CN101977849A - Process and equipment for recovering phosphoric acid from phosphoric acid-containing water - Google Patents
Process and equipment for recovering phosphoric acid from phosphoric acid-containing water Download PDFInfo
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- CN101977849A CN101977849A CN2009801092474A CN200980109247A CN101977849A CN 101977849 A CN101977849 A CN 101977849A CN 2009801092474 A CN2009801092474 A CN 2009801092474A CN 200980109247 A CN200980109247 A CN 200980109247A CN 101977849 A CN101977849 A CN 101977849A
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Abstract
A process and equipment for recovering high-purity phosphoric acid useful as a recycled material in the form of a high -concentration transportable liquid from phosphoric acid -containing water at a low cost and high efficiency by simple constitution and operation without using a special chemical or the like while inhibiting the development of microorganisms such as mould or yeast. The process comprises adjusting phosphoric acid-containing water to a pH of 2 or below, a concentration of 600 mg/L or above, and an electric conductivity of 200 mS/m or above, subjecting the resulting phosphoric acid-containing water to reverse osmosis treatment in a first RO unit (4) to conduct the permeation of acids other than phosphoric acid and water to a permeate chamber (4b) side and the concentration of phosphoric acid on a concentrate chamber (4c) side, subjecting the permeate to post treatment to recover pure water (7a), feeding the concentrate into a second RO unit (5), circulating part of the concentrate formed in the second RO unit (5) as a phosphoric acid solution (9a) for adjustment, and feeding the remainder of the concentrate into an evaporative concentration unit (8) to remove volatile components and water and thus recover a concentrated phosphoric acid solution (10a).
Description
Technical field
The invention relates to that a kind of reverse osmosis equipment that utilizes reclaims the method and the device of phosphoric acid from phosphorous sour water, and particularly relevant for valuable material such as a kind of phosphoric acid that can from the washes that contains phosphoric acid behind etching crystal liquid substrate or wafer and other electronicss, reclaim the generation that can suppress microorganisms such as fungi, yeast with as the method and the device of the recovery phosphoric acid of the pure water for the treatment of water.
Background technology
In the etching of crystal liquid substrate or wafer and other electronicss, use the etching solution that contains phosphoric acid.The spent etching solution of the high density that produces in the etch process is recovered with regeneration, but the electronics after the etching washs through pure water, generates the washes of a large amount of lower concentrations.Above-mentioned washes is except that containing phosphoric acid as liquid etching composition, nitric acid, acetic acid and other acid becomes to grade, and also contain by etching and metal ion and other impurity of stripping, but major part is a pure water.
In the past, above-mentioned etching washes is mixed with other waste water handle.As the treatment technology of the waste water of general phosphoric acid or fluoric acid, can enumerate coagulation sedimentation and handle.But, phosphoric acid or fluoric acid are carried out coagulation sedimentation when handling, owing to use a large amount of medicines and produce a large amount of mud, thereby produce problems such as processing cost rising, carrying capacity of environment increase.In addition, owing in coagulation sedimentation is handled, add a large amount of medicines, so water soluble ion is increased, when this reclaims with water the working pressure of reverse osmosis membrane technology rise that the power cost that causes increases, water quality treatment worsens, produce dirt (scale) and in ion exchange method the usage quantity increase of regenerator relevant.
Open in 2006-75820 number the Japanese Patent spy, make spent ion exchange resin remove the ion of phosphoric acid, nitric acid etc., reclaim pure water and phosphoric acid salt.But, though being form with phosphoric acid salt (SODIUM PHOSPHATE, MONOBASIC etc.), this method reclaims, and phosphoric acid salt almost finds no market, and the sodium salt of phosphoric acid is because solubleness is little, so the containing ratio of phosphoric acid is low when aqueous, is difficult to transportation, the price height of potassium hydroxide during formation sylvite.In addition, in order to form SODIUM PHOSPHATE, MONOBASIC, the someone has showed the method that feeds liquid in H shape resin cation (R.C.), but has following shortcoming: in the regeneration of resin cation (R.C.), acid such as hydrochloric acid are consumed; And in the regeneration of resin anion(R.A), used sodium hydroxide is also discharged etc. in vain.
