CN1741967A - Method for removing phosphorus in wastewater - Google Patents
Method for removing phosphorus in wastewater Download PDFInfo
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- CN1741967A CN1741967A CNA2004800028552A CN200480002855A CN1741967A CN 1741967 A CN1741967 A CN 1741967A CN A2004800028552 A CNA2004800028552 A CN A2004800028552A CN 200480002855 A CN200480002855 A CN 200480002855A CN 1741967 A CN1741967 A CN 1741967A
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Inorganic Chemistry (AREA)
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Abstract
A method for removing phosphorus in wastewater, which comprises a first crystallization step of reacting, in a first crystallization vessel, a phosphorus-containing wastewater, calcium chloride and a recycled hydroxyapatite slurry recycled form a precipitation tank and crystallizing, while adjusting the pH of the reaction mixture by the use of a pH-adjusting agent, a second crystallization step of feeding the slurry formed in the first step to a second crystallization vessel, adding calcium chloride to the slurry, to carry out further reaction and crystallization at a pH higher than that in the first crystallization vessel and of 11 or lower, and a step of feeding the slurry formed in the second step to a precipitation tank, carrying out precipitation and separation, discharging a resultant supernatant to the outside of the system as a treated water, and recycling most of the resultant concentrated slurry as the above-mentioned hydroxyapatite slurry. The above method allows the removal of phosphorus in a waste water without the use of a coagulant and also the formation of a hydroxyapatite excellent in filtration and dewatering characteristics from a phosphorus-containing waste water.
Description
Technical field
The present invention relates to the dephosphorizing method of draining, in detail, relate to the dephosphorizing method that from the phosphoric acid draining, carries out the settlement separate draining of hydroxyapatite without flocculation agent.
Background technology
In recent years, the pollution of enclosed waterss such as inland sea, lake had become problem, was the eutrophication that phosphorus compound causes as one of this pollution cause.Therefore, before this dephosphorization treatment method of phosphorous draining all discussions have been carried out.Wherein, the spy of patent documentation 1 opens clear 56-33082 communique, discloses phosphatic water in the presence of calcium ion, after the crystal seed of phosphoric acid calcium contacts, and the phosphatic water treatment method that contacts with activated alumina again.In addition, the spy of patent documentation 2 opens clear 58-143884 communique, after disclosing the employing biologic treatment process and handling organic sewage, contacts the method for processing with the dephosphorization material of the granular solids of phosphoric acid calcium.In addition, the spy of patent documentation 3 opens clear 62-38291 communique, when disclosing the phosphorus compound that contains in removing waste water, separates out material as the dephosphorization crystal, adopts the dephosphorization treatment method by the jointing compound of phosphate ion pre-treatment.Any of these methods all is to carry out crystal by contact to separate out isolating dephosphorization treatment method.
In addition, to the waste water of discharging from the chemical plant of manufacturing or use yellow phosphorus, phosphoric acid, phosphoric acid salt and phosphorus compound etc., and make the waste water that the plated by electroless plating factory of reductive agent discharges with phosphorous acid, for example carry out oxidation and after producing the oxo phosphate ion, handle the waste water that this contains the oxo phosphate ion again.In this embodiment, because the phosphoric acid concentration in the processed water reaches the high density of 300～30000ppm, so separate out partition method if want to adopt above-mentioned existing crystal by contact, with calcareous granular solids dephosphorization agent with before packing layer or fluidised bed contact, in stoste, add the calcium agent, or the pH value is adjusted to meta-alkalescence.At this moment, the problem of existence is to generate trickle hydroxylapatite crystal, and liquid becomes the white casse of milk sample, can not effectively remove phosphate ion.
When this draining that contains high-concentration phosphoric acid is handled, can adopt sulfuric acid alumina [Al
2(SO
4)
3] or iron(ic) chloride (FeCl
3) etc., as insoluble aluminum phosphate or tertiary iron phosphate, the method for from waste water, removing.At this moment, only pH value is arranged, adjust Ph and, carry out coagulative precipitation at settling bowl with after medicament mixes.From the white casse liquid of milk sample, remove phosphoric acid for the dephosphorization agent that adopts calcareous granular solids, have to adopt and add the method that polymeric flocculant carries out coagulative precipitation.
