CN106007080B - A kind of method of biochemical tail water step oxidation depth purification - Google Patents

A kind of method of biochemical tail water step oxidation depth purification Download PDF

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CN106007080B
CN106007080B CN201610521105.0A CN201610521105A CN106007080B CN 106007080 B CN106007080 B CN 106007080B CN 201610521105 A CN201610521105 A CN 201610521105A CN 106007080 B CN106007080 B CN 106007080B
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oxidation
tail water
biochemical tail
water
hydrogen peroxide
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CN201610521105.0A
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CN106007080A (en
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刘福强
罗堃
双陈冬
胡大波
赵伟
姜笔存
闫婷婷
李建华
李爱民
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南京大学
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultra-violet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/32Details relating to UV-irradiation devices
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

Abstract

The invention discloses a kind of methods of biochemical tail water step oxidation depth purification, belong to biochemical tailrace advanced processing technology field.The mode of oxidizing that the present invention uses ferrous iron and hydrogen peroxide to participate in jointly first pre-oxidizes, iron cement is formed by when being then 2.5~6 using subsequent just heavy stage pH, and adsorption-flocculation is carried out to waste water, partial organic substances and Phos are removed, the organic loading of photocatalysis enhanced oxidation section is reduced and weakens the influence of Phos;Organic matter further is removed using photocatalysis enhanced oxidation depth, iron cement is formed when by subsequent two heavy stage pH by 6~9 and is back to pre-oxidation section, as catalyst recycling, reduces medicine consumption and sludge output.The present invention has played pre-oxidation section hydroxyl radical reaction rapidly simultaneously and has had the characteristics that broad spectrum activity, and the characterization of adsorption and catalytic activity of the formed iron cement of difference pH range when being effectively utilized neutralization precipitation, significantly improve reaction efficiency, reagent consumption is low, and effectively realizes the recycling of iron cement.

Description

A kind of method of biochemical tail water step oxidation depth purification

Technical field

The invention belongs to biochemical tailrace advanced processing technology fields, more specifically to a kind of biochemical tail water step oxygen Change the method for deep purifying.

Background technique

Studies have shown that including in industrial wastewater biochemical tail water: microbial metabolic products, organic intermediate, natural organic matter, Trace harmful toxic matter etc., it is difficult to which further biochemical degradation needs to carry out advanced treating.In numerous further treatment techniques, Fenton Technology is widely used as a kind of high-level oxidation technology because it is cheap, efficient, simple.And it is super for certain total phosphorus contents The processing method of target biochemical tail water, especially municipal wastewater and sanitary wastewater is mostly oxidation ditch process, activated sludge process, and dephosphorization is de- Nitrogen stability is poor, generally requires to add chemical agent to reduce water outlet total phosphorus concentration, how to subtract under the premise of Fenton oxidation It is worthy of further study to add or be not added less chemical agent dephosphorization.

Fenton oxidation technology is the wastewater treatment method that chemical oxidation is carried out with Fenton reagent.Fenton reagent is by H2O2With Fe2+The very strong oxidant of a kind of oxidability mixed.Its oxidation mechanism mainly in acid condition (general pH < 3.5), H2O2In Fe2+Catalytic action under generate the hydroxyl radical free radical OH with high reaction activity and strong oxidizing property, hydroxyl from It generates organic free radical with hardly degraded organic substance in aqueous solution by base and is allowed to structure destruction, final oxygenolysis.Fe simultaneously2+Quilt It is oxidized to Fe3+Coagulating sedimentation is generated, large amount of organic is condensed and is removed, to realize the efficient oxidation processing of industrial tail water. The key reaction of Fenton oxidation technology is as follows:

Fe2++H2O2→Fe3++OH-+·OH

Fe3++H2O2+OH-→Fe2++H2O+·OH

Fe3++H2O2→Fe2++H++H2O

HO2+H2O2→H2O+O2↑+·OH

This results in its tool, and there are two apparent defects: a large amount of iron cement is generated after a large amount of acid and alkali consumption and alkali tune, It results in waste of resources.

In order to overcome defect existing for Fenton technology, the especially big problem of iron cement yield, scholars to carry out largely It attempts.On the one hand, the heterogeneous Fenton technology of ferropexy is developed, more mature application at present is Fenton fluidization.Separately On the one hand it is also widely studied by intake energy to enhance the homogeneous Fenton of oxidability, common Energy intaking form includes Ultrasound, microwave, electricity, light etc..Wherein, although light-Fenton technology reagent consumption is reduced, energy consumption is larger, the development side of next step To should improve the efficiency of light energy utilization, shorten the reaction time, application prospect is more considerable.

Such as: Chinese Patent Application No. 201410511377.3 discloses a kind of fenton sewage treatment process and its equipment, should Method is ferrous mode by electroxidation contact break and electroreduction ferric iron, realizes that iron cement recycles, but before electroxidation Need to be molten to iron cement progress acid, in addition this method is more demanding to electroxidation and electroreduction device, and iron cement recycling is at high cost, by In the presence of organic matter, heavy metal etc., the process of electro-redox is difficult to be normally carried out;Chinese Patent Application No. 201410492228.7 disclosing a kind of method of Fenton fluidized bed deep treatment biochemical tail water, this method uses fluidized bed work Skill is crystallized by the out-phase of iron, realizes the minimizing of ferrous iron dosage to a certain extent, but crystal can be with certain centres Product combines and forms solubilised state organic complex, leads to the loss of iron, the dosage of iron is still higher, and is difficult to realize resource Change;Chinese Patent Application No. 200410065398.3 discloses a kind of light and helps Fenton's reaction, flocculation, biodegrade combination processing useless The method of water, it is shown that very strong synergistic effect, but this method energy consumption for illumination is big, and the biochemical reaction time is long, takes up a large area, and flows Journey is cumbersome, and in this method iron loss it is also more serious, impact resistance is poor.Open article " disposition of Fenton iron cement and the resource built Change utilize " in refer to be iron hydroxide using the main component of Fenton iron cement, the trivalent ferrous solution being mixed with strong acid can Replace high polymer coagulant as water treatment coagulant part, however this method needs the acid adding dissolution again with after in alkali tune It is more sensitive to pH as flocculant, strict control pH range is needed, it is not easy to operate.