If use reverse osmosis (RO) film to replace above-mentioned ion exchange resin to carry out concentrating and separating, then harmful microorganism such as fungi, yeast is bred on face, and intermembranous pressure reduction rises, and sees through the water yield and descends.During harmful microorganisms such as control fungi, yeast, physics control (breeding inhibition, degerming, blocking-up, sterilization), physical chemistry control (propagation suppresses), chemical control (propagation inhibition, medicine sterilization), biology control are arranged.Wherein, propagation suppresses to comprise: temperature control, chemical substance (antiblastic); Sterilization comprises: cold sterilization, High Temperature Sterilization, electromagnetic wave sterilization (γ line, ultraviolet ray, microwave etc.), high pressure sterilization (pressure), electric sterilization (high-voltage pulse); The medicine sterilization comprises: gaseous disinfectant (EO, formaldehyde, ozone, hydrogen peroxide etc.), liquor sterilant (alcohol, aquae hydrogenii dioxidi, organic system sterilant etc.), solid bactericide (silver is that sterilant, photocatalyst are sterilant etc.), immobilization sterilant (silicon is the 4th ammonium etc.) etc.
But there is following shortcoming in aforesaid method: energy expenditure is big, and the cost of equipment height causes detrimentally affect (oxidation, by chemisorption or the rotten obstruction that causes), the degradation of reverse osmosis membrane etc. to reverse osmosis membrane.Need to prove that also there is the problem of toxicity or carrying capacity of environment in the medicine that gaseous disinfectant (EO, formaldehyde etc.), organic system sterilant etc. are used for chemical control.If harmful microorganisms such as fungi, yeast are bred on face, resin or reverse osmosis membrane are stopped up, can't steady running, and microorganisms such as the fungi that produces, yeast are difficult to remove, particularly in ion exchange resin or reverse osmosis membrane, owing to can not use oxygenant, so there is not corresponding method.
Summary of the invention
Problem of the present invention is to provide a kind of method and device that reclaims phosphoric acid, this method is not used special medicine etc., utilize simply to constitute and operation, can be low-cost and expeditiously from phosphorous sour water with the transportable aqueous recovery of high density suppress microorganisms such as fungi, yeast generation, can be used as the highly purified phosphoric acid of regenerant.
The present invention proposes a kind of method and device that reclaims phosphoric acid from the phosphoric acid ionized water.
(1) a kind of method that reclaims phosphoric acid is used reverse osmosis equipment that phosphorous sour water is carried out membrane sepn and is handled to reclaim phosphoric acid, and this method comprises:
In reverse osmosis equipment, to be adjusted to pH smaller or equal to 2, phosphoric acid concentration carries out membrane sepn more than or equal to 600mg/L and electric conductivity more than or equal to the phosphorous sour water of the adjustment of 200mS/m and handles.
(2) a kind of method that reclaims phosphoric acid is used reverse osmosis equipment that phosphorous sour water is carried out membrane sepn and is handled to reclaim phosphoric acid, and this method comprises:
Be adjusted to pH smaller or equal to 2, phosphoric acid concentration supplies with reverse osmosis equipment more than or equal to 600mg/L and electric conductivity discontinuously more than or equal to the phosphorous sour water of the adjustment of 200mS/m, handle to carry out membrane sepn.
(3) method of being put down in writing as above-mentioned (1) or (2), wherein reverse osmosis equipment forms the formation more than or equal to two sections,
In first section reverse osmosis equipment, carry out the membrane sepn processing to adjusting phosphoric acid water,
In second section later reverse osmosis equipment, the Phosphoric Acid Concentration liquid of first section reverse osmosis equipment is carried out second section later membrane sepn handle.
(4) as each method of putting down in writing in above-mentioned (1)～(3), the phosphorous sour water of adjustment of wherein supplying with reverse osmosis equipment is to add phosphoric acid with the phosphorous sour water of the adjustment that is adjusted to preset value in processed phosphorous sour water.
(5) as each method of putting down in writing in above-mentioned (1)～(4), the phosphorous sour water of adjustment of wherein supplying with reverse osmosis equipment is to add the Phosphoric Acid Concentration liquid of reverse osmosis equipment and/or the phosphoric acid solution of evaporation concentration device in processed phosphorous sour water, with the phosphorous sour water of the adjustment that is adjusted to preset value.
