CN110382422A

CN110382422A - For biology go to denitrogenate and the activated sludge process of phosphorus simultaneously

Info

Publication number: CN110382422A
Application number: CN201780084849.3A
Authority: CN
Inventors: 松村正利; 阿洛依修斯·查尔塞都尼·提尤; 奥布里·卡拉姆帕塔纳; 梅尔文·海纳姆帕斯; 安吉洛·T·维克特·达马斯科
Original assignee: Aum Manufacturing Co Ltd; Menelard Water; Phil Global Management Services
Current assignee: Om Mfg Co ltd; Phil-Japan Worldwide Management Service Inc
Priority date: 2016-12-19
Filing date: 2017-07-03
Publication date: 2019-10-25
Also published as: JP6188264B1; JP2018099641A; WO2018116507A1

Abstract

The present invention, which provides, a kind of for biology while to go to denitrogenate and the activated sludge process of phosphorus.A kind of method that the present invention provides the phosphorus compound by sewage and nitrogen compound removal, include following step: step (A), it is characterized in that, it is that the sewage is supplied in the treatment trough comprising activated sludge, to the step of forming mixture of the sewage with the activated sludge, additional volatile fatty acid or its salt are added in the way of making the volatile fatty acid total amount in the mixture become the threshold value or more；The mixture is carried out non-Aerobic Process for Treatment in the treatment trough by step (B)；The mixture for having carried out non-Aerobic Process for Treatment is carried out Aerobic Process for Treatment in the treatment trough by step (C)；Step (D) settles the activated sludge in the mixture, to be separated into the activated sludge and processing water；And step (E), at least part of the processing water is extracted out from the treatment trough.The activated sludge includes at least nitrobacteria, denitrifying bacteria and stores phosphobacteria.

Description

For biology go to denitrogenate and the activated sludge process of phosphorus simultaneously

Technical field

The present invention relates to a kind of activated sludge processes, by adding volatile fatty acid at specific time point so as to life Object ground goes to denitrogenate simultaneously and phosphorus.

Background technique

It about biology goes to denitrogenate and the technology of phosphorus simultaneously, has also carried out tasting based on steady and continuous activated sludge process Examination, but go the ability of dephosphorization unstable.It therefore, can be by using chemical coagulants such as PAC (aluminium polychloride) by phosphorus chemistry Property precipitate, but remaining aluminium ion and/or iron ion makes the ecosystem in the increase due to worrying mud or processing water At influence, so the addition of chemical coagulant should be limited to minimal utilization (non-patent literature 1).In addition, right For steady and continuous activated sludge process, precipitation tank, reactive tank, final precipitation tank, foldback sludge plant are minimum limits at first It is required.

On the other hand, SBR (Sequencing Batch Reactor, sequencing batch reactor) is although method is similarly living Property sludge, but in single slot based on the scheduled time distribute and implement repeatedly raw water flow into (FILL), reaction (REACT), settle (SETTLE), processing water extraction (DRAW), excess sludge extraction (IDLE) whole processing, equipment it is required Area and cost are few, in addition, equity can also easily be answered by changing even if raw water influx, as distributed small-scale place For reason facility, it is believed that be (non-patent literature 2) appropriate.

But it about using phosphobacteria releasing phosphorus is stored, for biology is important for phosphorus ligands, but more in rainfall Region, due to rainfall by sewage organic matter dilute, in order to store phosphobacteria release phosphorus necessary to organic matter do not fill sometimes Point.In addition, releasing phosphorus to make to store phosphobacteria, need to be reduced to certain certain level, phosphorus under anaerobic and by associativity oxygen While concentration of the removal also by associativity oxygen influenced, it is highly unstable and difficult.

Existing technical literature

Non-patent literature

Non-patent literature 1:van Loosdrecht et al., " Biological phosphorous removal process”,Applied Microbiology and Biotechnology,48(3),289-296(1997).

Non-patent literature 2:Widerer, P.A.et al., (2001) " Sequencing batch reactor technology”,IWA scientific and technical report no.10,London,UK.

Summary of the invention

Solution for solving the problem

The present invention provide it is a kind of for biology while the method that removes the nitrogen and phosphorus in waste water, the waste water is that do not have There is the waste water of sufficient organic matter.

The inventors of the present invention are in order to realizing biology while go to denitrogenate and phosphorus, for aerobic and non-aerobic setting position It sets and the conditions such as time distribution, circulation time obtained from the composition ratio otherwise for the carbon and nitrogen that consider in sewage, Various researchs are carried out, as a result, it has been found that a kind of be suitable for biology while going to denitrogenate and the SBR basic sequence of phosphorus (sequence), so as to complete the present invention.In addition, the inventors of the present invention have found for inducing the institute for phosphorus ligands required Phosphorus release, the additive amount appropriate of volatile fatty acid and addition opportunity.

Therefore, the present invention provides project for example below.

(project 1)

A kind of method, to include following step for the method for phosphorus compound and nitrogen compound removal in sewage:

Step (A), which is characterized in that for the sewage is supplied in the treatment trough comprising activated sludge, to form the dirt The step of mixture of water and the activated sludge, adding additional volatile fatty acid or its salt in the step makes in the mixture Volatile fatty acid content become the threshold value more than,

The mixture is carried out non-Aerobic Process for Treatment in the treatment trough by step (B),

The mixture for having carried out non-Aerobic Process for Treatment is carried out Aerobic Process for Treatment in the treatment trough by step (C),

Step (D) settles the activated sludge in the mixture, to be separated into the activated sludge and processing Water, and

Step (E) extracts at least part of the processing water from the treatment trough out,

The activated sludge includes at least nitrobacteria, denitrifying bacteria and stores phosphobacteria.

(project 2)

Step (A), which is characterized in that for the sewage is supplied in the treatment trough comprising activated sludge, to form the dirt The step of mixture of water and the activated sludge, which, which adds additional volatile fatty acid or its salt, makes in the mixture Volatile fatty acid content becomes threshold value or more,

The mixture for having carried out non-Aerobic Process for Treatment is carried out Aerobic Process for Treatment in the treatment trough by step (C-1),

Carbon source is supplied in the treatment trough by step (C-2),

Step (C-3), by the non-Aerobic Process for Treatment of mixture further progress in the treatment trough,

Step (C-4) will carry out the mixture further progress Aerobic Process for Treatment of non-Aerobic Process for Treatment in the treatment trough,

(project 3)

The method according to project 1 or 2, which is characterized in that at least by abovementioned steps (B) carry out to aforementioned mixture at For anaerobic state.

(project 4)

According to method described in project 3, which is characterized in that at least carry out abovementioned steps (B) extremely to utilize denitrifying bacteria It takes in nitric acid and releases phosphorus using phosphobacteria is stored.

(project 5)

The method according to any one of project 1~4, which is characterized in that at least by abovementioned steps (C), (C-1) or (C-4) it carries out taking in phosphorus to using aforementioned storage phosphobacteria.

(project 6)

Method described in any one of project 3~5 according to project 2 or in the case where being subordinated to project 2, feature It is, in abovementioned steps (C-2), amount as aforementioned denitrifying bacteria intake nitric acid can be utilized to add aforementioned carbon source.

(project 7)

Method described in any one of project 3~6 according to project 2 or in the case where being subordinated to project 2, feature It is, at least carries out abovementioned steps (C-3) to become anaerobic state to aforementioned mixture.

(project 8)

The method recorded in project 7, which is characterized in that at least carry out abovementioned steps (C-3) extremely to utilize aforementioned denitrification Bacterium takes in nitric acid.

(project 9)

The method according to any one of project 1~8, wherein aforesaid threshold values are about 15mg/L~about 30mg/L.

(project 10)

According to method described in project 9, wherein aforesaid threshold values are about 20mg/L.

(project 11)

Method described in any one of project 3~10 according to project 2 or in the case where being subordinated to project 2, feature It is, when the BOD in aforementioned sewage is 5 or more relative to the concentration ratio of ammoniacal nitrogen and ammoniacal nitrogen is 40mg/L or less, before use Sewage is stated as aforementioned carbon source.

(project 12)

The method according to any one of project 1~11, wherein aforementioned additional volatile fatty acid or its salt are selected from The group being made of acetic acid or propionic acid or their salt.

(project 13)

The method according to any one of project 1~12, wherein the pH of the aforementioned mixture in abovementioned steps (B) is About 7.5 or more.

(project 14)

The method according to any one of project 1~13, wherein the aforementioned additional volatility rouge in abovementioned steps (A) The additive amount of fat acid or its salt, is determined based on the BOD of aforementioned sewage, ammonia nitrogen concentration and Vfa Concentration.

(project 15)

The method according to any one of project 1~14 does not include the step of adding chemical coagulant.

(project 16)

The method according to any one of project 1~15, wherein the nitric nitrogen concentration of aforementioned processing water is about 1~ 5mg/L。

(project 17)

Method described in any one of project 3~16 according to project 2 or in the case where being subordinated to project 2, wherein Aforementioned carbon source is volatile fatty acid or its salt.

