CN102276084B - Industrial wastewater decoloring treatment process - Google Patents
Industrial wastewater decoloring treatment process Download PDFInfo
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- CN102276084B CN102276084B CN2011101727791A CN201110172779A CN102276084B CN 102276084 B CN102276084 B CN 102276084B CN 2011101727791 A CN2011101727791 A CN 2011101727791A CN 201110172779 A CN201110172779 A CN 201110172779A CN 102276084 B CN102276084 B CN 102276084B
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Abstract
The invention discloses an industrial wastewater decoloring treatment process. The process comprises the following steps: the pH value of wastewater is adjusted, an adsorption and oxidation reactor filled with adsorption resin is introduced, a lot of chormophoric organics are adsorbed in the resin, when the chroma removal rate is less than 60%, drainage is performed, a liquid-phase oxidant is added in the adsorption resin to perform oxidative decoloration, the resin is activated and regenerated; and after the pH value of the discharged water of the adsorption and oxidation reactor is adjusted, the discharged water enters a catalytic oxidation reactor, the adsorption resin loaded with a transition metal catalyst is filled in the reactor, and the liquid-phase oxidant is added to perform heterogeneous catalytic oxidation decoloration and remove the small molecules and nonpolar chormophoric organics which are difficult to be adsorbed by the adsorption and oxidation unit. By adopting the method, the polar and nonpolar chormophoric organics with wide molecular weight range can be removed and the effects of efficient decoloring and wide applications can be achieved.
Description
Technical field
The present invention relates to water pollution control and wastewater processing technology, particularly a kind of trade effluent decolorizing process technique.
Background technology
Trade effluents such as pharmacy waste water, dyeing waste water and wastewater from chemical industry are the waste water hard to manage of generally acknowledging, chroma in waste water often becomes the bottleneck index of these wastewater to reach standard processing and middle water reuse.Contain diversified color development organism in these waste water, undersaturated chromophoric groups such as common ethylene linkage, carboxyl, carboxamido-group, sulfoamido, carbonyl and phenyl ring in the color development organism, and common-NH
2,-NHR ,-NR
2,-OR ,-OH and-auxochrome groups such as SH, their interaction makes the colourity of waste water very high.
See that from the wastewater processing technology of present application effectively the waste water decoloring treatment process has Coagulation Method, absorption method, chemical oxidization method and biological process etc.
1, Coagulation Method
Coagulation decoloration is in waste water, to add a certain amount of coagulating agent, reaction process such as process is taken off surely, bridge formation, and the color development organism in the aggegation and the waste water that flocculates reaches the decolouring purpose through separating.During the trade effluent decolouring is handled there be coagulating agent commonly used: iron(ic)chloride, ferrous salt, bodied ferric sulfate, Poly aluminum Chloride (PAC), PAFS, SEPIGEL 305 etc.The coagulation decoloration technology has the advantage that investment cost is low, equipment takes up an area of less, treatment capacity is big, is the decolouring technology that a kind of quilt generally adopts.This technology has removal effect preferably to the hydrophobicity color development organism in the waste water, and poor to water-soluble color development removal effect of organic matter.
2, absorption method
The adsorption bleaching technology is to rely on the adsorption of sorbent material to remove colourity.Sorbent material commonly used comprises regenerable sorbent (like gac, permutite, polymeric adsorbent) and non-renewable sorbent material (like natural mineral such as wilkinite, zeyssatite, industrial wastes such as cinder, flyash), and wherein gac is the most commonly used.Yet since higher regeneration expense and lower strong mechanical constraints its use occasion.
3, chemical oxidization method
The chemical oxidization method decolouring is meant and utilizes chlorine, ClO
2, O
3, H
2O
2And the oxidisability of hypochlorite etc., make the chromophoric group in the waste water fracture take place or change its chemical structure under certain condition, thereby reach the purpose of waste water decoloring.Chlorine, ClO
2, O
3, H
2O
2Though Deng having very strong oxidation capacity; Yet the oxidative decoloration effect has very strong selectivity; Bigger with the substituent kind dependency on the organism; Tracing it to its cause possibly be that the activation energy of oxygenant and some organism reaction is too high, causes reacting being difficult for taking place, and selects appropriate catalyst just to seem particularly important.