In conclusion lower using medicament utilization rate when existing homogeneous Fenton technical treatment biochemical tail water, the residence time is long, Iron cement yield is big;It is at high cost when using using fluidized bed Fenton as a kind of heterogeneous Fenton technical treatment biochemical tail water of representative, The loss of iron compound is serious, and catalytic capability is caused to decline;Light help Fenton's reaction, flocculation, biodegrade associated with segmented work Then there is the problems such as process is tediously long, and energy consumption is big, impact resistance is poor in skill.In addition, for certain phosphorous exceeded biochemical tail waters, It is needed before the oxidation toward contact or dosing later carries out chemical dephosphorization, increase solid waste yield.Article and patent are previously mentioned The mode process of iron cement reuse is cumbersome, poor operability, in addition, all of above patent and article be not from sludge separate-recycling Angle illustrates the measure of sludge reduction, results in waste of resources.

Summary of the invention

1, it to solve the problems, such as

It is an object of the invention to overcome deficiency existing for above-mentioned sewage treatment process, a kind of biochemical tail water step is provided The method of oxidation depth purification.It can efficiently be removed in tail water using biochemical tail water step oxidation depth purification method of the invention Organic matter, effectively shorten the reaction time, significantly improve the utilization efficiency of catalyst and oxidant, reduce iron cement to the maximum extent Discharge amount, realizes the recycling of iron cement, and significantly reduces acid and alkali consumption amount also, and deep phosphorous removal effect is obvious, work Skill is simply mature, can be realized engineering.

2, technical solution

To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:

A kind of method of biochemical tail water step oxidation depth purification of the invention, method includes the following steps:

Step 1: pre-oxidation section: biochemical tail water to be processed enters the stage, adjusts pH value, and ferrous iron and dioxygen is added Water carries out pre-oxidation treatment to biochemical tail water;

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet enters stage progress adsorption-flocculation, and completes system row Mud;

Step 3: photocatalysis enhanced oxidation section: the water outlet of adsorption-flocculation spoil disposal section being passed through this stage, continues to add divalent Iron and hydrogen peroxide keep mechanical or hydraulic mixing, waste water are made to carry out photocatalysis enhanced oxidation under light radiation;

Step 4: neutralization precipitation section: to photocatalysis enhanced oxidation treated water outlet carry out neutralization precipitation processing, after neutralization Water after settling of floccus separates qualified discharge.

Further, the building that pre-oxidation function is realized in step 1 is in homogeneous Fenton pond or Fenton fluidized bed It is a kind of.

Further, the molar ratio of the ferrous iron and hydrogen peroxide that are added in step 1 is 1:1~1:100, biochemical tail water The mass concentration ratio of COD and the hydrogen peroxide of addition is 1~12.

Further, the pH value that biochemical tail water is adjusted in step 1 is 2~6, stop of the biochemical tail water in pre-oxidation section Time is 5~15min.

Further, the neutralization precipitation section of step 4 includes just heavy and two sink two stages, wherein just the heavy stage generates Iron cement be back to adsorption-flocculation spoil disposal section adsorption-flocculation carried out to pre-oxidation section water outlet, the iron cement that two heavy stages generated is back to Pre-oxidize section.

Further, just the pH value in heavy stage is adjusted to 2.5~6 in the step 4, and the pH value in two heavy stages is adjusted To 6~9.

Further, the just iron cement reflux ratio in heavy stage and two heavy stages control is 30~150%, and through just heavy and two Treated drains after water stands 30~50min for heavy neutralization precipitation.

Further, the mass concentration of the hydrogen peroxide and photocatalysis enhanced oxidation stage influent COD that are added in step 3 Than being 0~12, the mass concentration ratio of ferrous iron and photocatalysis enhanced oxidation section influent COD is 0~5.

Further, radiant light used is ultraviolet-visible, the preferred mesohigh mercury lamp of light source, radiation intensity in step 3 For 10~1000KW/m3, and residence time of the tail water in photocatalysis enhanced oxidation tower is 1~10min.

Further, in step 1 biochemical tail water to be processed need first to remove before entering pre-oxidation section it is outstanding in tail water Floating object.

3, beneficial effect

Compared with the prior art, the invention has the benefit that

(1) method of a kind of biochemical tail water step oxidation depth of the invention purification is catalyzed dioxygen first with ferrous iron Water generates the very fast feature of hydroxyl radical free radical and pre-oxidizes to tail water, then helps reaction can more efficient generation oxygen using light The removal of the characteristics of compound kind is difficult to be pre-oxidized the organic matter of removal, by shortening preoxidation time, so that unglazed and have light Pollutant under system remains higher degradation rate, effectively shortens the reaction time, saves occupied area, and this hair It is bright to can make full use of Fenton medicament, the step oxidation depth purification to waste water is realized, is efficiently solved using traditional Fenton It is simple to use when especially the inorganic ion concentrations such as chloride ion, bicarbonate radical are higher when the higher waste water of technical treatment salt content When Fenton oxidation degrading waste water Dissolved Organic Matter, it is big often to there is Fenton reagent dosage, and hydrogen peroxide is using not exclusively, iron cement The problems such as amount is more, and water treatment effect is bad.

(2) method of a kind of biochemical tail water step oxidation depth of the invention purification, to photocatalysis enhanced oxidation Water outlet after reason carries out the processing of two-stage neutralization precipitation, and the pH value of strict control different phase, the iron cement that the first heavy stage is generated It is back to adsorption-flocculation spoil disposal section, had both taken full advantage of the adsorption capacity of the stage iron cement, pre-oxidation section water outlet is adsorbed Flocculation without additionally adding other high polymer coagulants, while taking full advantage of again and not being deposited isolated iron compound Catalytic action, is greatly saved ferrous additive amount in subsequent handling, and the filter effect for avoiding bulky grain wadding body urges light Change the negative interaction of enhanced oxidation reaction;The iron cement that two heavy stages generated is back to pre-oxidation section, takes full advantage of the stage iron The catalytic action of mud reduces iron cement yield, and since pre-oxidation section need to carry out pH value adjusting originally, there is no need to first to iron Mud is acidified is back to pre-oxidation section again, greatly reduces soda acid usage amount.