In the present invention, one or more above-mentioned features are intended to provide the combination of the combination and further progress expressed.It closes In furthermore other embodiments of the invention and advantage, if understood as desired by detailed description below is read, It can then be recognized by one skilled in the art.

Invention effect

According to the method for the present invention, for store phosphobacteria release phosphorus for necessary organic matter it is insufficient sometimes In sewage, it can efficiently realize the biological methods of nitrogen and phosphorus while remove.Therefore, method of the invention is applicable to drop Rainfall is more and wastewater collection is being lauched of being diluted of interflow formula, volatile fatty acid, and it is few to be in addition applicable to organic matter content Industrial wastewater.In addition, according to the method for the present invention, although it is few to handle the nitrogen phosphorus BOD ingredient comprising high concentration Waste pond sludge solid-liquid separating.

Detailed description of the invention

[Fig. 1] Figure 1A is shown in the storage phosphobacteria under anaerobic state (Anaerobic) and aerobic state (Aerobic) The skeleton diagram of metabolism.Figure 1B shows the change released phosphorus using phosphobacteria is stored and take in typical phosphorus concentration caused by phosphorus again Change.

[Fig. 2] Fig. 2 shows the spectrograms (A) and NH4- of the typical dissolved oxygen (DO, dissolved oxygen) in SBR The spectrogram (B) of N and NO3-N.

[Fig. 3] Fig. 3 shows the skeleton diagram and photo of the SBR simulator used in embodiment.

PO4 caused by [Fig. 4] Fig. 4 is shown because of addition sodium acetate^3-And the variation of the concentration of NO3-N.

[Fig. 5] Fig. 5 shows influence caused by sodium acetate addition releases induction to phosphorus.The longitudinal axis of the curve graph of Fig. 5 A indicates phosphorus The concentration (mg/L) of acid, the longitudinal axis of the curve graph of Fig. 5 B indicate the concentration (mg/L) of VFA.By 0.5g, 1.0g, 2.0g and 4.0g Sodium acetate make an addition to the processing water of 22.8L.

[Fig. 6] Fig. 6 shows the spectrogram (A) and NH4- of the dissolved oxygen (DO) in two steps supply (Two step-feeding) The spectrogram (B) of N and NO3-N.

[Fig. 7] Fig. 7 shows the change of the concentration of COD, VFA, PO4, NO3-N and NH4-N in 1 circulation of two steps supply Change.

[Fig. 8] Fig. 8 shows the activated sludge suspended solid in the SBR in the case where being added to 10%PAC aqueous solution (MLSS) variation.

[Fig. 9] Fig. 9 shows the feelings for having used two steps to supply in the processing of waste pond sludge (Septage) solid-liquid separating The concentration spectrogram of PO4, NH4-N and NO3-N under condition.

[Figure 10] Figure 10 shows the case where Two-step dosing has been used in the processing of Septage solid-liquid separating Under NH4-N and NO3-N concentration spectrogram.

[Figure 11] Figure 11 shows the case where Two-step dosing has been used in the processing of Septage solid-liquid separating Under COD and PO4 concentration spectrogram.

Specific embodiment

It should be appreciated that the term used in this specification, as long as no especially mentioning, be just construed as with the neck In domain usually used meaning carry out using.Therefore, as long as not being defined at other sections, then using in the present specification Whole buzz words and scientific and technical term have with the those skilled in the art in field belonging to present invention institute usually The identical meaning of the meaning of understanding.In contradictory situation, this specification is preferential.

(definition of term)

It is exemplified below the definition of the term particularly used in the present specification.

" biochemical oxygen demand (BOD) (BOD) " (Biochemical oxygen demand) and " COD (COD) " (chemical oxygen demand) is the index of usually used water quality, their value is bigger, then means the quilt in dampening Oxidizing substance is more, more pollutes.BOD refers to, microorganism is in order to aoxidize the being oxidized property substances such as organic matter in water The amount of necessary oxygen.On the other hand, COD refers to, necessary when chemically aoxidizing the being oxidized property substance in water The amount of oxygen.

BOD indicates the reduction amount of the dissolved oxygen by sample in closed container when maintaining 5 days for 20 DEG C, will survey in this wise Surely the value obtained is known as " BOD5 "." BOD " expression " BOD5 " used in this specification.About COD, make sample by finding out It is consumed when being reacted with oxidant (for example, potassium bichromate (potassium dichromate), potassium permanganate etc.) Oxygen amount is to measure." COD " used in this specification indicates COD's obtained from being measured by using potassium bichromate Value." BOD " and " COD " can be measured by using commercially available kit or device.

In the case of using in this manual, " phosphorus compound " refers to compound in the molecule with phosphorus atoms, example Phosphoric acid (PO can such as be enumerated₄ ^3-), but not limited thereto.Term as " PO4-P " used in this specification refers to phosphoric acid state Phosphorus, in the sentence of concentration for recording PO4-P or phosphoric acid state phosphorus, concentration indicates the phosphorus (P) being based only in phosphoric acid (PO4) Weight and calculated concentration.The concentration of phosphoric acid (PO4) and the concentration of phosphoric acid state phosphorus (PO4-P) can be converted mutually.For example, In the case where having used HACH reagent, since its measured value is indicated with the concentration of phosphoric acid (PO4), so can be by by phosphoric acid (PO4) concentration exports the dense of phosphoric acid state phosphorus (PO4-P) multiplied by 0.326 (the ratio between atomic weight and the molecular weight of PO4 of P) Degree.

In the case of using in this manual, " nitrogen compound " refers to the compound that intramolecular contains nitrogen-atoms, for example, Ammonium ion (NH can be enumerated₄ ⁺), nitrite ion (NO₂ ^-) and nitrate ion (NO₃ ^-), but not limited thereto.This explanation Term as " NH4-N " used in book refers to ammoniacal nitrogen, in the sentence of concentration for recording NH4-N or ammoniacal nitrogen, Concentration indicates the weight of nitrogen (N) being based only in ammonia (NH4) and calculated concentration." NO3-N " used in this specification Such term refers to nitric nitrogen, and in the sentence of concentration for recording NO3-N or nitric nitrogen, concentration indicates only base The weight of nitrogen (N) in nitric acid (NO3) and calculated concentration.

In the case of using in this manual, " sewage " refers to: from the waste water of family and/or plant emissions, pig raising excrement Solid-liquid separating etc. of urine and/or waste pond sludge, for any waste water of purified treatment.

In the case of using in this manual, " activated sludge " refers to comprising micropopulation, animalcule and organic The sludge of the floating materials such as object.In a preferred embodiment, activated sludge used in the present invention, which includes at least, stores phosphobacteria, nitre Change bacterium and denitrifying bacteria.

In the case of using in this manual, " volatile fatty acid (VFA) " refers to the fat below of carbon atom number 6 Acid, for example, formic acid, acetic acid, propionic acid and butyric acid, but not limited thereto.As volatile fat hydrochlorate, Ke Yiju Sodium salt, sylvite, calcium salt, magnesium salts etc. out, but not limited thereto.Volatilization in sewage or in the mixture of sewage and activated sludge The total amount of property fatty acid, is measured by using any means well known in the art.Volatility used in this specification The concentration of fatty acid (VFA) refers to the concentration determined using the HACH reagent TNT872 based on esterification by colorimetric analysis.

In the case of using in this manual, " carbon source " refers to necessary as energy source for Bacterial Development Biodegradable organic matter.

In the case of using in this manual, " aerobic state " refers to the state of the oxygen there are molecularity." aerobic place Reason " refers to for example, being aerated the mixture comprising sewage and activated sludge by oxygen or air.Make in the present specification In the case where, " non-aerobic state " refers to the state of the oxygen there is no molecularity, including anaerobic state and anaerobic state. " non-Aerobic Process for Treatment " is to instigate the mixture comprising sewage and activated sludge ingress of air does not contact oxygen yet, also without exposing Gas disposal." there is no the oxygen of molecularity " refers to using dissolved oxygen meter and chemical analysis method and in detectable limit.It is typical The oxygen of molecularity is referred to as not present when the oxygen of molecularity is about 0.1mg/L or less in ground.

In the case of using in this manual, " anaerobic state " refers to the oxygen there is no molecularity but there are associativities Oxygen state, the case where nitrate ion especially will be present is known as " anaerobic state ".This is because the knot in activated sludge Conjunction property oxygen amount substantially depends on nitrate ion amount." anaerobic state " refers to the oxygen (O there is no molecularity₂) also there is no knots The state of the oxygen (nitrate ion) of conjunction property." nitrate ion is not present " refers to that nitric acid is about 1mg/L or less.

In the case of using in this manual, " nitrobacteria ", which refers to have, is oxidized to nitrite ion for ammonium ion (NO₂ ^-) ability any bacterium and have nitrite ion (NO₂ ^-) it is oxidized to nitrate ion (NO₃ ^-) ability Any bacterium general name.Observe ammonium ion towards nitrous when contacting ammonia and activated sludge under aerobic state The oxidation of acid ion and nitrite ion towards nitrate ion oxidation in the case where, which includes nitrification Bacterium.