(6) a kind of phosphoric acid retrieving arrangement reclaims phosphoric acid from phosphorous sour water, and described device comprises:
Phosphorous sour water adjustment part, its with processed phosphorous sour water be adjusted to pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to the phosphorous sour water of the adjustment of 200mS/m;
Reverse osmosis equipment, its to be adjusted to pH smaller or equal to 2, phosphoric acid concentration carries out membrane sepn more than or equal to 600mg/L and electric conductivity more than or equal to the phosphorous sour water of the adjustment of 200mS/m and handles, so that together seeing through, acid beyond the phosphoric acid and water extremely sees through the liquid chamber side, and at concentrated liquid chamber side concentrated phosphoric acid;
Phosphoric acid water supply portion, its concentrated liquid chamber side to reverse osmosis equipment is supplied with and is adjusted phosphorous sour water;
See through liquid taking-up portion, its liquid chamber side-draw that sees through from reverse osmosis equipment goes out through liquid;
Circulating path, it is circulated to phosphorous sour water adjustment part with a part of concentrated phosphoric acid liquid from the concentrated liquid chamber side of reverse osmosis equipment; And
Concentrated phosphoric acid liquid taking-up portion, it takes out the remainder from the concentrated liquid chamber side of reverse osmosis equipment.
(7) device of being put down in writing as above-mentioned (6), wherein reverse osmosis equipment forms two sections formation,
Have first section Phosphoric Acid Concentration liquid supply unit, above-mentioned supply unit is supplied with first section Phosphoric Acid Concentration liquid of first section reverse osmosis equipment to second section reverse osmosis equipment;
Wherein the constituted mode of circulating path is: the part of second section Phosphoric Acid Concentration liquid is circulated to phosphorous sour water adjustment part from the concentrated liquid chamber side of second section reverse osmosis equipment;
The constituted mode of concentrated phosphoric acid liquid taking-up portion is: the remainder that goes out second section Phosphoric Acid Concentration liquid from the concentrated liquid chamber side-draw of second section reverse osmosis equipment.
(8) device of being put down in writing as above-mentioned (7), it has evaporation concentration device, the remainder of second section Phosphoric Acid Concentration liquid that above-mentioned evaporation concentration device evaporation concentration goes out from the concentrated liquid chamber side-draw of second section reverse osmosis equipment.
Among the present invention, as the phosphorous sour water of process object so long as contain the water of phosphoric acid and get final product, without limits, but (phosphoric acid concentration of adjusting phosphorous sour water is during more than or equal to 1500mg/L less than 600mg/L more than or equal to 50mg/L for the phosphate ion that wherein contains, the phosphate ion that contains in the phosphorous sour water more than or equal to 50mg/L less than 1500mg/L), pH surpasses 2 and (pH that adjusts phosphorous sour water was smaller or equal to 1.5 o'clock smaller or equal to 3, the pH of phosphorous sour water is above 1.5 and smaller or equal to 3), and electric conductivity is less than 200mS/m (electric conductivity of adjusting phosphorous sour water more than or equal to 1800mS/m time, the electric conductivity of phosphorous sour water is less than 1800mS/m).
Under any situation, sour water is as process object, preferably, except that containing phosphate ion, all can contain positively charged ion and other impurity such as sour composition such as nitrate ion, acetic acid ion, other negatively charged ion and metal ion, but preferably, first decationize before processing.Among the present invention, be particularly suitable for from the phosphorous sour water that contains other sour compositions such as nitrate ion, acetic acid ion, removing other sour compositions such as nitrate ion, acetic acid ion, to reclaim highly purified phosphoric acid.Particularly as the preferable phosphorous sour water of process object, be included in the washes of the lower concentration that produces when carrying out the pure water washing behind the etching solution etching crystal liquid substrate that utilizes phosphoric acid or wafer and other electronicss.
