CN1099378C - Method for treatment of waste liquid containing phosphorous ions - Google Patents

Method for treatment of waste liquid containing phosphorous ions Download PDF

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Publication number
CN1099378C
CN1099378C CN99102065A CN99102065A CN1099378C CN 1099378 C CN1099378 C CN 1099378C CN 99102065 A CN99102065 A CN 99102065A CN 99102065 A CN99102065 A CN 99102065A CN 1099378 C CN1099378 C CN 1099378C
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Prior art keywords
iron
phosphate anion
aluminium
wastewater treatment
electrode
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Expired - Fee Related
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CN99102065A
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CN1234372A (en
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森泉雅贵
福本明広
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention relates to a method for treating waste water with phosphate ions, which is capable of keeping the efficiency of removing the phosphate ions in a higher level during a long period. After iron ions and/or aluminum ions are precipitated out from the waste water with phosphate ions by electrodes made of iron and/or aluminum in an electrochemical manner, phosphate ions and iron and/or aluminum are precipitated at the form of insoluble salt. The mol ratio between the iron and/or aluminum and the phosphate ions is limited to 1-4 by controlling the electric current.

Description

The wastewater treatment method that contains phosphate anion
Technical field
The present invention relates to the treatment process that waste water that especially home-use waste water of a kind of waste water or condominium use etc. contains the sanitary wastewater of phosphoric acid.
Background technology
One of reason of the abundant nutrient laden in rivers and creeks or lake exists for phosphorus compound is arranged, and this is known.This phosphorus compound exists in the sanitary wastewater of general family in a large number again, but the purifying treatment difficulty can't be taked effective countermeasure at present.
The treatment unit of phosphorus compound has various motions, for the electrolysis liberation method (spy opens flat 3-89998 communique, and C02F 3/12) of the known iron of domestic waste water.This technology is to make phosphate anion in the waste water and iron ion reaction back with water-insoluble salt FePO for example 4Or Fe (OH) x(PO 4) yCoagulation sedimentation and the technology of removing makes it separate out iron ion in waste water after being arranged at the iron electrifying electrodes in the electrolyzer.
, in the conventional method, because of the relation of the amount of separating out of the concentration of not considering phosphate anion and metal, thus phosphate anion remove the efficient instability, can't stably purify liquid waste.
Summary of the invention
The present invention figures out in view of above-mentioned problem, and its purpose is to provide a kind of wastewater treatment method that contains phosphate anion, can make the efficient of removing of phosphate anion keep high-level efficiency for a long time.
The present invention's the wastewater treatment method that contains phosphate anion, after using the electrode of iron content and/or aluminium in containing the waste water of phosphate anion, to separate out iron ion and/or aluminum ion with the electrochemical method order, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron and/or aluminium; It is characterized in that: the mol ratio of phosphorus concentration that control current makes precipitating metal be disposed at the electrolyzer of wastewater treatment equipment with respect to inflow becomes 1～4.
Again, the present invention's the wastewater treatment method that contains phosphate anion, after using the electrode of iron content and/or aluminium in containing the waste water of phosphate anion, to separate out iron ion and/or aluminum ion with the electrochemical method order, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron and/or aluminium; It is characterized in that: the mol ratio of phosphorus concentration of electrolyzer that control current makes precipitating metal be disposed at the circulating path of wastewater treatment equipment with respect to inflow becomes 1～4.
Again, the present invention's the wastewater treatment method that contains phosphate anion, after using the electrode of iron content or aluminium in containing the waste water of phosphate anion, to separate out iron ion or aluminum ion with the electrochemical method order, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron or aluminium; It is characterized in that: for the mol ratio of phosphorus concentration that makes precipitating metal be disposed at the electrolyzer of wastewater treatment equipment with respect to inflow becomes 1～4, control current makes under the situation of electrode iron content, separate out concentration and become 1～60mg/l, or contain the situation of aluminium at electrode, separate out concentration and become 0.5～30mg/l.
The present invention's the wastewater treatment method that contains phosphate anion, after using the electrode of iron content or aluminium in containing the waste water of phosphate anion, to separate out iron ion or aluminum ion with the electrochemical method order, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron or aluminium; It is characterized in that: for the mol ratio of phosphorus concentration of electrolyzer that makes precipitating metal be disposed at the circulating path of wastewater treatment equipment with respect to inflow becomes 1～4, control current makes under the situation of electrode iron content, separate out concentration and become 1.5～40mg/l, or contain the situation of aluminium at electrode, separate out concentration and become 1～20mg/l.