(patent documentation 1) spy opens clear 56-33082 communique (claim 1～3)
(patent documentation 2) spy opens clear 58-143884 communique (claim 1)
(patent documentation 3) spy opens clear 62-38291 communique (claim 1)
(patent documentation 4) spy opens 2001-70951 communique (claim 1)
But, adopting sulfuric acid alumina [Al2(SO
4)
3] or iron chloride (FeCl3) etc. method in because this sulfuric acid alumina etc. except as the crystallizing agent, also can be used as flocculant to use, so, must use the above a large amount of medicaments of phosphoric acid equivalent, exist the problem that processing cost raises. In addition, produce pro rata a large amount of mud with the medicament injection rate, but because this mud is clamminess, settleability, concentrated property and dehydration property extreme difference are so exist the problem that the processing cost such as dry expense rises. In addition, the JP 2001-70951 communique of patent documentation 4 is developed, after in the mud regulating tank, calcium compound and mud being mixed, for example stop more than 5 days, particularly stop 7～50 days long-time after, in the reactive tank that is consisted of by a groove, mix with phosphorous water, obtain the calcium salt of phosphorus, add again the flocculant such as polyacrylamide and carry out coagulative precipitation and process, after the Separation of Solid and Liquid, the part of the mud that obtains is transferred to the processing method of the phosphorous water that is returned behind pH7～12. Yet, in this method, owing to use flocculant, so processing cost raises, exist the problem that can not get the good mud of filterability.
Therefore, the purpose of this invention is to provide and a kind ofly do not use flocculant and remove phosphoric acid in the draining, simultaneously, from the phosphoric acid draining, generate the draining dephosphorization method of the good hydroxyapatite of filterability and dehydration property.
Summary of the invention
The invention provides a kind of dephosphorizing method of draining, this method adopts by the order of the 1st crystallizer tank, the 2nd crystallizer tank and the subsider treatment unit of configured in series successively, from the phosphoric acid draining, Crystallization Separation goes out the dephosphorizing method of the draining of hydroxyapatite, it is characterized in that, in above-mentioned the 1st crystallizer tank, return hydroxyapatite mud with above-mentioned phosphorous draining, calcium chloride and from what above-mentioned subsider returned, the limit is regulated the pH limit with the pH regulator agent and is reacted and separate out crystalline the 1st Crystallization Procedure; Make the mud that obtains from the 1st Crystallization Procedure flow into the 2nd crystallizer tank, add calcium chloride and pH regulator agent, at the pH height of pH than the 1st crystallizer tank, and under the situation below the pH11, further crystalline the 2nd Crystallization Procedure is separated out in reaction; Make the mud that obtains in above-mentioned the 2nd Crystallization Procedure flow into subsider, carry out settlement separately, supernatant liquor is drained into outside the system as treating water, the mud that major part is concentrated is as the above-mentioned draining dephosphorizing method that returns hydroxyapatite mud.
Description of drawings
Fig. 1 is one of the treatment unit that uses in a draining dephosphorizing method of the present invention example.
Fig. 2 is the solubility curve figure of hydroxyapatite.
Embodiment
The dephosphorizing method of the draining that the present invention relates to, adopt by the order of the 1st crystallizer tank, the 2nd crystallizer tank and the subsider treatment unit of configured in series successively, carry out the 1st Crystallization Procedure, the 2nd Crystallization Procedure and precipitate and separate successively, from going out hydroxyapatite as Crystallization Separation the phosphoric acid draining of processed liquid.
In the 1st Crystallization Procedure, flow into phosphoric acid draining, calcium chloride and return hydroxyapatite (below title " HAP ") mud from what subsider returned to the 1st crystallizer tank.As this phosphoric acid draining, be not particularly limited, for example can enumerate the draining of phosphorous acid number ppm to number weight %, wherein, be particularly suitable for the dephosphorization of the high density draining of phosphoric acid 100ppm～10000ppm.Specifically, be that the draining from phosphoric acid production factory, fertilizer plant, metal finishing factory, plated by electroless plating factory or semiconductor device factory, the draining of general family reach water treatment draining down etc.As calcium chloride, be not particularly limited, as long as industrial availablely all can adopt.
Return HAP mud, mean the HAP mud that in subsider, is concentrated, supply to the unit time feed rate of the 1st crystallizer tank, with respect to unit time feed rate 100 parts by volume of the phosphoric acid draining that supplies to the 1st crystallizer tank, be more than 50 parts by volume, be preferably more than 100 parts by volume.In addition, supply to the unit time feed rate that is converted into solids component of returning HAP mud of the 1st crystallizer tank, be converted into unit time feed rate 100 weight parts of HAP with respect to the phosphoric acid that contains in the phosphoric acid draining that will supply to the 1st crystallizer tank, be more than 2500 weight parts, be preferably more than 4000 weight parts.With the HAP that produces in the 1st crystallizer tank, by contacting with its a large amount of HAP crystal seeds more than 25 times of weight, the HAP crystallization is separated out on the HAP particle, in device, carry out repeatedly circulation more than 25 times by the HAP that is increased grain, can obtain stokes particle diameter 10 μ m above, particle dia is big and settleability and the good HAP of filterableness.Also have, in the 1st crystallizer tank, return the solid component concentration of HPA mud, it is preferred often reaching more than the 2 weight %.When this concentration was lower than 2 weight %, crystal seed was very few, and the crystallization of HAP can not be carried out on the crystal seed of the HAP mud that returns, and generated grain, had the worry that produces gonorrhoeaization, so be unfavorable.
