CN104761114B - Enhanced wastewater phosphorus removal method - Google Patents
Enhanced wastewater phosphorus removal method Download PDFInfo
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- CN104761114B CN104761114B CN201410641499.4A CN201410641499A CN104761114B CN 104761114 B CN104761114 B CN 104761114B CN 201410641499 A CN201410641499 A CN 201410641499A CN 104761114 B CN104761114 B CN 104761114B
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Abstract
The invention discloses an enhanced wastewater phosphorus removal method applicable to biological treatment process of wastewater, and belongs to the technical field of wastewater depth treatment. The method includes removal and recycling of phosphorus in sludge mixed solution in sludge anaerobic tank through crystallization of blue-iron stone (Fe3(PO4)2.H2O); and removal of phosphorus in wastewater in an aerobic biological reaction tank through the flocculation precipitation of ferric iron. The method employs crystallization of blue-iron stone as the main process for phosphorus removal, adopts a of biological and chemical combined method for phosphorus removal, has high phosphorus removal efficiency, does not produce chemical sludge, and can realize the recycling of phosphorus resource in sewage and save the operation cost of the sewage treatment. The method is an environmentally friendly novel technology for wastewater phosphorus removal.
Description
Technical field
The invention belongs to sewerage advanced treatment process technical field is and in particular to a kind of utilize microbial action and chemistry anti-
The method that sewage should be processed, is carried out a biological disposal upon and chemicrystallization method dephosphorization by anaerobic and aerobic particularly to one kind, and real
Existing reclamation of phosphorus resource and the sewage water treatment method of excess sludge reduction.
Background technology
Growth with municipal sewage treatment amount and the raising for the treatment of effeciency, as the accessory substance excess sludge of sewage disposal
Quantity also grow with each passing day.All there is certain office in traditional mud decrement and processing mode in terms of technology and Environmental security
Limit.For the various sludge reduction technology adopting both at home and abroad at present, an insoluble problem is：When mud decrement effect
When good, excess sludge production reduces, the phosphorus content entering in mud also reduces therewith, thus leads to the phosphorus ligands effect of sewage bright
Aobvious reduction.And the aggravation with body eutrophication trend, the removal of the nutriment such as nitrogen, phosphorus has become as municipal sewage treatment
One of most important task, the recovery of phosphor in sewage and recycling become the research emphasis of sewage disposal.The phosphorus of sewage returns
Receipts technology is it is simply that adopt certain technical method by the phosphorus in sewage can be reused (in phosphate industry or fertilizer industry)
Form carry out separating and recovery, and be not singly that phosphorus is transferred in excess sludge.
The dirty water living creature processing technique of achievable dephosphorization is more, and wherein conventional has A2The techniques such as/O, SBR and oxidation ditch.
However, these biological removal of phosphorus in wastewater techniques still suffer from problems with：(1) requirement to sludge age for the dephosphorization process is strict, realizes high
During effect dephosphorization, sludge age should be in below 8d；(2) need periodic exhaustion excess sludge in sewage treatment process, these excess sludge warps
Concentrate and Anaerobic Digestion after, intracellular phosphorus is released, if excess sludge is not rationally disposed, can be to being nearby subject to
Water body of receiving causes secondary pollution；(3) phosphorus in sewage is persistently transferred in excess sludge it is difficult to realize reusing, and causes phosphorus
The huge waste of resource；(4) due to containing substantial amounts of phosphorus in returned sludge, lead to the dephosphorization effect that biological wastewater treatment process is overall
Rate is not high, in water outlet the concentration of phosphorus be difficult to up to standard.
