CN1184782A - Method and apparatus for treating wastewater contg. phosphoric acid radical - Google Patents
Method and apparatus for treating wastewater contg. phosphoric acid radical Download PDFInfo
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- CN1184782A CN1184782A CN97125437A CN97125437A CN1184782A CN 1184782 A CN1184782 A CN 1184782A CN 97125437 A CN97125437 A CN 97125437A CN 97125437 A CN97125437 A CN 97125437A CN 1184782 A CN1184782 A CN 1184782A
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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
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- 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
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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Abstract
An electrolytic elution method is carried out in a state where the concentration of calcium ion and/or magnesium ion in a drain to be treated is not less than 2 mg/liter. The ratio of removal of phosphoric acid ion in a drain containing phosphoric acid ion by electrolytic elution method of iron or aluminum can be improved, whereby enabling power-saving.
Description
As everyone knows, one of the eutrophication reason in river, lake is because the existence of phosphorus compound.And owing to compare to plant effuent, these phosphorus compounds more are present among the sanitary sewage of general family, thereby are difficult to purifying treatment, this are not also had at present effective countermeasure.
To the purifying treatment method of phosphorus compound, many schemes have been proposed, the known electrolysis stripping method (spy opens flat 3-89998 communique) that iron is arranged concerning domestic sewage.This kind technology is phosphate anion and the insoluble salt of iron ion water generation reaction that makes in the sewage, as FePO
4Or Fe (OH)
x(PO
4)
yDeng, thus coagulation sedimentation and removed technology, be by giving electrifying electrodes made of iron in sewage the stripping iron ion.
Yet this electrolytic iron stripping method is to the removal efficient of phosphate anion, even the amount of phosphate anion is identical, also can great changes will take place because of the kind of sewage, and the problem of stably purifying waste water of can't realizing is arranged.
The inventor etc. further investigate its reason, found that, the concentration of calcium ion and magnesium ion has confidential relation in the clearance of phosphate anion and the water, when the concentration of calcium ion or magnesium ion was lower than 2 mg/litre, the efficient of removing phosphate anion by iron ion can reduce significantly.
As the waste disposal plant that adopts aforementioned electrolysis stripping method, also having method is that the sanitary sewage that will flow into the anaerobism filter vat carries out after the anaerobic treatment, in aerator tank, carry out aerobic treatment, then the treating water in the aerator tank is returned to the anaerobism filter vat through the dissolved ferric iron device of stripping iron ion, in the anaerobic bed groove, by the iron ion of dissolved ferric iron device stripping and the former phosphatase reaction in the treating water, with the aggegation of insoluble chemical compound form, precipitation, insoluble phosphorus compound of when making regular check on anaerobism filter vat bottom being piled up and the mud that is returned to the anaerobism filter vat are attracted to remove (opening flat 7-108296 communique with reference to the spy).
But, even this method also exists the phosphate anion amount when identical, dephosphorization acid ion efficient also alters a great deal because of the sewage kind is different, can't realize the problem to the stable purification of sewage.
On the other hand, as to the phosphorus compound purifying treatment method, in sewage, add CaCl in addition
2Or FeCl
3Method Deng agglutinant.
Yet this purifying treatment method for improving the clearance of phosphorus, must be regulated the pH value according to the kind of agglutinant.For example adopt CaCl
2In the time of as agglutinant,, must add NaOH solution as the pH regulator agent in order to reach the highest pH9 of tp removal rate～10.Thereby aforesaid this purifying treatment method in order to remove phosphorus compound, must add agglutinant and two kinds of medicines of pH regulator agent, and must monitor the problem of pH in addition at any time.In addition, aforesaid agglutinant, for example CaCl
2And FeCl
3Input amount with respect to the amount of phosphor in sewage, being scaled mol ratio all is Fe/P2～3 and Ca/P=2～3.So, have again big with respect to the agglutinant consumption of phosphorus, the problem that cost is high.
In addition, the purifying treatment method of the various phosphorus compounds that proposed, because of handle the time standby environment is brought the destructive medicine, thereby must carry out aftertreatment, and use multiple medicine, restive, have some problems.
Thus, the inventor etc., in order to realize high-level efficiency and environmentally safe sewage purification, through further investigation, found that: when sewage contains phosphate anion and calcium ion and/or magnesium ion,, then can be easier to form water-insoluble salt if the pH value of this sewage is adjusted to more than 8, can realize purification, thereby finish the present invention aforementioned sewage.
The objective of the invention is to electrolysis stripping method, improve, and reach the purpose of economize on electricity the clearance in the removal method that contains phosphate anion phosphor in sewage acid ion by iron or aluminium.The present invention also aims to not use the pH regulator agent just can easily carry out the control of pH.In addition, the object of the invention also is efficiently and purifies safely the sewage that contains phosphate anion and calcium ion and/or magnesium ion.
The 1st invention of the present invention is the treatment process of phosphorus-containing acid ion sewage, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, in the sewage of phosphorus-containing acid ion, make iron ion and/or aluminum ion stripping with electrochemical method, make phosphate anion and iron ion and/or the aluminum ion form coagulation sedimentation with water-insoluble salt, the total concentration of the calcium ion concn in the processed sewage, magnesium ion concentration or calcium ion and magnesium ion is more than 2 mg/litre.
The 2nd invention of the present invention is the treatment process of phosphorus-containing acid ion sewage, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, in the sewage of phosphorus-containing acid ion, make iron ion and/or aluminum ion stripping with electrochemical method, make phosphate anion and iron ion and/or aluminum ion form coagulation sedimentation, in former electrodes, exist calcium ion and/or magnesium ion that the source takes place with water-insoluble salt.
The 3rd invention of the present invention is the treatment unit of phosphorus-containing acid ion sewage, it is characterized in that, be immersed in the electrode in the indoor sewage of this sewage disposal and the power supply of this electrifying electrodes formed by sewage disposal chamber, at least a portion of having effluent stream inlet and spout, electrode has at least 1 to have calcium ion and/or magnesium ion generation source and iron ion and/or aluminum ion generation source.
The 4th invention of the present invention is the treatment process that contains phosphate anion sewage, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, with electrochemical method stripping iron ion and/or aluminum ion in the sewage of phosphorus-containing acid ion, make phosphate anion and iron ion and/or aluminum ion form coagulation sedimentation, in sewage, have the generation source of calcium ion and/or magnesium ion with water-soluble salt.
The 5th invention of the present invention is the treatment process of sewage, it is characterized in that used in the method calcium and/or magnesium ion generation source are contained from calcium metal, MAGNESIUM METAL and can be sewage in the group formed of the compound of stripping calcium ion and/or magnesium ion optional a kind.
The 6th invention of the present invention is the treatment unit of phosphorus-containing acid ion sewage, it is characterized in that, be immersed in the electrode in the sewage in this treatment chamber and the power supply of this electrifying electrodes formed by sewage disposal chamber, at least a portion of having effluent stream inlet and spout, electrode has at least 1 to have iron ion and/or aluminum ion the source takes place, and before aforementioned influx or be provided with the generation source of calcium ion and/or magnesium ion in the sewage disposal chamber.