In the case of using in this manual, " denitrifying bacteria " refers to that having nitrate reduction is nitrogen Any bacterium of ability.When contacting nitrate ion and activated sludge under anaerobic state, nitric acid is being observed Radical ion towards nitrogen reduction in the case where, the activated sludge include denitrifying bacteria.

In the case of using in this manual, it " stores phosphobacteria " to refer to: under non-aerobic state (for example, anaerobic state) It absorbs organic matter and releases phosphorus compound, the organic matter absorbed is metabolized under aerobic state behind and is proliferated, Any bacterium of intake excessive phosphorus compound compared with the phosphorus compound released simultaneously.For example, about phosphobacteria is stored, non- Volatile fatty acid is absorbed under aerobic state and releases PO₄ ^3-, the volatile fatty acid that will be absorbed under aerobic state behind The PO for being metabolized and being proliferated, while can absorbed and be released₄ ^3-Compared to excessive PO₄ ^3-.Keep organic matter and activity dirty In the case that mud is contacted, carbon source is absorbed under anaerobic state, releases phosphorus compound, behind under aerobic state, observation To phosphorus compound excessive compared with the phosphorus compound released intake in the case where, the activated sludge include store phosphobacteria.

In the case of using in this manual, " about " before numerical value indicates ± the 10% of the numerical value connected below.

(effect of the microorganism in activated sludge process)

In the present invention, in terms of the removal of nitrogen, the effect of nitrobacteria and denitrifying bacteria is required.In 1 reality It applies in mode, about nitrobacteria of the invention, including has and ammonium ion is oxidized to nitrite ion under aerobic state (NO₂ ^-) ability ammonia oxidizing bacteria (Nitrosomonas) and have nitrite ion (NO₂ ^-) it is oxidized to nitric acid Radical ion (NO₃ ^-) ability nitrite-oxidizing bacteria (Nitrobactor), but do not limit this.These bacteriums are in the reaction The autotrophic bacteria of organic carbon source is not needed.It in terms of nitrogen removal, is shown below, ammonia oxidation bacteria (Nitrosomonas) is by ammonia It is aoxidized and nitrous acid is made, subsequent nitrite-oxidizing bacterium (Nitrobactor) is by nitrite-oxidizing for nitric acid.

[chemical formula 1]

In 1 embodiment, denitrifying bacteria of the invention refer to have under anaerobic by nitrate ion also It originally was the bacterium of the ability of nitrogen.About this bacterium as heterotrophicy bacteria, hydrogen, methanol and/or second are needed in reduction reaction The carbon sources such as acid become electron donor, utilize hydrogen (Metcalf the et al., " Wastewater generated by its hydrolysis Engineering:treatment and reuse.4^th,Mc Graw-Hill,Boston (2003)；This paper is quoted in this In specification).It is commonly referred to as C/N ratio, the concentration of carbon for electron in waste water and nitric nitrogen concentration balance ten as a result, Divide important.It about denitrifying bacterium, is shown below, by nitrate reductase to nitrogen under non-aerobic state.

[chemical formula 2]

On the other hand, in terms of the removal of phosphorus, it is required for storing the effect of phosphobacteria.About phosphobacteria is stored, preferably do not having There is the oxygen (NO of molecular oxygen also being not bound with property₃ ^-) anaerobic state under, by the volatile fatty acids such as acetic acid or propionic acid (VFA) It takes in in thallus, using the energy (ATP) generated and endobacillary polyphosphoric acid is hydrolyzed, synthesis is as in thallus Accumulate the polyhydroxyalkanoates (PHA) of substance.The PO generated by the decomposition of the polyphosphoric acid₄It is outer (Figure 1A) to be released to thallus. Then, when being set as aerobic state, then the phosphorus more than spued amount is taken in again and is carried out the accumulation (figure of polyphosphoric acid by the bacterium 1B).The ATP used in the synthesis of the polyphosphoric acid is generated using the decomposition of the PHA previously accumulated under anaerobic state, Electron acceptor in this decomposition reaction is oxygen (Mino et al., " Microbiology and biochemistry of the enhanced biological phosphate removal process”,Water Research,32,3193- 3207(1998)；This paper is quoted in this manual).By will be based on the bacterium conduct of these reaction mechanism Excess free enthalpies phosphorus Excess sludge is extracted from reactor, to realize the phosphorus ligands in waste water.

Known one kind can carry out simultaneously denitrification under carbon-free oxygen free condition and take in the denitrification storage phosphobacteria of phosphorus (DNPAO) (Japanese Unexamined Patent Publication 2003-285096 bulletin；It is quoted in this manual with reference pattern).DNPAO is in sludge Concentration is low, in order to keep DNPAO dominant, in order to inhibit the denitrification based on denitrifying bacterium under anaerobic, needs carbon source It is limited, there are phosphorus and NO₃It is raised and train under such particular surroundings and makes DNPAO dominant, such state passes through Actual be lauched is not easy to realize.In specific embodiment of the invention, used activated sludge can also not include DNPAO. In another embodiment of the present invention, used activated sludge also may include DNPAO, but with denitrifying bacteria or store phosphorus In comparison DNPAO will not more exist bacterium in activated sludge, that is, DNPAO is without dominance.In activity of the invention In sludge, when carrying out non-Aerobic Process for Treatment supply denitrification necessary to amount carbon source, due under anaerobic there are Carbon source, so will not maintain for a long time so that the dominant such environment that carbon source is not present of DNPAO, DNPAO will not be dominant.Cause This, the biology of nitrogen of the invention and phosphorus removes to disobey simultaneously is against DNPAO.

(addition of additional volatile fatty acid)

It in embodiments of the present invention, is released to induce based on the phosphorus for storing phosphobacteria, additional volatile fatty acid is added It is added on treatment trough.Herein, in the present invention, in order to reduce the external additive amount of volatile fatty acid, inhibit by thin in addition to storing phosphorus The competitive consumption of volatile fatty acid caused by bacterium other than bacterium, this is 1 feature.Volatile fatty acid is as anti-nitre The electron donor of change is also highly effective, and in order to remove dephosphorization and nitrogen, denitrifying bacterium is the important partner for storing phosphobacteria (partner), but it is also the competition object of volatile fatty acid consumption.Therefore, present invention contemplates that utilizing having in sewage Machine substance carries out denitrification as far as possible, adds volatile fatty acid at the time point that denitrification has almost terminated.

In contrast, it is reported that: by SBR with nitrogen, phosphorus removal and cause typical dissolved oxygen (DO), The variation of oxidation-reduction potential (ORP) and pH are illustrated, at the end of the inflection point detection of DO, ORP and pH are denitrifying Between point (S.Marsili-Libelli, " Control of SBR switching by fuzzy pattern recognition",Water Research(2006)；This paper is quoted in this manual).But it is waved in the addition from outside In the case where hair property fatty acid, application interference, it is difficult to obtain the pattern (pattern) of ideal DO, ORP and pH.In addition, hair Bright people etc. are actually tested, as a result, BOD can not detect turning for script in the big sewage of the condition variations such as ammonia amount Point.

In the present invention, by expressly also using volatile fatty acid as denitrifying electron donor, thus rapidly Denitrification is realized on ground, as a result, induction is released based on the phosphorus for storing phosphobacteria.Herein importantly, addition is added Amount as volatile fatty acid all consumes not due to denitrification.About for induce store phosphobacteria phosphorus release threshold value, It as described in Example 2, can be by monitoring the phosphorus (PO in the case where being added to additional volatile fatty acid₄) and volatility rouge The concentration of fat acid so that it is determined that.

About the additive amount of additional volatile fatty acid, the volatilization in the mixture of measurement sewage and activated sludge can be passed through The total amount of property fatty acid, find out the difference of the total amount and threshold value so that it is determined that.It should be noted that in SBR, due to handling It hardly include volatile fatty acid in water, so the total amount of the volatile fatty acid in the mixture of sewage and activated sludge, The total amount for the volatile fatty acid being considered as in the sewage supplied in FILL can be equal to.Therefore, additional in 1 embodiment The additive amount of volatile fatty acid can by measure the volatile fatty acid in supplied sewage total amount so that it is determined that.

In a preferred embodiment, the addition volatile fatty acid of addition is acetic acid or propionic acid, particularly preferably second Acid.In another embodiment, the fatty acid of addition is also possible to the volatile fatty acid of salt form.

It is also excellent from the viewpoint of inhibiting competition microorganism about the addition of additional volatile fat hydrochlorate.For example, second Sour sodium dissolves when water, then occurs to ionize and be dissociated into acetate ion (CH₃COO^-) and sodium ion (Na⁺).This acetate ion It is reacted with hydrone, make acetic acid as described below and generates hydroxide ion, alkalescent is made in aqueous solution.

