CN104192979B - A kind of method of Fenton fluidized bed deep treatment biochemical tail water - Google Patents
A kind of method of Fenton fluidized bed deep treatment biochemical tail water Download PDFInfo
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Abstract
The invention discloses a kind of method of Fenton fluidized bed deep treatment biochemical tail water, belong to field of waste water treatment.It comprises crystal growth phase and biochemical tailrace advanced treatment stage, in crystal growth phase, Fenton reagent energy Fast Load carries out crystal growth to filling surface; Biochemical tailrace advanced treatment stage, by extending the residence time of biochemical tail water in fluidized-bed a little, make full use of the heterocatalysis performance oxidative degradation waste water of the crystal in filling surface growth, no longer ferrous sulfate is added in treating processes, achieve the target of uncomfortable soda acid, zero iron mud and zero-emission slag, economic environmental protection; Select yellow sand cheap and easy to get etc. as filler, filling surface electric charge is negative value, effects on surface has very strong keying action with the ferriferous oxide crystallization of positive charge, more stable crystallization can be formed faster, there is better water treatment effect, the present invention can recycle, and the life-span is long, reasonable in design, medicament utilization ratio is high.
Description
Technical field
The invention belongs to field of waste water treatment, more particularly, relate to a kind of method of Fenton fluidized bed deep treatment biochemical tail water.
Background technology
Trade effluent has that concentration is high usually, toxicity is large, be difficult to the features such as biological degradation, and after causing its biological treatment, waste water (biochemical tail water) is difficult to reach emission standard.Research shows, comprises in industrial biochemistry tail water: microbial metabolites, organic intermediate, natural organic matter, trace harmful toxic matter etc., be difficult to further biochemical degradation, need to carry out advanced treatment.In numerous further treatment technique, Fenton technology, as a kind of high-level oxidation technology, is widely used because it is cheap, efficient, simple.But reaction pH (2 ~ 4) condition of Fenton technology the best and needs ferrous iron cause it to have two obvious defects as catalyzer: produce a large amount of iron mud after a large amount of acid and alkali consumptions, alkali tune.And the preparation that numerous method utilizing preparative different-phase catalyst to carry out class Fenton's reaction also exists catalyzer is expensive, loaded down with trivial details, catalyst preparing and water treatment disconnect and cause the problems such as extra cost.
Usually, higher in field of waste water treatment advanced treatment running cost, therefore, in wastewater treatment process, generally adopt the measure optimizing front-end process treatment effect to reduce the pressure of advanced treatment, make concentration generally lower than 150mg/L, but most biochemical tail water still exceeds standard.
Fluidized-bed Fenton technology introduces fluidized-bed crystallization technique in Fenton's reaction, by the ferric iron produced in Fenton-like system mud is coated on filler particles surface with the form of crystallization, the effect of realize retaining ferric iron, cutting down the generation of iron mud, filler particles after load simultaneously has heterocatalysis effect, therefore reaches the minimizing that identical treatment effect can realize ferrous dosage.Chinese Patent Application No. 201410056665.4 discloses a kind of Fenton fluidized bed processor and method of wastewater treatment thereof, and the method has certain universality, but pending waste water needs acid-alkali accommodation to pH3.0-4.0, and acid-base reagent consumption is large; In addition, there is a small amount of iron mud to produce in treating processes, need regularly to get rid of residue; The method that China Patent Publication No. CN101486518A discloses a kind Fenton-fluidized bed sewage processor and disposes of sewage, although the iron mud amount that the treatment process in this patent produces is few, but still have acid-alkali accommodation and need the problem of regular deslagging, and complex operation.Meanwhile, the method for these Fenton fluidized bed processing waste water does not make full use of the advantage of the heterocatalysis of filler particles after load.
Published patent shows, exist during fluidized-bed Fenton technology advanced treatment biochemical tail water: need acid-alkali accommodation, have a small amount of iron mud to produce, regularly have the problems such as macrobead residue discharge, cause alkali reagent consumption large, during the generation of iron mud, medicament utilization ratio does not maximize.