In the 1st Crystallization Procedure, the unit time feed rate that supplies to the calcium chloride of the 1st crystallizer tank is set at, and the phosphoric acid that supplies to the phosphoric acid draining of the 1st crystallizer tank is converted into below the necessary theoretical equivalent of HAP.Being set in the following reason of theoretical equivalent is, because in the 1st crystallizer tank, be in phosphate ion concentration and carry out reactive crystallization under the high state, therefore, by reducing calcium ion as another material of reaction, the solubleness of HAP is strengthened, and degree of supersaturation reduces, thereby can suppress the generation as 1 nuclear of grain.
As the pH in the 1st crystallizer tank, adjust to 5.5～8.0, preferably adjust to 6.5～7.5 scope.The pH of this moment adjusts, and is different with the occasion of pure water, is in the centre of phosphoric acid ionic the 1st point of neutralization and the 2nd point of neutralization, so adjust than being easier to carry out pH.In the 1st crystallizer tank, if pH is adjusted to 5.5～8.0, then the solubleness of the HAP in the 1st crystallizer tank strengthens, and degree of supersaturation descends, so can suppress the generation of 1 nuclear.When pH was lower than 5.5, the dissolving of the HAP that crystallization is separated out became easily, was unfavorable.
As the pH regulator agent of using in the 1st crystallizer tank, can enumerate basic solutions such as sodium hydroxide or potassium hydroxide, and acidic solutions such as hydrochloric acid or nitric acid.As basic solution, sodium hydroxide is preferred, and as acidic solution, hydrochloric acid is preferred.Though cheap as the calcium hydroxide of basic solution, when regulating pH because also influential to calcium ion concn, so, during use with sodium hydroxide also with being preferred.
When the pH regulator agent of using in the 1st crystallizer tank during as basic solution, with this basic solution with above-mentioned return hydroxyapatite mud and mix after, it is preferred supplying to the 1st crystallizer tank.Its reason is, returns HAP mud, and phosphate ion concentration is minimum in device, be alkalescence, optimum as the thinner of basic solution, adopt that it dilutes in advance, supply with the 1st crystallizer tank behind the increment, dispersion, then can not cause partial pH too high in the 1st crystallizer tank, be difficult to generate trickle HAP.
When the pH regulator agent of using in the 1st crystallizer tank during as acidic solution, with after the phosphoric acid draining mixes, it is preferred supplying to the 1st crystallizer tank with this acidic solution.Its reason is, will in advance with supplying to the 1st crystallizer tank after a large amount of phosphoric acid draining dilutions, increment, the dispersion, then can not cause partial pH to reduce in the 1st crystallizer tank as the acidic solution of pH regulator agent, and perhaps HAP can be not dissolved fall.In addition, in the phosphoric acid draining that has mixed acidic solution, do not observe the variation that crystalline is separated out and so on.
In the 1st crystallizer tank, be not particularly limited as the interpolation place of calcium chloride, but same with acidic solution, be preferred with supplying to the 1st crystallizer tank after the phosphoric acid draining mixes.Its reason is, when carrying out dilution, increment, the dispersion of calcium chloride with the phosphoric acid draining in advance, can obtain CaHPO
42H
2The crystallization of O (secondary calcium phosphate 2 water salt), but generate 2 moles hydrochloric acid simultaneously, thus best and above-mentioned acidic solution handle equally, and, in the 1st crystallizer tank, can avoid the calcium ion concn part to become high density, suppress trickle HPA crystalline and generate.
In the 2nd Crystallization Procedure, the HAP mud that the 1st crystallizer tank is obtained flows into the 2nd crystallizer tank, adds calcium chloride, and it is high slightly and below the pH11, under the preferred situation below 8.7, further carry out reactive crystallization that pH is adjusted to pH than the 1st crystallizer tank.Promptly in the 2nd crystallizer tank, will be controlled to high pH zone, high-calcium ionic concentration range, thereby do one's utmost to reduce the phosphoric acid concentration in the treating water.
In the 2nd crystallizer tank, when pH greater than 11 the time, generate lime carbonate or calcium hydroxide, thereby the result who causes the consumption of calcium chloride to increase is unfavorable.In addition, for the pH that makes the 2nd crystallizer tank is in the pH regulator agent of using in the above-mentioned scope, can list with the 1st crystallizer tank in the same pH regulator agent used, according to the same reason of the 1st crystallizer tank, as the pH regulator agent that liquid is transferred to meta-alkalescence, sodium hydroxide is preferred.
