~5h of aeration reaction under ultraviolet irradiation, water outlet must be handled.Class Fenton oxidation substantially increases the degradation efficiency of photochemical catalytic oxidation to the removal of chroma in waste water, and the two has synergistic effect, and the treatment effect that the two combines is far longer than the simple adduction of the independent treatment effect of the two.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to the pretreatment side of one kind 2,4-D acid synthesis technology waste water
Method.
Background technique
2,4-D acid are efficient, interior suction, herbicide and plant growth regulator with high selectivity, are had by force to plant
Strong physiological activity.2,4-D acid have good herbicidal effect and cheap product price, when using extensively and using at home
Between it is long, while 2,4-D acid are the raw materials of the serial herbicides such as 2,4-D butyl ester, isopropyl ester, amine salt and diamine salts.
Industrially, using phenol and monoxone as raw material, product 2,4-D acid are obtained through phenol chlorination, synthesis, acid out.In work
Industry metaplasia produces the waste water that 2,4-D acid generates, containing 2 micro, 4-D, 2,6-D and 2,4- Dichlorophenol, 2,6- Dichlorophenol and higher
Phenol, hydroxyacetic acid and sodium chloride, the concentration of organic wastewater height, strong toxicity, biological degradability are poor, studies have shown that: useless
2,4-D acid contained in water has carcinogenicity, and the degradation of 2,4-D acid is very slow under natural conditions, and average degradation time is 20
It, degradation product can accumulate in water or in soil, and local soil and water body can be polluted if direct emission, bring serious
Environmental hazard, threaten to human health.The wastewater treatment is difficult, and processing cost is high, as the common water process work such as flocculation
The concentration of 2,4-D acid cannot be reduced to the emission level of permission by skill.
The processing method of current 2,4-D acid producing waste water mainly has resin adsorption method, organic solvent extractionprocess, liquid film extraction
Method, Fenton oxidation method etc..First three methods are physical partition method, only for production waste water in 2,4- Dichlorophenol, 2,
6- Dichlorophenol and hydroxyacetic acid play certain separation inspissation, obtained 2,4- Dichlorophenol, 2,6- Dichlorophenol and hydroxyl second
The concentration of useless 2,6- Dichlorophenol and hydroxyacetic acid is high in acid blend, and useful 2,4- Dichlorophenol concentration are low, therefore again
What is utilized has little significance, and recycling influences whether that 2,4-D calculates product quality instead, it is also necessary to be further processed.In addition in waste water
2,4-D, the pollutants such as 2,6-D still need to be further processed, it is seen then that use resin adsorption method, organic solvent extractionprocess, liquid film extraction
Method is unsatisfactory to handle 2,4-D production waste water.Fenton oxidation method is a kind of advanced oxygen combined by ferrous salt and hydrogen peroxide
Change technology, but the effective pH value range of Fenton oxidation system is relatively narrow, is 2~4, therefore the application of Fenton oxidation method is only limitted to acid
Property environment, under alkaline condition, the dehydration rate and COD removal rate of waste water all can sharp fall, and 2,4-D acid synthesis technologies are useless
Water is larger in alkaline and coloration, then needs 2,4-D acid synthesis technology waste water according to the processing of Fenton oxidation method with largely
Acid is adjusted to acidity, and the technology oxidizer is big, and processing cost is high, and 650 yuan of wastewater treatment expense per ton or so, enterprise
It is difficult to bear.
Photocatalysis oxidation technique is aoxidized using light excitation by O2、H2O2Equal oxidants are combined with light radiation.It uses up main
For ultraviolet light, including UV-H2O2、UV-O2Etc. techniques, can be used for handling the hard-degraded substance in waste water.In addition, ultraviolet having
In the Fenton system of light, there is synergistic effects between ultraviolet light and iron ion, make H2O2Decompose the speed for generating hydroxyl radical free radical
Rate is greatly speeded up, and promotes the oxidation removal of organic matter.But the coloration of waste water influences the efficiency of photochemical catalytic oxidation.