Summary of the invention
1. the problem that will solve
Acid-alkali accommodation is there is for fluidized-bed Fenton technical finesse biochemical tail water in prior art, a small amount of iron mud produces, medicament utilization ratio does not maximize, the problems such as regular deslagging, the present invention proposes a kind of method of Fenton fluidized bed deep treatment biochemical tail water, it can make full use of the heterocatalysis performance of filler after load, improve medicament utilization ratio, reduce acid and alkali consumption, the generation of basically eliminate iron mud, realize " zero-emission slag ", it is a kind of method being particularly useful for the modified version Fenton fluidized bed deep treatment waste water of the biochemical tail water processing COD<150mg/L.
2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A method for Fenton fluidized bed deep treatment biochemical tail water, its treatment step is:
(1) in fluidized-bed, add filler, the density of filler is 80 ~ 150g/L;
(2) regulate inlet flow-patterm to be 4.0 ~ 6.0, control flooding velocity, the residence time keeping current in fluidized-bed is 30 ~ 60min;
(3) by fluidized-bed top effluent recycling to bottom, regulate reflux ratio, controlling the upflow velocity of liquid in fluidized-bed is 30 ~ 100m/h, adds hydrogen peroxide respectively and copperas solution reacts in fluidized-bed; The control of reflux ratio be on the basis controlling retention time of sewage to keep the upflow velocity of liquid in fluidized-bed for 30 ~ 100m/h, there is no particular requirement;
(4) maintenance condition (1)-(3), run the crystal growth that 2 ~ 6 weeks carry out filling surface continuously;
(5) after crystal growth terminates, intake herein and do not need to adjust pH, change traditional concept, control flooding velocity, keep the residence time of current in fluidized-bed to be 30-120min, in fluidized-bed, add the hydrogen peroxide with step (3) moderate, carry out the advanced treatment of biochemical tail water, do not need to add ferrous sulfate, there is very large difference in this point and existing instrument herein;
(6) after running 6 ~ 12 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
Preferably, in described step (1), filler is a kind of or several arbitrarily combination in yellow sand, quartz sand, zeolite, gac, ceramic particle, and particle diameter is 0.2 ~ 0.8mm.
Preferably, the COD<150mg/L of handled biochemical tail water.
Preferably, in described step (3), the dosage of hydrogen peroxide is 2 ~ 10mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 100 ~ 400mg/L.
Contriver, for prior art defect, in conjunction with Fenton design of Fluidized bed and service experience for many years, the present invention proposes this method being particularly useful for the modified version Fenton fluidized bed deep treatment waste water of the biochemical tail water processing COD<150mg/L.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) the present invention finds according to the accident of the present inventor, by extending the residence time of biochemical tail water in fluidized-bed, make full use of the heterocatalysis performance oxidative degradation waste water of filler after load, no longer ferrous sulfate is added in treating processes, achieve the target of uncomfortable soda acid, zero iron mud and zero-emission slag, economic environmental protection, changes traditional concept;
(2) the present invention selects yellow sand cheap and easy to get etc. as filler, yellow sand, quartz sand, zeolite, activated carbon surface electric charge are negative value, effects on surface has stronger keying action with the ferriferous oxide crystallization of positive charge, therefore can form more stable crystallization faster, there is better water treatment effect;
(3) crystal growth phase is combined with wastewater treatment by the present invention, according to common fluidized-bed Fenton process flow operation, realizes the Fast Load of filler particles while waste water is effectively addressed, and has the advantages such as medicament utilization ratio is high, iron mud generation is few;
(4) the present invention takes full advantage of a large amount of carboxyls of existing in biochemical tail water to ferric complexing action, slows down Fe
3+precipitation, improve the inlet flow-patterm (4.0 ~ 6.0) of crystal growth phase equalizing tank, higher by 1.0 ~ 2.0 than ordinary fluidized bed Fenton technology, only need in crystal growth phase adjust ph in whole wastewater treatment process, save acid adjustment alkali tune amount in a large number, running cost reduces greatly;
(5) hydrogen peroxide concentration used in the present invention is low, effectively can prevent because dense decomposing hydrogen dioxide solution produces foaming and damage dosing pump while increasing operation rate;
