CN102659235B - Method for treating dye wastewater - Google Patents
Method for treating dye wastewater Download PDFInfo
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- CN102659235B CN102659235B CN 201210152982 CN201210152982A CN102659235B CN 102659235 B CN102659235 B CN 102659235B CN 201210152982 CN201210152982 CN 201210152982 CN 201210152982 A CN201210152982 A CN 201210152982A CN 102659235 B CN102659235 B CN 102659235B
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- waste water
- dyestuff
- hydrogen peroxide
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- fenton
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- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 80
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 31
- 238000007254 oxidation reaction Methods 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- -1 iron ions Chemical class 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- IZYOJOIBDJFMOI-UHFFFAOYSA-N [O-2].[Fe+2].[Cl+] Chemical compound [O-2].[Fe+2].[Cl+] IZYOJOIBDJFMOI-UHFFFAOYSA-N 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 20
- 229940012189 methyl orange Drugs 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 19
- 238000012545 processing Methods 0.000 description 17
- 238000005070 sampling Methods 0.000 description 15
- 239000001048 orange dye Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 239000012028 Fenton's reagent Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
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- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
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- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 1
- JMEVHYCNAPFOAB-UHFFFAOYSA-N 2-(3-hydroxy-5-sulfo-1H-indol-2-yl)-3-oxoindole-5-sulfonic acid Chemical compound Oc1c([nH]c2ccc(cc12)S(O)(=O)=O)C1=Nc2ccc(cc2C1=O)S(O)(=O)=O JMEVHYCNAPFOAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 235000016936 Dendrocalamus strictus Nutrition 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- 241000187654 Nocardia Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
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- 238000004061 bleaching Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
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- 229940068840 d-biotin Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
- 229960003988 indigo carmine Drugs 0.000 description 1
- 235000012738 indigotine Nutrition 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
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- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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Abstract
The invention discloses a method for treating dye wastewater. According to the method, a multi-phase Fenton catalytic oxidation mode, namely a method for degrading the organic wastewater by catalytically oxidizing hydrogen peroxide with chlorine iron oxide, is adopted; the method is simple, mild in reaction conditions, high in speed and easy to operate, and well overcomes the defects of homogeneous Fenton oxidation, namely (1) consumption of a large quantity of acid is avoided because an acid condition is not required and the pH value is not required to be regulated in reaction; (2) Fe(OH)3 sediment is not formed in the reaction, and secondary pollution is not produced; (3) because the chlorine iron oxide is not dissolved in water and iron ions are not ionized in the water, the treated water is not yellow; (4) compared with similar Fenton oxidation, conditions such as ultraviolet, visible light, ultrasonic, microwave and electricity are not required to be introduced, and oxidative degradation can be performed in light-free reaction, so that waste of resources is avoided; and (5) due to multi-phase catalysis, the catalyst can be reclaimed and reused. The degradation rate reaches 99 percent in 10 minutes under the optimal conditions; and the method is an efficient and simple organic wastewater treatment method.
Description
Technical field
The present invention relates to environmental protection technical field, particularly a kind of useless treatment process of quick catalysis degradating organic dye.
Background technology
Water is Source of life, also is that the mankind depend on for existence and the valuable natural resources of social development.But because industrial expansion, especially the manufactures such as petrochemical complex, medicine, dyestuff, agricultural chemicals develops rapidly, output and the kind of organic compound grow with each passing day, they enter water body by different way, it pollutes transworld each corner, such as river, lake, ocean, underground water etc.Along with the fast development of China's economy, oneself becomes one of country that discharge amount of pollution is maximum in the world, the discharge amount of pollution increase is the fastest China.According to " China Environmental State Bulletin in 2006 " of in June, 2007 State Environmental Protection Administration's issue, national surface water overall water quality belongs to intermediate pollution.2006 annual national wastewater emission amounts are hundred million tons of 537.O, and wherein discharged volume of industrial waste water is 239.5 hundred million tons, and the sanitary sewage quantity discharged is 297.5 hundred million tons.Water pollution problems has become restriction China's Economic development and has improved the bottleneck of people's living standard.So oneself is extremely urgent in water pollution control.