The 7th invention of the present invention is the treatment process of phosphorus-containing acid ion sewage, it is characterized in that, with the form coagulation sedimentation of the phosphate anion in the sewage with water-insoluble salt, at least there is pair of electrodes in the water and passes to direct current, near negative electrode, drop into the generation source of calcium ion and/or magnesium ion, simultaneously/or near anode, drop into iron ion and/or aluminum ions generation source.
The 8th invention of the present invention is the treatment unit of phosphorus-containing acid ion sewage, it is characterized in that, form by the sewage disposal chamber that has effluent stream inlet and spout, at least one pair of electrode and to the power supply that this counter electrode is switched on, said pair of electrodes is configured in the treatment chamber, and at least a portion is by the sewage submergence, when aforesaid pair of electrodes is switched on, dispose the device that can drop into calcium ion and/or magnesium ion generation source near the electrode as negative electrode, simultaneously/or near anode, have the device that can drop into iron ion and/or aluminum ion generation source.
The 9th invention of the present invention is the treatment process of sewage, it is characterized in that the pH that contains the sewage of phosphate anion and calcium ion and/or magnesium ion is adjusted to more than 8.
The 10th invention of the present invention is the treatment process of sewage, it is characterized in that, the treatment unit of sewage that contains phosphate anion and calcium ion and/or magnesium ion is by forming with the lower section:
Detect the pH meter of sewage pH value,
In sewage, add the pH regulator agent adding apparatus and
When the detection pH of this pH meter less than 8, send interpolation pH regulator agent instruction to keep sewage pH value at the control device more than 8 to pH regulator agent adding apparatus.
Brief Description Of Drawings
Fig. 1 is the brief description figure for a kind of embodiment of the waste disposal plant of implementing the 1st inventive method.Fig. 2 is the synoptic diagram of the relation of calcium ion concn and phosphate anion clearance when adopting the ferroelectric utmost point in the 1st inventive embodiment 1 of expression.Fig. 3 is the synoptic diagram of the relation of magnesium ion concentration and phosphate anion clearance when adopting the ferroelectric utmost point in the 1st inventive embodiment 2 of expression.Fig. 4 is the synoptic diagram of the relation of calcium ion concn and phosphate anion clearance when adopting the aluminium electrode in the 1st inventive embodiment 3 of expression.Fig. 5 is the synoptic diagram of the relation of magnesium ion concentration and phosphate anion clearance when adopting the aluminium electrode in the 1st inventive embodiment 4 of expression.Fig. 6 is a kind of explanatory view of embodiment of the phosphorus-containing acid ion wastewater treatment equipment of the 3rd invention.Fig. 7 is the explanatory view of another embodiment of the phosphorus-containing acid ion wastewater treatment equipment of the 3rd invention.Fig. 8 is the diagrammatic illustration figure of other configuration examples of the electrode in the 2nd～3 invention of expression.Fig. 9 is the explanatory view of other examples of the electrode in the 2nd～3 invention of expression.Figure 10 is the explanatory view of other the other examples in the 2nd～3 invention of expression.Figure 11 is a kind of explanatory view of embodiment of the phosphorus-containing acid ion waste disposal plant of the 6th invention of expression.Figure 12 is the explanatory view of another embodiment of the waste disposal plant of the 6th invention of expression.Figure 13 is the explanatory view of an embodiment again of the waste disposal plant of the 6th invention of expression.Figure 14 is a kind of explanatory view of embodiment of treatment unit of the phosphorus-containing acid ion sewage of the 8th invention of expression.Figure 15 is the explanatory view of another embodiment of treatment unit of the phosphorus-containing acid ion sewage of the 8th invention of expression.Figure 16 is the explanatory view of another embodiment of treatment unit of the phosphorus-containing acid ion sewage of the 8th invention of expression.Figure 17 is the explanatory view of another embodiment of treatment unit of the phosphorus-containing acid ion sewage of the 8th invention of expression.Figure 18 is the diagrammatic illustration figure of a kind of embodiment of the waste disposal plant that uses in the 9th～10 inventive embodiment.
Below, treatment process and the treatment unit thereof to phosphorus-containing acid ion sewage of the present invention is described in detail with reference to the accompanying drawings.
The processing of phosphorus-containing acid ion sewage being carried out with the electrolysis stripping method of iron is the reaction (reaction A) that utilizes the iron ion of stripping in the electrode and the insoluble phosphoric acid molysite of phosphor in sewage acid ion water generation reaction, but owing to has hydroxide ion (OH in the sewage
-Ion), the iron of stripping also can react (reaction B) with hydroxide ion.Reaction B is faster than reaction A, therefore must add high-amperage and the iron ion stripping quantity is increased in order to catch phosphate anion.Its result causes the increase of electrode and power consumption.
The 1st invention of the present invention be characterised in that, in order to suppress the reaction B of iron ion and hydroxide ion, the reaction A that makes iron ion and phosphate anion to be efficiently carrying out, so that the concentration of calcium ion that exists in the sewage and/or magnesium ion more than 2 mg/litre.
If have calcium ion or magnesium ion in the sewage, its ion will react with hydroxide ion (reaction D) then.Because this reaction D is more preferential than the reaction B of iron ion and hydroxide ion generation, thereby reaction B is suppressed, and can effectively utilize the reaction A that iron ion and phosphate anion carry out.And because calcium ion and magnesium ion also can generate water-fast salt (reaction E) with the phosphate anion reaction, this removal to phosphate anion also has contribution.
, above-mentioned reaction A promoted that therefore react A and take place at anode easily, reaction E takes place at negative electrode easily owing to being promoted to react E at acidic region (pH4～5) at basic region (pH9～11).
In addition, the reaction A of phosphate anion and iron ion, and the reaction E of phosphate anion and calcium ion or magnesium ion are because the difference of reaction conditions can generate the water-insoluble salt of various forms such as independent salt, moisture salt.Therefore, in the present invention, comprise the salt that phosphoric acid and iron, calcium and magnesium form as water-insoluble salt with phosphoric acid formation.
Calcium ion or magnesium ion are removed the transition point that phosphate anion begins to produce considerable influence to iron ion, shown in accompanying drawing 2 and the accompanying drawing 3, are when the concentration in sewage is 2 mg/litre when calcium ion or magnesium ion as described later.When the concentration in sewage was 2 mg/litre～10 mg/litre when calcium ion or magnesium ion, the clearance of phosphate anion sharply rose corresponding to the concentration of calcium or magnesium ion, as surpass 10 mg/litre then the phosphate anion rising of removing rate become slow.
In addition, form the also available iron replacement of aluminium of water-insoluble salt among the present invention with phosphate anion, but also both use also.With the situation of aluminium shown in accompanying drawing 4, accompanying drawing 5, though the existence of calcium ion does not make it to produce as with the sort of rapid variation under the situation of iron, because the phosphate anion rate of removing that exists of calcium ion or magnesium ion has raise really.
