CN105461183A - Treatment method for excess activated sludge in AOX pollution - Google Patents

Abstract

The invention discloses a method for treating excess activated sludge polluted by AOX. The method comprises: adding modified fly ash loaded with iron and manganese elements to the excess activated sludge, mixing evenly, and then adding an oxidant to carry out oxidation reaction After the reaction is completed, a skeleton agent is added to the reaction solution to adjust the pH value to 8-9, and plate and frame pressure filtration is performed to obtain filtrate and sludge filter cake. Before the present invention carries out the Fenton-like/persulfate advanced oxidation reaction, the modified fly ash loaded with nanometer Fe ₃ O ₄ and Mn ²⁺ is used to improve the adsorption capacity and catalytic capacity of the original fly ash, thereby Efficiently degrade the pollutants in the sludge and the sludge itself, not only effectively remove the organic pollutants in the remaining activated sludge, but also reduce the water content of the sludge, and realize the harmless and reduction treatment of sludge and Comprehensive utilization of fly ash resources.

Description

The treatment process of the residual active sludge that a kind of AOX pollutes

Technical field

The present invention relates to environmental engineering and pollution plot engineering field, particularly relate to the treatment process of the residual active sludge that a kind of AOX pollutes.

Background technology

Halogenated organic compounds is important industrial chemicals, intermediate and organic solvent, and it is widely used in the industries such as dyestuff, pharmacy, weaving, printing and dyeing, electronics, pollutes very extensive in waste water.Organohalogen compounds are of a great variety, represent the total amount of halogenated organic matters in the world with adsorbable organic halogen (AOX).

The fat-soluble height of AOX, have " three cause " effect, difficulty is biodegradable, and is class persistent pollutant, and American-European countries has concluded corresponding emission standard to it more for a long time.An international water-quality guideline has been become with the Organohalogen compounds that AOX characterizes.And the research of China to AOX is started late, AOX was just listed in integrated wastewater discharge standard and pulping and paper-making by China in recent years, heterocyclic pesticide is industrial, textile dyeing and finishing is industrial, flax spinning industry Wastewater Pollutant emission standard.

China is one of maximum halogenated organic compounds producing country, organic halide is widely used in process of production and causes a large amount of AOX to enter waste water, biological process is widely used in the improvement of trade effluent and municipal wastewater, due to the fat-soluble height of AOX class material, difficult for biological degradation is easily adsorbed in mud and accumulates, thus in mud, AOX pollutes also general serious.If do not deal carefully with disposal, secondary pollution certainly will be caused to environment.In " land reclamation of urban wastewater treatment firm sludge disposal with shale (GB/T2460-2009) " standard of Germany's relevant criterion and China, all specify that mud AOX is lower than 500mg/kg.

Often producing a large amount of excess sludges with when Wastewater Treated by Activated Sludge Process municipal effluent and trade effluent, these mud bulky, complicated component, flocculation structure in colloidal, have wetting ability and the retentiveness of height, dewatering extreme difference, water ratio is usually up to 95% ~ 99.5%.And no matter be sanitary landfill, anhydration and incineration, anaerobically fermenting, or compost etc. has all been made strict technology to moisture percentage in sewage sludge and has been defined, and therefore dehydration and decrement pre-treatment are the important steps in sludge treatment and disposal process.Dehydration not only can reduce sludge volume, reduce transportation cost, is also easy to follow-up disposal simultaneously.

At present, most widely used treatment process adds organic polymer coagulating agent to be aided with mechanical dehydration, moisture percentage in sewage sludge can be down to 70% ~ 80%, but aforesaid method is difficult to reduce moisture percentage in sewage sludge further, is still unfavorable for the follow-up disposal of mud.Major cause is that the wetting ability flocculation structure that mud extracellular polymeric (EPS) is formed can fetter large quantity of moisture, limits sludge dewatering effect.Adding of organic polymer coargulator does not change the form of EPS in mud flco, distribution and character etc., can only remove part free water, can not improve the dehydration degree of depth.In addition, just dosing coagulant can not remove the objectionable impurities in mud.