Brief description of drawings
Fig. 1 is the explanatory view of the wastewater treatment equipment of one of expression the present invention example;
Fig. 2 partly cuts stereographic map for the electrolyzer that is illustrated in Fig. 1;
Fig. 3 is the explanatory view of expression electrode unit.
Detailed description of the preferred embodiment
The following wastewater treatment method that contains phosphate anion with reference to description of drawings the present invention.
Fig. 1 is the explanatory view of the wastewater treatment equipment of expression one of the present invention example, and Fig. 2 partly cuts stereographic map for the electrolyzer in the presentation graphs 1, and Fig. 3 is the explanatory view of expression electrode unit.
The present invention is used for for example merging wastewater treatment equipments such as purification tank.This wastewater treatment equipment as shown in Figure 1, constitute by the first lonely filter vat A, second lonely filter vat B, the biofiltration groove C, processing tank D and disinfection trough E, make after each groove is handled the waste water that flows into this first lonely filter vat A, it is discharged from disinfection trough E.And, electrolyzer 1 be arranged at make utilize pneumatic pump F from this processing tank D take out treating water return the first circulating path L that is sick of filter vat A.
This electrolyzer 1 is shown in Fig. 1～3, comprise: wastewater treatment chamber 4 with influx 2 and spout 3 of waste water, be configured at least a portion and be immersed in electrode 5,6 in the interior waste water of this treatment chamber 4, in order to power supply 7 to these electrode 5,6 energisings, have in order to the polarity inversion circuit of the polarity of switching electrode 5,6 every the fixed time and in order to the controller 8 of the current control circuit of the electric current of control counter electrode 5,6 energisings, and in order to the charge of air device 9 to air supply in the interior waste water in this wastewater treatment chamber 4.
This electrode 5,6 can be by iron ion and/or the making of aluminum ion generation source such as iron, iron alloy, aluminium, aluminium alloy or iron-aluminium alloys.
This electrode 5,6 shown in Fig. 2～3, as in cell 10 across 11 of handles electrode units 12 at a distance of the fixed intervals collections, in electrolyzer 1, for example utilize every excellent 13 groups and go into 4 groups.Again, utilize screw to fix or welding etc. is connected with terminal 14 at this electrode 5,6, this terminal 14 lead 15 of pulling out is connected with junctor 16 certainly.Again, be formed with the influx 10a and the spout 10b of waste water, and form air inflow aperture 10c at this cell 10.
The diffuser 17 of described charge of air device 9 hole matter more than the end central authorities that are arranged at wastewater treatment chamber 4 or diffusing gas plate and constitute in order to pressurized air is sucked the pneumatic pump that does not show on the figure of this diffuser 17, this diffuser 17 utilizes pipe 18 to be connected with pneumatic pump.
In this example, this diffuser 17 is arranged at the end central authorities of wastewater treatment chamber 4, but limit especially so in the present invention, can suitably select and stir behind the waste water and the outflow of waste water is provided with after making the position of the easy outflow of water water-insoluble salt of resultant of reaction of the iron ion (aluminum ion) of separating out as the phosphate anion in the waste water and self-electrode together.Again, also can by in the waste water in the treatment chamber with diffuser up and down direction move, and make the convection current be easy to generate waste water.In addition, in this example, utilize the stirring of this waste water, also can make the reactivity of iron ion and phosphate anion improve.
The electrolysis liberation method of iron (aluminium) can adopt existing known method, and the energising of counter electrode is no matter be successive, or all can of alternate, pulse feature.; though the energising amount is different because of the concentration of phosphoric acid or other ions, the flow of waste water etc.; but, be preferably 1.5～2.0 and get final product as long as the mol ratio (being designated hereinafter simply as " Fe/P ") of the concentration/phosphorus concentration in the waste water of iron ion and/or aluminum ion is adjusted to 1.0～4.0.That is, the phosphorus in the waste water exists with phosphate anion, makes the reaction of this phosphate anion and iron ion generate FePO 4Or Fe (OH) x(PO 4) yAnd make its precipitation, and for this reason, for example at FePO 4Situation under, the mol ratio of Fe and P is 1 just enough, but when considering reaction efficiency, does not remove efficient if mol ratio is not the 1 high phosphorus that can't obtain more than 70～80% when above.And mol ratio becomes 4 when above, and the phosphorus rate of removing becomes (that is, efficient reaches capacity) more than 99%, even further improve mol ratio, unnecessary iron is also discharged from the outflow side, may cause running expense to rise or environmental pollution.