When above-mentioned processed phosphorous sour water and above-mentioned adjustment phosphoric acid water than pH height and concentration when low, fungi, harmful microorganisms such as yeast are in the face breeding of reverse osmosis membrane, cause film to stop up, so in the present invention, in order from phosphorous sour water, to reclaim phosphoric acid, in reverse osmosis equipment, to phosphorous sour water, particularly removed cationic phosphorous sour water and be adjusted to pH smaller or equal to 2, preferably smaller or equal to 1.5, phosphoric acid concentration is more than or equal to 600mg/L, preferably more than or equal to 1500mg/L, and electric conductivity is more than or equal to 200mS/m, preferably carrying out membrane sepn more than or equal to the phosphorous sour water of the adjustment of 1800mS/m handles.As long as the phosphorous sour water of above-mentioned adjustment reaches above-mentioned pH, phosphoric acid concentration and electric conductivity treatment stage of membrane sepn, so in membrane sepn is handled, when being concentrated, as long as under enrichment stage, reach above-mentioned pH, phosphoric acid concentration and electric conductivity by the concentration compartments of reverse osmosis equipment.
In stage from processed phosphorous sour water to reverse osmosis equipment that supply with, if processed phosphorous sour water and above-mentioned adjustment phosphoric acid water than pH height and concentration is low, are then adjusted processed phosphorous sour water.Reverse osmosis equipment be one section and more than or equal to two sections situation under, supply with first section processed phosphorous sour water and the above-mentioned adjustment phosphoric acid water of reverse osmosis equipment than pH height and concentration is low.Reverse osmosis equipment be more than or equal to two sections situation under because the Phosphoric Acid Concentration liquid of first section reverse osmosis equipment reaches low pH, high density, so needn't adjust to the pH and the concentration of second section Phosphoric Acid Concentration liquid of supplying with later on.
When the processed phosphorous sour water of high pH, lower concentration is adjusted to low pH, high density, preferably, in processed phosphorous sour water, inject acid to adjust pH and concentration; Good especially is to add phosphoric acid as acid, with the phosphorous sour water of the adjustment that is adjusted to preset value.The phosphoric acid that joins in the processed phosphorous sour water can use the Phosphoric Acid Concentration liquid of reverse osmosis equipment and/or the phosphoric acid solution of evaporation concentration device.Phosphoric Acid Concentration liquid in the reverse osmosis equipment, wherein impurity such as nitric acid, acetic acid is removed, and therefore the phosphoric acid concentration height preferably recycles.Concentrated phosphoric acid solution when the phosphoric acid solution in the evaporation concentration device is the concentrated solution of the concentrated solution of reverse osmosis equipment, particularly second section of evaporation concentration can recycle.
So be adjusted to the phosphorous sour water of adjustment of low pH, high density, handle if in reverse osmosis equipment it is carried out membrane sepn, then harmful microorganism such as fungi, yeast is inhibited in the breeding of the face of reverse osmosis membrane.Therefore, even do not use sterilizing units such as special medicine such as oxygenant or ultraviolet ray etc., the obstruction of the reverse osmosis membrane that the breeding by microorganism causes can not take place yet, the rising of intermembranous pressure reduction can not occur or see through the decline of the water yield, reverse osmosis equipment can steady running.Can continue to a certain degree because harmful microorganism suppresses effect, adjust phosphorous sour water, adjust phosphorous sour water but preferably continue to supply with so also can supply with discontinuously.
That is, be adjusted to the phosphorous sour water of adjustment of low pH, high density, preferably supply with reverse osmosis equipment usually and handle, handle to carry out membrane sepn but also can supply with reverse osmosis equipment discontinuously to carry out membrane sepn.Under latter event, normally will be and the low processed phosphorous sour water of concentration is directly supplied with reverse osmosis equipment and handled to carry out membrane sepn than the pH height of the phosphorous sour water of above-mentioned adjustment, can supply with discontinuously the phosphorous sour water of adjustment that is adjusted to low pH, high density, for example supplied with in 1～2 day 1 time, for example supply with about 1～2 hour, handle to carry out membrane sepn.In this case, processed phosphorous sour water is directly supplied with reverse osmosis equipment handle, can inject phosphoric acid discontinuously, with pH and the concentration of adjusting phosphorous sour water to carry out membrane sepn.