CH₃COO^-+H₂O→CH₃COOH+OH^-

Phosphorus ligands are not contributed in glycogen accumulation bacterium (GAO), but due to energetically taking in VFA in thallus, thus It is the rival for storing phosphobacteria (PAO).In order to efficiently go dephosphorization, it is necessary to reduce the quantity and/or activity of GAO.PAO exists Acetic acid intake speed under anaerobism surpasses the GAO as competition microorganism in pH7.5 or more.It should be noted that sodium propionate It is with sodium acetate on this point in effect likewise, still considering to be more preferably sodium acetate from smell this point.

(sewage)

It present invention can be suitably applied to the solid-liquid point for being originated from the waste water of family and/or factory, raise pigs fecaluria and/or waste pond sludge The big cataclysmal any sewage of the conditions such as chaotropic.It is mixed for example, being used as in the state of not distinguishing storm wastewater with domestic waste water Waste water and the region handled dilute the carbon source in waste water due to rainfall.The present invention can handle such to going to denitrogenate and phosphorus For the few waste water of necessary carbon source.Further, the present invention can also handle extremely reluctant waste pond sludge (Septage) Solid-liquid separating.

The difficulty of Septage solid-liquid separating processing is that water quality is very different with being lauched as shown in table 1.Such as Shown in table 1, such as when the data of United States of America's environmental protection Room (US EPA) are compared with sewage, then BOD is 33 Times, COD be 136 times, T-N is 19 times, T-P is 60 times, be it is much high, can not be coped in general sewage farm, need Want dedicated facility.In order to carry out the removal of nitrogen phosphorus to such sewage, new treatment process is needed.

Table 1

^*1Purification tank (Jokaso) mud and sewage treatment plant's mud are almost phase same level.

^*2US EPA handbook waste pond Treatment of Sludge and removing.

In order to lower Septage high concentration organic substance concentration, utilize belt compacting (belt press), centrifugation point Implement to be separated by solid-liquid separation from, spiral compacting (screw press) etc..Table 2 is to carry out pig raising fecaluria using spiral compacting Separation of solid and liquid in the case where flow out to various dissolution concentration (Jimieson et al., " Evaluation of a in liquid Mechanical solid-liquid separator for swine manure ", Solid-liquid Separation of Swine Waste；Final Report, December (2001)；This paper is quoted in this manual).It can be bright by table 2 Aobvious to find out, it is 42% that transfer amount of the BOD5 into separating liquid is made using separation of solid and liquid, largely rests on solid phase.In phosphorus (P) aspect is also the same, and 20% namely a considerable amount remains in solid phase, but for nitrogen (N), is most transferred to separation In liquid.About the concentration in the separating liquid after separation of solid and liquid, BOD5 7,500mg/L, T-N 3,200mg/L, T-P are 740mg/L is extremely high value compared with sewage.

[table 2]

Ingredient in 2. fecaluria of table and the liquid distillate isolated

Project	Unit	Raw material (raw)	Filtrate (filtrate)	%Conc.
									Reduction amount

					T-S	(mg/L)	54,000	40,000	26
BOD5	(mg/L)	13,000	7,532	42
					TSS	(mg/L)	13,333	13,200	1
T-P	(mg/L)	922	736	20
					T-N	(mg/L)	3,448	3,177	8
T-K	(mg/L)	1,477	1,534	-4

(preferred embodiment)

The preferred embodiment of the present invention is illustrated below.Embodiment presented below is in order to better understand It is of the invention and offer, it will be appreciated that the scope of the present invention should not be defined in record below.Therefore it is clear that, this field Technical staff can carry out being suitable for change within the scope of the invention by considering the record in this specification in light of actual conditions.In addition it is understood that originally The following embodiments and the accompanying drawings of invention can be used alone or also combine them and use.

A kind of method is provided in an embodiment of the invention, is by the phosphorus compound and nitrogen compound in sewage The method of removal includes following step:

Step (A), which is characterized in that for the sewage is supplied in the treatment trough comprising activated sludge, to form the dirt The step of mixture of water and the activated sludge, which, which adds additional volatile fatty acid or its salt, makes in the mixture Volatile fatty acid total amount becomes the threshold value or more,

A kind of method is provided in other embodiment of the invention, is by the phosphorus compound and nitrification in sewage The method of object removal, includes following step:

Step (A), which is characterized in that for the sewage is supplied in the treatment trough comprising activated sludge, to form the dirt The step of mixture of water and the activated sludge, adding additional volatile fatty acid or its salt in the step makes in the mixture Volatile fatty acid total amount become threshold value more than,

Step (C-2), supplies carbon source into the treatment trough,

In order to illustrate the present invention, step (A) and (B) are known as FILL sometimes, step (C) is known as REACT, by step (C-1) it is known as REACT I, step (C-2) and (C-3) is known as REACT II, step (C-4) is known as REACT III, it will Step (D) is known as SETTLE, and step (E) is known as DRAW.

In one embodiment, method of the invention can be phosphorus compound in " biology " removal sewage and The method of nitrogen compound.In a preferred embodiment, the phosphorus compound and nitrogen compound in " biology " removal sewage Method, the step of not including addition PAC (aluminium polychloride) etc. chemical coagulants.When using chemical coagulant, then due to life At a large amount of excess sludge, adverse effect further is caused to the microorganism in activated sludge, thus needs to be arranged precipitation tank work To add equipment, so that impaired using such SBR that single slot carries out original advantage.

About the circulation time in SBR, can be fitted according to the amount of sewage to be processed, content of the polluter of sewage etc. Work as adjusting, but in the embodiment of a part, circulation time be about 6~about 10 hours (for example, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours), circulation time is typically about 8 hours.About 1 circulation in FILL, REACT, REACT I, REACT II, REACT III, SETTLE and DRAW respective time, those skilled in the art can be according to following Ring time, the state of activated sludge, the state of sewage are suitably set.

About FILL, sewage supply can be started at first.It is small that the service time of sewage can carry out about 0.5 hour~about 1.5 When, it can preferably carry out about 1 hour.As needed, in FILL, additional volatile fatty acid or its salt can be added.About chasing after Add volatile fatty acid or the addition of its salt, before the supply that can be sewage, be also possible between or later.Specifically In embodiment, about the addition of additional volatile fatty acid or its salt, can supplied with sewage start while, start about After ten minutes, start about after twenty minutes, start about 30 minutes after, start about after forty minutes, start about 50 minutes after or start About carry out after sixty minutes.FILL is carried out using non-Aerobic Process for Treatment, and nitrate reductase is released nitrogen by denitrifying bacterium.It is non-aerobic Processing refers to stirs in the state of being added without air.Due to the effect of this denitrifying bacterium, the nitric acid as associativity oxygen is reduced, The mixture of sewage and activated sludge is close to anaerobic state.It is not necessarily required to be anaerobic state based on the phosphorus releasing for storing phosphobacteria, only The concentration for wanting nitric nitrogen is about 5mg/L hereinafter, can then carry out releasing based on the phosphorus for storing phosphobacteria, preferably from about 1mg/L or less. It is released about phosphorus, using phosphobacteria is stored for the taking in again of phosphorus is required in the Aerobic Process for Treatment for connecting progress hereafter 's.Therefore, FILL at least carries out releasing phosphorus to using storage phosphobacteria.More specifically, it in FILL, is carried out first based on anti-nitre The nitric acid intake for changing bacterium is released with nitrogen, can simultaneously or behind carry out the releasing of phosphorus.In specific embodiment party In formula, FILL is about 1~about 4 hour, preferably from about 2~3 hours, even more preferably about 3 hours.

It can be suitable for true according to the BOD and/or ammonia nitrogen concentration in sewage about the amount of the sewage supplied in FILL It is fixed.The supply amount of sewage is known as filling rate (Filling ratio) relative to the ratio between processing total amount, filling rate usually can be About 10%~about 40%, it can be by being suitable for increasing and decreasing filling rate, so that the sewage quantity relative to activated sludge is diluted adjustment. For example, in the case that those skilled in the art are appreciated that the height of the ammoniacal nitrogen in sewage filling rate can be reduced, to improve institute The dilution rate of the sewage of supply.

REACT REACT I is carried out under aerobic condition, is stored phosphobacteria and is carried out taking in again for phosphorus, on the other hand, will Ammoniacal nitrogen is aoxidized and releases nitric nitrogen.REACT REACT I can be carried out at least to the intake for carrying out phosphorus.Specific Embodiment in, REACT REACT I is about 1~about 3 hour, preferably from about 2 hours.