At present, the reinforced phosphor-removing technology in biological wastewater treatment process mainly has Enhanced Biological Phosphorus Removal method, chemical precipitation to remove
Phosphorus method and crystallisation etc..Enhanced Biological Phosphorus Removal method hydrolyzes intracellular polyphosphate particle release phosphorus under anaerobic using polyP bacteria and (carries
Energizing quantity), utilize PHB to produce energy Excess free enthalpy phosphorus (synthesis polyphosphate storage from sewage simultaneously under aerobic condition
In intracellular) characteristic, so that phosphorus is removed from sewage by continuous discharge rich phosphorous sludge.The method operating cost is low, but surely
Qualitative difference, the corresponding standard of water outlet phosphorus concentration difficult to reach.Meanwhile, Enhanced Biological Phosphorus Removal technology is difficult to thoroughly fix in sewage
Phosphate (only makes phosphorus be transferred to mud phase from aqueous phase).For realizing the recycling of phosphor in sewage resource, phosphatic chemical precipitation
Become indispensable link.The fifties in last century, chemical precipitation dephosphorization technique is applied first in Switzerland, is also to work as simultaneously
One of topmost sewage dephosphorization technology in front Practical Project.In processing procedure, Fe2+/Fe3+、Al3+Or Ca2+Deng metal ion
On the one hand generation insoluble phosphate precipitation can be reacted with the phosphate radical in water, on the other hand so that phosphorus is had by flocculation
Effect removes.However, traditional chemical can generate a large amount of chemical sludges when being deposited in the phosphate removing in sewage biological treatment system,
Wherein it is mingled with more organic substance and activated sludge.The dehydration of these chemical sludges, transport and disposal costs are sufficiently expensive, return
Receive phosphate therein also very difficult.
In recent ten years, the direction reclaimed to phosphorus with sewage phosphorus ligands is developed, and phosphate crystal method is sunk as phosphorus chemistry
A kind of improved technology formed sediment, is widely studied, its primary crystalline product has birds droppings in terms of the phosphor resource in recovery sewage
Stone (MAP) and two kinds of hydroxyapatite (HAP), course of reaction such as formula 1 and formula 2.
Mg2++NH4 ++PO4 3-+6H2O→MgNH4PO4·6H2O (1)
5Ca2++3PO4 3-+OH-→Ca5(PO4)3OH (2)
The preferable phosphorus of purity can be obtained based on the sewage phosphate crystallization technique of MAP and HAP and reclaim product, so that sewage phosphorus is returned
The industrialization received is possibly realized, but both approaches still suffer from the defect that some are difficult to overcome.Due to fitting of MAP and HAP crystallization
Preferably pH level is respectively 8.5～9.5 and 9.0～10.5, efficiently carries out for making both phosphate crystals react, and generally requires to throw
Plus substantial amounts of alkali lye.And there is substantial amounts of CO in phosphate level highest excess sludge digestion unit2/CO3 2-, can be to body
The pH of system adjusts and produces huge cushioning effect, so that the amount of required alkali lye is sharply increased, or makes CO2Stripping operation necessitates.
For HAP crystallizing system, CO3 2-Also can be with Ca 2+Reaction, makes added amount of chemical increase.These defects considerably increase MAP and HAP
The cost of phosphorus recovery technology.Therefore, traditional biology/chemical dephosphorization technology is improved for the efficiency improving sewage dephosphorization
It is respectively provided with important realistic meaning with the phosphor resource reclaiming useful.
Content of the invention
The purpose of the present invention is that phosphor-removing effect is poor, reclamation of phosphorus resource difficult for existing in existing biological removal of phosphorus in wastewater technology
Etc. technical problem, a kind of step reinforced phosphor-removing method of sewage is proposed.The inventive method is crystallized as main body dephosphorization with blue iron-stone
Journey, using biological-chemical joint dephosphorization technique, dephosphorization efficiency is high, neither produces chemical sludge, can achieve phosphor in sewage resource again
Effective recovery, reduce the operating cost of sewage disposal, be a kind of environmentally friendly sewage dephosphorization novel technical method.
For realizing the purpose of the present invention, the present invention provides a kind of reinforced sewage phosphorus removing method, including in anaerobic sludge digestion
Strengthen the crystallization of blue iron-stone in pond, remove phosphorus in mud mixed liquid.
Wherein, described crystallization strengthening process includes：Add Fe in anaerobic sludge digestion pond3+Compound, Fe3+Through micro-
Biological agent is reduced to Fe2+, and the phosphate anion being discharged in anaerobic digestion process with mud reacted, and generates blue iron-stone crystallization
Precipitation, thus remove the phosphorus in mud.
Particularly, described Fe3+The dosage of compound should make Fe3+With mud total phosphorus content in anaerobic sludge digestion pond
Mol ratio is 1.8-2.2：1, preferably 1.9-2.1：1.