(6) the present invention controls upflow velocity by the part water outlet at fluidized-bed top is entered bottom by recycle pump outer circulation, can improve the fluidized state that upflow velocity realizes filler again, reduce influent load;
(7) after running 6 ~ 12 months continuously, crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), this is because entered crystal growth phase every 6 ~ 12 months, supplement because biochemical tail water is to the loss of the different-phase catalyst that load causes in the slight stripping of the ferriferous oxide of filling surface.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
A method for Fenton fluidized bed deep treatment biochemical tail water, the steps include:
(1) in fluidized-bed, the yellow sand of 80g/L is added, particle diameter 0.2mm;
(2) regulate inlet flow-patterm to be 6.0, control flooding velocity, keep the residence time in fluidized-bed to be 30min;
(3) upflow velocity controlling liquid in fluidized-bed by water part, fluidized-bed top being back to bottom is 30m/h, hydrogen peroxide is added respectively and copperas solution reacts in fluidized-bed, the dosage of hydrogen peroxide is 2mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 100mg/L;
(4) maintenance condition (1)-(3), run the crystal growth (crystal growth phase) carrying out filling surface for 2 weeks continuously;
(5), after crystal growth terminates, uncomfortable pH of intaking, controls flooding velocity, keeps the residence time of current in fluidized-bed to be 30min, adds the hydrogen peroxide with step (3) moderate, carry out the advanced treatment of biochemical tail water in fluidized-bed; Wherein do not need to think that traditional treatment process adds ferrous sulfate like that;
(6) after running 6 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
The biochemical tail water of certain nitration waste water of process, COD is 108mg/L, and according to the fluidized-bed Fenton Tailwater Depth treatment process of the present embodiment, water outlet COD is 35mg/L, and ferrous clearance is 60%; Do not add ferrous sulfate after crystal growth phase terminates, residence time 30min, water outlet COD is 41mg/L.
Compare with traditional Fenton method with ordinary fluidized bed Fenton method, its result is as shown in table 1, the method of a kind of Fenton fluidized bed deep treatment biochemical tail water provided by the invention, only need carry out acid-alkali accommodation in crystal growth phase, and very sour without the need to what adjusted by pH, when long-time running without the need to regulating pH, in water outlet, iron level is very low, achieve " zero-emission slag ", economic environmental protection.
Table 1 compares the result of the biochemical tail water of the present invention and ordinary fluidized bed Fenton method and traditional Fenton method process nitration waste water
Embodiment 2
A method for Fenton fluidized bed deep treatment biochemical tail water, the steps include:
(1) in fluidized-bed, the quartz sand of 100g/L is added, particle diameter 0.4mm;
(2) regulate inlet flow-patterm to be 5.0, control flooding velocity, keep the residence time in fluidized-bed to be 45min;
(3) upflow velocity controlling liquid in fluidized-bed by water part, fluidized-bed top being back to bottom is 50m/h, hydrogen peroxide is added respectively and copperas solution reacts in fluidized-bed, the dosage of hydrogen peroxide is 5mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 200mg/L;
(4) maintenance condition (1)-(3), run continuously and within 3 weeks, carry out crystal growth (crystal growth phase);
(5) after crystal growth terminates, to intake uncomfortable pH, control flooding velocity, keep the residence time of current in fluidized-bed to be 60min, in fluidized-bed, add the hydrogen peroxide with step (3) moderate, do not add the advanced treatment that ferrous sulfate carries out biochemical tail water;
(6) after running 8 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
Process the biochemical tail water of certain garden waste water, COD is 116mg/L, and according to the fluidized-bed Fenton Tailwater Depth treatment process of the present embodiment, water outlet COD is 38mg/L, and ferrous clearance is 71%; Do not add ferrous sulfate after crystal growth phase terminates, residence time 60min, water outlet COD is 41mg/L.
Compare with traditional Fenton method with ordinary fluidized bed Fenton method, its result is as shown in table 2, the method of a kind of Fenton fluidized bed deep treatment biochemical tail water provided by the invention, only need carry out acid-alkali accommodation in crystal growth phase, and very sour without the need to what adjusted by pH, when long-time running without the need to regulating pH, in water outlet, iron level is very low, achieve " zero-emission slag ", economic environmental protection.