REACT II is carried out under non-aerobic state, and denitrifying bacterium carries out denitrification, that is, is restored nitric nitrogen and is released Nitrogen.In addition, in REACT II carbon source can be added as needed.This is thin for denitrifying denitrification in order to supply The nutrient source of bacterium.About the denitrification carried out using denitrifying bacterium, it is not necessarily required when being released using the phosphorus for storing phosphobacteria progress The carbon source (i.e. volatile fatty acid) of easy decomposability as required.Therefore, carbon source can be the energy water under anaerobic state The arbitrary organic matter of the Biodegradable of solution.As the carbon source added in REACT II, can enumerate sewage, fatty acid or its Salt, starch, methanol, ethyl alcohol, propyl alcohol, sugar or the mixture as them agricultural waste.In 1 embodiment, In the case where sewage is added in REACT II as carbon source, it can be added with few amount compared with the amount of the sewage supplied in FILL Add sewage.It, can be to reduce the initial stage concentration of the nitric nitrogen in next circulation (that is, FILL's is first about this REACT II The initial stage concentration of interim nitric nitrogen) for the purpose of, it carries out as needed.This is because by reducing the nitric acid in circulation The initial stage concentration of state nitrogen, the denitrification in FILL promptly carry out, and thus can quickly achieve anaerobic state, promote to store phosphobacteria Phosphorus is released.Therefore, in REACT II, as long as the initial stage concentration for reducing the nitric nitrogen in next circulation can be realized Purpose, then not needing to fully complete denitrification and anaerobic state is made.Therefore, REACT II may proceed to sewage and activity The mixture of sludge becomes anaerobic state.It is undesirable to be bound by theory, as long as example, the concentration of nitric nitrogen can be reduced to about 5mg/L is hereinafter, can be realized as reducing the purpose of the initial stage concentration of nitric nitrogen.In specific embodiment, REACT II It can be about 0.5 hour~about 1.5 hours, can be preferably from about 1 hour.

REACT III is carried out under aerobic state.Nitrobacteria can be carried out to the intake of ammoniacal nitrogen and to nitric nitrogen Releasing and store intake of the phosphobacteria to phosphorus.Then there is water quality when in addition, the processing water of anaerobic state being discharged into outside system The worry of deterioration, thus in order to improve the dissolved oxygen of processing water, Aerobic Process for Treatment is carried out as REACT III.For example, in REACT In III, dissolved oxygen may proceed to as about 3mg/L or more, preferably as 5mg/L or more.Therefore, REACT III can be carried out about It 10 minutes~about 60 minutes, preferably carries out about 30 minutes.In addition, excess sludge can be carried out as needed in REACT III Removal.

In SETTLE, stops the stirring of the mixture of sewage and activated sludge, settle activated sludge, thus point From for the activated sludge and processing water.In an embodiment of the invention, the nitric nitrogen concentration for handling water can be about 1~ 5mg/L.As long as nitric nitrogen concentration is about 1~5mg/L, the denitrification in the FILL of next circulation can be promptly carried out. In DRAW after SETTLE, at least part for handling water is extracted out from treatment trough.

In a preferred embodiment, the threshold value of the total amount of the volatile fatty acid in the mixture of sewage and activated sludge It is the amount of the effective volatile fatty acid for storing phosphobacteria and releasing phosphorus.About effective for storing phosphobacteria and releasing phosphorus Volatile fatty acid amount, quality of the BOD and/or activated sludge that can be dependent in sewage etc. and change, but as implement It, can be by monitoring the phosphorus (PO in the case where being added to volatile fatty acid shown in example 2₄) and volatile fatty acid concentration So that it is determined that.In specific embodiment, the threshold value of the total amount of the volatile fatty acid in mixture be about 10mg/L or more, About 11mg/L or more, about 12mg/L or more, about 13mg/L or more, about 14mg/L or more, about 15mg/L or more, about 16mg/L with Upper, about 17mg/L or more, about 18mg/L or more, about 19mg/L or more, about 20mg/L or more, about 21mg/L or more, about 22mg/L Above, about 23mg/L or more, about 24mg/L or more, about 25mg/L or more, about 26mg/L or more, about 27mg/L or more, about 28mg/ L or more, about 29mg/L or more or about 30mg/L or more, but not limited thereto.In a preferred embodiment, in mixture The threshold value of total amount of volatile fatty acid be about 15mg/L or more.Volatilization in preferred embodiment, in mixture The threshold value of the total amount of property fatty acid is about 20mg/L or more.

About the addition volatile fatty acid of addition or the amount of its salt, the volatile fat in mixture may be such that Sour total amount becomes the such amount of the threshold value or more.In addition, the amount about additional volatile fatty acid or its salt, considers above-mentioned anti- Electron donor necessary to nitrifying, can be added volatile fatty acid or the amount of its salt.Volatile fatty acid about addition Or the amount of its salt, it can be according to the BOD and ammoniacal nitrogen (NH in sewage₄) concentration and Vfa Concentration and estimate. Specifically, according to the formula of [chemical formula 1] and [chemical formula 2], as long as those skilled in the art then can easily push away The amount of additional volatile fatty acid or its salt added by fixed.Specifically, can be according to the formula of [chemical formula 1], according to dirt NH in water₄ ⁺Amount and calculate NO to be processed₃ ^-Amount, can according to the formula of [chemical formula 2], calculate supply for restoring NO₃ ^-Hydrogen when necessary volatile fatty acid or its salt amount.It should be noted that, although [chemical formula 2], which describes, to be made Use acetic acid or sodium acetate as the reaction equation in the case where simple illustrate, it is to be understood that can be used in addition to acetic acid and second Volatile fatty acid or its salt other than sour sodium.It should be noted that the lower alcohols such as methanol as shown in [chemical formula 2] can also be made It is used for denitrifying electron donor.Therefore, in the embodiment of alternative, it is possible to use alcohol (methanol, second such as methanol Alcohol, propyl alcohol etc.) it is used as electron donor, to substitute the volatile fatty acid or its salt that are added.

In one embodiment, additional volatile fatty acid or its salt at least about 30mg/L, at least about 40mg/L, At least about 50mg/L, at least about 60mg/L, at least about 70mg/L, at least about 80mg/L, at least about 90mg/L, at least about 100mg/ L, at least about 110mg/L, at least about 120mg/L, at least about 130mg/L, at least about 140mg/L, at least about 150mg/L, at least About 160mg/L, at least about 170mg/L, at least about 180mg/L, at least about 190mg/L, at least about 200mg/L, at least about The concentration of 220mg/L, at least about 240mg/L, at least about 260mg/L, at least about 280mg/L or at least about 300mg/L carry out Addition.In another embodiment, additional volatile fatty acid or its salt with about 30~about 300mg/L, about 40~about 280mg/L, about 50~about 250mg/L, about 80~about 220mg/L concentration be added.In a preferred embodiment, additional Volatile fatty acid or its salt are added with the concentration of about 80~about 220mg/L.

In the case where adding sodium acetate as additional volatile fatty acid or its salt, sodium acetate is at least about 50mg/ L, at least about 60mg/L, at least about 70mg/L, at least about 80mg/L, at least about 90mg/L, at least about 100mg/L, at least about 110mg/L, at least about 120mg/L, at least about 130mg/L, at least about 140mg/L, at least about 150mg/L, at least about 160mg/ L, the concentration of at least about 170mg/L, at least about 180mg/L, at least about 190mg/L or at least about 200mg/L are added. In a preferred embodiment, additional sodium acetate is added at least about concentration of 88mg/L.

In an embodiment of the invention, carbon source can be sewage, fatty acid, starch, methanol, ethyl alcohol, propyl alcohol, sugar or The arbitrary organic matters such as agricultural waste of the person as their mixture.In 1 embodiment, the BOD in sewage is opposite In ammoniacal nitrogen concentration ratio be 5 or more, and ammoniacal nitrogen be 40mg/L situation below under, sewage can be added as carbon source.This The sewage of the condition of sample can be used as the reason of carbon source and be, also fully have and be used for denitrifying nutrient source.Therefore, exist In REACT II, seek nitric nitrogen concentration being reduced to about 5mg/L or less.In embodiment of the addition sewage as carbon source In, sewage can be added in REACT II with few amount compared with the amount of the sewage supplied in FILL.In addition sewage conduct In the case where carbon source, typically, amount few compared with the amount of the sewage added in FILL is added, for example, added in FILL The volume ratio of the sewage added in sewage and REACT II can be about 6:4~about 9:1, about 6.5:3.5~8.5:1.5 or About 7:3~about 8:2, preferably from about 8:2.

BOD and ammoniacal nitrogen in sewage other than above-mentioned condition under conditions of, that is, the BOD phase in sewage For ammoniacal nitrogen concentration than the carbon other than sewage can be added less than 5 or in the case that ammoniacal nitrogen is more than 40mg/L Source.In the case where the condition of such sewage, due to insufficient for denitrifying nutrient source, thus as carbon source, do not use Sewage, but addition can be hydrolyzed under anaerobic state Biodegradable arbitrary organic matter, for example fatty acid, starch, Methanol, ethyl alcohol, propyl alcohol, sugar or as their agricultural waste of mixture etc..Using the carbon source other than sewage In the case where, it can add and be filled for enabling to that nitric nitrogen concentration is reduced to about 5mg/L or less in REACT II The amount divided.It is undesirable to be bound by theory, about the addition of carbon source, due to by the way that nitric nitrogen concentration is reduced to about 5mg/L Below to reduce the nitric nitrogen concentration at circulation initial stage for the purpose of, as long as thus to reach about 5mg/L nitric nitrogen below dense Arbitrary carbon source can be used in degree.