Development and improvement along with wastewater processing technology, simple for composition, the organic waste water that biological degradability is good can be controlled effectively, but for complex structure, high toxicity, Persistent organic pollutants are persistence organic pollutant (Prsistent Organic Pouutam also, POPs), such as nitro-compound, chlorinatedorganic, polycyclic aromatic hydrocarbons, phenolic compound, sterilant, dyestuff etc., these pollutents are difficult to biological degradation in physical environment, biochemical reaction there are inhibition and toxic action, be difficult to process with biochemical method, also be difficult for eliminating gradually by the biological self-purification of environment after being discharged into the physical environment such as water body.Can be taken in rear being difficult for by organism and decompose, and constantly amplify along food chain is concentrated in the migration of atmospheric environment medium and long distance and deposition after entering the natural mediums such as water body, soil, enter at last human body.That a lot of persistence organic pollutants not only have is carcinogenic, aberration inducing, mutagenicity also Endocrine interference effect is arranged because the persistence of these pollutents constitutes a serious threat to human survival procreation, biological growth and breeding and Sustainable development.
In these difficult degradation pollutents, average every day, nearly 150 tons of dyestuffs were discharged in the water body the main emission source that dyestuff is just becoming environmental pollutant in the world.China is DYE PRODUCTION and uses big country that the waste water from dyestuff of annual untreated discharging surpasses 1.6 * 10
9Cubic meter.Contain the groups such as a large amount of phenyl ring, naphthalene nucleus, amino and azo in the dye molecule, its factory effluent complicated component, colourity be dark, have peculiar smell, organism and inorganic salt content high, HUMAN HEALTH produced greatly threaten.Along with the development of chemical engineering industry, dye species increases, and structurally number of rings increase, carbon chain growth, dyeing group are a lot, and the BOD/COD ratio of waste water descends, thereby waste water becomes and is difficult to biochemical treatment.The dyestuff of discharging is the source of environmental pollutant maximum, and in addition, dyestuff produces two amido benzene, naphthalene and aromatics under microbial process.Under anaerobic be reduced into such as azo and nitro class dyestuff and have carcinogenic aromatic amines compound.Also have some metallic complicated dyestuffs such as chrome complex dye can discharge chromium, also can produce carcinogenesis.The decentralized dyestuff can be built up in vivo.Waste water from dyestuff has following characteristics: the one, and complicated component, hard-degraded substance is many, concentration is high, and the COD value is high, and general DYE PRODUCTION basic raw material is benzene class, naphthalene class, fear quinone system and aniline, oil of mirbane, phenols etc.; The 2nd, high chroma; The 3rd, can biochemical weak effect, and towards anti-oxidant, antibiont degraded future development.Germany is after finding that the azoic dyestuff of part take aromatic amine as the basis can have a negative impact to human body for printed fabrics, and oneself bans use of and these azoic dyestuffs of import, and India is also in production and the use of preparing to forbid similar azoic dyestuff.At present, for the processing of waste water from dyestuff, often adopt the method for physico-chemical process, chemical method and biochemical process and combination thereof.By having than the natural adsorbent of bigger serface or by the sorbent material after the modification waste water from dyestuff is carried out adsorption bleaching such as treatment technologies such as traditional physical adsorption, chemisorption, effect is more obvious, and the removal of colourity and COD has all been obtained certain effect.But adsorption technology not only needs a large amount of chemical agents, and the thing of can only transferring the pollution, thoroughly degradable organic pollutant.Biological process is to utilize the method that thereby organism is purified liquid waste in microbiological oxidation, decomposition, the absorption waste water.Most of organism is can be biodegradable in the waste water from dyestuff, even benzene ring structure also can be decomposed by Nocardia bacteria, annular micrococcus, under the effect of d-Biotin SCOA, the phenyl ring cracking is decomposed into organic acid, finally is oxidized to C0
2And H
20.The shortcoming of biological process is that dyestuff itself does not have non-biodegradation, and microbial growth has certain requirement to conditions such as nutritive substance, pH, temperature, is difficult to adapt to the characteristics that the dyeing waste water variation water quality is large, kind of dyes is many, toxicity is high; Simultaneously biological process have also that floor space is large, complex management, to shortcomings such as colourity and COD clearance are low.And chemical complete oxidation treatment process requirement condition is higher, equipment is complicated, and process cost is high.Adopt the method processing such as burning, not only power consumption is large, and easily causes secondary pollution.But because the special character of this class waste water of organic pollutant of difficult degradation is higher to the Technology development general requirement, and do not satisfy more and more higher environmental requirement.The processing problem of waste water from dyestuff is a difficult problem of current water pollution control field face.Therefore, research economy, environmental friendliness, efficient novel difficult for biological degradation dye wastewater treatment technology become one of focus of water pollution control technology.