Table 2 compares the result of the biochemical tail water of the present invention and ordinary fluidized bed Fenton method and traditional Fenton method process garden waste water
Embodiment 3
A method for Fenton fluidized bed deep treatment biochemical tail water, the steps include:
(1) in fluidized-bed, the zeolite of 120g/L is added, particle diameter 0.6mm;
(2) regulate inlet flow-patterm to be 4.0, control flooding velocity, keep the residence time in fluidized-bed to be 60min;
(3) upflow velocity controlling liquid in fluidized-bed by water part, fluidized-bed top being back to bottom is 80m/h, hydrogen peroxide is added respectively and copperas solution reacts in fluidized-bed, the dosage of hydrogen peroxide is 10mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 400mg/L;
(4) maintenance condition (1)-(3), run continuously and within 4 weeks, carry out crystal growth (crystal growth phase);
(5) after crystal growth terminates, to intake uncomfortable pH, control flooding velocity, keep the residence time of current in fluidized-bed to be 90min, in fluidized-bed, add the hydrogen peroxide with step (3) moderate, do not add the advanced treatment that ferrous sulfate carries out biochemical tail water;
(6) after running 10 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
The biochemical tail water of certain paper waste, COD is 148mg/L, and according to the fluidized-bed Fenton Tailwater Depth treatment process of the present embodiment, water outlet COD is 46mg/L, and ferrous clearance is 83%; Do not add ferrous sulfate after crystal growth phase terminates, residence time 60min, water outlet COD is 54mg/L.
Compare with traditional Fenton method with ordinary fluidized bed Fenton method, its result is as shown in table 3, the method of a kind of Fenton fluidized bed deep treatment biochemical tail water provided by the invention, only need carry out acid-alkali accommodation in crystal growth phase, and very sour without the need to what adjusted by pH, when long-time running without the need to regulating pH, in water outlet, iron level is very low, achieve " zero-emission slag ", economic environmental protection.
Table 3 compares the result of the biochemical tail water of the present invention and ordinary fluidized bed Fenton method and traditional Fenton method process paper waste
Embodiment 4
A method for Fenton fluidized bed deep treatment biochemical tail water, the steps include:
(1) in fluidized-bed, the ceramic particle of 150g/L is added, particle diameter 0.8mm;
(2) regulate inlet flow-patterm to be 5.0, control flooding velocity, keep the residence time in fluidized-bed to be 60min;
(3) upflow velocity controlling liquid in fluidized-bed by water part, fluidized-bed top being back to bottom is 100m/h, hydrogen peroxide is added respectively and copperas solution reacts in fluidized-bed, the dosage of hydrogen peroxide is 6mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 200mg/L;
(4) maintenance condition (1)-(3), run continuously and within 6 weeks, carry out crystal growth (crystal growth phase);
(5) after crystal growth terminates, to intake uncomfortable pH, control flooding velocity, keep the residence time of current in fluidized-bed to be 120min, in fluidized-bed, add the hydrogen peroxide with step (3) moderate, do not add the advanced treatment that ferrous sulfate carries out biochemical tail water;
(6) after running 12 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
Process the biochemical tail water of certain dyeing waste water, COD is 104mg/L, and according to the fluidized-bed Fenton Tailwater Depth treatment process of the present embodiment, water outlet COD is 36mg/L, and ferrous clearance is 78%; Do not add ferrous sulfate after crystal growth phase terminates, residence time 120min, water outlet COD is 42mg/L.
Compare with traditional Fenton method with ordinary fluidized bed Fenton method, its result is as shown in table 4, the method of a kind of Fenton fluidized bed deep treatment biochemical tail water provided by the invention, only need carry out acid-alkali accommodation in crystal growth phase, and very sour without the need to what adjusted by pH, when long-time running without the need to regulating pH, in water outlet, iron level is very low, achieve " zero-emission slag ", economic environmental protection.
Table 4 compares the result of the biochemical tail water of the present invention and ordinary fluidized bed Fenton method and traditional Fenton method process dyeing waste water
Embodiment 5
A method for Fenton fluidized bed deep treatment biochemical tail water, the steps include:
(1) in fluidized-bed, the gac of 80g/L is added, particle diameter 0.6mm;
(2) regulate inlet flow-patterm to be 4.0, control flooding velocity, keep the residence time in fluidized-bed to be 30min;
(3) upflow velocity controlling liquid in fluidized-bed by water part, fluidized-bed top being back to bottom is 40m/h, hydrogen peroxide is added respectively and copperas solution reacts in fluidized-bed, the dosage of hydrogen peroxide is 5mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 200mg/L;
(4) maintenance condition (1)-(3), run continuously and within 4 weeks, carry out crystal growth (crystal growth phase);
(5) after crystal growth terminates, to intake uncomfortable pH, control flooding velocity, keep the residence time of current in fluidized-bed to be 120min, in fluidized-bed, add the hydrogen peroxide with step (3) moderate, do not add the advanced treatment that ferrous sulfate carries out biochemical tail water;
(6) after running 10 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
Process the biochemical tail water of certain dyeing waste water, COD is 110mg/L, and according to the fluidized-bed Fenton Tailwater Depth treatment process of the present embodiment, water outlet COD is 30mg/L, and ferrous clearance is 75%; Do not add ferrous sulfate after crystal growth phase terminates, residence time 120min, water outlet COD is 40mg/L.