The unit time amount that supplies to the calcium chloride of the 2nd crystallizer tank is, the equivalent insufficient section of the calcium chloride that uses in the 1st crystallizer tank operation with respect to the phosphoric acid in the phosphoric acid draining being carried out more than the normal at least 10 weight % of the necessary theory of phosphatic rockization, being preferably the mistake surplus sum more than the 20 weight %.When the calcium chloride addition is not enough, then is equivalent to not enough unreacted phosphoric acid partly and flows out.
In the precipitate and separate operation, make the mud that the 2nd crystallizer tank obtains flow into subsider, carry out settlement separately, supernatant liquor is drained into outside the system as treating water, with the major part of the mud that is concentrated as the above-mentioned HAP of returning mud.
As the specifically amount of returning of returning HAP mud, can be according to particle diameter of the pH in the 1st crystallizer tank and average reaction time, the concentration of returning HAP mud and HAP etc., in not producing the scope of gonorrhoea, treating water suitably do not select, rather than stipulate without exception, for example, supply to the unit time feed rate of returning HAP mud of the 1st crystallizer tank, as mentioned above, preferably with respect to unit time feed rate 100 parts by volume to the phosphoric acid draining that supplies to the 1st crystallizer tank, be 50～400 parts by volume, be preferably 100～200 parts by volume.When the amount of returning of returning HAP mud is lower than 50 parts by volume, in the 1st crystallizing layer, returns HAP mud and can not fully play effect as crystal seed, beyond crystal seed, generate HAP grain, make settlement separate difficulty, the gonorrhoeaization for the treatment of water becomes easily, is unfavorable.In addition, when the amount of returning during greater than 400 parts by volume, increase though the HAP surface of seed is long-pending, but because excessive dilution, phosphoric acid concentration in the 1st crystallizer tank became low, and the crystallization velocity of HAP descends, and average reaction time shortens, phosphoric acid concentration in the treating water rises, and therefore thinks that an optimum range is arranged.
In addition, the present invention is at the crystallizer tank that can also be provided with between the 1st crystallizer tank and the subsider more than 1, the pH in this crystallizer tank, compare with the pH of above-mentioned the 2nd crystallizer tank, the rising or identical gradually along with migrated downstream, and, be preferred in the scope below pH11.
Crystallization in the dephosphorizing method of draining of the present invention in the 1st crystallizer tank, is controlled and does not generate the following abominable HAP of settleability of Stokes diameter 1 μ m, and separates out HAP returning on the HAP particle surface, and this HAP particle is grown up.The so-called Stokes diameter here, be meant according to stokes resistance rule, from the settling velocity of determined particle, suppose the equivalent diameter of obtaining when particle is spherical, concerning HAP, settling velocity is 3.2mm/h during 1 μ m, during 10 μ m settling velocity be 320mm/h (about the detailed content of Stokes diameter, can (chemical engineering can be compiled, and ball is kind to be published with reference to the chemical industry dictionary, 267～268 pages, change 3 editions clear and on March 20th, 61)).
Phosphoric acid in the draining in the 1st crystallizer tank, under the situation of control pH, calcium, the crystal seed of a large amount of HAP more than 25 times by the HAP that produces with the unit time contacts, HAP deposits on the HAP particle, the HAP that increases grain a little is by at the groove internal recycle, can obtain Stokes diameter 10 μ m above, particle diameter is big and settleability and the good HAP of filterableness.
Secondly, the difference to the processing in processing in the 1st crystallizer tank and the 2nd crystallizer tank describes with reference to Fig. 2.Fig. 2 represents that the longitudinal axis is phosphoric acid concentration (phosphorus amount), the hydroxyapatite [Ca when transverse axis is pH
5(OH) (PO
4)
3] solubility curve.In addition, in Fig. 2, A is the HAP solubility curve of the calcium ion concn in the aqueous solution when being 0mg/l, and B is the HAP solubility curve of the calcium ion concn in the aqueous solution when being 40mg/l, and C is the HAP solubility curve of the calcium ion concn in the aqueous solution when being 100mg/l.That is, Fig. 2 is the generation of expression HAP and the relation of phosphoric acid concentration, calcium ion concn and the pH in when dissolving.By the comparison of A, B and C, as can be known for effective dephosphorization from draining, rising pH when preferably raising calcium ion concn, that is, roughly Y zone in the drawings makes it crystallization.But, in the 1st Crystallization Procedure,, thereby exist that crystalline HAP becomes trickle crystallization and gonorrhoeaization can not settled problem if directly make it crystalline words in the Y zone.Therefore, in the processing of the 1st crystallizer tank in the present invention, override is separated and is never produced gonorrhoeaization, it is the problem that override solves the particle diameter that strengthens HAP, though recognize and only depend on the 1st crystallizer tank phosphoric acid concentration can fully not reduce, can still select low pH zone, low calcium ion concn zone, add the HAP mud that returns of specified quantitative simultaneously and make crystal seed, whereby, do not generate the crystallization treatment (the about X zone among Fig. 2) of grain, secondly, at the 2nd crystallizer tank and later crystallization treatment towel, select high pH zone, high-calcium ionic concentration range (the about Y zone among Fig. 2) fully reduces the phosphoric acid concentration in the treating water.Also have, X zone in Fig. 2 and Y zone only indicate for convenience of explanation and in addition, are not limitation of the invention strictly speaking.