Catalyst system therefor can be divided into two types of homogeneous catalyst and heterogeneous catalyst by form in the general catalytic oxidation.Homogeneous catalyst adds with solubility solution form, on molecule or ion concentration, reaction process is played katalysis, but it is miscible in waste water; Be prone to run off; Be prone to cause secondary pollution, the easily separated recovery of heterogeneous catalyst, thereby become the research emphasis of field of waste water treatment catalyzer.Heterogeneous catalyst comprises catalytic active component and carrier.In catalytic oxidation, use transition metal oxide and precious metal widely as the catalyst activity component.Carrier is dispersion agent, binding or the supporter of active ingredient in the heterogeneous catalyst, is the skeleton of load active component.Because heterogeneous catalytic reaction is carried out on the interface, and often to be activity of such catalysts increase with the increase of specific surface, in order to obtain higher activity, often with active constituent loading on the large specific surface carrier.Gac is the support of the catalyst of using always.
4, biological process
The biological process decolouring is to utilize microbial enzyme to come oxidation or reduction coloured molecule, destroys its unsaturated link(age) chromophoric group and reaches the decolouring purpose.
Biological process is divided into aerobic method and anaerobic process, and aerobic method mainly contains sequencing batch active sludge, conventional activated sludge process, biological contact oxidation process etc., and anaerobic process mainly contains up-flow anaerobic sludge blanket method, composite anaerobic reactor etc.Biological process is the most widely used treatment process of waste water decoloring and organic matter degradation, but for the trade effluent of bio-refractory, the biochemical process decolorizing effect is undesirable, needs earlier through the additive method pre-treatment.
Trade effluents such as pharmacy waste water, dyeing waste water and wastewater from chemical industry adopt single method generally to be difficult to make colourity up to standard.Coagulation Method is to water miscible color development organic matter removal weak effect; There are problems such as adsorbent reactivation expense height in absorption method; Chemical oxidization method has very strong selectivity, selects appropriate catalyst the most key; Biological process is not high to the organic decolorizing efficiency of difficult degradation color development.
Summary of the invention
To the problems referred to above, the invention provides the technology that a kind of adsorption and oxidation method associating heterogeneous catalytic oxidation method is removed colourity in the trade effluent, but efficient decolorizing, widely applicable significantly reduces running cost.
A kind of trade effluent decolorizing process technique; Comprise: regulate wastewater pH, input is filled with the adsorption and oxidation reactor drum of polymeric adsorbent, and a large amount of color development organism are attracted in the resin; When chroma removal rate draining less than 60% time; Add the liquid-phase oxidation agent to polymeric adsorbent, carry out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor after regulating pH, is filled with the polymeric adsorbent of loading transition metallic catalyst in the catalyst oxidation reactor, adds the liquid-phase oxidation agent to catalyst oxidation reactor, carries out the heterogeneous catalytic oxidation decolouring.Described liquid-phase oxidation agent dosage is 0.1～2.0kg/m
3Waste water.
Described liquid-phase oxidation agent is a kind of in chlorine bleach liquor, ClO 2 solution or the ydrogen peroxide 50, and the pH of adsorption and oxidation reaction and catalytic oxidation is 6～9.The residence time of waste water in the adsorption and oxidation reactor drum is 0.5～3.0h, and the residence time in catalyst oxidation reactor is 0.5～2.0h.
Described polymeric adsorbent is Semi-polarity or polar macroporous adsorption resin.
Described transition-metal catalyst is the single component oxide compound or the bi component oxide of copper, cobalt, nickel, titanium.
The reaction mechanism of technology of the present invention is following:
1, adsorption and oxidation decolouring mechanism
The organism that color development organism, especially molecular weight are big, polarity is stronger is got into the hole of resin then through the surface of diffusion arrival polymeric adsorbent by the surface; The color development organism that gets into the hole is by resin absorption; Enrichment in the hole of polymeric adsorbent has improved the oxidation efficiency of oxygenant, and chromophoric group fracture takes place or changes its chemical structure under the oxygenant effect; Thereby reach the purpose of waste water decoloring, the simultaneous oxidation process also is the activating and regenerating process of polymeric adsorbent.