Especially, described Fe3+Compound select unformed FeOOH, hydrated ferric oxide, di-iron trioxide or
Iron-containing slag.
Particularly, also include adding blue iron-stone particle in anaerobic sludge digestion pond as crystal seed to strengthen crystallization process.
Especially, the described average grain diameter adding blue iron-stone particle is 2-4mm, preferably 3mm.
Another aspect of the present invention provides a kind of step phosphorus removing method of sewage/mud, comprises the steps：
1) add Fe in anaerobic sludge digestion pond3+Compound, Fe under anaerobic3+The micro- life of anaerobism in digested pond
Thing is reduced into Fe2+, and with mud in anaerobic digestion process the phosphate anion of release react, generate blue iron-stone crystallization and sink
Form sediment；
Wherein, step 1) described in anaerobic sludge digestion pond can be A2Science and engineering at the different sewage such as/O, SBR, oxidation ditch process
Anaerobic sludge digestion pond in skill；
2) strengthen the supernatant after crystallization treatment, second pond returned sludge and through in anaerobic sludge digestion pond through blue iron-stone
Sewage after level (preliminary sedimentation tank) is processed enters two stage biological reaction tank together, generally comprises anaerobic pond/section, anoxic pond/section is become reconciled
Oxygen pond/section, the iron ion priority in two stage biological reaction tank as phosphate radical precipitating reagent (anaerobic pond/section and Aerobic Pond/
In section) and coagulant (in Aerobic Pond/section) performance step dephosphorization function；
3) mixed liquor of aerobe reaction pond/section enters in second pond and carries out mud-water separation, and the supernatant of second pond goes out
Water is the sewage disposal plant effluent after reinforced phosphor-removing.
Particularly, using enhanced biological phosphorus removal sewage treatment process as described sewage disposal two stage biological reaction tank
Main body handling process.
Wherein, step 1) described in Fe3+The dosage of compound should make Fe3+With mud total phosphorus in anaerobic sludge digestion pond
The mol ratio of content is 1.8-2.2：1, preferably 1.9-2.1：1.
Especially, described Fe3+Compound select unformed FeOOH, hydrated ferric oxide, di-iron trioxide or
Iron-containing slag.
Particularly, when adding di-iron trioxide or iron-containing slag in anaerobic sludge digestion pond, need simultaneously to sludge anaerobic
Add electron transit mediator, to improve Fe in digester3+Reduction efficiency and speed.
Wherein, described electron transit mediator selects 2,6- disulfonic acid anthraquinone (AQDS) or humus, preferably AQDS.
Especially, the addition of electron transit mediator is that in anaerobic sludge digestion pond, every 1L mud interpolation 1-1.5g is preferably 1g
AQDS or 2-2.5g is preferably 2g humus.
Particularly, step 1) in also include adding in anaerobic sludge digestion pond blue iron-stone particle as blue iron-stone crystallization at
The crystal seed of reason.
Especially, the described average grain diameter adding blue iron-stone particle is 2-4mm, preferably 3mm.
Wherein, step 1) in anaerobic sludge digestion pond digestion temperature be 35-55 DEG C, preferably 50-55 DEG C.
Particularly, also include making anaerobism using digestive juice interior circulation or by the way of being passed through sludge anaerobic digestion gas production compressed gas
The reaction zone of digester obtains the hydraulic disturbance optimizing.
Especially, described digestive juice interior circulation or be passed through sludge anaerobic digestion gas production compressed gas and make on the mud of digester center
Rising flow velocity is 0.04-0.06m/s, preferably 0.05m/s.
In anaerobic sludge digestion pond, iron-reducing bacterium in mud will be added by the use of digested sludge as electron donor
Fe3+It is reduced to Fe2+, and it is allowed to the condition existing with the phosphate anion of anaerobic sludge digestion release in crystal seed indigo plant iron-stone particle
Under, blue iron-stone crystal is generated by induction crystallization strengthening.Meanwhile, the blue iron-stone crystal grain growing to certain particle diameter overcomes anaerobism
By digestive juice interior circulation or be passed through the hydraulic disturbance that digestion aerogenesis compressed gas causes in digester, it is settled down at the bottom of pond portion and is divided
From.Periodically discharge the blue iron-stone crystal grain in anaerobic sludge digestion at the bottom of pond portion, after washing is dried, obtains phosphorus and reclaim product.