Summary of the invention
The present invention provides the preprocess method of one kind 2,4-D acid synthesis technology waste water, and this method is easy to operate, treatment effeciency
Height handles the good biodegradability of water outlet, subsequent to carry out biochemical treatment, and this method processing cost is lower.
The preprocess method of one kind 2,4-D acid synthesis technology waste water, comprising:
(1) pH value of 2,4-D acid synthesis technology waste water is adjusted to 5~9, H is added2O2, in mass, H2O2Addition
Amount is the 0.1~10% of wastewater quality, and reaction temperature is 20~70 DEG C, and using immobilized AlCl_3 catalyst, 2,4-D acid synthesis technologies are useless
The mass space velocity of water process is 0.5~5h-1, the pH value of system is maintained at 5~9 in reaction process, after processing treatment fluid I；
(2) H is added into treatment fluid I2O2, in mass, H2O2Additional amount be treatment fluid I mass 1~20%, will
The pH value of system is maintained at 5~9,20~50 DEG C of 1~5h of aeration reaction under ultraviolet irradiation, must handle water outlet.
2,4-D acid synthesis technology chroma in waste water and COD higher, biodegradability are poor.The present invention using class Fenton oxidation method with
Photocatalytic oxidation, which combines, handles 2,4-D acid synthesis technology waste water, is first carried out using class Fenton oxidation method to waste water
The coloration of waste water is reduced to 200 times hereinafter, to improve the efficiency of subsequent photochemical catalytic oxidation, while hardly possible is aoxidized by decolorization
The macromolecular substance of degradation is decomposed into small molecule substance, and subsequent photochemical catalytic oxidation further removes the COD in waste water, will
Macromolecular substance oxygenolysis is the small molecule substance that can be bioavailable.In processing method of the invention, class Fenton oxygen
Change and photochemical catalytic oxidation acts synergistically, improve the biodegradability of waste water, after the processing of two step synergistic oxidations, processing water outlet can be carried out
Biochemical treatment, to reach discharge standard.
The tool such as preprocess method Pyrogentisinic Acid's class waste water, carboxylic acids waste water, aromatic hydrocarbons waste water and waste water containing oils of the invention
There is preferable treatment effect, especially suitable for the processing to 2,4-D acid synthesis technology waste water.
Preferably, before step (1) further include: to 2,4-D acid synthesis technology waste water be added adsorbent absorption 0.1~
10h, in mass, the additional amount of adsorbent are the 0.1~10% of wastewater quality, carry out subsequent reactions after filtering.
Adsorbent adsorbs flocculent deposit and solid particle in waste water, improves subsequent class Fenton oxidation and photocatalytic-oxidation
The efficiency of change.
In step (1):
The Fenton oxidation method of standard refers to Fe2+/H2O2System, wherein Fe2+Mainly as the catalyst of reaction, and H2O2It is logical
It crosses the OH that reaction generates and plays oxidation.Class Fenton's reaction be in addition to Fe (II), Fe (III), iron-bearing mineral and its
His some transition metal such as Co, Cd, Cu, Ag, Mn, Ni etc. can accelerate or substitute Fe (II) and to H2O2Play catalytic action
The general name of one kind reaction.
The pH value of 2,4-D acid synthesis technology waste water is first adjusted to 5~9, if generating flocculent deposit, adsorbent suction can be added
Attached 0.1~10h, in mass, the additional amount of adsorbent are the 0.1~10% of wastewater quality, carry out class Fenton oxygen after filtering again
Change reaction.
Preferably, the adsorbent is a kind of or several in active carbon, activated alumina, silica and diatomite
Kind；Most preferably, the preferred active carbon of the adsorbent.The optional activated coke of active carbon, active carbon particle, active carbon powder and activity
One or more of Carbon fibe.
Preferably, the carrier of immobilized AlCl_3 catalyst is activity in class Fenton oxidation reaction in step (1) of the present invention
Charcoal, aluminium oxide, molecular sieve, silica or diatomite, the active constituent of immobilized AlCl_3 catalyst are in iron, cobalt, manganese, cerium and palladium
One or more.