(3) method of a kind of biochemical tail water step oxidation depth of the invention purification is transitioned into photocatalysis from pre-oxidation section Enhanced oxidation section is not necessarily to or only needs fine tuning pH value, and during subsequent alkali tune neutralization precipitation, double due to hardly remaining Oxygen water, pH are adjusted to partial neutral, to further save base amount.

(4) method of a kind of biochemical tail water step oxidation depth of the invention purification pre-oxidizes section by Fenton, absorption is wadded a quilt with cotton The mutual cooperation of solidifying section and photocatalysis enhanced oxidation section, and the technological parameter in each stage is optimized, so as to have Effect guarantees the treatment effect of biochemical tail water, and method of the invention can be used in handling COD < 1000mg/L, salt content < 5% The waste water of bio-refractory, biochemical tail water COD removal rate solve conventional Fenton and are confined to handle up to 65%~95% The waste water of COD < 150mg/L and the technical problem influenced by salinity.

Detailed description of the invention

Fig. 1 is the process flow chart for the method that a kind of biochemical tail water step oxidation depth of the invention purifies.

Specific embodiment

To further appreciate that the contents of the present invention, now in conjunction with embodiment, the present invention is described in detail.

Embodiment 1:

The biochemical tail water of certain petrochemical wastewater, COD 756mg/L are handled, the biochemical tail water step of the present embodiment aoxidizes deep The method of purification is spent, the dosage of pre-oxidation section green vitriol is 300ppm, and (30% is quality point to 30% hydrogen peroxide Dosage number, similarly hereinafter) is 1000ppm, and molar ratio is ferrous: hydrogen peroxide ≈ 1.2:10, mass concentration ratio biochemical tail water COD: double Oxygen water=2.52;Photocatalysis enhanced oxidation stage influent COD is 215mg/L, and final outflow water COD is 45mg/L, total COD removal rate It is 94%;Light intensity oxidation stage is ferrous without adding, and continues to supplement 30% hydrogen peroxide 500ppm, supplement ferrous iron and the stage The mass concentration ratio of influent COD is 0, and the mass concentration ratio of supplement hydrogen peroxide and the stage influent COD is 0.7.

The method of the biochemical tail water step oxidation depth purification of the present embodiment, process flow is as shown in Figure 1, its specific step It is rapid as follows:

Step 1: pre-oxidation section: the biochemical tail water to be processed after sand filter removes oil removal is passed through homogeneous Fenton pond, adjusts PH to 3~4 is saved, and adds green vitriol 300ppm, the dosage of 30% hydrogen peroxide is 1000ppm, is stirred evenly, right Biochemical tail water carries out pre-oxidation treatment, and residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through setting pot and carries out adsorption-flocculation, and completes system Spoil disposal realizes mud-water separation.The present embodiment completes the spoil disposal of whole system in adsorption-flocculation section, effectively eliminates biochemical tail Partial organic substances and Phos in water, and the negative interaction that bulky grain wadding body reacts photocatalysis enhanced oxidation is eliminated, have Effect remains the photocatalysis performance of form of small iron particles oxide wadding body, conducive to the progress of photocatalysis enhanced oxidation.

Step 3: photocatalysis enhanced oxidation section: without adjusting pH value, the water outlet of adsorption-flocculation spoil disposal section being passed directly into light and is urged Change enhanced oxidation tower, keep hydraulic mixing, and continue to add 30% hydrogen peroxide 500ppm, is 150KW/m in intensity3Middle pressure mercury Lamp irradiation is lower to carry out photocatalysis enhanced oxidation, which is 10min.The present embodiment is in photocatalysis enhanced oxidation Section makes full use of remaining iron compound after remaining hydrogen peroxide, adsorption-flocculation section to continue catalytic degradation organic matter, thus greatly The utilization efficiency for improving catalyst and oxidant greatly, reduces the usage amount of catalyst and oxidant.It simultaneously can be according to front Photocatalysis enhanced oxidation section hydrogen peroxide and ferrous dosage is adjusted flexibly in the effect of section, ensure that outlet effect, impact resistance Load-bearing capacity is strong.

The present embodiment optimizes the parameter of radiant light by experiment, final choice 150KW/m3Medium pressure mercury lamp radiation Intensity, medium pressure mercury lamp radiation belong to ultraviolet-visible, and penetration capacity is preferable, can effectively ensure that the photocatalysis enhanced oxidation of waste water Effect, and its technical costs is relatively low.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH in two stages is adjusted, and the water after neutralization continues to discharge after standing 30min is up to standard after settling of floccus separates.In the present embodiment Just heavy stage pH is adjusted to 4.5, and the iron cement of formation is back to adsorption-flocculation spoil disposal section and carries out adsorption-flocculation to pre-oxidation section water outlet, Two heavy stage pH are adjusted to 6, and the iron cement of formation is back to homogeneous Fenton pond and participates in preoxidation process.Above-mentioned just heavy stage iron cement is returned Flow to setting pot and two heavy stage iron cements to be back to the iron cement reflux ratio in homogeneous Fenton pond be respectively 100% and 30%.

Inventor combines practical experience to find that neutralization stage is to photocatalysis enhanced oxidation section by lot of experiments When water outlet carries out pH adjusting, when pH is lower than 6, the ferriferous oxide of generation has a surface hydroxyl abundant, and the adsorption-flocculation stage Environment meta-acid, ferriferous oxide easily protonate, and especially have preferable removal effect to electronegative organic matter etc., and phosphorus is through aoxidizing Afterwards in the form of orthophosphates there are in the majority, it is easy to Adsorption.When pH is higher than 6, Iron activiation in the ferriferous oxide of formation Based on ferrous iron, this part iron cement still has catalysis characteristics, can be back to pre-oxidizing stage as catalyst.Therefore, Treated that water outlet carries out two-stage neutralization precipitation processing, and strict control different phase to photocatalysis enhanced oxidation for the present embodiment The iron cement that the first heavy stage generates is back to adsorption-flocculation spoil disposal section, had both taken full advantage of the adsorption energy of the stage iron cement by pH value Power carries out adsorption-flocculation to pre-oxidation section water outlet, without additionally adding other chemical coagulators, while taking full advantage of again not It is deposited the catalytic action of isolated iron compound, ferrous additive amount in subsequent handling is greatly saved, avoids big The negative interaction that the filter effect of grain wadding body reacts photocatalysis enhanced oxidation.The iron cement that two heavy stages generated is back to pre-oxidation Section, takes full advantage of the catalytic action of the stage iron cement, reduces iron cement yield, and since pre-oxidation section is to need to adjust originally Soda acid greatly reduces soda acid usage amount there is no need to be first acidified to be back to pre-oxidation section again to iron cement.