2, catalyzed oxidation decolouring mechanism
The small molecules of the difficult absorption of macroporous resin and nonpolar color development organism are through the heterogeneous catalytic oxidation decolouring, and its reaction mechanism is following: the active site combines with the activated complex form on (1) color development organism and the catalyzer, makes the activation energy reduction of reaction; (2) catalyzer makes oxygenant and color development organism have very high density at catalyst surface to oxygenant and the organic strong adsorption effect of color development, and reaction conditions improves, and efficient improves greatly; (3) catalyst surface exists a large amount of oxy radicals, and oxygenant is stimulated also can produce the extremely strong radical of multiple oxidation capacity, like hydroxyl radical free radical (HO), and the carrying out of promotes oxidn reaction.Color development organism and oxygenant have also improved life of catalyst greatly at the dynamic process of the continuous absorption of catalyst surface, consumption, desorption in addition.Its reaction process can be summarized as follows:
Adsorption process:
Catalyzed reaction:
Desorption dissociates:
The beneficial effect of technology of the present invention is following:
1, the adsorption and oxidation unit is primarily aimed at the organic decolouring processing of molecular weight color development big, that polarity is stronger; Catalytic oxidation unit loads on transition metal oxide on the polymeric adsorbent; Produce the stronger oxygenants such as hydroxyl radical free radical of oxidisability through katalysis; Further destroy adsorption and oxidation unmanageable chromonic material, particularly small molecules and nonpolar color development organism.Both combine and can remove polarity, nonpolar and color development organism that molecular weight ranges is bigger, thereby reach efficient decolorizing, widely applicable effect.
2, the adsorption and oxidation unit improves the oxidative decoloration efficient of oxygenant through absorption with macroporous adsorbent resin enrichment color development organism.Because oxidising process is resin activating and regenerating process simultaneously, thereby has saved resin desorption and manipulation of regeneration, can significantly reduce running cost.
3, adopt macroporous adsorbent resin as sorbent material and support of the catalyst, physical strength is high, long service life.
Description of drawings
Fig. 1 is the process flow diagram of technology of the present invention.
Embodiment
Embodiment 1:
Regulate pharmacy waste water pH; Input is filled with NKA-9 polar macroporous adsorption resin (manufacturer: adsorption and oxidation reactor drum Chemical Plant of Nankai Univ.); A large amount of color development organism are attracted in the resin, when chroma removal rate draining less than 60% time, add H to polymeric adsorbent
2O
2, carry out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor after regulating pH, is filled with the polymeric adsorbent of copper loaded oxide compound in the reactor drum, adds H
2O
2, carry out the catalyzed oxidation decolouring, remove the small molecules and the nonpolar color development organism of the difficult absorption in adsorption and oxidation unit.
Influent waste water water quality: colourity is 5000 times;
Adsorption and oxidation reactor drum ydrogen peroxide 50 dosage: 0.5kg/m
3Waste water;
Catalyst oxidation reactor ydrogen peroxide 50 dosage: 0.3kg/m
3Waste water;
Adsorption and oxidation reaction pH:6.5;
Catalytic oxidation pH:6.2;
The absorption residence time: 1.2h;
The oxidation residence time: 0.5h;
The catalyzed oxidation residence time: 1.0h;
Water quality behind the adsorption and oxidation: colourity is 1000 times;
Water quality behind the catalyzed oxidation: colourity is 60 times.
Embodiment 2:
Regulate dyeing waste water pH; Input is filled with NKA-II polar macroporous adsorption resin (manufacturer: adsorption and oxidation reactor drum Chemical Plant of Nankai Univ.); A large amount of color development organism are attracted in the resin, when chroma removal rate draining less than 60% time, add ClO to polymeric adsorbent
2Solution carries out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor, is filled with the polymeric adsorbent of nickel-loaded oxide compound in the reactor drum, adds ClO
2Solution carries out the catalyzed oxidation decolouring, removes the small molecules and the nonpolar color development organism of the difficult absorption in adsorption and oxidation unit.
Influent waste water water quality: colourity is 1000 times;
Adsorption and oxidation reactor drum ClO
2Dosage: 0.2kg/m
3Waste water;
Catalyst oxidation reactor ClO
2Dosage: 0.1kg/m
3Waste water;
Adsorption and oxidation reaction pH:8.0;
Catalytic oxidation pH:7.1;
The absorption residence time: 1.5h;
The oxidation residence time: 0.6h;
The catalyzed oxidation residence time: 0.8h;
Water quality behind the adsorption and oxidation: colourity is 400 times;
Water quality behind the catalyzed oxidation: colourity is 30 times.
Embodiment 3:
Regulate coking chemical waste water pH; Input is filled with HPD400 Semi-polarity macroporous adsorbent resin (manufacturer: the adsorption and oxidation reactor drum precious grace chemical industry in Cangzhou ltd); A large amount of color development organism are attracted in the resin, when chroma removal rate draining less than 60% time, add H to polymeric adsorbent
2O
2, carry out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor after regulating pH, is filled with the polymeric adsorbent of load cobalt/nickel bi component oxide in the reactor drum, adds H
2O
2, carry out the catalyzed oxidation decolouring, remove the small molecules and the nonpolar color development organism of the difficult absorption in adsorption and oxidation unit.