Unreacted excessive Fe in sludge-digestion liquid2+Be transported to the main body biological processing unit of sewage, anaerobic pond/
Successively step dephosphorization function is played as the precipitating reagent of phosphate radical and coagulant in section, anoxic pond/section and Aerobic Pond/section.In anaerobism
In pond/section, polyP bacteria in returned sludge using the organic substance in raw sewage and sludge-digestion liquid as carbon source, in suboxides also
Under the anaerobic condition of former current potential, release phosphorus, and dissolubility Fe brought into sludge-digestion liquid in a large number2+Generate calcium phosphate precipitation.Remaining
Fe2+Enter aerobic reaction tank/section, reduction-state Fe with mud mixed liquid after anoxic pond/section2+It is Fe by Quick Oxidation3+.Logical
The precipitation of peroxophosphoric acid iron and Fe3+Coagulation, the phosphate radical in sewage Aerobic Pond is biological inhale phosphorus while obtain strong
Compoundization removes, and in secondary treatment yielding water, the concentration of phosphorus can reach country-level emission standard A.
Fe in Aerobic Pond/section mud3+Finally it is back to excess sludge anaerobic digestion with mud through second pond and concentration basin
Pond.These Fe3+Sludge digestion tank is reduced again, and discharge with anaerobic sludge digestion in the presence of blue iron-stone crystal seed
There is strengthening crystallization reaction in phosphate, ultimately forming blue iron-stone crystal makes phosphate be removed further and reclaim.
The present invention has the advantages that：
1st, the reinforced phosphor-removing method phosphor-removing effect of the present invention good hence it is evident that reduce sewage second-level carry out a biological disposal upon water outlet in phosphorus dense
Degree, the removal efficiency of phosphor in sewage is high, and dephosphorizing rate reaches more than 95%.
2nd, the present invention adds Fe into anaerobic sludge digestion pond3+Compound and blue iron-stone crystal grain, blue iron-stone crystal is made
For the crystal seed of induction crystallization, promote phosphate radical and the Fe of anaerobic sludge digestion release3+Obtain through iron-reducing bacterium reduction in mud
Fe2+Reaction, generates and reclaims blue iron-stone crystal, that is, reduce the phosphate level of system, and effectively reclaimed in sewage
Phosphor resource.
3rd, the reinforced phosphor-removing method of the present invention is carried out under conditions of pH neutrality or weakly acidic pH, that is, in sewage and Treatment of Sludge
During do not need adjust pH, thus overcoming the technological deficiency that traditional chemical crystallizing-dephosphorizing method is carried out in the basic conditions, section
Save the expense that chemical agent adds, reduced the cost of sewage disposal, also reduce chemical agent using to environment simultaneously
Pollution.
4th, added Fe in phosphorus removing method of the present invention3+Iron in compound is recycled in the crystallization process of blue iron-stone,
Meanwhile also achieve the recycling of phosphor resource in sewage and mud.Whole process does not only increase the fortune of sewage treatment plant
Row cost, has also reclaimed the phosphor resource in sewage, thus having great economic benefit and environmental benefit.
5th, the reinforced sewage phosphorus removing method of the present invention is simple to operate, stability is high, operating procedure condition is controlled, does not increase dirt
Water process link and processing cost, and the phosphate of high-quality can be reclaimed it is adaptable to strengthening removes and reclaims municipal sewage or industry
Phosphate in waste water, beneficial to large-scale promotion.
Brief description
Fig. 1 is the process chart of reinforced sewage dephosphorization of the present invention；
Fig. 2 is blue iron-stone crystallized product photo in anaerobic sludge digestion pond；
Fig. 3 is the XRD spectrum of anaerobic sludge digestion pond crystallized product indigo plant iron-stone.
Specific embodiment
To further describe the present invention with reference to specific embodiment, advantages of the present invention and feature will be with description and
Apparent.But these embodiments are only exemplary, any restriction is not constituted to the scope of the present invention.People in the art
Member should be understood that can be to enter to the details of technical solution of the present invention and form under without departing from the spirit and scope of the present invention
Row modification or replacement, but these modifications and replacement each fall within protection scope of the present invention.