In the last few years, the technology such as chemical oxidation was also applied to the dewatering improving mud.Fenton (Fenton) energy of oxidation degradation of organic substances, dissolves and cracks EPS, cell walls, realize the decrement of mud and improve dewatering performance of sludge.Fenton oxidation conditioning excess sludge its obvious processing effect, rates of oxidative degradation be fast, applied widely, do not have secondary pollution, and the hazardous and noxious substances in mud of degrading.But the pH scope of Fenton reaction is narrower, presetting sludge pH is often wanted to be acid.Such as: application publication number is that the application for a patent for invention document of CN102180583A discloses a kind of Fenton reagent and polyacrylamide and to act synergistically sludge conditioning technology, before Fenton reaction treatment thickened sludge, will acidified process in advance, but mud is as a very complicated buffer system, acid adjustment more difficult and increase processing cost, and sludge pH is still acid after acid adjustment Fenton reaction, directly carry out sludge conditioning with polyacrylamide is collaborative, pH can not be adjusted to neutral, also easily form secondary pollution.Except Fenton oxidation, persulphate high-level oxidation technology conditioning of mud also can obtain the effect similar with Fenton, and same pH is more conducive to the carrying out reacted in acid condition.And at present for removal and the sludge dewatering aspect of polluting harmful organic contaminants in residual active sludge by AOX, realize these two objects and technique means easy and simple to handle is still less simultaneously.

And current, seek the noxious pollutant in suitable method lignin-sludge, the deep dehydration simultaneously realizing mud is again the active demand of recycling sludge utilization and field of sludge treatment.

Flyash is refuse and the byproduct of fuel-burning power plant and concentrated supply of heating in the city boiler, and the flyash quantity discharged of countries in the world is all the trend increased year by year.The stacking of a large amount of flyash, not only occupies valuable land resources, and its airborne dust produced also pollutes the environment.Therefore, Appropriate application flyash, the utilization ratio improving flyash also becomes the focus of current research.

Its major ingredient of flyash is Al ₂o ₃and SiO ₂, simultaneously also containing part carbon granule and other a small amount of material, as a kind of loose porous and the larger solid particulate of specific surface area, as the sorbent material in wastewater treatment or coagulating agent, have cheap outstanding advantage.Further, flyash, as a kind of " zero cost " industrial waste, for the conditioning of mud, can reach " treatment of wastes with processes of wastes against one another ", both for the utilization of flyash provides outlet, can reach again the object reducing sludge conditioning cost.But directly utilize flyash for sludge conditioning, to reach good effect, there is the drawback that dosage is excessive, causing very large trouble to the subsequent disposal of mud, so must dosage be controlled.

For this reason, be necessary to carry out modification to flyash, to improve its effectiveness, make flyash after modification, its primary characteristic can be kept, there is again new function.

Summary of the invention

The invention provides the treatment process of the residual active sludge that a kind of AOX pollutes, the method efficiently can remove the organic pollutant in residual active sludge, and reduce the water content of mud, achieve innoxious, the minimizing process of mud and the comprehensive utilization of resources of flyash.

A treatment process for the residual active sludge that AOX pollutes, comprising:

In residual active sludge, add the modified coal ash of load iron manganese element, after mixing, then add oxygenant, carry out oxidizing reaction, after having reacted, in reaction solution, add skeleton agent, adjust ph is 8 ~ 9, carries out filter press, obtains filtrate and sludge filter cake.

Test finds, through the modified coal ash of ferrimanganic load, can part pollutent in active adsorption mud, and efficiently catalyzing and oxidizing agent produces strong oxidizing property free radical, makes the AOX in mud and other organic pollutant efficient degradation, simultaneous oxidation mud cell, change sludge structure, degraded EPS, thus release mud cell interior water and EPS surface-bonded water, improve the dewatering of mud greatly.

Usually, need adjust ph before the reaction of Fenton's reaction, class Fenton's reaction or persulphate advanced oxidation, to guarantee efficiently carrying out of reaction; And the present invention is because adopting modified coal ash, without the need to carrying out acid adjustment, just can efficiently catalyzing and oxidizing agent.

In Oxidative Degradation Process, mineral acid, organic acid and other products such as the oxidized generation of AOX class material HCl, HBr, and other organic pollutants are also by mineralising or be degraded into small organic molecule, part generates organic acid, cracking of mud cell also can discharge organic acid, the mineral acid of a large amount of generation and organic acid, make sludge pH reduce, thus be more conducive to noxious pollutant and mud itself in modified coal ash catalytic oxidant oxidative degradation mud.