Influent waste water water quality: colourity is 3000 times;
Adsorption and oxidation reactor drum H
2O
2Dosage: 0.3kg/m
3Waste water;
Catalyst oxidation reactor H
2O
2Dosage: 0.2kg/m
3Waste water;
Adsorption and oxidation reaction pH:8.5;
Catalytic oxidation pH:8.1;
The absorption residence time: 1.8h;
The oxidation residence time: 1.0h;
The catalyzed oxidation residence time: 1.2h;
Water quality behind the adsorption and oxidation: colourity is 800 times;
Water quality behind the catalyzed oxidation: colourity is 70 times.
Embodiment 4:
Regulate waste water from dyestuff pH; Input is filled with HPD500 polar macroporous adsorption resin (manufacturer: the adsorption and oxidation reactor drum precious grace chemical industry in Cangzhou ltd); A large amount of color development organism are attracted in the resin, when chroma removal rate draining less than 60% time, add the chlorine bleach liquor to polymeric adsorbent; Carry out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor after regulating pH; Be filled with the polymeric adsorbent of load nickel/titanium bi component oxide in the reactor drum; Add the chlorine bleach liquor, carry out the catalyzed oxidation decolouring, remove the small molecules and the nonpolar color development organism of the difficult absorption in adsorption and oxidation unit.
Influent waste water water quality: colourity is 6000 times;
Adsorption and oxidation reactor drum Youxiaolin dosage: 1.2kg/m
3Waste water;
Catalyst oxidation reactor Youxiaolin dosage: 0.6kg/m
3Waste water;
Adsorption and oxidation reaction pH:7.2;
Catalytic oxidation pH:8.8;
The absorption residence time: 2.0h;
The oxidation residence time: 0.8h;
The catalyzed oxidation residence time: 0.8h;
Water quality behind the adsorption and oxidation: colourity is 800 times;
Water quality behind the catalyzed oxidation: colourity is 20 times.
Claims (6)
1. trade effluent decolorizing process technique; Comprise: regulate wastewater pH, input is filled with the adsorption and oxidation reactor drum of polymeric adsorbent, and a large amount of color development organism are attracted in the resin; When chroma removal rate draining less than 60% time; Add the liquid-phase oxidation agent to polymeric adsorbent, carry out oxidative decoloration, simultaneously the activating and regenerating resin; The water outlet of adsorption and oxidation reactor drum gets into catalyst oxidation reactor after regulating pH, is filled with the polymeric adsorbent of loading transition metallic catalyst in the described catalyst oxidation reactor, adds the liquid-phase oxidation agent, carries out the heterogeneous catalytic oxidation decolouring; The pH of described adsorption and oxidation reaction and catalytic oxidation is 6～9; Described transition-metal catalyst is the single component oxide compound or the bi component oxide of copper, cobalt, nickel, titanium.
2. technology according to claim 1 is characterized in that: described liquid-phase oxidation agent dosage is 0.1～2.0kg/m
3Waste water.
3. technology according to claim 1 is characterized in that: a kind of in chlorine bleach liquor, ClO 2 solution or the ydrogen peroxide 50 of described liquid-phase oxidation agent.
4. technology according to claim 1 is characterized in that: the residence time of waste water in the adsorption and oxidation reactor drum is 0.5～3.0h.
5. technology according to claim 1 is characterized in that: the residence time of waste water in catalyst oxidation reactor is 0.5～2.0h.
6. technology according to claim 1 is characterized in that: described polymeric adsorbent is Semi-polarity or polar macroporous adsorption resin.
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| CN108545760A (en) * | 2018-06-13 | 2018-09-18 | 环境保护部南京环境科学研究所 | The system and method for ammonium sulfate is recycled in a kind of spent acid from dye industry |
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Denomination of invention: A decolorization process for industrial wastewater Effective date of registration: 20201211 Granted publication date: 20121107 Pledgee: Jiangcun sub branch of Hangzhou United Rural Commercial Bank Co.,Ltd. Pledgor: HANGZHOU ZHEDA YITAI ENVIRONMENT TECHNOLOGY Co.,Ltd. Registration number: Y2020330001184 |
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