In general, it is higher in field of waste water treatment advanced treating operating cost in the prior art, therefore, in wastewater treatment process In generally use the measure of optimization front-end process treatment effect to reduce the pressure of advanced treating, but most of biochemical tail water according to It is so exceeded.The present embodiment uses the superiority that optimization front-end process processing makes full use of light to help Fenton's reaction again, and plays The main efficiency of different shape iron, guarantee Tailwater Depth processing it is up to standard on the basis of, to greatest extent realize iron cement minimizing and Recycling.Specifically, removal of the present embodiment mainly for Dissolved Organic Matter in biochemical tail water, and also have for Phos Certain removal ability, first with ferrous iron catalysis hydrogen peroxide generate the very fast feature of hydroxyl radical free radical to tail water into Row pre-oxidation is formed by iron cement when being then 2.5~6 using subsequent just heavy stage pH and carries out adsorption-flocculation, removal to waste water Partial organic substances and Phos reduce the organic loading of photocatalysis enhanced oxidation section and weaken the influence of Phos;Further benefit It uses up and more efficient the characteristics of the generating oxide species depth removal of reaction energy is helped to be difficult to be pre-oxidized the organic matter of removal, pass through shortening Preoxidation time, so that being effectively shortened anti-unglazed and there is the pollutant under body of light system to remain higher degradation rate Between seasonable, occupied area is saved, iron cement is formed when by subsequent two heavy stage pH by 6~9 and is back to pre-oxidation section, as urging Agent recycles, and effectively reduces medicine consumption and sludge output.Meanwhile the present embodiment can make full use of Fenton medicament, realize The step oxidation depth of waste water is purified, when efficiently solving waste water higher using traditional Fenton technical treatment salt content, It is organic using Fenton oxidation degrading waste water dissolubility merely when especially the inorganic ion concentrations such as chloride ion, bicarbonate radical are higher When matter, it is big often to there is Fenton reagent dosage, and hydrogen peroxide is using not exclusively, and iron cement amount is more, and water treatment effect is bad to ask Topic.The present embodiment is transitioned into photocatalysis enhanced oxidation section from pre-oxidation section, is not necessarily to or only needs fine tuning pH value, and in subsequent alkali tune During neutralization precipitation, due to the raising of dioxygen water application efficiency, pH is adjusted to partial neutral, to further save alkali Dosage.

Embodiment 2:

The biochemical tail water of certain pharmaceutical wastewater is handled, COD 750mg/L is aoxidized according to the biochemical tail water step of the present embodiment The method of deep purifying, pre-oxidation section green vitriol dosage are 30ppm, and the dosage of 30% hydrogen peroxide is 1250ppm, molar ratio are ferrous: hydrogen peroxide ≈ 1:100, mass concentration ratio biochemical tail water COD: hydrogen peroxide=2;Oxygen is strengthened in photocatalysis Change stage influent COD is 205mg/L, and final outflow water COD is 45mg/L, and total COD removal rate is 94%;Light intensity oxidation stage is mended Seven hydrated sulfate ferrous iron 200ppm are filled, 30% hydrogen peroxide 100ppm is supplemented, supplement the quality of ferrous iron and the stage influent COD Concentration ratio is 0.19, and the mass concentration ratio of supplement hydrogen peroxide and the stage influent COD is 0.15.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: the biochemical tail water to be processed after sand filter removes oil removal enters homogeneous Fenton pond, adjusts PH to 3~4 is saved, and adds green vitriol 30ppm, the dosage of 30% hydrogen peroxide is 1250ppm, is stirred evenly, right Biochemical tail water carries out pre-oxidation treatment, and residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through setting pot and carries out adsorption-flocculation, and completes system Spoil disposal realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: without adjusting pH value, the water outlet of adsorption-flocculation spoil disposal section being passed directly into light and is urged Change enhanced oxidation tower, keep hydraulic mixing, supplement seven hydrated sulfate ferrous iron 200ppm, continues to add 30% hydrogen peroxide 100ppm;It is 150KW/m in intensity3Medium pressure mercury lamp irradiation lower carry out photocatalysis enhanced oxidation, the stage retention time of sewage For 10min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH in two stages is adjusted, and just heavy stage pH is adjusted to 4.5, and the iron cement of formation is back to setting pot, and two heavy stage pH are adjusted to 9, the iron cement of formation is back to homogeneous Fenton pond and participates in pre-oxidation section, drains after standing 30min.Wherein, just heavy stage iron cement is returned Flow to setting pot and two heavy stage iron cements to be back to the iron cement reflux ratio in homogeneous Fenton pond be respectively 150% and 30%.

Embodiment 3:

The biochemical tail water of certain garden waste water is handled, COD 308mg/L is aoxidized according to the biochemical tail water step of the present embodiment The method of deep purifying, pre-oxidation section green vitriol dosage are 200ppm, and the dosage of 30% hydrogen peroxide is 1025ppm, molar ratio are ferrous: hydrogen peroxide ≈ 0.8:10, mass concentration ratio COD: hydrogen peroxide=1;The photocatalysis enhanced oxidation stage Influent COD is 108mg/L, water outlet COD be 30mg/L, removal rate 90%, the stage add green vitriol 100ppm, Hydrogen peroxide is not supplemented, the mass concentration ratio for supplementing ferrous iron and the stage influent COD is 0.19.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: the biochemical tail water to be processed after sand filter removes oil removal enters homogeneous Fenton pond, PH to 2.5~4 is adjusted, and adds green vitriol 200ppm, the dosage of 30% hydrogen peroxide is 1025ppm, and stirring is equal It is even, pre-oxidation treatment is carried out to biochemical tail water, residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through rotational flow grit chamber and carries out adsorption-flocculation, to remove Suspended matter and sediment, and system spoil disposal is completed, realize mud-water separation.