According to initial above-mentioned facts of finding such as the inventor, the 1st invention of the present invention be make calcium ion concn in the sewage, magnesium ion concentration or its add up to concentration be 2 milligrams/or more than, under the state of preferred 2～10 mg/litre, remove phosphate anion with the electrolysis stripping method of iron or aluminium.
Make in the sewage calcium ion or magnesium ion keep the method for the above concentration of 2 mg/litre not have special restriction, for example can enumerate as calcium ion or magnesium ion are taken place the source with monomer, with and compound such as water-soluble salt with the form of the solid or the aqueous solution in the sewage continuously or adding intermittently; Also add one by one again during the density loss of calcium ion that can in original sewage, exist or magnesium ion; Can adopt the method for configuration device for continuously adding medicine in sewage in addition or in electrode, dispose above-mentioned calcium ion or the method in magnesium ion generation source.
Can enumerate as calcium chloride (solubleness is 59.5 grams/100 gram water) as the water-soluble salt of calcium or magnesium, calcium hydroxide (solubleness is 185 milligrams/100 gram water), lime carbonate (solubleness is 1.4 milligrams/100 gram water), caoxalate (solubleness is 0.67 milligram/100 gram water), magnesium chloride (solubleness is 52.8 grams/100 gram water), magnesium hydroxide (solubleness is 0.9 milligram/100 gram water), magnesiumcarbonate (solubleness is 10.6 milligrams/100 gram water), magnesium oxalate (solubleness is 70 milligrams/100 gram water) or the like.At this wherein, realize the slow release effect of stripping bit by bit, preferred especially lime carbonate, magnesium hydroxide and caoxalate for making calcium ion or magnesium ion.In addition, in the salt that adopts good water solubility, used water perviousness film carries out dressing etc., realizes slow-releasing from the outside.
The electrolysis stripping method of iron (aluminium) can adopt existing known method, as electrode available iron, iron alloy, aluminium, aluminium alloy etc.Step mode can be a successive, alternate, or pulsed, the energising amount can be different with other ionic concns, the discharge of sewage etc. because of phosphate anion, but should be 0.8～3.0 according to the ratio that makes iron ion in the sewage or aluminium ion concentration/phosphorus acid ion concentration (following), be preferably 1.0～2.5 and regulated with " Fe/P " simple expression.According to the present invention, the energising amount can reduce significantly, thereby can saves energy and can reduce the stripping quantity of iron and aluminium.
Sewage water treatment method of the present invention as aforementioned to the processing of domestic sewage particularly useful.So can use separately, also can be such as activated sludge process, membrane separation process, the aerobic circulation method of anaerobism etc. are used in combination the composite wastewater purification system of using as home-use and condominium with other purification systems.In addition, it also can be used for extensive treatment system (night soil plant).
Followingly the method for the 1st invention of the present invention is described, but the present invention is not limit by these embodiment according to embodiment.
Adopting the electrolysis stripping waste disposal plant of iron as shown in Figure 1 is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (with H to the phosphorus acid ion concentration that contains as confession examination sewage
3PO
4The form adding), Na
+The water of 200 mg/litre is handled.
1 is the sewage disposal chamber among Fig. 1, and it has the influx 3 and the spout 4 of sewage 2.In the sewage disposal chamber 1, two iron electrodes 5 of high purity that are immersed in the sewage 2 are arranged, they are connected with power supply 6.The energising amount Fe/P of electrode is 0.9,1.8 and 2.7, is respectively 467 milliamperes, 933 milliamperes and 1400 milliamperes, and any situation all is 30 minutes reversal of polarity with electrode of every energising.Toward for adding the calcium hydroxide that the source takes place as calcium ion in the examination sewage, make calcium ion concn be respectively 0,2,3,4,5,10 and 50 mg/litre, sewage flows into 0.5 liter/minute flow.The sewage that energising beginning was collected from spout 4 after 2 hours is that 0.45 micron filter filters by the aperture, and gained filtrate is analyzed according to the full phosphorus analytical method (46.3) of JIS K0102, thereby determines to handle the phosphorus acid ion concentration in the sewage of back.
The result as shown in Figure 2.
From Fig. 2 as seen, the rate of removing that begins phosphate anion when ionic concn is 2 mg/litre sharply rises.And Fe/P to remove rate when increasing more also big more.
Calcium ion among the embodiment 1 is replaced (the generation source is a magnesium chloride) with magnesium ion, make for its concentration in the examination sewage and be respectively 0,3,5,10 and 50 mg/litre, other is constant, carries out same sewage disposal, and the phosphorus acid ion concentration of handling in the sewage of back is measured with same procedure among the embodiment 1.
The result as shown in Figure 3.
In Fig. 3 obviously as seen, magnesium ion concentration be 2 mg/litre near the rate of removing of phosphate anion sharply rise, and if Fe/P become greatly, the rate of removing also raises.
Use the electrode among the embodiment 1 instead electrode that raffinal is made, regulating the energising amount makes A1/P (ratio of aluminium ion concentration/phosphorus acid ion concentration in the processed sewage) be respectively 0.6,1.2,1.8, regulate for the calcium ion concn in the examination sewage and make it to be respectively 0.5 and 10 mg/litre, other is identical with embodiment 1, carry out sewage disposal, the phosphorus acid ion concentration of handling in the sewage of back is measured with same procedure among the embodiment 1.
The result as shown in Figure 4.
From Fig. 4 as seen, A1/P is when 1 front and back, and it is to begin about 5 mg/litre to rise from calcium ion concn that phosphate anion is removed rate, and big if A1/P becomes, then the rate of removing just begins to rise when calcium ion concn is 2 mg/litre.
Calcium ion among the embodiment 3 is replaced (the generation source is a magnesium chloride) with magnesium ion, add in the examination sewage, other is identical, carries out sewage disposal, and the phosphorus acid ion concentration of handling in the sewage of back is measured with same procedure among the embodiment 1.
The result as shown in Figure 5.
Can find out obviously in from Fig. 5 that when adding magnesium ion, from lower concentration (2 mg/litre), phosphate anion is removed rate and just risen gradually.
The method of the 1st invention according to the present invention can be removed the phosphate anion in the decontaminated water efficiently, and can reduce as the iron of electrode or the consumption and the electric energy that is used for stripping of aluminium, and waste disposal plant can be turned round in long-time continuous under the low power consumption.
Below explanation the 2nd～3 invention of the present invention.
As shown in Figure 6, treatment unit is by the sewage disposal chamber 1 with effluent stream inlet 3 and spout 4, the formations such as power supply 6 that have at least a part to be immersed in the electrode 7,8 in treatment chamber 1 sewage and this electrode 7,8 is switched on.
In former electrodes 7,8, in substrate metals such as iron, iron alloy, aluminium, aluminium alloy or iron-aluminium alloy, can be incorporated as remove phosphate anion the calcium in source or the water-soluble salt of magnesium take place as ion.As for the specific examples of these water-soluble salts, can enumerate the water-soluble salt among the 1st of the present invention as described above.
Contain the method that the source takes place ion in the electrode base material metal as making, can be used on method of when making substrate metal foundings such as aforementioned lime carbonate being gone into (in mold, adding matrix metal and lime carbonate etc.) or ion implantation (method of doping calcium ion in matrix metal) etc. with the method for naturally cooling again after the fusions such as electric arc scorification.