Among the present invention, before with phosphoric acid water supply reverse osmosis equipment, can carry out pre-treatment, promptly remove the impurity that comprises positively charged ion and/or negatively charged ion, particularly by to have removed cationic phosphorous sour water as process object, can be adjusted to above-mentioned phosphoric acid concentration, improve membrane sepn and handle phosphoric acid and other the sour separating effects that is produced.In this case, can carry out pre-treatment, promptly remove solid matter by precipitate and separate, filtration etc., can also carry out pre-treatment, promptly utilize Zeo-karb to remove positively charged ions such as metal ion, can also utilize anionite-exchange resin to remove negatively charged ion of perchloric acid, organic acid misfit thing etc. etc.As the pretreating device that uses in the above-mentioned pre-treating technology, use the general device that above-mentioned purpose adopted.
The metal ion of contained indium, iron, aluminium etc. causes reverse osmosis (RO) film to stop up in membrane separation process in the washes after the etching, and perchloric acid etc. cause membrane damage when reaching high density, therefore by removing above-mentioned positively charged ion and negatively charged ion, can prevent film obstruction and damage etc., therefore preferable.As Zeo-karb, can use strongly-acid or weakly acidic Zeo-karb, but when using the storng-acid cation exchange resin of H shape to exchange to remove above-mentioned positively charged ion, the sour composition of treatment solution increases, be adjusted to easily smaller or equal to pH3, therefore preferable.As Zeo-karb, can be resin.Anionite-exchange resin can use strong basicity or weakly alkaline anionite-exchange resin.Anionite-exchange resin uses with sour forms such as phosphoric acid, and phosphoric acid, nitric acid, acetic acid etc. are passed through, and removes other impurity negatively charged ion.
In the present invention, reverse osmosis equipment in the membrane separation process is also referred to as the RO device, be divided into through liquid chamber and concentrated liquid chamber by reverse osmosis (RO) film, the constituted mode of this reverse osmosis equipment is: with phosphorous sour water pH smaller or equal to 2, phosphoric acid concentration supplies with under more than or equal to the condition of 200mS/m more than or equal to 600mg/L and electric conductivity and concentrates the liquid chamber side, handle to carry out reverse osmosis membrane, phosphoric acid acid and water is in addition together seen through to seeing through the liquid chamber side, simultaneously at concentrated liquid chamber side concentrated phosphoric acid.Concentrated liquid chamber side at reverse osmosis equipment is formed with: supply with the phosphoric acid water supply portion of phosphorous sour water and the concentrated phosphoric acid liquid taking-up portion that takes out concentrated phosphoric acid liquid.The liquid chamber side that sees through at reverse osmosis equipment is formed with the liquid taking-up portion that sees through that sees through liquid that takes out.Can form circulating path between concentrated phosphoric acid liquid taking-up portion and phosphoric acid water supply portion, above-mentioned circulating path will be circulated to as the phosphoric acid of adjusting usefulness from the concentrated phosphoric acid liquid that concentrated phosphoric acid liquid taking-up portion takes out and concentrate the liquid chamber side.
When reverse osmosis equipment is two sections formations, have first section Phosphoric Acid Concentration liquid supply unit, this supply unit is supplied with second section reverse osmosis equipment with first section Phosphoric Acid Concentration liquid of first section reverse osmosis equipment, and the constituted mode of circulating path is: the concentrated liquid chamber side that the part of second section Phosphoric Acid Concentration liquid is circulated to first section reverse osmosis equipment from the concentrated liquid chamber side of second section reverse osmosis equipment; And the constituted mode of concentrated phosphoric acid liquid taking-up portion can be: the remainder that goes out second section Phosphoric Acid Concentration liquid from the concentrated liquid chamber side-draw of second section reverse osmosis equipment.Whereby, the Phosphoric Acid Concentration liquid of first section reverse osmosis equipment can be supplied with second section reverse osmosis equipment handles to carry out membrane sepn, and with the part of the Phosphoric Acid Concentration liquid of second section reverse osmosis equipment as adjusting the concentrated liquid chamber side that is circulated to first section reverse osmosis equipment with phosphoric acid, reclaim remainder simultaneously.