Step 3: photocatalysis enhanced oxidation section: fine tuning pH value to 2.9, it is then that the water outlet of adsorption-flocculation spoil disposal section is directly logical Enter photocatalysis enhanced oxidation tower, keep hydraulic mixing, continues to add green vitriol 100ppm;It is 10KW/m in intensity3 Medium pressure mercury lamp irradiation it is lower carry out photocatalysis enhanced oxidation, which is 8min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH in two stages is adjusted, and just heavy stage pH is adjusted to 6, and the iron cement of formation is back to rotational flow grit chamber, and two heavy stage pH are adjusted To 8.5, the iron cement of formation is back to homogeneous Fenton pond, drains after standing 40min.Wherein, it is heavy to be back to eddy flow for primary sedimentation tank iron cement The iron cement reflux ratio that sand pond and secondary settling tank iron cement are back to homogeneous Fenton pond is respectively 80% and 150%.

Embodiment 4:

The biochemical tail water of certain paper waste, COD 178mg/L, according to the biochemical tail water step oxidation depth of the present embodiment The method of purification, pre-oxidation section green vitriol dosage are 80ppm, and the dosage of 30% hydrogen peroxide is 150ppm, is rubbed You are than ferrous: hydrogen peroxide ≈ 2.2:10, mass concentration ratio biochemical tail water COD: hydrogen peroxide=3.96;The photocatalysis enhanced oxidation stage Influent COD is 66mg/L, and final outflow water COD is 36mg/L, and total COD removal rate reaches 80%, which does not add ferrous iron, supplement 30% hydrogen peroxide 500ppm, mass concentration ratio ferrous iron: COD=0, the hydrogen peroxide of supplement and the quality of the stage influent COD are dense Spend ratio=2.28.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: biochemical tail water to be processed enters Fenton fluidized bed, and pH control is 4~5, adds seven hydrations The dosage of ferrous sulfate 80ppm, 30% hydrogen peroxide are 150ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, this Residence time of the embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through rotational flow grit chamber, removes suspended matter and precipitating Object completes system spoil disposal, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: water outlet fine tuning pH to 3.5 keeps waterpower into photocatalysis enhanced oxidation tower Stirring continues to add hydrogen peroxide 500ppm, is 300KW/m in intensity3Medium pressure mercury lamp irradiation it is lower carry out photocatalysis enhanced oxidation, The stage retention time of sewage is 10min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and just heavy stage pH is adjusted to 3.5, and the iron cement of formation is back to rotational flow grit chamber and carries out adsorption-flocculation, and two The heavy stage is adjusted to 8, and the iron cement of formation is back to Fenton fluidized bed, drains after standing 50min.Wherein, just heavy stage iron cement is returned Flow to rotational flow grit chamber and two heavy stage iron cements to be back to the iron cement reflux ratio of Fenton fluidized bed be respectively 120% and 80%.

Embodiment 5:

The biochemical tail water of certain dyeing waste water is handled, COD 404mg/L is aoxidized according to the present embodiment mesophytization tail water step The method of deep purifying, pre-oxidation section green vitriol dosage are 100ppm, and the dosage of 30% hydrogen peroxide is 250ppm, molar ratio are ferrous: hydrogen peroxide ≈ 1.6:10, mass concentration ratio COD: hydrogen peroxide=5.38;Photocatalysis enhanced oxidation rank Section influent COD is 188mg/L, and water outlet COD is 35mg/L, and total COD removal rate is 91%;Light intensity oxidation stage does not add Asia Iron supplements 30% hydrogen peroxide 400ppm, mass concentration ratio=0.64 of the hydrogen peroxide of supplement and the stage influent COD.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: biochemical tail water to be processed enters Fenton fluidized bed, and pH control is 4~5, adds seven hydrations The dosage of ferrous sulfate 100ppm, 30% hydrogen peroxide are 250ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, Residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: section water outlet will be pre-oxidized and be passed through the sedimentation basin progress adsorption-flocculation with agitating paddle, Sediment is removed, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, waste water no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing, continues to add hydrogen peroxide 400ppm, is 1000KW/m in intensity3Medium pressure mercury lamp irradiation under stop 5min is stayed to carry out photocatalysis enhanced oxidation.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and just heavy stage pH is adjusted to 5.5, and the iron cement of formation is back to adsorption-flocculation section, and two heavy stage pH are adjusted To 7.5, the iron cement of formation is back to Fenton fluidized bed, drains after standing 30min.Wherein, primary sedimentation tank iron cement is back to absorption wadding It is respectively 30% and 120% that solidifying section and secondary settling tank iron cement, which are back to the iron cement reflux ratio of Fenton fluidized bed,.

Embodiment 6:

The biochemical tail water of certain dyeing waste water of processing, COD 478mg/L, according to the biochemical tail water step oxygen of the present embodiment Change the method for deep purifying, pre-oxidation section green vitriol dosage is 120ppm, and the dosage of 30% hydrogen peroxide is 800ppm, molar ratio are ferrous: hydrogen peroxide ≈ 6:100, mass concentration ratio biochemical tail water COD: hydrogen peroxide=2;Oxygen is strengthened in photocatalysis Change stage influent COD is 96mg/L, and water outlet COD is 52mg/L, and total COD removal rate is 89%, which supplements seven hydrated sulfuric acids The mass concentration ratio of ferrous 120ppm, 30% hydrogen peroxide 500ppm of supplement, the ferrous iron of supplement and the stage influent COD= 0.25, mass concentration ratio=1.56 of the hydrogen peroxide of supplement and the stage influent COD.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: the biochemical tail water to be processed after sand filter removes oil removal enters homogeneous Fenton pond, PH is adjusted to 3~4, and adds green vitriol 120ppm, the dosage of 30% hydrogen peroxide is 800ppm, it stirs evenly, Pre-oxidation treatment is carried out to biochemical tail water, residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 10min.