With one of the treatment unit of the dephosphorizing method of the flowcharting of Fig. 1 enforcement draining of the present invention example.Treatment unit 10, by the order of the 1st crystallizer tank the 1, the 2nd crystallizer tank 2 and subsider 3 by configured in series successively.Here so-called configured in series, meaning the phosphoric acid draining is handled successively by the order of the 1st crystallizer tank, the 2nd crystallizer tank and subsider, concrete ground means, and the treatment solution that the 1st crystallizer tank was handled supplies to the 2nd crystallizer tank, and the treatment solution that the 2nd crystallizer tank was handled supplies to subsider simultaneously.Also have, the treatment solution of in Fig. 1 the 1st crystallizer tank 1 being handled supplies to the pipe arrangement of the 2nd crystallizer tank 2, as the 1st overflow port pipe arrangement, represents with 21, the pipe arrangement that the treatment solution that the 2nd crystallizer tank 2 was handled only supplies to subsider 3 is represented with 31 as the 2nd overflow port pipe arrangement.Also have, consider that from making crystallization reaction more successfully carry out this point preferably, the 1st crystallizer tank and the 2nd crystallizer tank are the complete tempering tanks that can stir, make current downflow on the whole liquid in the groove.In addition, be provided with in the bottom of subsider 3 be connected with the 1st crystallizer tank 1 return pipe arrangement 14, the while is provided with slush pump 16 in this pipe arrangement 14, settled HAP mud supplies to the 1st crystallizer tank 1 by slush pump 16 in subsider 3.Mud stops in the subsider bottom, if the HAP that generates increases, the mud interfacial level rises, and is retracted to the mud groove, the HAP filter cake is taken out in press filtration on the 1st～3 1 time.
Embodiment
Enumerate the present invention of embodiment more specific description below, but this only illustrates, rather than restriction the present invention.
Adopt the treatment unit 10 of flowcharting shown in Figure 1, the dephosphorization treatment of carrying out the phosphoric acid draining.Also have, the 1st crystallizer tank 1 and the 2nd crystallizer tank 2 adopt complete tempering tank, and its diameter is that 2400mm, the high 4200mm of being, effective volume are 16m
3, having diameter in groove center and underwater and be 600mm, highly have a variable-ratio stirrer that diameter is the band blade of 550mm for the sedimentation pipe of 2700mm and in this sedimentation pipe inside, the motion by this stirrer makes current downflow on whole tank liquors or the mud.
At first, the former water of the phosphoric acid draining that multiple facility is discharged imports former tank 4 by pipe arrangement 41, mixes making concentration even in former tank 4.Its result, the phosphoric acid draining in the former tank 4 reaches the composition shown in the table 1.In addition, prepare calcium chloride mud in the calcium chloride storage tank 8 and the aqueous sodium hydroxide solution in the sodium hydroxide storage tank 7 respectively, make to reach shown in the table 1 and form.In addition, operating under the steady state of present embodiment carried out.
The 1st Crystallization Procedure
At first, the phosphoric acid draining from former tank 4,, is supplied on the liquid level of the 1st crystallizer tank 1 under the condition shown in " the phosphoric acid draining " of table 2 by pipe arrangement 11 with pump 15.Also have, pipe arrangement 11 is near the place of the 1st crystallizer tank and pipe arrangement 12 connections that are connected calcium chloride storage tank 8, the phosphoric acid draining be re-supplied to the 1st crystallizer tank after calcium chloride mud mixes.Calcium chloride mud uses pump 24 condition shown in " calcium chloride solution " of table 2 of pressing to supply with.In addition, return HAP mud, by pump 16 and return pipe arrangement 14 and supply on the liquid level of the 1st crystallizer tank 1 by the condition shown in the table 2.In addition, aqueous sodium hydroxide solution is suitably supplied with from sodium hydroxide storage tank 7, the pH that adjusts in the 1st crystallizer tank 1 makes it to reach the value shown in the table 2.At this moment, connect the pipe arrangement 22 of sodium hydroxide storage tank 7, and return pipe arrangement 14 and be connected, aqueous sodium hydroxide solution and return and supply to the 1st crystallizer tank after HAP mud mixes at interflow, place near the 1st crystallizer tank.Mean residence time in the 1st crystallizer tank 1 is about 1.1 hours.