In addition, the reduction of pH also makes flyash stripping part Al ³⁺, Fe ³⁺and H ₂siO ₃deng composition, Al ³⁺, Fe ³⁺flocculating settling effect can be played, collecting suspended particle, H ₂siO ₃also Coagulation and Adsorption bridging action can be played to the mud disintegrated.After oxidizing reaction terminates, then add skeleton agent, and adjust ph is 8 ~ 9, can make the Al of stripping in reaction ³⁺, Fe ³⁺deng formation flocculation agent, promote the flocculating settling of disintegration mud.The skeleton agent added and modified coal ash, play the effect of mud skeleton, promote sludge dewatering further.

Because modified coal ash can work in coordination with efficiently catalyzing and oxidizing agent, Strong oxdiative mud cell, change sludge structure, degraded EPS, thus release mud cell interior water and EPS surface-bonded water, greatly can improve the dewatering of mud, so the method for the flyash conditioning mud of comparing traditional, in present method, modified coal ash consumption can reduce greatly.

As preferably, in described modified coal ash, load has nanometer Fe ₃o ₄and Mn ²⁺.

Flyash has efficient adsorption catalysis performance, and the major ingredient of flyash is Al ₂o ₃and SiO ₂, be a kind of loose porous and the larger solid particulate of specific surface area, can be used as sorbent material or coagulating agent; As flyash-supporting nanometer Fe ₃o ₄and Mn ²⁺after, make flyash reaction site more, absorption property is stronger, after modified coal ash adds and fully contacts with mud in active sludge, and can partial adsorbates pollutent.

In addition, flyash itself is also containing the Fe that part is free ₂o ₃and part C, add the nanometer Fe of load ₃o ₄(simultaneously containing Fe ²⁺and Fe ³⁺) and Mn ²⁺, make the performance of modified coal ash catalytic decomposition oxygenant generation strong oxidizing property free radical stronger.

In the present invention, the nanometer Fe of load in modified coal ash ₃o ₄good biocompatibility, and the Mn of load ²⁺fewer, adding skeleton agent and behind adjust ph to 8 ~ 9, manganese and other heavy metals stabilized, can not secondary pollution be caused.In addition compare with other ferriferous oxide, the nanometer Fe of load ₃o ₄in containing Fe ²⁺, the performance that catalytic oxidant produces strong oxidative free radical is stronger, and Mn ²⁺load is at flyash or Fe ₃o ₄on, be compared to oxide form, the performance that its catalytic oxidant produces strong oxidative free radical is also stronger.

Nanometer Fe in modified coal ash ₃o ₄and Mn ²⁺charge capacity all have impact to the adsorptive power of modified coal ash and catalytic capability, as preferably, in massfraction, Fe in described modified coal ash ₃o ₄charge capacity be 1 ~ 40%, Mn ²⁺charge capacity be 0.5 ~ 20%.

More preferably, in massfraction, nanometer Fe in described modified coal ash ₃o ₄charge capacity be 5 ~ 20%, Mn ²⁺charge capacity be 1 ~ 5%.

Particularly, the preparation method of described modified coal ash is as follows:

(1) under nitrogen protection, in flyash, Fe is added ³⁺solution and Fe ²⁺solution, after being uniformly dispersed, drips NH ₃h ₂after O reacts for some time, obtain loading nanometer Fe ₃o ₄flyash;

(2) loading nanometer Fe is cleaned ₃o ₄flyash, add Mn wherein under nitrogen protection ²⁺solution, after stirring, dries material under nitrogen protection, and grinding, obtains load Fe ₃o ₄and Mn ²⁺modified coal ash.

Wherein, described Fe ³⁺solution is solubility trivalent iron salt; Described Fe ²⁺solution is solubility divalent iron salt; Described Mn ²⁺solution is solubility manganous salt.

As preferably, described Fe ³⁺fe in solution ³⁺, Fe ²⁺fe in solution ²⁺with NH ₃h ₂the mol ratio of O is 2:1:14.5 ~ 16.

As preferably, the dosage of described modified coal ash is that 20 ~ 200mg/g. does SS.The dosage unit mg/g. mentioned in the present invention " the dry SS " done in SS all refers to dry weight (SS) amount of residual active sludge.