Step 2: adsorption-flocculation spoil disposal section: section water outlet will be pre-oxidized and be passed through the sedimentation basin progress adsorption-flocculation with agitating paddle, Sediment is removed, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, no longer adjusting pH is directly entered photocatalysis enhanced oxidation Tower keeps hydraulic mixing, supplements green vitriol 120ppm, is 800KW/m in intensity3The lower light that carries out of mercury lamp irradiation urge Change enhanced oxidation, which is 3min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and just heavy stage pH is adjusted to 4.5, and the iron cement of formation is back to adsorption-flocculation section, and two heavy stages were adjusted to 7.5, the iron cement of formation is back to homogeneous Fenton pond, drains after standing 35min.Wherein, just heavy stage iron cement is back to absorption wadding It is 100% that solidifying section and two heavy stage iron cements, which are back to the iron cement reflux ratio in homogeneous Fenton pond,.

Embodiment 7:

The biochemical tail water of certain petrochemical wastewater of processing, COD 448mg/L, according to the biochemical tail water step oxygen of the present embodiment Change the method for deep purifying, pre-oxidation section green vitriol dosage is 100ppm, and the dosage of 30% hydrogen peroxide is 350ppm, molar ratio are ferrous: hydrogen peroxide ≈ 1.2:10, mass concentration ratio COD: hydrogen peroxide=4.27;Photocatalysis enhanced oxidation rank Section influent COD is 207mg/L, and water outlet COD is 80mg/L, and total COD removal rate is 82%, which does not supplement hydrogen peroxide, simultaneously Also ferrous iron is not added, mass concentration ratio ferrous iron: COD=0, hydrogen peroxide: COD=0.

Specific step is as follows for the biochemical tail water step oxidation depth purification method of the present embodiment:

Step 1: pre-oxidation section: biochemical tail water to be processed enters Fenton fluidized bed, and pH is adjusted to 5~6, and adds seven hydrations The dosage of ferrous sulfate 100ppm, 30% hydrogen peroxide are 350ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, Residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 15min.

Step 2: adsorption-flocculation spoil disposal section: section water outlet will be pre-oxidized and be passed through the sedimentation basin progress adsorption-flocculation with agitating paddle, Remove sediment.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing, in 300KW/m3Medium pressure mercury lamp irradiation it is lower carry out photocatalysis enhanced oxidation, which stops Staying the time is 1min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and first segment is completed in primary sedimentation tank, and pH is adjusted to 4, and the iron cement of formation is back to adsorption-flocculation section, and second Section is completed in secondary settling tank, and pH is adjusted to 6, and the iron cement of formation is back to Fenton fluidized bed, is drained after standing 40min.Wherein, just Heavy pond iron cement is back to adsorption-flocculation section and secondary settling tank iron cement be back to Fenton fluidized bed iron cement reflux ratio be respectively 100% and 80%.

Embodiment 8:

The biochemical tail water of certain petrochemical wastewater of processing, COD 448mg/L, according to the biochemical tail water step oxygen of the present embodiment Change the method for deep purifying, pre-oxidation section green vitriol dosage is 320ppm, and the dosage of 30% hydrogen peroxide is 125ppm, molar ratio are ferrous: hydrogen peroxide ≈ 1:1, mass concentration ratio biochemical tail water COD: hydrogen peroxide=12;Photocatalysis enhanced oxidation Stage influent COD is 267mg/L, and final outflow water COD is 50mg/L, and total COD removal rate is 89%, which supplements 30% dioxygen Water 200ppm, while green vitriol ferrous iron 250ppm is added, mass concentration ratio ferrous iron: COD=0.18, hydrogen peroxide: COD=0.22.

Specific step is as follows:

Step 1: pre-oxidation section: biochemical tail water to be processed enters Fenton fluidized bed, and pH is adjusted to 5~6, and adds seven hydrations Ferrous sulfate 320ppm, the dosage of 30% hydrogen peroxide are 50ppm, pre-oxidation treatment are carried out to biochemical tail water, in the present embodiment Residence time of the biochemical tail water in homogeneous Fenton pond is 15min.

Step 2: adsorption-flocculation spoil disposal section: section water outlet will be pre-oxidized and be passed through the sedimentation basin progress adsorption-flocculation with agitating paddle, Remove sediment.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing, supplements green vitriol 250ppm, continues to add hydrogen peroxide 200ppm, in 300KW/m3 Medium pressure mercury lamp irradiation it is lower carry out photocatalysis enhanced oxidation, which is 1min.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and first segment is completed in primary sedimentation tank, and pH is adjusted to 4, and the iron cement of formation is back to adsorption-flocculation section, and second Section is completed in secondary settling tank, and pH is adjusted to 6, and the iron cement of formation is back to Fenton fluidized bed, is drained after standing 40min.Wherein, just Heavy pond iron cement is back to adsorption-flocculation section and secondary settling tank iron cement be back to Fenton fluidized bed iron cement reflux ratio be respectively 100% and 80%.

Embodiment 9:

The biochemical tail water of certain pharmaceuticals industry of processing, COD 1000mg/L, according to the biochemical tail water step oxygen of the present embodiment To change the method for deep purifying, pre-oxidizes section green vitriol 40ppm, the dosage of 30% hydrogen peroxide is 550ppm, mole Than ferrous iron: hydrogen peroxide ≈ 2.9:100, mass concentration ratio COD: hydrogen peroxide=6.06;Photocatalysis enhanced oxidation stage influent COD is 84mg/L, water outlet COD are 36mg/L, and total COD removal rate is 96%, which supplements 30% hydrogen peroxide 3360ppm, adds seven water Close ferrous sulfate 2100ppm, mass concentration ratio ferrous iron: COD=5, hydrogen peroxide: COD=12.

Specific step is as follows:

Step 1: pre-oxidation section: biochemical tail water to be processed enters Fenton fluidized bed, and pH is adjusted to 4~5, and adds seven hydrations Ferrous sulfate 40ppm, the dosage of 30% hydrogen peroxide are 550ppm, stop 10min.

Step 2: adsorption-flocculation spoil disposal section: section water outlet will be pre-oxidized and be passed through the sedimentation basin progress adsorption-flocculation with agitating paddle, Remove sediment.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet fine tuning pH to 3.0 is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing, supplements green vitriol 2100ppm, continues to add hydrogen peroxide 3360ppm, in 300KW/ m3Medium pressure mercury lamp irradiation under, the 1min that stays on carry out photocatalysis enhanced oxidation.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and first segment pH is adjusted to 4.5, and the iron cement of formation is back to adsorption-flocculation section, and second segment is adjusted to 6.5, The iron cement of formation is back to Fenton fluidized bed, drains after standing 50min.Wherein, neutralization precipitation pond iron cement is back to adsorption-flocculation Section and the iron cement reflux ratio of Fenton fluidized bed are respectively 90% and 50%.