Reverse osmosis membrane is a kind of semi-permeable membranes, and its utilization is soaked into to press water to be seen through or be forced on the contrary to soak into and pressed high high pressure to supply with processed liquid, by reverse osmosis water is seen through; On the other hand, it stops seeing through of salinity, other solutes.As long as the material of reverse osmosis membrane has above-mentioned characteristic, be not particularly limited, polyamide-based film, the polyimide system of seeing through for example arranged through film, the cellulose-based film etc. that sees through, also can be asymmetric reverse osmosis membrane, have the compound reverse osmosis membrane of selecting active surface separatory in fact but preferably on little porousness supporter, be formed with.
As long as reverse osmosis equipment possesses above-mentioned reverse osmosis membrane, but preferably, possess reverse osmosis membrane and supporting mechanism, the reverse osmosis equipment of the incorporate membrane modules (module) such as mechanism that catchment.Membrane module is not particularly limited, tubular film assembly, planar film assembly, spiral membrane assembly, hollow fiber membrane module etc. are for example arranged.The reverse osmosis equipment that possesses above-mentioned membrane module can use known reverse osmosis equipment, preferably the reverse osmosis equipment of the high-permeability of under low pressure operating.
With phosphorous sour water, particularly removed cationic phosphorous sour water and in reverse osmosis equipment, carried out membrane sepn under smaller or equal to 2 condition when handling at pH, acid beyond the phosphoric acid such as nitric acid, acetic acid and water together see through reverse osmosis membrane, move to and see through the liquid chamber side, go out from seeing through the liquid chamber side-draw.Phosphoric acid is prevented from seeing through reverse osmosis membrane, residues in concentrated liquid chamber side and is concentrated, and therefore can be used as Phosphoric Acid Concentration liquid and reclaims from concentrating the liquid chamber side.At this moment, though there is a spot of acid except that phosphoric acid to remain in the concentrated solution, but carry out membrane sepn under more than or equal to the condition of 600mg/L when handling at phosphoric acid concentration, therefore the prevention rate step-down of the acid beyond the phosphoric acid and transmitance uprises can reclaim highly purified Phosphoric Acid Concentration liquid.The pressure of supplying with the phosphorous sour water of reverse osmosis equipment can be 0.3～5MPa, preferably 0.5～3MPa.
In the seeing through of reverse osmosis membrane, during the seeing through of reference ion material and nonionic material, even the molecular weight of same degree, but aspect reverse osmosis membrane prevention rate, we can say that ionic substance is prevented from utterly easily than the nonionic material.But, being difficult for dissociated, pH at phosphoric acid and carrying out reverse osmosis membrane under smaller or equal to 2 condition when handling, the prevention rate of phosphoric acid uprises utterly than nitric acid and acetic acid, can reclaim acid and phosphoric acid beyond the phosphoric acid such as nitric acid and acetic acid respectively.
If the phosphoric acid concentration of concentrated solution is too high, then can't carry out film and handle owing to soak into the relation of pressure, so the phosphoric acid concentration of concentrated solution on be limited to 15 weight percents (wt%), preferably 10wt%.The concentrated solution of above-mentioned phosphoric acid concentration if circulate in the limit, the limit adds processed phosphorous sour water in the round-robin concentrated solution, the concentrated solution piecemeal is taken out as Phosphoric Acid Concentration liquid, then can keep above-mentioned phosphoric acid concentration and handle expeditiously to carry out a processing of crossing formula.
Film is carried out when handling in circulation concentrated solution limit, limit, and the cycle index of concentrated solution is many more, and the acid beyond the phosphoric acid contact with reverse osmosis membrane and to see through the chance of film just many more, can further reduce the concentration of phosphoric acid acid in addition in the concentrated solution.At this moment, if phosphoric acid concentration surpasses 15wt%, then can't carry out film and handle, so adding dilution water in concentrated solution dilutes, circulate afterwards and carry out reverse osmosis and handle, thereby can further reduce the concentration of the acid beyond the phosphoric acid, can reclaim highly purified Phosphoric Acid Concentration liquid.As dilution water, can recycle the recycle-water of from permeate water, having removed impurity.