In 1 embodiment, carbon source can be fatty acid or its salt.It, can about the fatty acid of addition or its salt Comprising carbon atom number be more than 6 medium chain fatty acid, long chain fatty acids perhaps their salt but preferably volatile fatty acid or Its salt.It is preferred that the addition volatile fatty acid added in FILL and the carbon source added in REACT II are identical volatility rouge Fat acid.In the case where adding volatile fatty acid or its salt as carbon source, the addition volatile fatty acid that is added in FILL Either in its salt and REACT II as carbon source and the volume ratio of the volatile fatty acid added or its salt can be about 6:4~ About 9:1 can be preferably from about 8:2.

It, can about the addition volatile fatty acid or its salt added in FILL in an embodiment of the invention It is selected from the group being made of formic acid, acetic acid, propionic acid, butyric acid and its salt.In specific embodiment, the additional volatilization of addition Property fatty acid or its salt can be selected from acetic acid, propionic acid or their salt.In a preferred embodiment, it can add and be selected from Addition volatile fat hydrochlorate in sodium acetate or sodium propionate.Sodium acetate can be added in most preferred embodiments.About Volatile fatty acid other than acetic acid, in addition to the smell the problem of other than, can be realized effect same as acetic acid.

In an embodiment of the invention, the pH of the mixture of sewage and activated sludge in FILL can be about 7.25 More than.In another embodiment, the pH of the mixture of the sewage in FILL and activated sludge can be about 7.5 or more, such as About 7.5~about 9.0, about 7.5~about 8.5, about 7.5~about 8.0, about 8.0~about 9.0, about 8.0~about 8.5 or about 8.5~about 9.0。

More than, for easy understanding, showing preferred embodiment, the present invention is described.Hereinafter, based on implementing Example illustrates the present invention, but above description and embodiment below are only to be provided with the purpose of illustration, are not for right Purpose that the present invention is defined and provide.Therefore, the scope of the present invention, which is not limited, in this manual specifically records Embodiment is also not limited in embodiment, is limited according only to claims.

Embodiment

(comparative example 1: not adding previous activated sludge process when fatty acid or its salt)

Fig. 2A is in 6 hours circulation time (FILL 1 hour, REACT 2 hours, SETTLE 1.5 hours, DRAW 1.5 Hour), the monitoring result of dissolved oxygen (DO) in 1 circulation carrying out under conditions of filling rate 25%.Such as the DO spectrogram of Fig. 2A It is shown, it about the DO of FILL Phase, as the inflow of waste water starts and reduces, becomes anaerobic state after 10 min. The zigzag of DO in the REACTPhase for carrying out air agitation changes, and is automatic control (the control DO range based on DO 2.5~4.5mg/L) and occur.In the SETTLE Phase for stopping air agitation, at this Phase initial stage, DO is caused to reduce, But become before and after 2mg/L certain.This is because, the sedimentation of activated sludge is completed about 30 minutes after stirring stops, thereafter, Sludge by significant is limited to only in solid liquid interface with the contact for wrapping oxygen containing water.

The concentration spectrogram of NH4-N and NO3-N is shown in Fig. 2 B.NH4-N in Fill Phase is because flowing into raw water NH4-N and increase, in aerobic REACT Phase by nitrification cause concentration reduction.On the other hand, it flows into raw water NO3-N it is essentially a zero, the initial value of FILL Stage reflects the raffinate concentration in preceding 1 circulation.Continuing anaerobic shape Between 1 hour of state, because of denitrification concentration is reduced, but is risen again in REACT Phase because of the nitrification of NH4-N It is high.In terms of SBR, the concentration variation of such NH4-N and NO3-N are general.

In terms of the removal processing of phosphorus, it is desirable that this FILL Phase is no dissolved oxygen and also without knot as NO3 Close the anaerobic state of oxygen.At the end of the FILL Phase of Fig. 2 B, also the NO3-N of 3~4mg/L of remaining or so, is anaerobic shape State rather than anaerobic state.In this wise, in previous activated sludge process, due to being not carried out for phosphorus releasing adequately Anaerobic state, thus the biology of nitrogen and phosphorus removes be difficult simultaneously.

(embodiment 1: SBR of the invention)

Hereinafter, the SBR that explanation uses in embodiment.

Use the small-sized SBR of shown in Fig. 3, actuation capacity (Working Volume) 35L (with blender, diffusion Film).In this SBR, horizon sensor (level sensor), thermistor with DO, pH and ORP, sequence, which controls, is It is carried out according to PLC (programmable logic controller, programmable logic controller (PLC)).The device is set to The sewage farm in the city Kui Song, Philippine (Quezon City).Utilize paper, the cloth, rubber in silk screen (screen) removal sewage The solid matters such as glue separate the solid swum by grid catcher (grid trap) and oily catcher (oil trap) Grease etc. has carried out pre-treatment, mainly uses the sewage through the pre-treatment as subjects.

It should be noted that the water quality because of caused by low wastewater processing technology reduces in view of Philippine, the Philippines government DENR Administrative Order No.2016-08 " Water Quality is disclosed on June 14th, 2016 Guidelines and General Effluent Standards of 2016 ", has newly formulated plant chimney stalk, public institution The nitrogen discharge and phosphorus discharge of waste water provides.Accordingly, the discharge benchmark about NH4-N, NO3-N and PO4-P, regardless of waters, wastewater flow rate How, it is set to 0.5,14 and 1.0mg/L, becomes extremely stringent.Below in an example, using the discharge benchmark as mesh It marks and is tested.

(embodiment 2: the condition research of the FILL Phase for inducing phosphorus to release)

In the present embodiment, when being released to induce based on the phosphorus for storing phosphobacteria, thus having studied FILL Phase continuation Between and addition volatile fat hydrochlorate Cmin.

The research of the continuation time of FILL Phase

FILL Phase so far is operated from becoming 2 hours within 1 hour, by the processing of obtained SBR As a result it is shown in table 3.By COD, NH4-N and NO3-N of efflux (EFFLUENT) when being compared afterwards before changing, COD with And NH4-N does not see big difference, but NO3-N shows very big effect.In efflux at FILL Phase 1 hour The average value of NO3-N is 18.6mg/L, has been more than the discharge a reference value 14.0mg/L of DENR.However, by being extended for 2 hours, So that NO3-N becomes the 5.4mg/L lower than discharge benchmark.NH4-N and COD at this time also respectively lower than discharges benchmark 0.5mg/L and 100mg/L is sufficient for removing countermeasure as nitrogen and COD.However, this FILL is after 2 hours NO3-N is not below 1mg/L.

[table 3]

Table 3

The effect as obtained from addition sodium acetate

After water extraction will be handled in DRAW Phase, the sodium acetate of 4g is made an addition into SBR (liquid measure 22.8L) (in SBR Concentration 176mg/L), pass through the intake of the phosphorus under the releasing and aerobic condition of phosphorus of (batch) experimental investigation in batches.It needs to illustrate , at the end of DRAW, VFA is substantially consumed and may be not present, thus can external addition of the direct surveys based on sodium acetate Obtained from effect.

By adding sodium acetate, the NO3-N of remaining general 4mg/L becomes anaerobism shape by extremely rapid denitrification State (Fig. 4).This indicates that sodium acetate is for the denitrifying excellent electron donor based on denitrifying bacteria.Add in sodium acetate 2 hours or so after adding, PO4 has reached 60mg/L.In addition, the intake of the phosphorus after migrating under aerobic condition is also at 2 hours or so It completes, shows the behavior of typical PAO.It is indicated above that even if the low feelings of the concentration of the volatile fat hydrochlorate in sewage Under condition, by adding sodium acetate, the denitrification based on denitrifying bacteria can also be promptly realized, further induction stores phosphobacteria Phosphorus release.

The research of the Cmin of sodium acetate necessary to inducing phosphorus to release

Into the SBR (liquid measure 22.8L) after DRAW Phase, sodium acetate is added from 0.5g to 4g, so that SBR It is 176mg/L that concentration changes from 22mg/L in interior liquid.Its result is as shown in Figure 5A, additive amount 2g (with the concentration of 88mg/L into Row addition) more than when be able to confirm that apparent PO4 is released.VFA concentration when for the additive amount for having confirmed that the releasing into Row investigation, as shown in Figure 5 B, causes stable releasing in the concentration of 15mg/L or more, will be used to induce the present invention of releasing Preferred threshold value be determined as 15mg/L.

(3: two step of embodiment supplies (Two-step feeding))

In the present embodiment, in order to inhibit the denitrifying bacteria in FILL Phase to the consumption of sodium acetate and promptly It realizes anaerobic state, is studied for the condition of the NO3-N concentration at the beginning of for reducing FILL Phase.Therefore it tastes It tries, by being handled under anaerobic after the FILL Phase of aerobic condition, so that under aerobic condition The NO3-N increased is lowered using anti-nitration reaction.It, must in order to supply denitrification when being handled under anaerobic The carbon source needed implements the Two-step feeding for supplying sewage again.