Embodiment 10:

The biochemical tail water of certain paper waste of processing, COD 209mg/L, according to the biochemical tail water step oxygen of the present embodiment Change the method for deep purifying, pre-oxidation section green vitriol dosage is 100ppm, and the dosage of 30% hydrogen peroxide is 450ppm, molar ratio are ferrous: hydrogen peroxide ≈ 1:10, mass concentration ratio COD: hydrogen peroxide=1.55;The photocatalysis enhanced oxidation stage Influent COD is 69mg/L, and water outlet COD is 32mg/L, and total COD removal rate is 84%, which supplements green vitriol 100ppm, 30% hydrogen peroxide 50ppm, mass concentration ratio ferrous iron: COD=0.29, hydrogen peroxide: COD=0.22.

Specific step is as follows:

Step 1: pre-oxidation section: biochemical tail water to be processed enters homogeneous Fenton pond, and pH is adjusted to 2~4, and adds seven hydrations The dosage of ferrous sulfate 100ppm, 30% hydrogen peroxide are 450ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, Residence time of the present embodiment mesophytization tail water in homogeneous Fenton pond is 5min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through rotational flow grit chamber, removes suspended matter and precipitating Object completes system spoil disposal, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing, supplements green vitriol 100ppm, continues to add hydrogen peroxide 50ppm, in 500KW/m3's Under medium pressure mercury lamp irradiation, the 2min that stays on carries out photocatalysis enhanced oxidation.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize The pH of two sections is adjusted, and first segment pH is adjusted to 2.5, and the iron cement of formation is back to adsorption-flocculation section, and second segment is adjusted to 7, shape At iron cement be back to homogeneous Fenton pond, drained after standing 30min.Wherein, first segment iron cement is back to rotational flow grit chamber and The iron cement reflux ratio that two iron leg mud are back to homogeneous Fenton pond is respectively 100% and 30%.

Embodiment 11:

The biochemical tail water of certain municipal wastewater of processing, COD 228mg/L, TP (total phosphorus) content is 1.45mg/L, according to this The method of the biochemical tail water step oxidation depth purification of embodiment, pre-oxidizes section green vitriol 180ppm, 30% dioxygen The dosage of water is 400ppm, and molar ratio is ferrous: hydrogen peroxide ≈ 1.8:10, mass concentration ratio COD: hydrogen peroxide=1.9;Photocatalysis Enhanced oxidation stage influent COD is 75mg/L, and water outlet COD is 36mg/L, and total COD removal rate is 84%, and water outlet TP is 0.35mg/ L reaches " urban wastewater treatment pollutant emission standard " (GB 18918-2002) level-one emission standard A;Light intensity oxidation degree Section supplement green vitriol 50ppm, supplements 30% hydrogen peroxide 50ppm, mass concentration ratio ferrous iron: COD=0.13, dioxygen Water: COD=0.2.

Specific step is as follows:

Step 1: pre-oxidation section: biochemical tail water to be processed enters homogeneous Fenton pond, and pH is adjusted to 3~4, adds seven hydration sulphur The dosage of sour ferrous iron 180ppm, 30% hydrogen peroxide are 400ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, this Residence time of the embodiment mesophytization tail water in homogeneous Fenton pond is 5min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through rotational flow grit chamber, removes suspended matter and precipitating Object completes system spoil disposal, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing 8min, continues to add green vitriol and each 50ppm of hydrogen peroxide, in 500KW/m3In Under pressure mercury lamp irradiation, the 6min that stays on carries out photocatalysis enhanced oxidation.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize Two-stage pH is adjusted, and first stage pH is adjusted to 4.5, and the iron cement of formation is back to adsorption-flocculation section, and second stage is adjusted to 7, shape At iron cement be back to homogeneous Fenton pond, drained after standing 30min.Wherein, first stage iron cement be back to rotational flow grit chamber and The iron cement reflux ratio that second segment iron cement is back to homogeneous Fenton pond is respectively 100% and 30%.

Embodiment 12:

The biochemical tail water of certain sanitary sewage of processing, COD 138mg/L, TP content is 1.36mg/L, according to the present embodiment The purification of biochemical tail water step oxidation depth method, pre-oxidize section green vitriol 80ppm, 30% hydrogen peroxide adds Amount is 200ppm, and molar ratio is ferrous: hydrogen peroxide ≈ 1.6:10, mass concentration ratio COD: hydrogen peroxide=2.3;Photocatalysis enhanced oxidation Stage influent COD is 63mg/L, and water outlet COD is 45mg/L, and total COD removal rate is 67%, and water outlet TP is 0.39mg/L, is reached " urban wastewater treatment pollutant emission standard " (GB 18918-2002) level-one emission standard A;Light intensity oxidation stage supplement 30% hydrogen peroxide 30ppm does not add ferrous iron, mass concentration ratio ferrous iron: COD=0, hydrogen peroxide: COD=0.14.

Specific step is as follows:

Step 1: pre-oxidation section: biochemical tail water to be processed enters homogeneous Fenton pond, and pH is adjusted to 3~4, adds seven hydrations The dosage of ferrous sulfate 80ppm, 30% hydrogen peroxide are 200ppm, are stirred evenly, and carry out pre-oxidation treatment to biochemical tail water, this Residence time of the embodiment mesophytization tail water in homogeneous Fenton pond is 6min.

Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet being passed through rotational flow grit chamber, removes suspended matter and precipitating Object completes system spoil disposal, realizes mud-water separation.

Step 3: photocatalysis enhanced oxidation section: after mud-water separation, water outlet no longer adjusts pH, is directly entered photocatalysis reinforcing Oxidizing tower keeps hydraulic mixing 8min, continues to add hydrogen peroxide 30ppm, in 500KW/m3Medium pressure mercury lamp irradiation under, continue to stop 8min is stayed to carry out photocatalysis enhanced oxidation.