From seeing through the permeate water of the reverse osmosis equipment that the liquid chamber side-draw goes out, owing to wherein contain acid such as the phosphoric acid that sees through, nitric acid, acetic acid, so, can reclaim pure water by utilizing impurities removing unit from the permeate water of reverse osmosis equipment, to remove above-mentioned acid and other impurity.In this case, impurities removing unit can adopt the ion exchange unit that makes spent ion exchange resin, biological treatment device etc.
On the other hand, from concentrating the Phosphoric Acid Concentration liquid that the liquid chamber side-draw goes out, though the major part of the acid beyond the phosphoric acid such as nitric acid wherein and acetic acid has been removed,, can carry out purifying by aftertreatment in order further to remove mentioned component to improve purity and the concentration that reclaims phosphoric acid liquid.As the purifying that is undertaken by aftertreatment, can from Phosphoric Acid Concentration liquid, remove phosphoric acid acid in addition by anionresin and carry out purifying.In this case, the anionresin device is set, concentrated solution is fed in the anion exchange resin layer, from concentrated solution, remove the strong acid ion of nitric acid etc., can reclaim the strong acid ionic high concentrations of phosphoric acid that contains nitric acid etc. hardly as purification devices.
When reverse osmosis equipment is during more than or equal to two sections formation, the reverse osmosis equipment of adjusting first section of phosphoric acid water supply is handled to carry out membrane sepn, the Phosphoric Acid Concentration liquid of first section reverse osmosis equipment is supplied with second section later reverse osmosis equipment handle to carry out second section later membrane sepn.In this case, reverse osmosis equipment has first section Phosphoric Acid Concentration liquid supply unit, this supply unit is supplied with second section reverse osmosis equipment with first section Phosphoric Acid Concentration liquid of first section reverse osmosis equipment, and the constituted mode of circulating path is: the part of second section Phosphoric Acid Concentration liquid is circulated to phosphorous sour water adjustment part from the concentrated liquid chamber side of second section reverse osmosis equipment; And the constituted mode of concentrated phosphoric acid liquid taking-up portion is: the remainder of the second section Phosphoric Acid Concentration liquid concentrated liquid chamber side-draw from second section reverse osmosis equipment is gone out.The above-mentioned second section Phosphoric Acid Concentration liquid that has taken out further carries out evaporation concentration with evaporation concentration device, can reclaim as Phosphoric Acid Concentration liquid.The Phosphoric Acid Concentration liquid of evaporation concentration can also be circulated to phosphorous sour water adjustment part, use phosphoric acid with adjusting.
Promptly, when in the phosphoric acid liquid that sees through with second section reverse osmosis equipment during residual acetic acid, promptly use anionite-exchange resin acetic acid can not be removed fully, therefore in order to remove volatile component such as acetic acid to improve purity and the concentration that reclaims phosphoric acid liquid, carry out evaporation concentration with evaporation concentration device, water and volatile component are together removed with concentrated phosphoric acid liquid, thereby can be reclaimed the high concentrations of phosphoric acid that contains volatile components such as acetic acid hardly.Evaporation concentration device can use known devices such as Rotary Evaporators.
The phosphoric acid that reclaims by aforesaid operations can be used as regenerant, and can transport with the aqueous of high density, and can be used as highly purified concentrated phosphoric acid and reclaim.In the present invention, though be under smaller or equal to the condition of pH2, to carry out the reverse osmosis processing, but processed phosphorous sour water is usually obtaining smaller or equal to the acid state of pH3, therefore by injecting the phosphoric acid that reclaimed as the pH regulator agent, can easily regulate.In addition, be used to reclaim the method and the device of phosphoric acid, by simple formation and operation, phosphorous sour water can be adjusted to pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to 200mS/m.
The effect of invention
Regulate pH, phosphoric acid concentration and electric conductivity by aforesaid operations, supply with to adjust Phosphoric Acid Concentration liquid, and carry out reverse osmosis and handle, thereby the generation of microorganisms such as inhibition fungi, yeast can be reclaimed high-purity phosphoric acid.Whereby, reduce the usage quantity of medicine and the growing amount of waste, reduced processing cost, can reclaim the highly purified concentrated phosphoric acid and the pure water that can be used as regenerant.Reclaim phosphoric acid except being used to adjust phosphorous sour water, can also flood the reverse osmosis assembly that takes out from reverse osmosis equipment, the generation that is used for microorganisms such as fungi, yeast suppresses to handle etc.