In the present embodiment, two electrodes all contain the generation source of calcium ion and/or magnesium ion respectively, and the present invention is not particularly limited this, also can have only a generation source of containing calcium ion and/or magnesium ion in two electrodes.And, as shown in Figure 7, electrode 14,15 also can be application on the substrate metal 16, stacked by on the compound layer 17 formed of aforementioned calcium ion and/or magnesium ion generation source and forming.This compound layer 17 for the metal ion that makes electrolysis stripping from the matrix metal 16 and the hydroxide ion that comparative electrode produces are difficult for exerting an influence, preferably makes it mutual subtend setting.In addition, used in the embodiment shown in Fig. 6～7 is pair of opposed electrodes, but all unqualified to its configuration and quantity in the present invention, can the antianode side and the number of electrodes of cathode side do suitably to set also can make many variations simultaneously to its configuration.For example, shown in Fig. 8 (a), can make the plural electrode array group 25 mutual subtend configurations of the plural electrode array group 24 and the anode side of cathode side.Or shown in Fig. 8 (b), can make electrode 34 alternately configured of the electrode 35 and the cathode side of anode side.In addition, the number of electrodes of anode side and cathode side also can be different.
In addition, used other electrodes for example shown in Fig. 9～10 among the present invention.Electrode shown in Figure 9 is with the generation source 41 of calcium ions such as granular filling lime carbonate and/or magnesium ion in the aperture of the substrate metal 40 with many apertures.In addition, electrode shown in Figure 10 is with calcium ion such as granular filling lime carbonate and/or magnesium ion source 51 to take place in the sieve aperture of the substrate metal 50 of mesh-like.
Followingly the 2nd invention of the present invention is described, but the present invention is not subjected to the restriction of these embodiment according to embodiment.
Embodiment 5
Use the electrolysis stripping waste disposal plant of iron shown in Figure 6, allow the phosphorus acid ion concentration be that 5 mg/litre are (as H
3PO
4Add) and contain Na
+Flowing into from the flow velocity of influx of 200 mg/litre with 1 liter/minute for examination sewage.
As the electrode employing of in sewage, flooding high purity iron plate is made the electrode that contains 1000 milligrams of lime carbonate with the electric arc melting method.For making Fe/P is 1.5, and the energising amount of electrode is 1.2 amperes, makes reversal of poles every half an hour.
By the electrolytic action of electrode, the stripping simultaneously of iron ion and calcium ion.The solubleness of lime carbonate is 15 mg/litre in 25 ℃ of water of temperature, and institute surpasses 2 mg/litre for calcium ion concn in the examination sewage, is 6 mg/litre.
Switching on after 2 hours, collect sewage from spout 4, is that 0.45 micron filter filters with the aperture, removes efficient more than 90% with what the result of full phosphorus analytical method (46.3) mensuration of JIS K0102 showed phosphorus.
Except that lime carbonate that electrode among the embodiment 5 is contained replaces with the higher calcium hydroxide of solubleness, other under same experiment condition, to carry out with sampling device.
Be 12 mg/litre from the effusive calcium ion concn for examination sewage of spout this moment.
Through embodiment 5 after half conduction time, measure the content of phosphorus with embodiment 5 same procedure, its result shows and removes efficient more than 90%.And the visible because calcium ion concn of present embodiment is 2 times of calcium ion concn of previous embodiment 5, and remove efficient (90% or more) for half of embodiment 5 just can realize identical phosphorus conduction time, and spent electric energy also reduces by half.
The 2nd～3 invention of the present invention can be expeditiously removes the phosphate anion in the decontaminated water, and can reduce the electric energy that expends as the consumption of the iron of electrode or aluminium and for stripping, thereby can make sewage disposal long-time continuous running under low power consumption.
Below explanation the 4th～5 invention of the present invention.
As shown in figure 11, treatment unit is by the sewage disposal chamber 1 with effluent stream inlet 3 and spout 4, source 60 takes place and constitutes in the power supply 6 that has at least a part to be immersed in the electrode 54,55 in treatment chamber 1 sewage and this electrode 54,55 is switched on, the ion in order to remove phosphate anion that disposes in the above-mentioned sewage disposal chamber.In addition, the 9th, the control device of 54,55 electric currents of control electrode.
Above-mentioned electrode 54,55 usefulness iron, iron alloy, aluminium, aluminium alloy or iron-aluminium alloy etc. are made.
Above-mentioned ion generation source has calcium ion that source, magnesium ion take place the ion that source and they combine to take place 3 kinds in source takes place.As above-mentioned calcium ion the source taking place can be with the water-soluble salt in the 1st invention of aforementioned the present invention.As the method that this ion generation source is configured in the above-mentioned sewage disposal chamber 1, have and granular or block ion taken place source 60 usefulness nets 61 or filter parcel are placed on the indoor method of sewage disposal, source 60 usefulness nets or filter parcel are taken place above-mentioned ion, and the method for sewage is put in suspension then, the cover of being packed in ion generation source is placed in the method etc. of inflow side more in addition, so long as make the method that calcium ion and/or magnesium ion can stripping in the sewage disposal chamber, be not limited in these.
The form of present embodiment is to settle ion that the source takes place in sewage disposal chamber 1, but is not limited in this for the present invention, and is for example shown in Figure 12, also can dissolving tank 62 be set in enter the mouth 3 front of effluent stream, and ion source 60 takes place is placed in the dissolving tank 62.Under the situation of this set dissolving tank 62, dissolving tank 62 can be connected by pump 63 usefulness pipelines with sewage disposal chamber 1, stripping has the sewage of calcium ion and/or magnesium ion to be drunk up by pump 63 in the dissolving tank 62, flows into sewage disposal chamber 1.Also can make dissolving tank be in the high position of ratio sewage treatment chamber in addition, the sewage that is dissolved with calcium ion and/or magnesium ion is flowed into naturally to sewage disposal chamber direction.
In the embodiment shown in Figure 12, owing to be that the sewage that is dissolved with calcium ion and/or magnesium ion is sent into the sewage disposal chamber, the outlet number and the position of above-mentioned pipeline can change, so can more easily control calcium ion and/or magnesium ion concentration in the sewage disposal chamber than embodiment shown in Figure 11.
The form of enforcement shown in Figure 13 is source 60 to be taken place ion place tradable cartridge type cover to be placed in the inflow side afterwards again.This formation be owing to can take off cover simply, so can easily carry out maintenance work such as supply ion generation source.
In addition, used the electrode of a pair of relative configuration in the embodiment shown in Figure 11～13, but for the present invention, the configuration of counter electrode and number can suitably be set the number of electrodes of anode side and cathode side and all changes are done in its configuration all without limits.For example, shown in Fig. 8 (a), the plural electrode array group 24 of cathode side and the plural electrode array group 25 of anode side are disposed relative to each other as described above.Or shown in Fig. 8 (b), can make electrode 34 alternately configured of the electrode 35 and the cathode side of anode side, in addition, the number of electrodes of anode side and cathode side is different also passable.