The embodiment of the specific embodiment of the invention adopts Enhanced Biological Phosphorus Removal to process for main body with municipal sewage plant
Technique illustrates as a example carrying out sewage disposal.
Embodiment 1
Take with A2/ O is certain secondary sedimentation tank of sewage treatment work activated sludge 5L of main body handling process, using the side of gravity concentration
Mud is placed 1d by method, and measuring its total phosphorus concentration is 700mg/L.This thickened sludge of 1L is taken to be placed in an anaerobic reactor, and anti-
Answer the blue iron-stone crystal that device bottom adds 50g, average grain diameter is 4mm.The temperature of setting anaerobic digestion is 35 DEG C, mud upper up-flow
Speed is 0.05m/s, adds the unformed FeOOH of 42.4mmol, reacts 21d, and monitors dissolubility phosphoric acid in sludge digestion system
The change of salt.Result shows, compared with control experiment final dissolved phosphorus concentration 240mg/L, adds FeOOH anaerobic sludge digestion
The final phosphorus concentration of system is 80mg/L, and phosphorus concentration reduces 67%.
Embodiment 2
Certain is with A2/ O is the second pond activated sludge of main body handling process sewage treatment plant, after gravity concentration 1d, mud
Total phosphorus concentration is 610～750mg/L.This thickened sludge is added a dischargeable capacity to include 10g for 1L as experiment material blue
In the CSTR reactor of iron-stone crystal seed (average grain diameter is 3mm), press Fe/ mud TP mol ratio is that 2.0 additions are unformed simultaneously
FeOOH, the temperature of setting anaerobic digestion is 55 DEG C, and mud upflow velocity is 0.05m/s, runs 108 days altogether.Confirm after testing,
After running a period of time, the blue iron-stone crystalline size in digester mud phase increased, and does not have other associated minerals to generate, thing
Mutually single, as shown in Figure 2 and Figure 3.
Claims (7)
1. a kind of step phosphorus removing method of sewage/mud is it is characterised in that comprise the steps：
1) add Fe in anaerobic sludge digestion pond3+Compound, Fe under anaerobic3+The anaerobe reduction in digested pond
Become Fe2+, and with mud in anaerobic digestion process release phosphate anion react, generate indigo plant iron-stone crystalline deposit；Wherein,
Step 1) described in anaerobic sludge digestion pond be A2Anaerobic sludge digestion in/O, SBR, oxidation ditch process different sewage handling process
Pond；
2) supernatant after crystallization treatment, second pond returned sludge and through at the beginning of one-level are strengthened in anaerobic sludge digestion pond through blue iron-stone
Sewage after heavy pond is processed enters two stage biological reaction tank together, and the iron ion priority in two stage biological reaction tank is as phosphoric acid
The precipitating reagent of root and coagulant play step dephosphorization function, and wherein, described two stage biological reaction tank includes anaerobic pond/section, anoxic
Pond/section and Aerobic Pond/section；Iron ion in anaerobic pond/section and Aerobic Pond/section as phosphate radical precipitating reagent, in Aerobic Pond/section
Play step dephosphorization function as coagulant；
3) carry out muddy water in the mixed liquor entrance second pond through anaerobic pond/section, anoxic pond/section, aerobe reaction pond/section to divide
From the supernatant water outlet of second pond is the sewage disposal plant effluent after step dephosphorization.
2. the step phosphorus removing method of sewage/mud as claimed in claim 1 is it is characterised in that step 1) described in add Fe3+
Mol ratio with mud total phosphorus in anaerobic sludge digestion pond is 1.8-2.2：1.
3. the step phosphorus removing method of sewage/mud as claimed in claim 1 or 2 is it is characterised in that step 1) described in contain
Fe3+Compound selects unformed FeOOH, hydrated ferric oxide, di-iron trioxide or iron-containing slag.
4. the step phosphorus removing method of sewage/mud as claimed in claim 1 or 2 is it is characterised in that step 1) in also include to
Blue iron-stone particle is added as the crystal seed of blue iron-stone crystalline deposit in anaerobic sludge digestion pond.
5. the step phosphorus removing method of sewage/mud as claimed in claim 1 or 2 is it is characterised in that step 1) in sludge anaerobic
The digestion temperature of digester is 35-55 DEG C.