Therefore, in this example,,, control the amount of separating out of required iron ion according to Faraday's law with the electric current of controller control to ferroelectric utmost point energising for the phosphorus concentration according to inflow makes Fe/P become 1～4.Can make phosphorus remove stabilised efficiency and remain on more than 70～80% by this.
At this, during with the amount of separating out of current control iron, its current value and flow into the phosphorus amount that merges purification tank and be directly proportional.
An average people one day was 1.2g in the phosphorus amount sanitary wastewater of this inflow, again, and because of it is generally acknowledged that one day wastewater flow rate of an average people is 200 liters, so the phosphorus concentration of inflow is to add up last numeric representation.When calculating the phosphorus concentration of inflow thus, be 6mg/l., low in fact slightly, be about 5mg/l.
Utilize the phosphorus of this electrolytic iron liberation method to remove Technology Need and know the phosphorus amount of inflow or the phosphorus concentration of inflow, the following parameter of phosphorus concentration needs of the phosphorus amount of decision inflows or inflow.
1. merging the number of users of purification tank or merging purification tank is several humans.
2. the measurement of the phosphorus concentration of inflow.
According to number of users decision by the flow in the electrolyzer (number of users * 200 liter * recycle ratio).
About the phosphorus concentration of inflow, also can measure phosphorus concentration in advance.Use statistical value 6mg/l also can again.But, when phosphorus concentration when flowing into change of state, having when phosphorus concentration is low is 0.5mg/l, and becomes the situation of 8mg/l when phosphorus concentration is high.Thereby, when paying attention to the stability of the phosphorus amount of removing, also the phosphorus concentration of inflow can be made as 6.5 high slightly～7mg/l.
In addition, the be treated to iron ion (aluminum ion) and the phosphate anion in the waste water that utilize self-electrode to separate out of the electrolysis liberation method that utilizes iron (aluminium) of the present invention's the waste water that contains phosphate anion react the processing that makes its reaction that generates the salt of water insoluble phosphoric acid of water and iron (aluminium) (reaction A), but have hydroxide ion in the waste water, the iron ion of being separated out (aluminum ion) also reacts (reaction B) with hydroxide ion.Because of reaction B is faster than reaction A, so in order to catch phosphate anion, needing increases the magnitude of current, increases the amount of separating out of iron ion (aluminum ion).
, when in waste water, having calcium ion or mn ion, these ions meetings and hydroxide ion reaction (reaction D).D is more preferential than the reaction B of iron ion (aluminum ion) and hydroxide ion because of this reaction, thus inhibited reaction B, iron ion (aluminum ion) effectively utilize in the reaction A of phosphate anion.In addition, calcium ion and mn ion also form water-insoluble salt with the phosphate anion reaction, help removing phosphate anion.
Thereby, in the present invention, add calcium ion or mn ion, can suppress the reaction B of iron ion (aluminum ion) and hydroxide ion, also can make the reaction A of iron ion (aluminum ion) and phosphate anion carry out expeditiously.By this, can reduce the energising amount, but power saving and can reduce iron or the amount of separating out of the aluminium.
The present invention's wastewater treatment equipment is as noted above, can effectively utilize especially in general domestic waste water.Therefore, separately use also can, but and for example can be used as the comprehensive wastewater purification system home-use, that condominium is used after other purification systems combinations such as activated sludge process, membrane separation process, the aerobic circulation method of being sick of.Also can be used in extensive treatment system (movement is handled the field) again.
Below, according to embodiment the present invention is described, but not to be defined as be this embodiment in the present invention.
Embodiment 1
Separate out in the wastewater treatment equipment in the electrolysis of iron shown in Figure 1, be immersed in the iron plate that 4 counter electrode in the waste water use high purity.In order to carry out the electrolysis of electrode, the reversal of poles time is controlled to be 6 hours with the two poles of the earth again.
And the sanitary wastewater that order comprises phosphorus concentration 3～5mg/l with 1200 liters of/day inflows, and is made as 6000 liters/day with the circular flow in the treatment unit from influx.After managing groove throughout and carrying out a biological disposal upon, the phosphorus concentration in the treating water when flowing into electrolyzer becomes 1～3mg/L.At this moment, the amount of separating out that Fe/P is made as 2 o'clock iron utilizes following formula (1) to calculate, and obtains (1～3/31) * 2 * 55.847=3.6～10.8mg/L.
(phosphorus concentration/phosphorus atom amount) * (mol ratio) * (iron atom amount) (1)
Therefore, the amount of separating out of iron is 3.6～10.8mg/L, because of internal circulating load is 6000 liters/day, be that the Faradaic current value of 21.6～64.g utilizes following formula (2) to calculate in order to the amount of separating out of guaranteeing 1 day iron, obtain (21.6～64.8/55.847) * 2 * 96500/ (24 * 60 * 60)=0.86～2.6A.(1 day the amount of separating out/iron atom amount) * (gram equivalent) * (quantity of electric charge)/(1 day number second) (2)