Using immobilized AlCl_3 catalyst be convenient for catalyst recycling, save the cost, and can prevent catalyst residual with
In waste water, the water quality of processing water outlet is influenced.
In immobilized AlCl_3 catalyst under the action of active constituent, H2O2It decomposes and generates OH, the oxidizing electrode current potential of OH is high
Up to 2.80V, and there is very strong addition reaction characteristic, it can be without most of organic matters in selective oxidation waste water, by macromolecular
Organic matter resolves into more degradable small organic molecule, and is easy to interrupt the chromophore of useless Organic substance in water, can be effective
The coloration of ground removal waste water.
In the reaction of class Fenton oxidation, the pH value of system has important influence to oxidation effectiveness.Preferably, step (1)
In, the pH value of system is maintained at 6~8, further preferably 7~8 in reaction process.The pH value of system is lower than 6 or can higher than 8
It can lead to catalyst inactivation.
Preferably, reaction temperature is 40~60 DEG C, most preferably, reaction temperature is 50 DEG C.Reaction temperature is less than 40 DEG C
When, catalyst activity is lower；When reaction temperature is greater than 60 DEG C, hydrogen peroxide is easy to decompose, and utilization rate is lower.
Preferably, after the coloration of 2,4-D acid synthesis technology waste water is down to 0~200 times, then executing step in step (1)
Suddenly (2).
After the coloration of 2,4-D acid synthesis technology waste water is down to 0~200 times, then the photochemical catalytic oxidation of step (2) is executed,
After the coloration of waste water reduces, ultraviolet light can sufficiently irradiate waste water, promote H2O2It decomposes and generates .OH, improve photochemical catalytic oxidation to waste water
Degradation efficiency.Therefore step (1) and step (2) have good synergistic effect.
In step (2):
Preferably, being additionally added ferrous ion in step (2), in mass, the additional amount of ferrous ion is wastewater quality
0.1%~1.0%.
H2O2Under the double action of ferrous ion and ultraviolet light, it can more fully decompose and generate OH.Ultraviolet light and Fe2+
To H2O2Catalytic decomposition there are synergistic effect, i.e., the generating rate of .OH is much larger than traditional Fenton oxidation and ultraviolet catalytic H2O2Point
The simple adduction of rate is solved, therefore, the heating of ferrous ion keeps the oxidative degradation effect of step (2) more preferable.
Preferably, photochemical catalyst is additionally added in step (2), it is further preferred that the photochemical catalyst being added is
TiO2。
Photochemical catalyst is the energy converted light energy into as chemical reaction, generates catalytic action, makes hydrone, oxygen, H2O2
It is excited into the OH i.e. O of great oxidizing force2 -。
A preferred technical solution are as follows:
The preprocess method of kind 2,4-D acid synthesis technology waste water, comprising:
(1) pH value of 2,4-D acid synthesis technology waste water is adjusted to 5~9, H is added2O2, in mass, H2O2Addition
Amount is the 0.1~10% of wastewater quality, and reaction temperature is 20~70 DEG C, using immobilized AlCl_3 catalyst, by system in reaction process
PH value be maintained at 5~9, after processing treatment fluid I, adjust 2,4-D acid synthesis technology wastewater treatment mass space velocity, make to handle
The coloration of liquid I is 0~200 times；
(2) ferrous ion and H are added into treatment fluid I2O2, in mass, ferrous ion additional amount is treatment fluid I mass
0.1~1.0%, H2O2Additional amount be treatment fluid I mass 1~20%, the pH value of system is maintained at 5~9,20~50
1~5h of aeration reaction DEG C under ultraviolet irradiation, must handle water outlet.
Compared with prior art, the invention has the benefit that
Processing method of the invention combines class Fenton oxidation and photochemical catalytic oxidation, goes first with the reaction of class Fenton oxidation
Except the chromophore of useless Organic substance in water, the coloration of waste water is effectively removed, and larger molecular organics are resolved into more degradable
Small organic molecule recycles photochemical catalytic oxidation that will be difficult to biodegradable organic pollutant degradation in waste water biochemical at being easier to
The substance of degradation substantially increases the biochemical property of processing water outlet, can carry out subsequent biochemical treatment.Class Fenton oxidation is to waste water
The removal of coloration substantially increases the degradation efficiency of photochemical catalytic oxidation, and the two has synergistic effect, the treatment effect that the two combines
It is far longer than the simple adduction of the independent treatment effect of the two.