Compare with traditional Fenton method with ordinary fluidized bed Fenton method, its result is as shown in table 5, the method of a kind of Fenton fluidized bed deep treatment biochemical tail water provided by the invention, only need carry out acid-alkali accommodation in crystal growth phase, and very sour without the need to what adjusted by pH, when long-time running without the need to regulating pH, in water outlet, iron level is very low, achieve " zero-emission slag ", economic environmental protection.
Table 5 compares the result of the biochemical tail water of the present invention and ordinary fluidized bed Fenton method and traditional Fenton method process dyeing waste water
A kind of or several arbitrarily combination in Fillers selection yellow sand of the present invention, quartz sand, zeolite, gac, ceramic particle, because by be their electric charge be negative value, effects on surface has stronger keying action with the ferriferous oxide crystallization of positive charge, therefore can form more stable crystallization faster, there is better de-ferrous effect; Principle communicates, as long as size controlling is being 0.2 ~ 0.8mm, their arbitrary combination, those of ordinary skill in the art are according to embodiments of the invention and in conjunction with this area general knowledge, also the arbitrary combination them can be inferred, so present specification is not repeating.
Claims (4)
1. a method for Fenton fluidized bed deep treatment biochemical tail water, its treatment step is:
(1) in Fenton fluidized-bed, add filler, the density of filler is 80 ~ 150g/L;
(2) regulate inlet flow-patterm to be 4.0 ~ 6.0, control flooding velocity, the residence time keeping current in Fenton fluidized-bed is 30 ~ 60min;
(3) by Fenton fluidized-bed top effluent recycling to bottom, the upflow velocity controlling liquid in Fenton fluidized-bed is 30 ~ 100m/h, adds hydrogen peroxide respectively and copperas solution reacts in Fenton fluidized-bed;
(4) maintenance condition (1)-(3), run the crystal growth that 2 ~ 6 weeks carry out filling surface continuously;
(5) after crystal growth terminates, control flooding velocity, keep the residence time of current in Fenton fluidized-bed to be 30-120min, in Fenton fluidized-bed, add the hydrogen peroxide with step (3) moderate, carry out the advanced treatment of biochemical tail water;
(6) after running 6 ~ 12 months continuously according to step (5), crystal growth is carried out with the loss of additional fillers surface crystal in repeating step (1)-(4), carries out biochemical tail water process after crystal growth terminates according to the condition in step (5).
2. the method for a kind of Fenton fluidized bed deep treatment biochemical tail water according to claim 1, it is characterized in that: in described step (1), filler is a kind of or several arbitrarily combination in yellow sand, quartz sand, zeolite, gac, ceramic particle, and particle diameter is 0.2 ~ 0.8mm.
3. the method for a kind of Fenton fluidized bed deep treatment biochemical tail water according to claim 1, is characterized in that: the COD<150mg/L of handled biochemical tail water.
4. the method for a kind of Fenton fluidized bed deep treatment biochemical tail water according to claim 1, it is characterized in that: in described step (3), the dosage of hydrogen peroxide is 2 ~ 10mM, by massfraction be 30% hydrogen peroxide first dilute 10 times after add, the dosage of crystal growth phase ferrous sulfate is 100 ~ 400mg/L.
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| CN104671500B (en) * | 2015-02-11 | 2016-08-17 | 福建工程学院 | Circulation speed change fluid bed Fenton catalytic oxidizing equipment |
| CN107473364B (en) * | 2017-08-01 | 2021-05-28 | 大连海事大学 | Catalytic filler for Fenton fluidized bed and preparation method thereof |
| CN115624974B (en) * | 2022-10-11 | 2024-09-27 | 麦王环境技术有限公司 | Preparation of Fenton fluidized bed carrier catalyst and industrial water treatment method |
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| US6502633B2 (en) * | 1997-11-14 | 2003-01-07 | Kent Cooper | In situ water and soil remediation method and system |
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