Predetermined sewage input amount is divided into secondary as follows: being 80% in the 1st investment in FILL Phase, It is 20% in 2nd investment.It will be set as circulation time 8 hours, and be changed to recycle for 1 day 3, and be from 25% increase by filling rate 35%, do not cause the reduction of every 1 day processing water.As a result, the concentration drop of the NO3-N at later half 2 hours FILLPhase Down to 0.5mg/L (Fig. 6 B).

(embodiment 4: being applicable in what is be lauched)

In the present embodiment, the middle condition research carried out based on the above embodiment, carries out the optimization of condition, under being applied to Water.

Determine minimum additive amount i.e. 3.07g/35L (the concentration 88mg/ in SBR for the sodium acetate having studied in example 2 L), electron donor necessary to denitrification is filled up by the BOD in sewage.In the FILL Phase for having started Raw sewage investment 30 minutes after be added to sodium acetate.Thereafter, according to following novel sequences (table 4), the operating of SBR has been carried out.By circulation time It is set as 8 hours, filling rate is set as 35%, therein 80% as supply (1st Feeding) for the first time and in FILL It is added in Phase, second of supply (2nd Feeding) of residue 20% is added in REACT II Phase.In REACT In III Phase, carry out the DO for improving processing water be aerated again and the extraction of remaining mud.

[table 4]

Table 4 is used for while going to denitrogenate and the sequence of phosphorus

In addition, Fig. 7 is shown, COD, VFA, NO3-N, NH4-N during handling herein in 1 circulation of middle measurement and The concentration of PO4 changes.VFA is steadily maintained the about 22mg/L more than threshold value, carries out the apparent releasing of PO4.It shows: logical Cross the releasing so where there is PAO can actively take in PO4 under aerobic condition.NO3- in FILL and REACT I The behavior of N and NH4-N clearly indicates the effect of denitrifying bacterium and nitrifier.In addition, having carried out second of supply In REACT II, the NO3-N being temporarily increased by nitration reaction is reduced again by denitrification.

Be shown in table 5 according to this sequence continued about 2 months processing when efflux COD, PO4, NO3-N and The concentration of NH4-N.Although flowing into concentration has occurred big variation, outflow concentration steadily meets the Philippines government formulation Discharge benchmark.

[table 5]

The quality of the processing water of table 5

(comparative example 2: using the phosphorus ligands of PAC)

There are following methods: removing nitrogen using the microbial reaction of nitration denitrification in SBR, then will PAC makes an addition in SBR and completes nitrogen removal by the method for phosphorus ligands (in-situ) and in SBR, thereafter for its processing Water, using the external cyclator prepared in SBR by the method (ex-situ) of phosphorus ligands.Herein, it has attempted not needing The processing of the new in-situ for preparing cyclator.10% is added in the REACT II of SBR for implementing the supply of two steps PAC aqueous solution 9.2ml (or using 5%PAC aqueous solution 18.5ml), implements processing in about 2 weeks.Processing result at this time and The variation of activated sludge suspended solid (MLSS) in SBR is shown in Fig. 8.The photo of Fig. 8 shows the MLSS in during processing Variation although implementing sludge extraction similarly to Example 4, but caused the increase of 80% MLSS through 2 weeks.

Following Table As is the knot of the in-situ PAC processing since rising on November 10th, 2016 (two steps supply control) Fruit is able to confirm that the NH4-N in processing water is incrementally increased.This shows the activity decline for leading to nitrobacteria because using PAC ?., it can be said that also including the heavy metal for hindering microorganism in PAC, nitrobacteria is hindered.

[Table A]

According to the above results it is found that using PAC, in order to avoid excess sludge excessive accumulation and The adverse effect caused by microorganism, it is necessary to the additional equipment such as cyclator.It is of the invention such without using PAC based on The superiority for the processing that microorganism carries out becomes clear.

(measurements of the various parameters of embodiment 5:Septage solid-liquid separating)

Table 6 is shown, and spirally suppresses septage in the Treatment stations that place is implemented in test and carries out solid-liquid The concentration for COD, NO3-N, NH4-N and the PO4 in separating liquid being isolated, their concentration change be it is fierce, separately The value of N and P is extremely high compared with the value of COD outside.The sewage of such typical low C/N ratio and low C/P ratio is to be extremely hard to Processing.

[table 6]

The content of the polluter of the solid-liquid separating of 6 waste pond sludge of table

Further the Biodegradable of the COD of separating liquid is compared with being lauched, is shown in table 7.About consolidating for Septage Liquid separating liquid, not only water quality changes acutely, but also it is shocking that despite the high concentration COD for being more than 400mg/L, but BOD5 It also is only the batch for occurring only having 30mg/L or so.The average BOD/COD ratio of solid-liquid separating during this monitoring is 22%, is shown It writes lower than the BOD/COD being lauched than 80%.There is also have BOD/COD ratio to be 5% (to be for the COD of 356mg/L The BOD of 18mg/L) as extreme example, they are the great reasons for keeping stable wastewater treatment extremely difficult.

[table 7]

Compared with BOD and COD of the 7 waste pond sludge of table in be lauched

(processing of embodiment 6:Septage solid-liquid separating)

As shown in table 6 and table 7, this is for examination waste water: BOD/COD ratio only 20% according to average, and The extremely difficult waste water of the processing of the average a height of 110mg/L of NH4-N concentration.In addition, PO4 also shows that high level, it is 45mg/L. In the present embodiment, it is studied for the SBR treatment process of sewage extremely intractable in this way.

1. the research of preparation

In the SBR processing of this waste water, by the VFA threshold value for being used to induce the phosphorus of PAO to release in the same manner as the case where being lauched It is set as 15mg/L.Sodium acetate minimum additive amount in FILL for realizing it is set as 3.07g/35L (concentration 88mg/ in SBR L), sodium acetate is added after the supply of sewage starts 30 minutes.As already mentioned as, this for try waste water BOD Content is extremely low, does not carry out carbon amounts necessary to denitrification removes containing the NH4-N for the 110mg/L that will be averaged.Sodium acetate Denitrifying effective electron donor, can the denitrifying metering-type according to shown in [chemical formula 1] and [chemical formula 2] and push away Calculate necessary amounts.The 70% of this reckoning amount is supplemented by the sodium acetate of outside addition, and remaining 30% is supplied by the BOD ingredient in waste water It answers.As a result, the sodium acetate amount about outside addition, the part released with induction phosphorus is merged as 5.04g/ circulation.

The operating of other SBR is carried out according to novel sequences (table 4).It will be set as circulation time 8 hours, filling rate will be set as 20%, therein 80% adds in FILL phase as supply for the first time, and second of supply of residue 20% is in REACT It is added in II phase.In REACT III phase, being aerated and remaining becoming silted up again for the DO for improving processing water is carried out The extraction of mud.It is carried out from September 30th, 2016 by the operating of this sequence on October 3rd, 2016,1 during this is followed The concentration variation of PO4, NH4-N and NO3-N in ring are shown in Fig. 9.

Fig. 9 shows to cause the releasing induction of phosphorus in FILL phase, it has been found that phosphorus in REACT I is taken the photograph again Enter.However, only causing the NH4-N as caused by inflow waste water to increase in second in REACT II supply, being led by denitrification The reduction of the NO3-N of cause is few.This shows that the BOD ingredient in inflow waste water used in denitrification is few, does not carry out anti-nitre Change.It is indicated above that the supply of two steps cannot achieve in the case where this is for high concentration NH4-N as examination waste water and low concentration BOD Its original purpose.

2. the change (two-step dosing) of sequence

Here, having started to supply sodium acetate, so-called two- in FILL phase and REACT II phase respectively step dosing.In addition, the inflow concentration of NH4-N also increases for initial stage envisaged value 110mg/L, concentration will be flowed into It resets as 180mg/L, sodium acetate additive amount is set as 5.49g/ circulation, its 80% first time in FILL phase is given It is added in agent (1st dosing), 20% is carried out in agent (2nd dosing) for the second time in REACT IIphase Addition.By using this two-step dosing, as shown in figs.10 and 11, the remaining concentration of NO3-N is reduced, The releasing of phosphorus can be met, reabsorbed.

However, NH4-N has occurred and is more than 200mg/L and reaches on October 24,19 days~2016 October in 2016 The abnormal situation of 300mg/L.Because this unexpected NH4-N increases, cause the NO3-N of FILLphase and REACT phase residual It deposits concentration to get higher, not only hinder the releasing of phosphorus but also also counteracts the re-absorption of phosphorus.Know that this mud is not septage, and It is the solid-liquid separating of the transience as obtained from being dehydrated the remaining mud of continuous active sludge treatment field.However, In order to mitigate the obstacle to activated sludge caused by increasing because of such unexpected NH4-N, 20% filling rate is reduced to 15%, processing has been continued.By these countermeasures, the activated sludge that damage is subject to because of high concentration NH4-N is extensive through 10 days Multiple, the water quality treatment after recovery meets the new waste water benchmark of DENR.Even in this way, the solid-liquid separating of septage it is such, It is extremely difficult while going to denitrogenate and the sewage of phosphorus, it can also be handled by using two-stepdosing.In addition, even if The NH4-N in sewage has occurred sharply increases equal abnormal situations, can also be by being suitable for changing filling rate to fully cope with (table 8).