The 2nd Crystallization Procedure
The 1st crystallizer tank mud with obtaining is transferred to the 2nd crystallizer tank continuously by the 1st overflow port pipe arrangement 21.In the 2nd crystallizer tank, carry out the crystallization treatment of HAP by the condition shown in the table 3.As the sodium hydroxide and the calcium chloride solution of pH regulator agent, behind the water dilution of usefulness 100L/h, the increment, disperse to supply with respectively.The 2nd crystallizer tank mud in that the 2nd crystallizer tank was handled is transferred to subsider continuously by the 2nd overflow port pipe arrangement 31.
Settlement separate operation
In subsider 3, carry out the HAP sedimentation by the condition shown in the table 4 and handle.This sedimentation with the supernatant liquor that obtains, is discharged by the 3rd overflow port pipe arrangement 32 after handling continuously, with it as treating water.The composition for the treatment of water etc. is shown in table 5.On the other hand, the settled HAP mud in the bottom of subsider 3, by pump 16, return pipe arrangement 14 and be back to the 1st crystallizer tank 1 as returning HAP mud, if when rising on the mud interface that HAP makes the subsider bottom because of generating, 1～3 day 1 time, through pump 17, be transferred to pressure filter 6 from mud Receiving bin 5, be separated into filter cake and filtered water.Because filter cake does not contain flocculation agent and is not clamminess, separated so can simply peel off from strainer, the filter cake after the separation is also dry easily.In addition, filtered water is back to former tank 4 by pipe arrangement 42, even HPA mud leaks during by filter cloth, also can not flow to the outside as draining.The phosphoric acid amount for the treatment of water, dephosphorization rate etc. are shown in table 5.
Table 1
| Raw material is formed | Unit | Embodiment 1 | | Comparative example 1 |
| Phosphoric acid concentration pH is formed in the phosphoric acid draining | ppm - | 720 6.8 | 1090 7.2 | 620 7.2 |
| Calcium chloride solution is formed calcium chloride concentration | Weight % | 35 | 35 | 35 |
| Return HAP mud and form the stokes particle diameter of mud concentration mud | Weight % μ m | 5.1 11.3 | 6.6 12.0 | 4.7 10.2 |
| Aqueous sodium hydroxide solution is formed naoh concentration | Weight % | 25 | 25 | 25 |
Table 2
| The condition of the 1st crystallizer tank | Unit | Embodiment 1 | | Comparative example 1 | |
| | m | 3 | 16 | 16 | 16 |
| Phosphoric acid draining influx phosphoric acid conversion amount | m 3/h kg/h | 7.2 5.18 | 5.1 5.56 | 9.8 6.08 | |
| Calcium chloride solution influx calcium chloride conversion amount | L/h kg/ | 15 6.8 | 20 9.1 | 20 9.1 |
| Unit time is supplied with the calcium chloride conversion amount that phosphoric acid that the calcium chloride conversion amount of the 1st crystallizer tank/unit time handles balances each other | ％ | 87 | 100 | 85 |
| Return HAP mud influx amount of sludge 1) | m 3/h kg/h | 7.2 378 | 10.0 680 | 4.7 228 |
| Mean residence time the 1st crystallizer tank of pH the 1st crystallizer tank of the 1st crystallizer tank return HAP mud concentration (calculated value) | -hour weight % | 7.3 1.1 2.6 | 7.5 1.1 4.5 | 7.4 1.1 1.6 |
1) solids component conversion amount
Table 3
| The condition of the 2nd crystallizer tank | Unit | Embodiment 1 | | Comparative example 1 | |
| | m | 3 | 16 | 16 | 16 |
| The mud influx of the 1st crystallizer tank | m 3/h | 14.4 | 15.1 | 14.5 | |
| Calcium chloride solution influx calcium chloride conversion amount | L/h kg/ | 15 6.8 | 10 4.6 | 10 4.6 | |
| Unit time is supplied with the calcium chloride conversion amount that phosphoric acid that the calcium chloride conversion amount of the 2nd crystallizer tank/unit time handles balances each other | ％ | 70 | 43 | 40 | |
| The mean residence time of pH the 2nd crystallizer tank of the 2nd crystallizer tank | -hour | 8.3 1.1 | 8.5 1.1 | 8.2 1.1 |
Table 4
| The condition of subsider | Unit | Embodiment 1 | | Comparative example 1 |
| The mud influx of the 2nd crystallizer tank | m 3/h | 14.5 | 15.2 | 14.6 |
| The pH of subsider | - | 8.3 | 8.5 | 8.1 |
Table 5
| The composition for the treatment of water etc. | Unit | Embodiment 1 | | Comparative example 1 |
| Output phosphoric acid conversion amount | m 3/h kg/h | 7.4 0.053 | 5.3 0.047 | 10.0 0.145 |
| Phosphoric acid concentration calcium ion concn pH | ppm ppm - | 7.1 232 8.3 | 8.9 140 8.5 | 14.5 130 8.1 |
| Whether dephosphorylation amount dephosphorylation rate gonorrhoea takes place | kg/h ％ - | 5.13 99.0 are not | 5.51 99.2 are not | 5.93 take place after 97.6 half days |
The possibility of industrial utilization
According to the dephosphorization method of the draining that the present invention relates to, can without flocculant, remove the phosphoric acid in the draining. In addition, be not clamminess because the filter cake that press filtration obtains after the sedimentation separation does not contain flocculant, therefore can simply peel off from filter and be separated, the filter cake after the separation is also dry easily, so can reduce processing cost.