Step 4: neutralization precipitation section: photocatalysis enhanced oxidation treated water outlet subsequently enter neutralization precipitation process, realize Two-stage pH is adjusted, and first stage pH is adjusted to 5.5, and the iron cement of formation is back to adsorption-flocculation section, and second stage is adjusted to 7.5, The iron cement of formation is back to homogeneous Fenton pond, drains after standing 30min.Wherein, first stage iron cement is back to rotational flow grit chamber And it is respectively 100% and 80% that second segment iron cement, which is back to the iron cement reflux ratio in homogeneous Fenton pond,.

To sum up embodiment 1-12, the present invention have played pre-oxidation section hydroxyl radical reaction rapidly simultaneously and have had broad spectrum activity The characteristics of, and when being effectively utilized neutralization precipitation the formed iron cement of difference pH range characterization of adsorption and catalytic activity, can will Preoxidation time is down to 5~15min, and the photocatalysis enhanced oxidation section time is down to 1~10min, and catalyst amount reduces by 20~ 50%.The present invention is integrated by Multi-regulation and optimization, i.e., pre-oxidizes section, adsorption-flocculation section and photocatalysis by Fenton and strengthen oxygen Change the mutual cooperation of section, and the technological parameter in each stage is optimized, so as to which the place of biochemical tail water is effectively ensured Effect is managed, there is many advantages, such as reaction efficiency is high, reagent consumption is low, iron cement yield is few, is suitable for processing COD < 1000mg/ L, salt content is up to the waste water of the bio-refractory of < 5%, and biochemical tail water COD removal rate solves often up to 65%~95% The technical problem that rule Fenton is confined to the waste water of processing COD < 150mg/L and is influenced by salinity.The present invention can be sufficiently simultaneously The soluble iron with photocatalysis that is lost in the process of running using Fenton or class Fenton and with colloid or compared with small particle Iron compound existing for aerosol form reduces the dosage of iron, consequently reduces iron cement amount, specifically, by light The water outlet of catalytic intensification oxidation panel carries out segmentation neutralization precipitation processing, and using the characteristic of different phase iron cement, it is back to respectively Adsorption-flocculation section and pre-oxidation section, the direct circulation that iron cement is realized without carrying out other extra process i.e. to iron cement utilize, Overcome need to carry out iron cement in the prior art pretreatment could recycle, the conditions such as pH need strict control and it is cumbersome not Foot, greatly reduces ferrous additive amount and iron cement discharge amount, and significantly reduce soda acid usage amount, is conducive to save money Source reduces cost, and technological operation is simple, is convenient for industrial applications.

Claims (6)

1. a kind of method of biochemical tail water step oxidation depth purification, it is characterised in that: method includes the following steps:
Step 1: pre-oxidation section: biochemical tail water to be processed enters the stage, adjusts pH value, and ferrous iron and hydrogen peroxide is added, right Biochemical tail water carries out pre-oxidation treatment;
Step 2: adsorption-flocculation spoil disposal section: pre-oxidation section water outlet enters stage progress adsorption-flocculation, and completes system spoil disposal;
Step 3: photocatalysis enhanced oxidation section: the water outlet of adsorption-flocculation spoil disposal section is passed through this stage, continue add ferrous iron and Hydrogen peroxide keeps mechanical or hydraulic mixing, waste water is made to carry out photocatalysis enhanced oxidation under light radiation;
Step 4: neutralization precipitation section: to photocatalysis enhanced oxidation, treated that water outlet carries out neutralization precipitation processing, water after neutralization The qualified discharge after settling of floccus separates;The neutralization precipitation section includes just heavy and two sink two stages, wherein the just heavy stage PH value be adjusted to 2.5~6, the pH value in two heavy stages is adjusted to 6~9, and the iron cement that just the heavy stage generates is back to absorption wadding Solidifying spoil disposal section, the iron cement that two heavy stages generated are back to pre-oxidation section.
2. a kind of method of biochemical tail water step oxidation depth purification according to claim 1, it is characterised in that: step 1 The molar ratio of the ferrous iron of middle addition and hydrogen peroxide is 1:1~1:100, and the quality of the hydrogen peroxide of biochemical tail water COD and addition is dense Degree is than being 1~12.
3. a kind of method of biochemical tail water step oxidation depth purification according to claim 1, it is characterised in that: step 1 The middle pH value for adjusting biochemical tail water is 2~6, and biochemical tail water is 5~15min in the residence time of pre-oxidation section.
4. a kind of method of biochemical tail water step oxidation depth purification according to any one of claim 1-3, feature Be: just the iron cement reflux ratio control in heavy stage and two heavy stages is 30~150%, and through just heavy and two heavy neutralization precipitation processing Water afterwards drains after standing 30~50min.
5. a kind of method of biochemical tail water step oxidation depth purification according to any one of claim 1-3, feature Be: the mass concentration ratio of the ferrous iron and photocatalysis enhanced oxidation section influent COD that add in step 3 is 0~5, pair of addition The mass concentration ratio of oxygen water and photocatalysis enhanced oxidation section influent COD is 0~12.
6. a kind of method of biochemical tail water step oxidation depth purification according to any one of claim 1-3, feature Be: the radiant light utilized in step 3 is ultraviolet-visible, and radiation intensity is 10~1000KW/m3, and tail water is urged in light The residence time for changing enhanced oxidation section is 1~10min.
CN201610521105.0A 2016-07-01 2016-07-01 A kind of method of biochemical tail water step oxidation depth purification CN106007080B (en)

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CN102464415A (en) * 2010-10-29 2012-05-23 新奥科技发展有限公司 Advanced treatment process for coal gasification wastewater
CN103387321A (en) * 2013-07-15 2013-11-13 枣庄市申龙水务有限公司 Processing method capable of recycling iron-containing sludge generated in advanced oxidation techniques
CN105668759A (en) * 2016-04-01 2016-06-15 浙江奇彩环境科技股份有限公司 Method for recycling Fenton iron mud

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JPS59162994A (en) * 1983-03-09 1984-09-13 Nippon Peroxide Co Ltd Treatment of waste water containing organic substance
CN102464415A (en) * 2010-10-29 2012-05-23 新奥科技发展有限公司 Advanced treatment process for coal gasification wastewater
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CN105668759A (en) * 2016-04-01 2016-06-15 浙江奇彩环境科技股份有限公司 Method for recycling Fenton iron mud

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