Following of the present invention the 4th～6 invention according to embodiment describes, but the present invention is not subjected to the restriction of these embodiment.
Use the electrolysis stripping waste disposal plant of iron shown in Figure 11, flowing into phosphorus acid ion concentration from influx with 1 liter/minute flow velocity is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (as H
3PO
4Add) and contain Na
+The confession examination sewage of 200 mg/litre.
As the electrode that floods in the sewage, make with highly purified iron plate.In addition, the ion generation source that disposes in the sewage disposal chamber is 1000 milligrams of lime carbonate with the net parcel.The energising amount of electrode 1.5 was set at 1.2 amperes for making Fe/P, made reversal of poles every 0.5 hour.
By carrying out electrolysis at electrode, the stripping simultaneously of iron ion and calcium ion.Because the solubleness of lime carbonate is 15 mg/litre in the water of 25 ℃ of temperature, institute above 2 mg/litre, is 6 mg/litre for the calcium ion concn in the examination sewage.
Switching on after 2 hours, collect sewage from spout 4, is that 0.45 micron filter filters with the aperture, and gained filtrate is according to full phosphorus analytical method (46, the 3) mensuration of JIS K0102, and what the result showed phosphorus removes efficient more than 90%.
Except the lime carbonate among the embodiment 7 is replaced with the higher calcium hydroxide of solubleness, other under same experiment condition, to carry out with sampling device.
Be 12 mg/litre from the effusive calcium ion concn for examination sewage of spout this moment.
Through embodiment 7 after half conduction time, measure the content of phosphorus with embodiment 7 same procedure, its result shows and removes efficient more than 90%.And, because the calcium ion concn of present embodiment is 2 times of calcium ion concn of previous embodiment 7, can obtains identical phosphorus and remove efficient (more than 90%) so be half of embodiment 7 visible conduction time, spent electric energy also can reduce by half.
From the above description as can be seen, can be according to the 4th～6 invention of the present invention efficiently except that the phosphate anion in the decontaminated water, and can reduce the electric energy that expends as the consumption of the iron of electrode or aluminium and for stripping, thereby can make sewage disposal long-time continuous running under low power consumption.
Below explanation the 7th～8 invention of the present invention.
As shown in figure 14, treatment unit is by the sewage disposal chamber 1 with effluent stream inlet 3 and spout 4, has at least a part to be immersed in the pair of electrodes in this treatment chamber 1 sewage and the power supply 6 that this electrode is switched on constituted.
Above-mentioned pair of electrodes 74,75 can be with any be made in platinum, gold, carbon, silver, the titanium etc., if but make with platinum, little metal or the carbon of golden plasma tendency, thereby then the life-span that makes electrode prolongs because the stripping of electrode self tails off.
In the present embodiment, if to above-mentioned electrode 74,75 energisings, then the liquid matter around the cathode side electrode 74 becomes alkalescence because of the hydroxide ion in the sewage, and the liquid matter around the anode side electrode 75 becomes acidity because of hydrogen ion concentration in the sewage increases.Like this, for making the CaCl that drops in the sewage
2Or FeCl
3Regulate and to need only the magnitude of current of regulating between the electrode 74,75 without the pH regulator agent Deng the pH value that reacts.For example, drop into CaCl
2When as calcium ion the source taking place, because CaC1
2The rate of removing to phosphorus under alkaline condition increases, and then it is dropped near electrode 74.The calcium ion of stripping and the insoluble phosphoric acid salt of phosphate anion water generation reaction in the sewage thus.Therefore, under the form of this enforcement, can save and be used to regulate the watching device of pH and the regular adding of pH regulator agent.
Concerning above-mentioned power supply 6, preferably with control electrode 74,75 between the control device 9 of electric current be connected.The surface of anode side electrode 75 produces the oxide film thereon of organism such as protein and inorganics, and the surface of cathode side electrode 74 is washed by the hydrogen that cathode side produces, and does not produce oxide film thereon.Thus, by above-mentioned control device 9, when the surface of anode side electrode 75 produces oxide film thereon and makes and make the polarity of electrode counter-rotating when resistance increases between two electrodes 74,75 at regular intervals at interval.So just can make the electric current between two electrodes 74,75 keep certain level substantially, the liquid matter that liquid matter around the cathode side is kept around alkalescence, the anode side is kept acidity.In addition, for the time of counter-rotating, preferred more than 1 hour.
In the scheme of this enforcement, be that the generation source of calcium ion and/or magnesium ion is dropped near the electrode 74 of cathode side.Shown in Figure 14 78 is the throwing device that sewage is dropped in above-mentioned ion generation source.As throwing device 78, when ion generation source is fluid states such as the aqueous solution, can be with the container in source taking place and the method for supplying that the source is formed by the feedwaies of quantitatively sending such as for example pump of constant delivery type is taken place ion for adding ion, when being saccharoid in ion generation source in addition, the source takes place by the feedway of quantitatively sending with ion in available loading hopper or funnel etc.
The source takes place for above-mentioned ion has calcium ion that source, magnesium ion take place respectively three kinds in ion generation source that source and they combine etc. takes place.The source takes place as above-mentioned calcium ion, can be with the water-soluble salt of calcium metal or calcium etc.The source takes place as above-mentioned magnesium ion, can with MAGNESIUM METAL or magnesium water-soluble salt.As the concrete example of water-soluble salt, except the former calcium chloride as agglutinant (solubleness is 59.5 grams/100 gram water) can also be with calcium hydroxide (solubleness is 1 85 millimeters/100 gram water), lime carbonate (solubleness is 1.4 milligrams/100 gram water), magnesium chloride (solubleness is that 52.8 grams/100 restrain water), magnesium oxalate (solubleness be 70 milligrams/100 restrain water) etc.At this wherein, if from directly being dissolved in aspect preferably calcium chloride, argon calcium oxide and the magnesium chloride etc. that just can produce a large amount of calcium ions or magnesium ion the water.In addition, when using the little salt of solubleness, can make it to become the aqueous solution in advance and drop into again.
In the embodiment shown in Figure 14, if with electrode 74,75 energising, then cathode side electrode 74 around become alkalescence, the insoluble phosphoric acid salt of phosphate anion water generation reaction in calcium ion of stripping (magnesium ion) and the sewage.
In the embodiment depicted in fig. 14, be near source input cathode side electrode 74 to be taken place for calcium ion and/or magnesium ion from throwing device 78, but for the present invention, be not limited in this, such as shown in figure 15, also can iron ion and/or aluminum ion generation source be dropped near anode side electrode 85 from throwing device 88.As above-mentioned iron ion the source taking place, can use the water-soluble salt of iron etc.As for the water-soluble salt specific examples of iron, can be iron protochloride, Iron nitrate, ferrous sulfate etc.At this wherein, from the direct aspect that just can produce a large amount of iron ions soluble in water, preferred iron protochloride.In addition, when using water-soluble little salt, also can be pre-formed aqueous solution form input.