Along with going deep into of water technology research, various New Wastewater Treatment Technology arts constantly are developed and use, its Trends of Advanced Oxidation Process Methods (Advanced Oxidation Processes, AOPs) show one's talent in 30 years in the past with its huge potentiality and unique advantage, high-level oxidation technology, claim again the deep oxidation technology, be characterized in using electricity, light, catalyzer, sometimes also be combined with oxygenant, in the catalyzed reaction step, produce active extremely strong free radical (such as OH), again by the adduction between free radical and the organic compound, replace, transfer transport, scission of link etc., make the hardly degraded organic substance oxidative degradation in the water body become low toxicity or nontoxic material, even directly be degraded into CO
2, H
2O or other inorganic salt, near permineralization, thus the harmless treatment of realization pollutent.
At present, high-level oxidation technology mainly comprises Fenton catalytic oxidation, ozone (O
3) oxidation, UV-light (UV) oxidation, ultrasonic oxidation etc.
In above-mentioned high-level oxidation technology, the advantage such as the Fenton catalytic oxidation is simple with its equipment, the gentle speed of reaction conditions reaches processing ease soon receives people's concern, at present existing nearly 10,000 pieces of relevant researchs reports.Yet traditional homogeneous phase Fenton oxidation style exists two problems: the one, and reaction system requires lower pH value (general about 2～3), pH is greater than reducing reaction efficiency because of ferric hydroxide precipitate more than 4.5, so under many circumstances, the pH value that needs to regulate waste water before and after the Fenton oxidation consumes a large amount of bronsted lowry acids and bases bronsted lowries; The 2nd, reaction also needs a large amount of iron containing sludges is processed after finishing.For addressing the above problem, over nearly 10 years, people's heterogeneous Fenton catalyzed oxidation technology that begins one's study.At present existing more than 300 piece of paper publishing, and be the trend that increases year by year, become one of research frontier of AoPs technology.
Early stage studied heterogeneous Fenton catalyzer mainly is loading type Fe (III) and ferriferous oxide etc., these heterogeneous Fenton catalyst treatment organic waste waters do not have strict pH value restriction, the easy recycling of catalyzer, can not produce a large amount of iron mud precipitations yet, but their stability, particularly catalytic activity can't be satisfactory.Therefore, the activity that how to improve heterogeneous Fenton catalyzer has become one of study hotspot of high-level oxidation technology.Have at present among several different methods exploring, they comprise: (1) inputs energy in heterogeneous Fenton reaction system, such as ultrasonic and light etc.; (2) use nano-iron oxide, to increase the avtive spot of catalyzer; (3) chemical environment of change iron is to accelerate the rate controlling step one ferric reduction rate of Fenton catalysis.
Homogeneous phase Fenton oxidation style: Dissolvable Fe
2+With H
2O
2Combination namely be called Fenton reagent (Fenton ' s Reagent), be the very strong oxygenant of a kind of oxidation capacity.Studies show that: the organic reaction of Fenton reagent oxidation is to pass through Fe
2+And H
2O
2Effect, produce hydroxyl radical free radical OH (its oxidizing potential up to+2.8V), act on each type organic by OH again and be C0 with its mineralising
2, H
20 and corresponding inorganics, the green method that therefore becomes pollutent control and cut down.
The Fenton-like oxidation style: people find the further investigation of Fenton reaction system, with the improvement technology after the introducing Fenton systems such as UV-light, visible light, oxalate, oxygen, Fenton reagent can be significantly strengthened to organic oxidative degradation ability, and consumption, the reduction processing cost of Fenton reagent can be reduced.Because the ultimate principle of these improvement technology and Fenton response class are seemingly, that play main oxygenizement in the process of processing organic pollutant all is OH, so be collectively referred to as the reaction of Fenton class or Fenton-like oxidation style.