[table 8]

The processing of 8 Septage solid-liquid separating of table is passed through

(discussion)

Summarized below: implementing to be lauched and while the nitrogen phosphorus of Septage solid-liquid separating when processing Important main points.

1) BOD in sewage is relative to the concentration of ammoniacal nitrogen than for 5 or more and situation that ammoniacal nitrogen is 40mg/L or less Under, implement the supply of two steps (adding sewage in REACT II as carbon source), is lowered as far as possible by denitrification in REACT II Generated NO3-N in phase.The anaerobic state of FILL phase easy to accomplish in next circulation as a result,.In this shape Under state, sodium acetate is added, which is used to ensure the threshold value of the required VFA for inducing from POA releasing phosphoric acid.Pass through The method, it can be achieved that nitrogen phosphorus in waste water while handle.

2) in the case where the waste water other than above-mentioned condition, that is, BOD extremely less and the profuse situation of ammoniacal nitrogen Under, the supply of two steps does not act in terms of the attenuating of NO3-N.In such waste water, the NO3- that is generated in REACT phase N adds electron donor by outside and reduces.Sodium acetate is excellent denitrifying electron donor, is classified as FILL phase Thrown with REACT II phase to two-step dosing be effective.Thrown in FILL phase to sodium acetate quilt Be used in induction denitrification and phosphorus release, thrown in REACT II to sodium acetate be used in denitrification.

(calculating of the additive amount of additional volatile fatty acid or its salt)

In embodiment 4 and 6, typically use sodium acetate as additional volatile fatty acid or its salt.It closes In the minimum additive amount of sodium acetate, 3.07g/35L (concentration 88mg/L in SBR) is set as studied in embodiment 2.Not In the case where in the presence of electron donor sufficient for carrying out denitrification, herein on the basis of minimum additive amount, it can increase anti- The amount of sodium acetate necessary to nitrifying.The calculation method of the amount of sodium acetate necessary to denitrification is as follows.

From the formula of [chemical formula 2], following formula is exported:

8NO₃+5CH₃COOH+10H₂O→4N₂+8OH+16H₂O+10CO₂

In order to by the NO of 1mol₃Denitrification is carried out, the acetic acid of 0.625mol is needed.

(1) additive amount of the sodium acetate in embodiment 4

It is new to flow into SBR's in the case where the average NH4-N flowed into waste water is about 30mg/L, filling rate is 35% The amount of NH4-N is (30mg/L) (35L × 0.35)=(367.5mg).NH4-N is subjected to complete oxidation in SBR and is converted to NO3-N(367.5mg).If it indicated by the mol of NO3-N, for 26.3mmol.According to above-mentioned relevant to denitrification Metering-type, CH necessary to denitrification₃COOH is 16.4mmol.In weight table note, CH3COOH 0.98g is corresponding CH3COONa is 1.35g.

However, the concentration of NO3-N is reduced to 2mg/L or so after being handled using the two steps supply of embodiment 3, Also become 3mg/L or so (Fig. 6 B) when the starting of FILL Phase, it is believed that be to carry out anti-nitre using the BOD ingredient flowed into waste water Change, does not carry out the addition for denitrifying sodium acetate.Therefore, make addition sodium acetate 3.07g/35L, for realizing It induces PAO to carry out phosphorus and releases threshold value 15mg/L necessary to aspect.

(2) embodiment 6 (researchs of 1. preparations)

It is new to flow into SBR's in the case where the average NH4-N flowed into waste water is about 110mg/L, filling rate is 20% The amount of NH4-N is (110mg/L) (35L × 0.2)=770mg.NH4-N carries out complete oxidation and is converted to NO3-N in SBR (770mg).If it indicated by the mol of NO3-N, for 55mmol.According to above-mentioned metering-type relevant to denitrification, instead CH necessary to nitrifying₃COOH is 34.3mmol.In weight table note, CH₃COOH becomes 2.06g, corresponding CH₃COONa As 2.81g.About solid-liquid separating, although including NH4-N with high concentration, BOD ingredient is few.Therefore, will The 70% of the sodium acetate calculated according to denitrifying metering-type carries out external addition, and remaining 30% by separation of solid and liquid BOD ingredient is filled up, and 1.97g is further added in minimum additive amount 3.07g.Therefore, the sodium acetate of addition is 5.04g/35L.

(3) embodiment 6 (changes of 2. sequences)

It is expected since the concentration of the NH4-N in being separated by solid-liquid separation is higher than, thus the average NH4-N concentration for flowing into waste water is set again It is set to about 180mg/L, it is 15% that Filing ration, which is reset, is counted again for the additive amount of the sodium acetate of addition It calculates.Sodium acetate additive amount is set as 5.49g/35L using calculation method same as (2).

As it appears from the above, instantiating the present invention using the preferred embodiment of the present invention, but it is appreciated that the present invention should be only Its range is explained according to claims.About patent quoted in this specification, patent application and document, it is appreciated that Its content itself, should be using its content as the ginseng to this specification in the same manner as the content specifically recorded in the present specification It examines and quotes.This application claims based in the excellent of Japan's application Patent 2016-245606 filed on December 19th, 2016 The interests first weighed quote the entirety of its content as reference.

Claims

1. a kind of method, to include following step for the method for phosphorus compound and nitrogen compound removal in sewage:

Step (A), which is characterized in that for by the sewage be supplied in the treatment trough comprising activated sludge, to formed the sewage with The step of mixture of the activated sludge, which adds additional volatile fatty acid or its salt makes waving in the mixture Hair property fatty acid amount becomes the threshold value or more,

Step (D) settles the activated sludge in the mixture, so that it is separated into the activated sludge and processing water, with And

2. a kind of method, for by the method for phosphorus compound and nitrogen compound removal in sewage, it includes following steps:

Step (A), which is characterized in that for by the sewage be supplied in the treatment trough comprising activated sludge, to formed the sewage with The step of mixture of the activated sludge, which adds additional volatile fatty acid or its salt makes waving in the mixture Hair property fatty acid amount becomes threshold value or more,

Step (C-2), supplies carbon source into the treatment trough,

Step (C-4), to the mixture further progress Aerobic Process for Treatment for having carried out non-Aerobic Process for Treatment in the treatment trough,

3. method according to claim 1 or 2, which is characterized in that at least carry out the step (B) to the mixture As anaerobic state.

4. according to the method described in claim 3, it is characterized in that, at least the step (B) is carried out to thin using denitrification Bacterium takes in nitric acid and releases phosphorus using phosphobacteria is stored.

5. method according to any one of claims 1 to 4, which is characterized in that at least by the step (C), (C-1) or Person (C-4) carries out taking in phosphorus to using the storage phosphobacteria.

6. side described in any one of claim 3~5 according to claim 2 or in the case where being subordinated to claim 2 Method, which is characterized in that in the step (C-2), can be taken in by the denitrifying bacteria described in such amount addition with nitric acid Carbon source.

7. side described in any one of claim 3~6 according to claim 2 or in the case where being subordinated to claim 2 Method, which is characterized in that at least carry out the step (C-3) to become anaerobic state to the mixture.

8. the method according to the description of claim 7 is characterized in that at least the step (C-3) is carried out described anti-to utilizing Nitrobacteria takes in nitric acid.

9. method described according to claim 1~any one of 8, wherein the threshold value is about 15mg/L~about 30mg/L.

10. according to the method described in claim 9, wherein, the threshold value is about 20mg/L.

11. described in any one of claim 3~10 according to claim 2 or in the case where being subordinated to claim 2 Method, which is characterized in that the BOD in the sewage is 5 or more relative to the concentration ratio of ammoniacal nitrogen and ammoniacal nitrogen is 40mg/L In situation below, use the sewage as the carbon source.

12. method described according to claim 1~any one of 11, wherein the additional volatile fatty acid or its salt Selected from the group being made of acetic acid or propionic acid or their salt.

13. method described according to claim 1~any one of 12, wherein the pH of the mixture in the step (B) It is about 7.5 or more.

14. method described according to claim 1~any one of 13, wherein waved about the addition in the step (A) Hair property fatty acid or its salt additive amount, BOD, ammonia nitrogen concentration and Vfa Concentration based on the sewage and It determines.

15. method described according to claim 1~any one of 14 does not include the step of adding chemical coagulant.

16. method described according to claim 1~any one of 15, wherein the nitric nitrogen concentration of the processing water is about 1 ~5mg/L.

17. described in any one of claim 3~16 according to claim 2 or in the case where being subordinated to claim 2 Method, wherein the carbon source is volatile fatty acid or its salt.