Processing method of the invention is easy to operate, and cost is relatively low, high treating effect.
Specific embodiment
Wherein chroma in waste water measuring method extension rate method measures.
Embodiment 1
2,4-D acid synthesis technology waste water, main component are phenol, hydroxyacetic acid and 2, and 4-D acid etc., dark brown is transparent
Liquid.Its pH=9.38, COD=18000mg/L, NH3- N=16mg/L, TN=60mg/L, coloration are 500 times, BOD/COD=
0.02, solid content 8.3%.
(1) class Fenton oxidation: being adjusted to 8.0 for the pH of waste water, and the hydrogen peroxide that mass percent concentration is 30% is added, with
Quality meter makes H in waste water2O2Quality be wastewater quality 1%, keep reaction temperature be 50 DEG C, used catalyst be it is immobilized
The carrier of type catalyst, immobilized AlCl_3 catalyst is active carbon, and active constituent is iron.
The mass space velocity of wastewater treatment is 2.0h-1, obtain treatment fluid I, the water quality for the treatment of fluid I: pH=7.8, COD=
16320mg/L, NH3- N=24mg/L, 50 times of coloration, BOD/COD=0.1；
(2) photochemical catalytic oxidation: the hydrogen peroxide that mass percent concentration is 30% being added into treatment fluid 1, adds in two times,
Every 1h addition is primary, in mass, makes H in treatment fluid I every time2O2Quality be wastewater quality 4.5%.It is persistently shone in mercury lamp
It penetrates down, keeping reaction temperature is 25 DEG C, aeration reaction 2 hours.Handle effluent quality: pH=8.2, COD=2800mg/L, NH3-
N=34mg/L, BOD/COD=0.7.
Embodiment 2
Paranitroanilinum waste water, it is reddish brown, opaque, there is strong pungent smell, pH=8.6, COD=
12000mg/L, NH3- N=647mg/L, TN=3351mg/L, coloration are 2300 times, BOD/COD=0.16.
(1) class Fenton oxidation: being adjusted to 7.5 for the pH of waste water, and the hydrogen peroxide that mass percent concentration is 30% is added, with
Quality meter makes H in waste water2O2Quality be wastewater quality 6%, keep reaction temperature be 50 DEG C, waste water is kept in reaction process
PH is 7.5, and used catalyst is immobilized AlCl_3 catalyst, and the carrier of immobilized AlCl_3 catalyst is active carbon, and active constituent is iron.
The mass space velocity of wastewater treatment is 1.5h-1, obtain treatment fluid I, the water quality for the treatment of fluid I: pH=7.2, COD=
4300mg/L, NH3- N=2100mg/L, 800 times of coloration, BOD/COD=0.28；
(2) photochemical catalytic oxidation: the hydrogen peroxide that mass percent concentration is 30% is added into treatment fluid 1 to be made in mass
H in treatment fluid I2O2Quality be wastewater quality 4.0%.Under mercury lamp prolonged exposure, keeping reaction temperature is 25 DEG C, aeration
Reaction 3 hours.Handle effluent quality: pH=6.7, COD=680mg/L, NH3- N=1200mg/L, BOD/COD=0.5.
Embodiment 3
Amino benzene analog waste water, deep blue purple color, pH=9.1, COD=5100mg/L, TOC=2400mg/L, NH3- N=
2100mg/L, TN=4600mg/L, coloration are 1800 times, BOD/COD=0.03.
(1) class Fenton oxidation: being adjusted to 7.6 for the pH of waste water, and the hydrogen peroxide that mass percent concentration is 30% is added, with
Quality meter makes H in waste water2O2Quality be wastewater quality 2%, keep reaction temperature be 50 DEG C, waste water is kept in reaction process
PH is 7.6, and used catalyst is immobilized AlCl_3 catalyst, and the carrier of immobilized AlCl_3 catalyst is active carbon, and active constituent is iron.