Since EisenhauerH.R. in 1964 was used for the research of phenolic waste water processing with Fenton reagent first, the research of Fenton method in wastewater treatment received concern both domestic and external day by day with application.Fenton class oxidation style has the advantages such as equipment is simple, reaction conditions is gentle, easy to operate, efficient, has application potential in processing poisonous and harmful difficult for biological degradation organic waste water.The subject matter of this method practical application is that processing costs is high, only is suitable for the processing of lower concentration, a small amount of waste water.With its pre-treatment or deep treatment method as organic wastewater with difficult degradation thereby, and with other treatment process (such as biological process, Coagulation Method etc.) coupling, then can reduce better cost for wastewater treatment, improve processing efficiency, and can widen the range of application of this technology.
Fenton and Fenton-type reagent have a wide range of applications in the degraded of sewage disposal and dyestuff, but also Shortcomings of traditional Fenton and Fenton-type reagent: (1) is because Fe
2+Or Fe
3+All may produce precipitation of hydroxide in neutral environment, its reaction conditions often is acid, and pH consumes a large amount of acid about 3, increase cost; (2) work as Fe
2+Reduction H
20
2Self is oxidized afterwards, forms Fe (OH)
3Precipitation causes secondary pollution; (3) although along with the increase of iron ion throwing amount, organic matter removal rate and percent of decolourization significantly improve, excessive Fe
3+Make the solution band after the processing yellow, percent of decolourization is descended, affect final treatment effect.For addressing the above problem, over nearly 10 years, people's heterogeneous Fenton catalyzed oxidation technology that begins one's study.
Summary of the invention
The objective of the invention is for solving the deficiency of homogeneous phase Fenton oxidation, a kind of heterogeneous Fenton catalyzed oxidation technology is provided, namely process the method for organic dye waste water with the oxidative degradation of oxychlorination iron catalyzing hydrogen peroxide, its method equipment is simple, the gentle speed of reaction conditions reaches processing ease soon, and well solved the deficiency that homogeneous phase Fenton oxidation exists, do not need acidic conditions not need to regulate the pH value during i.e. (1) reaction, avoided the consumption of a large amount of acid; (2) can not form Fe (OH) in the reaction
3Precipitation can not cause secondary pollution; (3) water after processing because oxychlorination iron is water insoluble, in water, can not ionize out iron ion, so can be with yellow; (4) compare with the Fenton-like oxidation and do not need to introduce the conditions such as ultraviolet, visible, ultrasonic, microwave, electricity, equally can oxidative degradation under the dark reaction condition, avoided the waste of resource; (5) owing to be heterogeneous catalyst, catalyzer can reclaim, and can repeatedly use.
The concrete technical scheme that realizes the object of the invention is:
A kind for the treatment of process of waste water from dyestuff, the method be take oxychlorination iron (FeOCl) as catalyzer, catalyzing hydrogen peroxide oxidative degradation waste water from dyestuff, and it comprises following concrete steps:
A, be provided with the wastewater disposal basin of whipping appts;
B, in the wastewater disposal basin of step a, inject waste water from dyestuff, add concentration and be 30% hydrogen peroxide and oxychlorination iron, open whipping appts; The add-on of its hydrogen peroxide is: 2.2～6.8kg/ ton waste water, the add-on of oxychlorination iron are 0.5～2.5kg/ ton waste water;
C, waste water from dyestuff carry out decoloring reaction under stirring action, churning time is controlled at 10～50 minutes, obtain colourless waste water, then are for further processing.
The present invention is a kind of heterogeneous Fenton catalysed oxidation processes, and its method is simple, and reaction conditions is gentle, and speed reaches processing ease soon, and has solved well the deficiency that homogeneous phase Fenton oxidation exists.
Description of drawings
Fig. 1 is the graphic representation of methyl orange rate of the present invention; As can be seen from the figure 10 minutes tropeolin-D of the present invention has been degraded 99%, and oxychlorination iron catalyzing hydrogen peroxide has very high degradation capability to tropeolin-D etc. as can be known.
Embodiment
Embodiment 1
A, produce oxychlorination iron, and with a large amount of acetone and water washing, to obtain pure oxychlorination iron;
B, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
C, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 0.5gFeOCl, stir degraded under the condition of natural light;
D, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 2
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 1.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 3
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 1.5gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 4
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.The figure of present embodiment is Fig. 1.
Embodiment 5
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.5gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 6
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 20mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 7
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 30mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 8
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 40mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 9
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methyl orange dye waste water, and the concentration that makes hydrogen peroxide is 50mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate the methyl orange rate.