Thereby, in order to the immersion surface-area of the electrode that current value is made as 0.86～2.6A current density is being made as 0.5mA/cm 2Shi Biancheng 1720～5200cm 2Therefore, the immersion surface-area with electrode is made as 1720～5200cm 2, for Fe/P becomes 2 and the Faradaic current value is controlled to be 0.86～2.6A.
And after iron ion that the electrolysis that utilizes electrode is separated out and the phosphate anion reaction, produce the water water-insoluble salt.Salt that is produced and inflow water flow out to the outflow side after being stirred by the air (2 liters/minute) from the diffuser generation together.Therefore, water-insoluble salt is piled up hardly.
Then will learn that it is more than 70～80% that phosphorus is removed efficient in the result of the filtered liquid behind the waste water filtering that spout is taked with the strainer of aperture 0.45 μ m according to full phosphorus analytical method (46.3) analysis of JISK 0102 specification.
The following describes other examples of the present invention.At this example, 0.5～8mg/L makes Fe/P become 1～4 for the foundation phosphorus concentration, with the electric current of controller control to ferroelectric utmost point energising, controls required iron or the amount of separating out of the aluminium according to Faraday's law.This amount of separating out utilizes following formula (3) to calculate, and under the situation of electrode iron content, is about 1～60mg/L (0.5/31 * 1 * 55.847～8/31 * 4 * 55.847mg/L).And, contain the situation of aluminium at electrode, utilizing formula (3) to try to achieve is 0.5～30mg/L (0.5/31 * 1 * 27～8/31 * 4 * 27mg/L).
(phosphorus concentration/phosphorus atom amount) * (mol ratio) * (iron or aluminium nucleidic mass) (3)
And, when the circulating treatment unit that is used in this example is carried out a biological disposal upon to waste water, cause is through biological treatment, the phosphorus concentration that flows into electrolyzer drops to 1～5mg/L, the amount of separating out when calculating, under the situation of electrode iron content, is about 1.5～40mg/L with above-mentioned the samely, contain at electrode under the situation of aluminium, be about 1～20mg/L.
Can make phosphorus remove stabilised efficiency and remain on more than 70～80% by this.
According to embodiment the present invention is described below, but not to be defined as be this embodiment in the present invention.
Embodiment 2
The same with the foregoing description 1, separate out in the wastewater treatment equipment in the electrolysis of iron shown in Figure 1, be immersed in the iron plate that 4 counter electrode in the waste water use high purity.In order to carry out the electrolysis of electrode, the reversal of poles time is controlled to be 6 hours with the two poles of the earth again.
And the sanitary wastewater that order comprises phosphorus concentration 3～5mg/L with 1200 liters of/day inflows, and is made as 6000 liters/day with the circular flow in the treatment unit from influx.After managing groove throughout and carrying out a biological disposal upon, the phosphorus concentration in the treating water when flowing into electrolyzer becomes 1～3mg/L.At this moment, Fe/P was made as 1～4 o'clock, the amount of separating out of iron utilizes above-mentioned formula (3) to calculate, and tries to achieve to be (1～3/31) * (1～4) * 55.847=11.8～21.6mg/L.
Therefore, the amount of separating out of iron is 11.8～21.6mg/L, because of internal circulating load is 6000 liters/day, in order to the amount of separating out of guaranteeing 1 day iron is that the Faradaic current value of 10.8～129.6g utilizes following formula (4) to calculate, and tries to achieve to be (10.8～64.8/55.847) * 2 * 96500/ (24 * 60 * 60)=0.43～5.18A.
(1 day the amount of separating out/iron atom amount) * (gram equivalent) * (quantity of electric charge)/(1 day number second) (4)
Thereby, in order to the immersion surface-area of the electrode that current value is made as 0.43～5.18A current density is being made as 0.5mA/cm 2The time be 860～10360cm 2Therefore, the immersion surface-area with electrode is made as 860～10360cm 2, for Fe/P becomes 1～4 and the Faradaic current value is controlled to be 0.43～5.18A.
And after iron ion that the electrolysis that utilizes electrode is separated out and the phosphate anion reaction, generate the salt of water-insoluble.The salt that is generated and flow into water one and reinstate air (2 liters/minute) stirring from diffuser generations after, flow out to the outflow side.Therefore, the salt of water-insoluble is piled up hardly.
Then will learn that it is more than 70～80% that phosphorus is removed efficient in the result of the filtered liquid behind the waste water filtering that spout is taked with the strainer of aperture 0.45 μ m according to full phosphorus analytical method (46.3) analysis of JISK 0102 specification.
In addition,, the electrolyzer of the circulating path that is arranged at wastewater treatment equipment has been described, but in the present invention, has limited so, for also can implementing of the small-scale purification tank of the groove in batches that for example is arranged at the batch-type wastewater treatment equipment etc. at above example.
As described above, if utilize the present invention, can keep the phosphorus of high-level efficiency to remove performance for a long time.