In addition, as aluminum ion the source taking place, can use the water-soluble salt of aluminium etc.As the water-soluble salt concrete example of above-mentioned aluminium, can enumerate aluminum nitrate, Tai-Ace S 150 etc.At this wherein, with direct a large amount of aluminum ions aspects preferred aluminum nitrate that sets out that just can produce soluble in water.In addition, when using water-soluble little salt, also can be pre-formed the aqueous solution and drop into again.
In the embodiment depicted in fig. 15, if with electrode 84,85 energising, then anode side electrode 85 around become acidity, the iron ion of stripping (aluminum ion) and the insoluble phosphoric acid salt of phosphor in sewage acid ion water generation reaction.
In addition as shown in figure 16, also can near cathode side electrode 94, drop into the generation source of calcium ion and/or magnesium ion from throwing device 98a, from throwing device 98b input iron ion and/or aluminum ions generation source near anode side electrode 95.
In addition, in the embodiment shown in Figure 14～16, because the sewage of sewage disposal chamber constantly flows, if the flow velocity of sewage is too fast, alkaline sewage around the cathode side electrode and the sour water around the anode side electrode mix easily, will be difficult to keep the acidity of liquid matter around the alkalescence of liquid matter around the cathode side and the anode side like this.In this case, preferably between two electrodes 104,105 shown in Figure 17, dispose barrier film 100, thereby the alkaline sewage of cathode side and the sour water of anode side can not mixed.As above-mentioned barrier film 100, can make with for example nylon, polypropylene etc.In addition as the configuration of barrier film 100, should be configured to make above-mentioned electrode 104,105 around the mobile of sewage become slow.Also can control drainage flow with earthen dividing plate replacement barrier films such as (aluminum oxide, zirconium whites).
In addition, used the electrode of a pair of subtend configuration in the embodiment shown in Figure 14～17, but for the present invention, the configuration of counter electrode and number are all unqualified, can suitably set the number of electrodes of anode side and cathode side and all changes are done in its configuration.For example, shown in Fig. 8 (a), can make the plural electrode array group 25 mutual subtend configurations of the plural electrode array group 24 and the anode side of cathode side as described above.Or shown in Fig. 8 (b), the electrode 35 of anode side and the electrode 34 of cathode side are become for configuration.In addition, the electrode number of anode side and cathode side also can be different.But, for the acidic region between the electrode that makes relative configuration and alkaline zone be unlikely to too near and need vacate certain distance, preferably can set barrier film (plate).
Followingly the 7th～8 invention of the present invention is described, but the present invention is not limit by these embodiment according to embodiment.
Use waste disposal plant shown in Figure 15, flowing into phosphorus acid ion concentration from influx with 1 liter/minute flow velocity is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (as H
3PO
4Add) and contain Na
+The confession examination sewage of 200 mg/litre.
As the electrode that floods in sewage platinum plate.And the source takes place as ion in 35 milligrams of calcium chloride of input near the cathode side electrode.For making Ca/P is that the 2.0 energising amounts with electrode are made as 1.2 amperes.
Switch on after 2 hours, collect sewage from spout, the filter that with the aperture is 0.45 micron is according to full phosphorus analytical method (46.3) mensuration of JIS K0102, and what the result showed phosphorus removes efficient more than 90%.
Use waste disposal plant shown in Figure 16, flowing into phosphorus acid ion concentration from influx with 1 liter/minute flow velocity is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (as H
3PO
4Add) and contain Na
+The confession examination sewage of 200 mg/litre.
As the electrode that floods in the sewage, use the platinum plate.And the source takes place as ion near the iron trichloride that drops into 39 milligrams anode side electrode.For making Fe/P is that the 2.0 energising amounts with electrode are made as 1.2 amperes.
Switch on after 2 hours, carry out the phosphorus content identical with embodiment 9 and measure, what its result showed phosphorus removes efficient more than 90%.
Embodiment 11
Use treatment unit shown in Figure 17, flowing into phosphorus acid ion concentration from influx with 1 liter/minute flow velocity is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (as H
3PO
4Add) and contain Na
+The confession examination sewage of 200 mg/litre.
The electrode that floods in sewage platinum plate.And the source takes place as ion in the calcium chloride of 7 milligrams of inputs near the cathode side electrode, and near the iron trichloride that drops into 31 milligrams simultaneously the electrode of anode side as ion the source takes place.Ca/P is 2.0 in order to make, Fe/P is that the 1.5 energising amounts with electrode are made as 1.2 amperes.
Through embodiment 9～10 after half time, carry out the phosphorus content identical and measure with embodiment 9～10, its result shows, at ion the source input amount takes place and removes efficient more than 90% for the half phosphorus of embodiment 9～10.
According to the 7th～8 invention of the present invention, can easily carry out the control of pH, and can remove phosphate anion at low cost.
Below explanation the 9th～10 invention of the present invention.
The 9th invention of the present invention relates to and will contain the above sewage water treatment method of sewage pH regulator to 8 of phosphate anion and calcium ion and/or magnesium ion.
If have phosphate anion, calcium ion and/or magnesium ion in the sewage, then calcium ion and/or magnesium ion and phosphate anion are at alkaline side water generation reaction insoluble salt.The 9th～10 invention of the present invention utilizes the calcium ion and/or the magnesium ion that exist in the sewage to remove phosphate anion just like this from sewage.
Sewage as the 9th～10 invention process object of the present invention, contain phosphate anion and calcium ion and/or magnesium ion, and above-mentioned ionic concn can get final product for the stoichiometry that can form water-insoluble salt, if but the aspect from can high-level efficiency handling then preferably contains phosphate anion 9～21 mg/litre, calcium ion and/or magnesium ion 6～23 mg/litre.
For above-mentioned water-insoluble salt,, may form the salt of various forms such as independent salt, moisture salt according to the reaction conditions difference.Therefore the said water-insoluble salt of the present invention is the salt that forms with phosphoric acid, comprises the salt that phosphoric acid and calcium and phosphoric acid and magnesium form.
The time that this phosphate anion and calcium ion and/or magnesium ion form water-insoluble salt approximately is to contain these ionic sewage to have alkaline the time, for the 9th～10 invention of the present invention, in order to make above-mentioned water-insoluble salt be easy to form, can regulate pH more than 8, preferably more than 9.
For the method for the pH of the sewage of regulating phosphorus-containing acid ion, calcium ion and/or magnesium ion, do not have special qualification, but from easy and simple to handle, general domestic sewage handled the aspect that is easy to adopt consider, preferably adding pH regulator agent in the sewage.
As the pH regulator agent under this situation, so long as can regulate above the getting final product of pH to 8 of above-mentioned sewage, but after using, need not aspects considerations such as processing and environmentally safe, preferably use damping fluid.
As this damping fluid, as long as can keep pH more than 8, such as can enumerate boric acid-sodium hydrate buffer solution, sodium bicarbonate-sodium hydrate buffer solution etc., but consider from the high aspect of reactivity, sodium bicarbonate-sodium hydrate buffer solution then preferably used.
In addition, if consider with calcium hydroxide also to be preferred from reaching additional calcium ion source effect aspect as the pH regulator agent from other viewpoint.
In addition, the 10th invention of the present invention relates to the waste disposal plant that can implement the aforementioned processing method.