More preferably, described modified coal ash crossed 200 mesh sieves before load iron manganese element.

As preferably, described oxygenant is H ₂o ₂, at least one in persulphate, these two kinds of oxygenants, as green reagent, can not cause secondary pollution to environment.

Particularly, persulphate is the one in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen persulfate sodium, potassium hydrogen persulfate.

As preferably, the dosage of described oxygenant is that 5 ~ 100mg/g. does SS; The time of oxidizing reaction is 20min ~ 2h.

More preferably, described oxygenant is by H ₂o ₂with persulphate composition, wherein, H ₂o ₂dosage be that 5 ~ 80mg/g. does SS; The dosage of persulphate is that 10 ~ 100mg/g does SS; The time of oxidizing reaction is 30min ~ 2h.

As preferably, described skeleton agent is at least one in lime, carbide slag, calcium carbonate, calcium oxide.Above-mentioned skeleton agent both can form mud skeleton together with modified coal ash, also had the function regulating reacting liquid pH value simultaneously, to environment non-secondary pollution, and can make the heavy metal stabilization in mud.

Compared with prior art, the present invention has following beneficial effect:

(1) the present invention is before carrying out class Fenton/persulphate advanced oxidation reaction, adopts load to have nanometer Fe ₃o ₄and Mn ²⁺modified coal ash, improve the adsorptive power of original flyash, modified coal ash is made effectively to adsorb portion of water in mud and pollutent, also improve the catalytic capability of flyash, catalytic oxidant produces more strong oxidizing property free radical, thus pollutent in efficient degradation mud and mud itself, not only efficiently eliminate the organic pollutant in residual active sludge, and reduce the water content of mud, achieve innoxious, the minimizing process of mud and the comprehensive utilization of resources of flyash.

(2) the inventive method is without the need to carrying out pre-acid adjustment to mud, reduces processing cost, simplifies treatment process.

(3) the inventive method treatment time is short, and structures are few, and operation is simple, easy handling.

(4) the present invention adopts solid waste flyash not only to achieve the object of the treatment of wastes with processes of wastes against one another, and because of the increase of dewatering performance of sludge, the reduction of water ratio, makes dehydrated sludge transport and processing costs minimizing.

Embodiment

Below in conjunction with embodiment, the present invention will be further described.

In the following example, the preparation method of modified coal ash is specific as follows:

(1) under nitrogen protection, in the flyash of mistake 200 mesh sieves, FeCl is added ₃solution and FeSO ₄solution, ultrasonic 10min, to being uniformly dispersed, drips NH while stirring ₃h ₂o, after dripping, reaction 10min, obtains loading nanometer Fe ₃o ₄flyash;

(2) with deionized water by loading nanometer Fe ₃o ₄flyash clean three times, under nitrogen protection, to loading nanometer Fe ₃o ₄flyash in add MnCl ₂solution, after stirring 2h, under nitrogen protection, dry material for 105 DEG C, grinding, obtains loading nanometer Fe ₃o ₄and Mn ²⁺modified coal ash.

In the following example, the difference of modified coal ash preparation method is only the consumption of raw material, thus causes nanometer Fe in modified coal ash ₃o ₄and Mn ²⁺charge capacity different.

Embodiment 1

In certain pharmacy corporation residual active sludge, AOX content is up to 5347mg/kg (dry mud), former mud water ratio 95.7%, and initial pH is 7.8.

The treatment process of above-mentioned residual active sludge is as follows:

(1) in residual active sludge, add the modified coal ash that 100mg/g. does the load iron manganese element of SS, stir with 180r/min, after mixing, obtain mixed solution; Wherein, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 10%, Mn ²⁺charge capacity be 2%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 21.5m ²/ g.

(2) in mixed solution, the H that 40mg/g. does SS is added ₂o ₂, stir with 180r/min, after oxidizing reaction 2h, obtain reaction solution.

After reaction 30min, reacting liquid pH value reduces to 3.4; After reaction 2h, residual active sludge AOX clearance reaches 75.2%.

(3) after having reacted, in reaction solution, add unslaked lime adjust ph to 9, stir with 180r/min, after filter press, obtain filtrate and sludge filter cake.