Claims (4)

1. wastewater treatment method that contains phosphate anion, after using the electrode of iron content and/or aluminium to make it in containing the waste water of phosphate anion, separate out iron ion and/or aluminum ion with electrochemical method, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron and/or aluminium; It is characterized in that: the mol ratio of phosphorus concentration that control current makes precipitating metal be disposed at the electrolyzer of wastewater treatment equipment with respect to inflow becomes 1～4.
2. wastewater treatment method that contains phosphate anion, after using the electrode of iron content and/or aluminium to make it in containing the waste water of phosphate anion, separate out iron ion and/or aluminum ion with electrochemical method, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron and/or aluminium; It is characterized in that: the mol ratio of phosphorus concentration of electrolyzer that control current makes precipitating metal be disposed at the circulating path of wastewater treatment equipment with respect to inflow becomes 1～4.
3. wastewater treatment method that contains phosphate anion, after using the electrode of iron content or aluminium to make it in containing the waste water of phosphate anion, separate out iron ion or aluminum ion with electrochemical method, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron or aluminium; It is characterized in that: for the mol ratio of phosphorus concentration that makes precipitating metal be disposed at the electrolyzer of wastewater treatment equipment with respect to inflow is 1～4, control current makes under the situation of described electrode iron content, separate out concentration and become 1～60mg/L, or contain at described electrode under the situation of aluminium, separate out concentration and become 0.5～30mg/L.
4. wastewater treatment method that contains phosphate anion, after using the electrode of iron content or aluminium to make it in containing the waste water of phosphate anion, separate out iron ion or aluminum ion with electrochemical method, make phosphate anion with the form coagulation sedimentation of the water-insoluble salt of iron or aluminium; It is characterized in that: for the mol ratio of phosphorus concentration of electrolyzer that makes precipitating metal be disposed at the circulating path of wastewater treatment equipment with respect to inflow is 1～4, control current makes under the situation of described electrode iron content, separate out concentration and become 1.5～40mg/L, or contain at described electrode under the situation of aluminium, separate out concentration and become 1～20mg/L.
CN99102065A 1998-03-06 1999-03-05 Method for treatment of waste liquid containing phosphorous ions Expired - Fee Related CN1099378C (en)

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Application Number Priority Date Filing Date Title
JP054825/98 1998-03-06
JP054825/1998 1998-03-06
JP5482598 1998-03-06

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CN1099378C true CN1099378C (en) 2003-01-22

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308227C (en) * 2005-06-08 2007-04-04 贵州宏福实业开发有限总公司 Process for comprehensive using waste water of phosphatic fertilize and phosphorous chemical industrial
KR101488283B1 (en) * 2014-06-16 2015-01-30 주식회사 에코너지 Waste water treatment apparatus using the Electrolysis flocculation and Pipe filtration and Waste water treatment methods

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