This waste disposal plant as shown in figure 18, be the treatment unit that contains phosphate anion and calcium ion and/or magnesium ion sewage, thereby add the pH regulator agent adding set 117 of pH regulator agent by the pH meter 115 that detects sewage pH value, in sewage and instruct the pH value that makes sewage to maintain that pH control device 116 more than 8 forms to pH regulator agent adding set transmission interpolation less than 8 the time when pH meter detects pH value.
In addition, the waste disposal plant of the 10th invention of the present invention as shown in figure 18, preferably is provided with the whipping appts 119 that is used to stir sewage 2 in the sewage treatment tank 1 with influx 3 and spout 4.
Also have, the pH regulator agent is that the instruction of pH regulator agent adding set 117 response pH control device 1 16 supplies in the treatment trough 1 from pH regulator agent groove 118, but what qualification this supply mode does not have.
Followingly the treatment process and the treatment unit of the 9th～10 invention of the present invention are described, but the present invention is not subjected to the restriction of these embodiment according to embodiment.
Embodiment 12～16 and comparative example 1
Using the waste disposal plant of the 10th invention of the present invention as shown in figure 18, is that 15 mg/litre or phosphorus concentration are that 5 mg/litre are (as H as using phosphorus-containing acid ion concentration for examination sewage
3PO
4Interpolation), Ca
2+14 mg/litre are (as Ca (OH)
2Add) and Mg
2+10 mg/litre are (with MgCl
2Mode is added) water (pH7).
Above-mentioned for of the flow inflow of examination sewage with 1 liter/hour.
In addition, as the pH regulator agent, can adopt various damping fluids: with (0.2MH with following composition
3BO
3+ 0.2MKCl): 0.2M NaOH: the buffer A (pH9) that water=50: 21: 130 (milliliter) ratio is made into, with (0.2MH
3BO
3+ 0.2MKCl): 0.2M NaOH: the buffer B (pH10) that water=50: 44: 110 (milliliter) ratio is made into, with 0.05M NaHCO
3: 0.1M NaOH: the damping fluid C (pH11) that water=50: 11: 40 (milliliter) ratio is made into, with 0.2M KCl: 0.2M NaOH: the damping fluid D (pH12) that water=25: 6: 70 (milliliter) ratio is made into, with 0.2M KCl: 0.2M NaOH: the damping fluid E (pH13) that water=25: 66: 9 (milliliter) ratio is made into, with 0.1M Trisaminomethane: 0.1MHCl: the damping fluid F (pH7) that water=50: 47: 5 (milliliter) ratio is made into etc.Each damping fluid is being measured its pH value after beginning to flow into 2 hours for examination sewage, as for the phosphorus acid ion concentration of handling in the sewage of back, gather sewage from spout 4, via hole diameter is that gained filtrate was measured according to the full phosphorus analytical method (46.3) of JIS K0102 after 0.45 micron filter filtered.
Its result is as shown in table 1.
Table 1
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative example 1 | |
| The kind of damping fluid | ????A | ????B | ????C | ????D | ????E | ????F |
| ????pH | ????8.0 | ????9.0 | ????10.0 | ????11.0 | ????12.0 | ????7.0 |
| Phosphorus acid ion concentration (mg/litre) | ????7.5 | ????1.5 | ????1.0 | ????1.0 | ????1.0 | ????15 |
Embodiment 17～21
Among the embodiment 12, except as being that 15 mg/litre or phosphorus concentration 5 mg/litre are (as H with containing phosphorus acid ion concentration for examination sewage
3PO
4Add) and Ca
2+16 mg/litre (are made Ca (OH)
2Add) water (pH7) in addition, other and embodiment 12 be the same to carry out identical sewage disposal, the sewage after the processing is also with the method mensuration phosphorus acid ion concentration identical with embodiment 12.
The result is as shown in table 2
Table 2
Embodiment 22～26
| Embodiment 17 | Embodiment 18 | Embodiment 19 | | Embodiment 21 | Comparative example 1 | |
| The kind of damping fluid | ????A | ????B | ????C | ????D | ????E | ????F |
| ????pH | ????8.0 | ????9.0 | ????10.0 | ????11.0 | ????12.0 | ????7.0 |
| Phosphorus acid ion concentration (mg/litre) | ????7.5 | ????1.0 | ????1.0 | ????1.0 | ????1.0 | ????15 |
Except to contain phosphorus acid ion concentration be that 15 mg/litre or phosphorus concentration 5 mg/litre are (as H as adopting for examination sewage
3PO
4 2Add) and Mg
2+11 mg/litre are (as MgCl
2Add) water (pH7) in addition, other and embodiment 12 be the same to carry out identical sewage disposal, the sewage after the processing is also with the method mensuration phosphorus acid ion concentration identical with embodiment 12.
The result is as shown in table 3
Table 3
| Embodiment 22 | Embodiment 23 | | | Embodiment 26 | Comparative example 1 | |
| The kind of damping fluid | ????A | ????B | ????C | ????D | ????E | ????F |
| ????pH | ??8.0 | ??9.0 | ??10.0 | ??11.0 | ??12.0 | ??7.0 |
| Phosphorus acid ion concentration (mg/litre) | ??9.0 | ??2.0 | ??2.0 | ??1.5 | ??1.5 | ??15 |
Can be according to the 9th～10 invention of the present invention expeditiously except that the phosphate anion in the decontaminated water.
Claims (20)
1. sewage water treatment method, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, with electrochemical method stripping iron ion and/or aluminum ion in containing the sewage of sewage, make phosphate anion and iron ion and/or the aluminum ion form coagulation sedimentation with water-insoluble salt, the total concentration of the calcium ion concn in the processed sewage, magnesium ion concentration or calcium ion and magnesium ion is more than 2 mg/litre.
2. sewage water treatment method, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, with electrochemical method stripping iron ion and/or aluminum ion in the sewage of phosphorus-containing acid ion, make phosphate anion and iron ion and/or aluminum ion form coagulation sedimentation, in former electrodes, have the generation source of calcium ion and/or magnesium ion with water-insoluble salt.
3. used electrode in the sewage water treatment method of claim 2 record is characterized in that generation source and the iron ion and/or the aluminum ions generation source of calcium ion and/or magnesium ion wherein arranged.
4. the treatment unit of a phosphorus-containing acid ion sewage, it is characterized in that, be immersed in the electrode in the sewage in this treatment chamber and the power supply of this electrifying electrodes formed by sewage disposal chamber, at least a portion with effluent stream inlet and spout, described electrode has at least one to have calcium ion and/or magnesium ion generation source and iron ion and/or aluminum ion generation source.
5. sewage water treatment method, it is characterized in that, employing contains iron ion and/or aluminum ions electrode, with electrochemical method stripping iron ion and/or aluminum ion in the sewage of phosphorus-containing acid ion, make phosphate anion and iron ion and/or aluminum ion form coagulation sedimentation, in sewage, have the generation source of calcium ion and/or magnesium ion with water-insoluble salt.