The mass space velocity of wastewater treatment is 1.2h-1, obtain treatment fluid I, the water quality for the treatment of fluid I: pH=7.2, COD=
3200mg/L, NH3- N=970mg/L, coloration are 850 times, BOD/COD=0.21；
(2) photochemical catalytic oxidation: the hydrogen peroxide that mass percent concentration is 30% is added into treatment fluid 1 to be made in mass
H in treatment fluid I2O2Quality be wastewater quality 4.0%.Under mercury lamp prolonged exposure, keeping reaction temperature is 25 DEG C, aeration
Reaction 3 hours.Handle effluent quality: pH=6.7, COD=370mg/L, NH3- N=320mg/L, BOD/COD=0.40.
Comparative example 1
2,4-D acid synthesis technology waste water, main component are phenol, hydroxyacetic acid and 2, and 4-D acid etc., dark brown is transparent
Liquid.Its pH=9.38, COD=18000mg/L, NH3- N=16mg/L, TN=60mg/L, coloration are 500 times, BOD/COD=
0.02, solid content 8.3%.
Photochemical catalytic oxidation: being adjusted to 8.0 for the pH of waste water, and the dioxygen that mass percent concentration is 30% is added into waste water
Water adds in two times, and every 1h addition is primary, in mass, makes H in treatment fluid I every time2O2Quality be wastewater quality
4.5%.Under mercury lamp prolonged exposure, keeping reaction temperature is 25 DEG C, aeration reaction 2 hours.Effluent quality: pH=5.7 is handled,
COD=12000mg/L, NH3- N=21mg/L, BOD/COD=0.2.
Comparative example 2
2,4-D acid synthesis technology waste water, main component are phenol, hydroxyacetic acid and 2, and 4-D acid etc., dark brown is transparent
Liquid.Its pH=9.38, COD=18000mg/L, NH3- N=16mg/L, TN=60mg/L, coloration are 500 times, BOD/COD=
0.02, solid content 8.3%.
(1) class Fenton oxidation: being adjusted to 3.0 for the pH of waste water, and the hydrogen peroxide that mass percent concentration is 30% is added, with
Quality meter makes H in waste water2O2Quality be wastewater quality 1%, keep reaction temperature be 50 DEG C, used catalyst be it is immobilized
The carrier of type catalyst, immobilized AlCl_3 catalyst is active carbon, and active constituent is iron.
The mass space velocity of wastewater treatment is 2.0h-1, obtain treatment fluid I, the water quality for the treatment of fluid I: pH=2.5, COD=
17100mg/L, NH3- N=13mg/L, 250 times of coloration, BOD/COD=0.11；
(2) photochemical catalytic oxidation: the hydrogen peroxide that mass percent concentration is 30% being added into treatment fluid 1, adds in two times,
Every 1h addition is primary, in mass, makes H in treatment fluid I every time2O2Quality be wastewater quality 4.5%.It is persistently shone in mercury lamp
It penetrates down, keeping reaction temperature is 25 DEG C, aeration reaction 2 hours.Handle effluent quality: pH=2.1, COD=5300mg/L, NH3-
N=26mg/L, BOD/COD=0.31.
Comparative example 3
2,4-D acid synthesis technology waste water, main component are phenol, hydroxyacetic acid and 2, and 4-D acid etc., dark brown is transparent
Liquid.Its pH=9.38, COD=18000mg/L, NH3- N=16mg/L, TN=60mg/L, coloration are 500 times, BOD/COD=
0.02, solid content 8.3%.
(1) class Fenton oxidation: being adjusted to 10.0 for the pH of waste water, and the hydrogen peroxide that mass percent concentration is 30% is added,
In mass, make H in waste water2O2Quality be wastewater quality 1%, keep reaction temperature be 50 DEG C, used catalyst is solid
The carrier of supported catalyst, immobilized AlCl_3 catalyst is active carbon, and active constituent is iron.