Claims (9)
1. the dephosphorizing method of a draining adopts by the order of the 1st crystallizer tank, the 2nd crystallizer tank and the subsider treatment unit of configured in series successively, from the phosphoric acid draining, gives Crystallization Separation with hydroxyapatite, it is characterized in that, comprising:
In above-mentioned the 1st crystallizer tank, return hydroxyapatite mud with above-mentioned phosphorous draining, calcium chloride and from what above-mentioned subsider returned, the limit is regulated the pH limit with the pH regulator agent and is reacted and separate out crystalline the 1st Crystallization Procedure;
Make the mud that from above-mentioned the 1st Crystallization Procedure, obtains flow into the 2nd crystallizer tank, add calcium chloride and pH regulator agent,, and under the situation below the pH11, further react and separate out crystalline the 2nd Crystallization Procedure at the pH height of pH than the 1st crystallizer tank;
Make the mud that obtains in above-mentioned the 2nd Crystallization Procedure flow into subsider, carry out settlement separately, supernatant liquor is drained into outside the system as treating water, the mud that major part is concentrated is as the above-mentioned hydroxyapatite mud that returns.
2. the dephosphorizing method of draining as claimed in claim 1, it is characterized in that, the above-mentioned unit time feed rate of returning hydroxyapatite mud that supplies to above-mentioned the 1st crystallizer tank is, with respect to unit time feed rate 100 parts by volume of the above-mentioned phosphoric acid draining that supplies to above-mentioned the 1st crystallizer tank, be more than 50 parts by volume.
3. the dephosphorizing method of draining as claimed in claim 1 or 2, it is characterized in that, what supply to above-mentioned the 1st crystallizer tank above-mentionedly returns the unit time feed rate that hydroxyapatite mud is converted into solids component and is, being converted into unit time feed rate 100 mass parts of hydroxyapatite with respect to the phosphoric acid of the above-mentioned phosphoric acid draining that will supply to above-mentioned the 1st crystallizer tank, is more than 2500 weight parts.
4. as the dephosphorizing method of any one described draining in the claim 1～3, it is characterized in that, the unit time feed rate that supplies to the above-mentioned calcium chloride of above-mentioned the 1st crystallizer tank is set at, and the phosphoric acid that supplies to the above-mentioned phosphoric acid draining of above-mentioned the 1st crystallizer tank is converted into below the necessary theoretical equivalent of hydroxyapatite.
5. as the dephosphorizing method of any one described draining in the claim 1～4, it is characterized in that, the unit time feed rate that supplies to the above-mentioned calcium chloride of above-mentioned the 2nd crystallizer tank is, supply to above-mentioned the 1st crystallizer tank above-mentioned calcium chloride the equivalent insufficient section with respect to the mistake surplus sum of the phosphoric acid in the phosphoric acid draining being carried out the necessary theory normal at least 10% of phosphatic rockization.
6. as the dephosphorizing method of any one described draining in the claim 1～5, it is characterized in that, when the pH regulator agent of using in above-mentioned the 1st crystallizer tank during, this basic solution after mixing, hydroxyapatite mud is supplied to above-mentioned the 1st crystallizer tank with above-mentioned returning as basic solution.
7. as the dephosphorizing method of any one described draining in the claim 1～6, it is characterized in that, when the pH regulator agent of using in above-mentioned the 1st crystallizer tank during,, and after mixing, above-mentioned phosphoric acid draining supplies to above-mentioned the 1st crystallizer tank with this acidic solution and above-mentioned calcium chloride as acidic solution.