6. the calcium ion that uses in the sewage water treatment method of claim 5 record and/or the generation source of magnesium ion, it is characterized in that, wherein contain from calcium metal, MAGNESIUM METAL and can be sewage select in the group formed of the compound of stripping calcium ion and/or magnesium ion at least a.
7. the treatment unit of a phosphorus-containing acid ion sewage, it is characterized in that, be immersed in the electrode in the sewage in this treatment chamber and the power supply of this electrifying electrodes formed by sewage disposal chamber, at least a portion with effluent stream inlet and spout, have at least an electrode to have iron ion and/or aluminum ion the source takes place, and before aforementioned influx or be provided with the generation source of calcium ion and/or magnesium ion in the sewage disposal chamber.
8. sewage water treatment method, it is characterized in that, with the form coagulation sedimentation of the phosphate anion in the sewage with water-insoluble salt, in sewage, there is pair of electrodes at least and passes to direct current, near negative electrode, drop into the generation source of calcium ion and/or magnesium ion, simultaneously/or near anode, drop into iron ion and/or aluminum ions generation source.
9. the sewage water treatment method of putting down in writing according to Claim 8 is characterized in that, is provided with barrier film or next door between anode and negative electrode.
10. treatment unit that contains phosphate anion sewage, it is characterized in that, form by the sewage disposal chamber that has effluent stream inlet and spout, at least one pair of electrode and to the power supply that this counter electrode is switched on, described electrode is set in the treatment chamber, and at least a portion is by the sewage submergence, when aforesaid pair of electrodes is switched on, near the device that has the generation source of dropping into calcium ion and/or magnesium ion the electrode as negative electrode, simultaneously/or near anode, have the device that drops into iron ion and/or aluminum ion generation source.
11. the waste disposal plant according to claim 10 record is characterized in that, is provided with barrier film or next door between anode and negative electrode.
12. the treatment process of a sewage is characterized in that, the pH value of the sewage of phosphorus-containing acid ion and calcium ion and/or magnesium ion is adjusted to more than 8.
13. the sewage water treatment method according to claim 12 record is characterized in that, regulates the pH value and realizes by adding the pH regulator agent.
14. the sewage water treatment method according to claim 13 record is characterized in that the pH regulator agent is a damping fluid.
15. the sewage water treatment method according to claim 12,13 or 14 each records is characterized in that, the pH value is adjusted to more than 9.
16. the sewage water treatment method according to claim 12,13,14 or 15 each records is characterized in that, wherein said sewage is sanitary sewage.
17. a treatment unit that contains the sewage of phosphate anion and calcium ion and/or magnesium ion, by forming with the lower section:
Detect the pH meter of sewage pH value,
In sewage, add the pH regulator agent pH regulator agent adding apparatus and
When the detection pH of this pH meter less than 8, send interpolation pH regulator agent instruction to pH regulator agent adding apparatus and keep sewage pH value at the pH value control device more than 8.
18. the treatment unit according to claim 17 record is characterized in that, setting control device is more than 9 with the pH that keeps sewage.
19. the treatment unit according to claim 17 or 18 records is characterized in that used pH regulator agent is a damping fluid.
20. the treatment unit according to claim 17,18 or 19 each records is characterized in that, wherein said sewage is sanitary sewage.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP327362/96 | 1996-12-06 | ||
| JP327362/1996 | 1996-12-06 | ||
| JP32736296 | 1996-12-06 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031381324A Division CN1515501A (en) | 1996-12-06 | 1997-12-05 | Treatment device of sewage water containing phosphate radical ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184782A true CN1184782A (en) | 1998-06-17 |
| CN1119292C CN1119292C (en) | 2003-08-27 |
Family
ID=18198305
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031381324A Pending CN1515501A (en) | 1996-12-06 | 1997-12-05 | Treatment device of sewage water containing phosphate radical ion |
| CN97125437A Expired - Fee Related CN1119292C (en) | 1996-12-06 | 1997-12-05 | Method and apparatus for treating wastewater contg. phosphoric acid radical |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031381324A Pending CN1515501A (en) | 1996-12-06 | 1997-12-05 | Treatment device of sewage water containing phosphate radical ion |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100404863B1 (en) |
| CN (2) | CN1515501A (en) |
| TW (1) | TW445240B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601270A (en) * | 2013-11-22 | 2014-02-26 | 苏州优德通力电气有限公司 | Electrolysis phosphorus removal device capable of reducing anode passivation |
| CN104603066A (en) * | 2012-08-06 | 2015-05-06 | 金属系统隔离有限责任公司 | Method and plant for the reduction of the concentration of pollutants and/or valuable elements in the water |
| CN105110523A (en) * | 2015-09-11 | 2015-12-02 | 燕山大学 | Method for treating swine wastewater |
| CN107298489A (en) * | 2017-07-25 | 2017-10-27 | 武汉轻工大学 | The method that high calcium high chloride ion coexists in electrochemical reactor and removal waste water |
| CN109179631A (en) * | 2018-08-06 | 2019-01-11 | 清华大学 | The anaerobism electrochemical membrane bioreactor of dephosphorization can be synchronized |
| CN115321649A (en) * | 2022-08-19 | 2022-11-11 | 常州大学 | Treatment device and treatment method for black and odorous water body |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100441405B1 (en) * | 2001-11-01 | 2004-07-23 | 한국과학기술연구원 | A method for anion removal by forming chemical precipitation under an electric field and a continuous process for anion removal |
-
1997
- 1997-11-14 TW TW086117052A patent/TW445240B/en active
- 1997-12-03 KR KR1019970065504A patent/KR100404863B1/en not_active IP Right Cessation
- 1997-12-05 CN CNA031381324A patent/CN1515501A/en active Pending
- 1997-12-05 CN CN97125437A patent/CN1119292C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104603066A (en) * | 2012-08-06 | 2015-05-06 | 金属系统隔离有限责任公司 | Method and plant for the reduction of the concentration of pollutants and/or valuable elements in the water |
| CN103601270A (en) * | 2013-11-22 | 2014-02-26 | 苏州优德通力电气有限公司 | Electrolysis phosphorus removal device capable of reducing anode passivation |
| CN105110523A (en) * | 2015-09-11 | 2015-12-02 | 燕山大学 | Method for treating swine wastewater |
| CN107298489A (en) * | 2017-07-25 | 2017-10-27 | 武汉轻工大学 | The method that high calcium high chloride ion coexists in electrochemical reactor and removal waste water |
| CN109179631A (en) * | 2018-08-06 | 2019-01-11 | 清华大学 | The anaerobism electrochemical membrane bioreactor of dephosphorization can be synchronized |
| CN115321649A (en) * | 2022-08-19 | 2022-11-11 | 常州大学 | Treatment device and treatment method for black and odorous water body |
| CN115321649B (en) * | 2022-08-19 | 2024-04-05 | 常州大学 | Black and odorous water body treatment device and treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| TW445240B (en) | 2001-07-11 |
| KR19980063730A (en) | 1998-10-07 |
| CN1515501A (en) | 2004-07-28 |
| KR100404863B1 (en) | 2004-03-30 |
| CN1119292C (en) | 2003-08-27 |
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