After process, sludge capillary water absorbing time is reduced to 19.9s by 265.6s, and sludge filter cake water ratio is reduced to 49.8%.

Excess sludge changing conditions of organic pollutant before and after oxide treatment is as shown in table 1.

Classes of compounds in table 1GC-MS detection embodiment 1 before and after residual active sludge process and peak area changing conditions

Embodiment 2

In the present embodiment, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 10%, Mn ²⁺charge capacity be 5%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 22.3m ²/ g.

In addition, all the other contents are identical with embodiment 1.

Result: after process, sludge capillary water absorbing time is reduced to 18.9s by 265.6s, and sludge filter cake water ratio is reduced to 49.1%, and mud AOX clearance is 76.8%.

Before and after oxide treatment, in mud, the change of principal pollutant is as shown in table 2.

Classes of compounds in table 2GC-MS detection embodiment 2 before and after residual active sludge process and peak area changing conditions

Embodiment 3

In the present embodiment, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 5%, Mn ²⁺charge capacity be 1%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 14.5m ²/ g.

In addition, all the other contents are identical with embodiment 1.

Result: after process, sludge capillary water absorbing time is reduced to 80.2s by 265.6s, and sludge filter cake water ratio is reduced to 60.2%, and mud AOX clearance is 66.2%.

Before and after process, in mud, the change of principal pollutant is as shown in table 3.

Classes of compounds in table 3GC-MS detection embodiment 3 before and after residual active sludge process and peak area changing conditions

Embodiment 4

In the present embodiment, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 20%, Mn ²⁺charge capacity be 5%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 28.9m ²/ g.

In addition, all the other contents are identical with embodiment 1.

Result: after process, sludge capillary water absorbing time is reduced to 16.2s by 265.6s, and sludge filter cake water ratio is reduced to 47.1%, and mud AOX clearance is 87.2%.

Before and after process, in mud, the change of principal pollutant is as shown in table 4.

Classes of compounds in table 4GC-MS detection embodiment 4 before and after residual active sludge process and peak area changing conditions

Comparative example 1

In this comparative example, adopt unmodified flyash, in addition, all the other content of operation are identical with embodiment 1.

Result: after reaction 30min, sludge pH is 7.3, after process, and sludge capillary water absorbing time is reduced to 166.2s by 265.6s, and sludge filter cake water ratio is reduced to 75.8%.Mud AOX clearance is only 18.2%.

Comparative example 2

In this comparative example, adopt Fe ₂o ₃and Mn ²⁺the modified coal ash of load, in massfraction, Fe ₂o ₃charge capacity be 10%, Mn ²⁺charge capacity be 2%, after flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 15.5m ²/ g.

In addition, all the other content of operation are identical with embodiment 1.

Result: after reaction 30min, sludge pH is 6.3, after process, and sludge capillary water absorbing time is reduced to 126.2s by 265.6s, and sludge filter cake water ratio is reduced to 68.3%.Mud AOX clearance is only 48.2%.

Comparative example 3

In this comparative example, adopt Fe ₂o ₃and MnO ₂the modified coal ash of load, in massfraction, Fe ₂o ₃charge capacity be 10%, MnO ₂charge capacity be 3.5%, after flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 17.6m ²/ g.

In addition, all the other content of operation are identical with embodiment 1.

Result: after reaction 30min, sludge pH is 6.5, after process, and sludge capillary water absorbing time reduces to 142.1s by 265.6, and sludge filter cake water ratio is reduced to 71.2%.Mud AOX clearance is only 40.8%.

Embodiment 5

In certain large-scale DYE PRODUCTION enterprise active sludge, AOX content is 2276mg/kg (dry mud), and former mud water ratio is 96.2%, and initial pH is 7.6.

The treatment process of above-mentioned residual active sludge is as follows:

(1) in residual active sludge, add the modified coal ash that 100mg/g. does the load iron manganese element of SS, stir with 180r/min, after mixing, obtain mixed solution; Wherein, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 8%, Mn ²⁺charge capacity be 5%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 18.7m ²/ g.

(2) in mixed solution, the H that 60mg/g. does SS is added ₂o ₂, stir with 180r/min, after oxidizing reaction 1.5, obtain reaction solution.

After reaction 30min, reacting liquid pH value reduces to 3.2, and after reaction 1.5h, in reaction solution, AOX clearance reaches 78.5%.