Embodiment 10
A, the waste water from dyestuff that 1L is contained rhodamine B are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the rhdamine B waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate percent of decolourization.
Embodiment 11
A, the waste water from dyestuff that 1L is contained methylene blue are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the methylene blue dye waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate percent of decolourization.
Embodiment 12
A, the waste water from dyestuff that 1L is contained methyl violet are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the dye methyl violet waste water, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate percent of decolourization.
Embodiment 13
A, the waste water from dyestuff that 1L is contained sodium alizarinsulfonate are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the sodium alizarinsulfonate waste water from dyestuff, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate percent of decolourization.
Embodiment 14
A, the waste water from dyestuff that 1L is contained indigo carmine are injected in the reaction vessel;
B, the hydrogen peroxide 30% join in the Indigo Carmine A red dye wastewater, and the concentration that makes hydrogen peroxide is 60mmol/L, add 2.0gFeOCl, stir degraded under the condition of natural light;
C, per 5,10,20,30,40,50Min sampling, centrifugal, measure the absorbancy of sample with ultraviolet-visible pectrophotometer, and calculate percent of decolourization.
Embodiment 15
A, the waste water from dyestuff that 1L is contained tropeolin-D are injected in the reaction vessel;
B, be a certain amount of massfraction that 30% hydrogen peroxide joins in the methyl orange dye waste water, the concentration that makes hydrogen peroxide is 60mmol/L, adds 2.0gFeOCl, stirs degraded under the condition of natural light;
C, get a sample every 10 min, centrifugal 10 min under 4000 rpm rotating speeds measure the absorbancy of sample supernatant liquor with ultraviolet-visible pectrophotometer.Then centrifuge tube lower sediment and supernatant liquor are refunded in the original solution, add again 0.01g tropeolin-D, stir and make its dissolving, add again hydrogen peroxide, making concentration is 60mmol/L, stirs the 10min sampling, centrifugal, with the absorbancy of ultraviolet-visible pectrophotometer mensuration sample ..., recirculation 5 times.
Claims (1)
1. the treatment process of a waste water from dyestuff is characterized in that the method take oxychlorination iron as catalyzer, and catalyzing hydrogen peroxide oxidative degradation waste water from dyestuff specifically may further comprise the steps:
A, be provided with the wastewater disposal basin of whipping appts;
B, in the wastewater disposal basin of step a, inject waste water from dyestuff, add concentration and be 30% hydrogen peroxide and oxychlorination iron, open whipping appts; The add-on of its hydrogen peroxide is: 2.2～6.8kg/ ton waste water, the add-on of oxychlorination iron are 0.5～2.5kg/ ton waste water;
C, waste water from dyestuff carry out decoloring reaction under stirring action, churning time is controlled at 10～50 minutes, obtain colourless waste water.
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| CN105251519B (en) * | 2015-11-25 | 2017-07-18 | 中国科学院合肥物质科学研究院 | FeOCl micron film of carried noble metal nano particle and preparation method thereof |
| CN107777751A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of new method for handling nitropheneol waste water |
| CN106517484B (en) * | 2016-12-27 | 2019-12-24 | 武汉纺织大学 | Method for treating organic wastewater by using ferric oxychloride to catalytically activate monopersulfate |
| CN106517485B (en) * | 2016-12-27 | 2019-07-23 | 武汉纺织大学 | The method of visible light collaboration FeOCl catalytic activation list organic wastewater treatment through persulfate |
| CN106517486B (en) * | 2016-12-27 | 2019-07-23 | 武汉纺织大学 | The method of visible light collaboration FeOCl catalytic activation peroxy-disulfuric acid salt treatment organic wastewater |
| CN107519900B (en) * | 2017-08-11 | 2019-10-11 | 北京科瑞多环保科技有限公司 | A kind of fenton catalyst and its preparation method and application |
| CN109956529A (en) * | 2019-04-01 | 2019-07-02 | 东华大学 | A kind of preparation method and application of FeOCl/CNT composite membrane |
| CN115245834B (en) * | 2021-04-08 | 2024-02-23 | 浙江理工大学 | Efficient neutral heterogeneous Fenton catalyst FeOF and preparation method and application thereof |
| CN114377701B (en) * | 2022-01-28 | 2024-05-07 | 湖南科技大学 | Limited domain type pyrite cinder/ferric oxychloride composite light-Fenton catalyst and preparation method and application thereof |
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