The mass space velocity of wastewater treatment is 2.0h-1, obtain treatment fluid I, the water quality for the treatment of fluid I: pH=9.3, COD=
16300mg/L, NH3- N=19mg/L, 350 times of coloration, BOD/COD=0.09；
(2) photochemical catalytic oxidation: the hydrogen peroxide that mass percent concentration is 30% being added into treatment fluid 1, adds in two times,
Every 1h addition is primary, in mass, makes H in treatment fluid I every time2O2Quality be wastewater quality 4.5%.It is persistently shone in mercury lamp
It penetrates down, keeping reaction temperature is 25 DEG C, aeration reaction 2 hours.Handle effluent quality: pH=7.1, COD=6800mg/L, NH3-
N=31mg/L, BOD/COD=0.45.
By embodiment 1, comparative example 1,2,3 it is found that class Fenton oxidation greatly improves the removal of chroma in waste water in the present invention
The degradation efficiency of photochemical catalytic oxidation, the two have a synergistic effect, both the treatment effect that the two combines is far longer than independent place
Manage the simple adduction of effect.
Claims (5)
1. one kind 2, the preprocess method of 4-D acid synthesis technology waste water characterized by comprising
(1) pH value of 2,4-D acid synthesis technology waste water is adjusted to 5 ~ 9, H is added2O2, in mass, H2O2Additional amount be useless
The 0.1 ~ 10% of water quality, reaction temperature are 20 ~ 70 DEG C, using immobilized AlCl_3 catalyst, 2,4-D acid synthesis technology wastewater treatments
Mass space velocity is 0.5 ~ 5h-1, the pH value of system is maintained at 6 ~ 8 in reaction process, by the coloration of 2,4-D acid synthesis technology waste water
After being down to 0 ~ 200 times, treatment fluid I is obtained after processing；
The carrier of immobilized AlCl_3 catalyst is active carbon, aluminium oxide, molecular sieve, silica or diatomite, immobilized AlCl_3 catalyst
Active constituent be iron, cobalt, manganese, cerium or palladium；
(2) H is added into treatment fluid I2O2, in mass, H2O2Additional amount be I mass for the treatment of fluid 1 ~ 20%, by the pH of system
Value is maintained at 5 ~ 9,20 ~ 50 DEG C of 1 ~ 5h of aeration reaction under ultraviolet irradiation, must handle water outlet.
2. the preprocess method of 2,4-D acid synthesis technology waste water according to claim 1, which is characterized in that step (1)
Before further include: adsorbent is added to 2,4-D acid synthesis technology waste water and adsorbs 0.1 ~ 10h, in mass, the additional amount of adsorbent
It is the 0.1 ~ 10% of wastewater quality.
3. the preprocess method of 2,4-D acid synthesis technology waste water according to claim 1, which is characterized in that step (1)
In, reaction temperature is 40 ~ 60 DEG C.
4. the preprocess method of 2,4-D acid synthesis technology waste water according to claim 1, which is characterized in that step (2)
In, it is additionally added ferrous ion, in mass, the additional amount of ferrous ion is the 0.1 ~ 1.0% of wastewater quality.
5. the preprocess method of 2,4-D acid synthesis technology waste water according to claim 1, which is characterized in that step (2)
In, it is additionally added photochemical catalyst.
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| CN104743652A (en) * | 2015-03-05 | 2015-07-01 | 武汉森泰环保工程有限公司 | Method for processing degradation-resistant organic wastewater and multi-element catalyst adopted by method |
| CN104923229A (en) * | 2014-03-21 | 2015-09-23 | 中国科学院大连化学物理研究所 | Activated carbon catalyst used for Fenton-like technology, and preparation and application thereof |
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| CN104923229A (en) * | 2014-03-21 | 2015-09-23 | 中国科学院大连化学物理研究所 | Activated carbon catalyst used for Fenton-like technology, and preparation and application thereof |
| CN104743652A (en) * | 2015-03-05 | 2015-07-01 | 武汉森泰环保工程有限公司 | Method for processing degradation-resistant organic wastewater and multi-element catalyst adopted by method |
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