(3) after having reacted, in reaction solution, add carbide slag adjust ph to 8.5, stir with 180r/min, after filter press, obtain filtrate and sludge filter cake.

After process, sludge capillary water absorbing time is reduced to 18.2s by 185.6s.After process, sludge filter cake water ratio reduces to 49.5%.

GC-MS analyzes and shows, after aforesaid method process, in mud 3,4-chlorophenesic acid, 3,4-dibromo aniline, 2, the halogenated organic matters such as 4-chlorophenesic acid, 4-chloroaniline, 3-chloroaniline, 2-bromo-dodecane are removed substantially entirely, 3,4-dichlorphenamide bulk powder, 3,5-dichlorphenamide bulk powder, 2,6-bis-chloro-p-Nitroaniline, 2,6-bis-bromo-p-Nitroaniline, 2-amino-5,6-dichlorobenzothiazole clearance is more than 85%, and the non-halogenated such as dibutyl phthalate, diisobutyl phthalate hazardous contaminant is also removed substantially.

Comparative example 4

In the present embodiment, residual active sludge used is with embodiment 5, a modified coal ash loading nanometer Fe ₃o ₄, charge capacity is 8%.In addition content of operation is identical with embodiment 5.

Result: after process, sludge capillary water absorbing time is reduced to 29.2s by the 185.6s of former mud, after process, sludge filter cake water ratio is reduced to 68..9%.Mud AOX clearance is 50.3%.

Comparative example 5

In the present embodiment, residual active sludge used is with embodiment 5, a modified coal ash load Mn ²⁺, charge capacity is 5%.In addition all the other content of operation are identical with embodiment 5.

Result: after process, sludge capillary water absorbing time is reduced to 78.9s by the 185.6s of former mud, after process, sludge filter cake water ratio is reduced to 75.9%.Mud AOX clearance is 37.5%.

Embodiment 6

In certain pesticide producing enterprise surplus active sludge, AOX content is 4896mg/kg (dry mud), and former mud water ratio is 95.3%, and initial pH is 7.5.

The treatment process of above-mentioned residual active sludge is as follows:

(1) in residual active sludge, add the modified coal ash that 150mg/g. does the load iron manganese element of SS, stir with 180r/min, after mixing, obtain mixed solution; Wherein, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 10%, Mn ²⁺charge capacity be 5%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 22.3m ²/ g.

(2) in mixed solution, add the Sodium Persulfate that 80mg/g. does SS, stir with 180r/min, after oxidizing reaction 1.5h, obtain reaction solution.

After reaction 30min, reacting liquid pH value reduces to 3.5, and after reaction 1.5h, in mud, AOX clearance reaches 78.8%.

(3) after having reacted, in reaction solution, add carbide slag adjust ph to 8, stir with 180r/min, after filter press, obtain filtrate and sludge filter cake.

After process, sludge capillary water absorbing time is reduced to 19.1s by 286.6s.After process, sludge filter cake water ratio reduces to 49.1%.

GC-MS analyzes and shows, after aforesaid method process, in mud 2, the halogenated organic matters such as 4-chlorophenesic acid, 3,5-dichlorobenzoic acids, 3,5-bis-chloro-2-benzaminic acid are removed substantially, the noxious pollutant toluene of non-halogenated, butyl phthalate is also substantially removed.

Embodiment 7

In certain large-scale fine chemistry industry garden sludge sewage, AOX content is 2108mg/kg (dry mud), and former mud water ratio is 96.1%, and initial pH is 7.3.

The treatment process of above-mentioned residual active sludge is as follows:

(1) in residual active sludge, add the modified coal ash that 120mg/g. does the load iron manganese element of SS, stir with 180r/min, after mixing, obtain mixed solution; Wherein, in massfraction, nanometer Fe in modified coal ash ₃o ₄charge capacity be 12%, Mn ²⁺charge capacity be 3%.

After flyash modified, specific surface area is by original 8.2m ²/ g, brings up to 24.5m ²/ g.(2) in mixed solution, the H that 40mg/g. does SS is added ₂o ₂, 30mg/g. does the Sodium Persulfate of SS, stir with 180r/min, after oxidizing reaction 1h, obtain reaction solution.