8. as the dephosphorizing method of any one described draining in the claim 1～7, it is characterized in that the pH regulator agent of using in above-mentioned the 1st crystallizer tank is sodium hydroxide or hydrochloric acid.
9. as the dephosphorizing method of any one described draining in the claim 1～8, it is characterized in that, crystallizer tank more than 1 is set between above-mentioned the 2nd crystallizer tank and the above-mentioned subsider again, pH in this crystallizer tank is with respect to the pH in above-mentioned the 2nd crystallizer tank, the rising or identical gradually along with migrated downstream, and in the scope below pH11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003033510A JP3977757B2 (en) | 2003-02-12 | 2003-02-12 | Dephosphorization method of waste water |
| JP033510/2003 | 2003-02-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1741967A true CN1741967A (en) | 2006-03-01 |
| CN100335428C CN100335428C (en) | 2007-09-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800028552A Expired - Fee Related CN100335428C (en) | 2003-02-12 | 2004-02-10 | Method for removing phosphorus in wastewater |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3977757B2 (en) |
| KR (1) | KR101031160B1 (en) |
| CN (1) | CN100335428C (en) |
| WO (1) | WO2004071970A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826640A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for treating organic phosphorus production wastewater |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4894139B2 (en) * | 2004-10-28 | 2012-03-14 | 栗田工業株式会社 | Method and apparatus for treating phosphoric acid-containing liquid |
| JP4600865B2 (en) * | 2005-03-31 | 2010-12-22 | 株式会社日立プラントテクノロジー | Method for crystallizing phosphorus-containing water |
| JP2009226250A (en) | 2008-03-19 | 2009-10-08 | Toshiba Corp | Phosphorus recovery method and system |
| JP5058129B2 (en) * | 2008-11-06 | 2012-10-24 | オルガノ株式会社 | Crystallization reaction method |
| KR101309565B1 (en) * | 2010-12-08 | 2013-09-17 | 서울시립대학교 산학협력단 | Method for Removing Phosphorus in wastewater Using Crystal from P-C SWRO system |
| CN103521155B (en) * | 2013-10-08 | 2014-12-31 | 中国农业大学 | Livestock wastewater phosphorus crystallization and fertilizer formation reactor and its application |
| CN105016523B (en) * | 2015-07-06 | 2017-07-28 | 重庆泰克环保科技股份有限公司 | A kind for the treatment of of Phosphorus Containing Waste Water cleaning system |
| CN105540770B (en) * | 2015-12-19 | 2018-06-29 | 湖南科技大学 | A kind of Magnetic guidance crystallization removal and the method and device of recycling phosphor in sewage |
| KR102114634B1 (en) * | 2020-03-03 | 2020-05-25 | 주식회사 지이테크 | Phosphorus treatment and recovery process of sewage using selective adsorption module |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187092A (en) * | 1981-05-15 | 1982-11-17 | Rasa Kogyo Kk | Treatment of waste water containing phosphoric acid |
| JP2856281B2 (en) * | 1988-12-19 | 1999-02-10 | 大阪瓦斯株式会社 | How to remove phosphorus from wastewater |
| JP2535744B2 (en) * | 1990-10-12 | 1996-09-18 | 工業技術院長 | Treatment method for wastewater containing phosphate ions |
| JP3918294B2 (en) * | 1998-03-30 | 2007-05-23 | オルガノ株式会社 | Method and apparatus for treating fluorine-containing wastewater |
| JP3903591B2 (en) * | 1998-05-26 | 2007-04-11 | 栗田工業株式会社 | Treatment method for fluorine and phosphorus containing wastewater |
| JP4190679B2 (en) * | 1999-11-02 | 2008-12-03 | 栗田工業株式会社 | Method and apparatus for treating phosphorus-containing water |
| JP2002348106A (en) * | 2001-05-29 | 2002-12-04 | Kiyoshi Suzuki | Method for recovering phosphorus and device used for the same |
-
2003
- 2003-02-12 JP JP2003033510A patent/JP3977757B2/en not_active Expired - Lifetime
-
2004
- 2004-02-10 CN CNB2004800028552A patent/CN100335428C/en not_active Expired - Fee Related
- 2004-02-10 KR KR1020057014943A patent/KR101031160B1/en not_active IP Right Cessation
- 2004-02-10 WO PCT/JP2004/001417 patent/WO2004071970A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826640A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for treating organic phosphorus production wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3977757B2 (en) | 2007-09-19 |
| KR20050114619A (en) | 2005-12-06 |
| KR101031160B1 (en) | 2011-04-27 |
| JP2004261640A (en) | 2004-09-24 |
| WO2004071970A1 (en) | 2004-08-26 |
| CN100335428C (en) | 2007-09-05 |
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