6. the step phosphorus removing method of sewage/mud as claimed in claim 1 or 2 is it is characterised in that step 1) in using digestion
Liquid interior circulation or be passed through the mode of sludge anaerobic digestion gas production compressed gas and obtain the hydraulics of optimization and make sludge digestion reaction zone
Phosphate radical and Fe2+It is sufficiently mixed and contacts, to strengthen the crystallization of blue iron-stone；Meanwhile, grow to the blue iron-stone of certain particle diameter
Crystal grain can overcome the hydraulic disturbance in anaerobic digester, is separated through being settled down at the bottom of pond portion.
7. the step phosphorus removing method of sewage/mud as claimed in claim 1 or 2 is it is characterised in that step 1) in sludge anaerobic
The digestion temperature of digester is 50-55 DEG C.
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| NL2018525B1 (en) * | 2017-03-15 | 2018-09-24 | Stichting Wetsus European Centre Of Excellence For Sustainable Water Tech | Method and system for phosphate recovery from a stream |
| CN108439719A (en) * | 2018-04-27 | 2018-08-24 | 易能环境技术有限公司 | A kind of sewage treatment process |
| CN108821444A (en) * | 2018-05-28 | 2018-11-16 | 天津大学 | Anaerobism phosphorus recovery method based on microorganism alienation metal reduction |
| CN109626570A (en) * | 2018-12-26 | 2019-04-16 | 同济大学 | A kind of preposition phosphorus removing method of vivianite crystallization based on AAO/AO technique |
| CN110240356A (en) * | 2019-05-31 | 2019-09-17 | 天津大学 | A kind of phosphorus recovery method of capacitive deionization combination anaerobism iron reduction synthesis indigo plant iron-stone |
| CN110961076A (en) * | 2019-08-12 | 2020-04-07 | 安徽国祯环卫科技有限公司 | Novel method for adsorbing phosphorus in sludge anaerobic digestion biogas slurry by low-temperature pyrolysis residues |
| CN110642460A (en) * | 2019-09-19 | 2020-01-03 | 济南大学 | Method for removing nitrogen and phosphorus by ferrate enhanced denitrification phosphorus removal biological filter |
| CN111056710B (en) * | 2019-12-28 | 2022-06-14 | 西安建筑科技大学 | Sewage advanced treatment and resource recovery system and method for anaerobic ectopic electric release iron membrane bioreactor |
| CN112279478A (en) * | 2020-10-23 | 2021-01-29 | 国河环境研究院(南京)有限公司 | Method for recovering phosphorus in excess sludge in form of vivianite |
| CN113666498B (en) * | 2021-08-06 | 2022-11-29 | 同济大学 | Ferrocyanite separation and kieselguhr recovery device and method for enhanced nitrogen and phosphorus removal system |
| CN114433618A (en) * | 2022-01-27 | 2022-05-06 | 北京林业大学 | Method for strengthening reduction and fixation of Cr (VI) in soil by microorganisms by using anaerobic digestion sludge dewatering filtrate |
| CN114477119A (en) * | 2022-02-18 | 2022-05-13 | 北京林业大学 | Method for enhancing recovery of phosphorus resources in municipal sludge hydrothermal carbonization liquid |
| CN114409101B (en) * | 2022-03-31 | 2022-07-12 | 北京林业大学 | Nitrogen and phosphorus removal sewage treatment system and method based on iron reduction and oxidation circulation |
| CN115180774B (en) * | 2022-07-31 | 2023-08-22 | 深圳同享投资有限合伙企业(有限合伙) | Method for recycling phosphorus from cultivation wastewater |
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| GB9723347D0 (en) * | 1997-11-05 | 1998-01-07 | Univ Waterloo | Treatment system for removing phosphorus from sewage water |
| CN101381183B (en) * | 2008-06-05 | 2010-10-13 | 北京桑德环境工程有限公司 | Sewage disposal system with biological phosphorus removal and bypass chemical phosphorus removal and disposal method |
| CN101955293A (en) * | 2009-07-11 | 2011-01-26 | 甘肃雪晶生化有限责任公司 | Method for processing high-concentration organic waste water |
| ES2749638T3 (en) * | 2012-05-24 | 2020-03-23 | Incro S A | Synthesis method of ferrous phosphate from waste materials |
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