After reaction 30min, reacting liquid pH value reduces to 3.3; After reaction 1h, in mud, AOX clearance reaches 80.1%, mud AOX reduces to 420mg/kg (dry mud), reaches the standard of " urban wastewater treatment firm sludge disposal land reclamation shale (GB/T2460-2009) " middle AOX lower than 500mg/kg.

(3) after having reacted, in reaction solution, add unslaked lime adjust ph to 8.5, stir with 180r/min, after filter press, obtain filtrate and sludge filter cake.

After mud conditioning, capillary water absorbing time reduces to the 17.6s after process by the 165.2s of former mud, and after process, sludge filter cake water ratio is reduced to 48.9%.

GC-MS analyzes and shows, after aforesaid method process, the chloro-4-fluoro acetophenone of 3-in mud, 2, 4-dichlorphenamide bulk powder, chlorooctadecane, 1-vaccenic acid SULPHURYL CHLORIDE, 1, 2-dibromo-dodecane, 2, 2, 2-trichloroethyl carbonic acid stearyl etc. is completely removed substantially, 3, 5-dichlorphenamide bulk powder, 2, 4, the pollutants removal rates such as 6-trichloroaniline are more than 83%, diisobutyl phthalate in mud, phthalic acid mono—n—butylester, dibutyl phthalate, benzothiazole, 4-benzyl-pyridine, 2, the non-halogenated hazardous contaminants such as 6-diisopropylnaphthalene are completely removed substantially.

Embodiment 8

In the present embodiment, residual active sludge used is with embodiment 7, and oxygenant only adds the H that 40mg/g. does SS ₂o ₂.In addition, all the other content of operation are identical with embodiment 7.

Result: after process, sludge capillary water absorbing time reduces to the 35.7s after process by the 165.2s of former mud, after process, sludge filter cake water ratio is reduced to 59.9%.Mud AOX clearance is 70.6%.

Embodiment 9

In the present embodiment, residual active sludge used is with embodiment 7, and oxygenant only adds the Sodium Persulfate that 30mg/g. does SS.In addition, all the other content of operation are identical with embodiment 7.

Result: after process, sludge capillary water absorbing time reduces to the 43.6s after process by the 165.2s of former mud, after process, sludge filter cake water ratio is reduced to 66.8%.Mud AOX clearance is 62.5%.

Claims (10)

1. A treatment method for the remaining activated sludge polluted by AOX, characterized in that, comprising: Add modified fly ash loaded with iron and manganese elements to the remaining activated sludge, mix evenly, then add oxidant to carry out oxidation reaction, after the reaction is completed, add skeleton agent to the reaction liquid, adjust the pH value to 8-9, Plate and frame filter press is carried out to obtain filtrate and sludge filter cake. 2. The treatment method according to claim 1, characterized in that, the modified fly ash is loaded with nano Fe ₃ O ₄ and Mn ²⁺ . 3. processing method as claimed in claim 2 is characterized in that, in mass fraction, in the described modified fly ash, nanometer Fe ₃ O _The loading capacity is 1～40%, and the loading capacity of Mn ²⁺ is 0.5-20%. 4. processing method as claimed in claim 2, is characterized in that, in mass fraction, in the described modified fly ash, nanometer Fe ₃ O _The loading capacity is 5～20%, and the loading capacity of Mn ²⁺ is 1 to 5%. 5. The treatment method according to claim 1, characterized in that the dosage of the modified fly ash is 20-200 mg/g. dry SS. 6. The processing method according to claim 1, wherein the modified fly ash passes through a 200-mesh sieve before loading iron and manganese elements. 7. _The treatment method according to claim ₁ , wherein the oxidizing agent is at least one of H2O2 and persulfate. 8. The treatment method according to claim 1, characterized in that, the dosage of the oxidizing agent is 5-100 mg/g. dry SS; the oxidation reaction time is 20 min-2 h. 9. The treatment method according to claim 1, wherein the oxidizing agent is composed of H ₂ O ₂ and persulfate, wherein the dosage of H ₂ O ₂ is 5-80 mg/g. dry SS; The dosage of persulfate is 10~100mg/g. dry SS; the oxidation reaction time is 30min~2h. 10. The treatment method according to claim 1, characterized in that, the framework agent is at least one of lime, carbide slag, calcium carbonate, and calcium oxide.