Based on above-mentioned, according to the present invention, because the constituted mode of reverse osmosis equipment is: in reverse osmosis equipment to phosphorous sour water, particularly removed cationic phosphorous sour water and be adjusted to pH smaller or equal to 2, phosphoric acid concentration is more than or equal to 600mg/L, and electric conductivity is carried out membrane sepn more than or equal to the phosphorous sour water of the adjustment of 200mS/m and is handled, so do not use special medicine etc., utilize simply to constitute and operation, can be low-cost and expeditiously from phosphorous sour water the transportable aqueous recovery with high density suppress fungi, the generation of microorganisms such as yeast, can be used as the highly purified phosphoric acid of regenerant.
Description of drawings
Fig. 1 is the phosphoric acid recovery method in the embodiment and the schema of device.
Fig. 2 is the graphic representation that shows embodiment result.
1: former tank 1a: former water
2: pretreating device 3: adjust liquid bath
3a: adjust 4: the 1RO devices of liquid
4a, 5a:RO film 4b, 5b: see through liquid chamber
4c, 5c: concentrate 5: the 2RO devices of liquid chamber
6: after-treatment device 7: reclaim tank
7a: recycle-water 8: evaporation concentration device
9: adjust and use phosphoric acid groove 9a: adjust and use phosphoric acid liquid
10: reclaim phosphoric acid groove 10a: reclaim phosphoric acid liquid
L1～L6: pipeline P1, P2: pump
Embodiment
Below, utilize diagram that embodiments of the present invention are described.Fig. 1 is the phosphoric acid recovery method in the embodiment and the schema of device.1 is former tank, stores former water (processed phosphorous sour water) 1a.2 is pretreating device, is made of cationic exchange device, anionresin device and other impurities removing unit, but preferably, constitutes according to the mode that is provided with cationic exchange device and decationize at least.3 for adjusting liquid bath, stores adjustment liquid (adjusting phosphorous sour water) 3a.4 is that 1RO (reverse osmosis) device, 5 is the 2RO device, is divided into through liquid chamber 4b, 5b and concentrated liquid chamber 4c, 5c by RO film 4a, 5a respectively.6 is after-treatment device, is made of ion exchange unit, biological treatment device and other impurities removing unit.7 for reclaiming tank, and 8 is evaporation concentration device, and 9 are the adjustment phosphoric acid groove, and 10 for reclaiming phosphoric acid groove.
Among Fig. 1, P1 is a force (forcing) pump, and its formation will be adjusted the former water supply portion that liquid (adjusting phosphorous sour water) 3a supplies with the concentrated liquid chamber 4c side of 1RO device 4.Adjust with phosphoric acid groove 9 and constitute concentrated phosphoric acid liquid taking-up portion.The pump P2, adjustment liquid bath 3 and the pH meter pH that are arranged on the circulating path L4 constitute phosphorous sour water adjustment part.
In above-mentioned phosphoric acid retrieving arrangement, will carry out former water 1a (phosphoric acid ionized water) pretreatment technology, that promptly removed impurity and import the former tank 1 from pipeline L1 by precipitate and separate, filtration etc.The former water 1a of former tank 1 imports the pretreating device 2 from pipeline L2, removes positively charged ions such as indium contained in the former water, other metal ions, but preferably, further removes the impurity such as negatively charged ion of perchloric acid, organic acid misfit thing etc.Pre-treatment water imports from pipeline L3 and adjusts the liquid bath 3.
Usually obtain smaller or equal to 3 acid state with pH as the phosphorous sour water of former water, but when pH carries out reverse osmosis under smaller or equal to 2 condition and handles, will adjust with phosphoric acid liquid 9a and be circulated to adjustment liquid bath 3 with phosphoric acid groove 9 through circulating path L4 from adjustment.At this moment, with the pH of the adjustment liquid 3a in the pH meter pH meter survey adjustment liquid bath 3, control is arranged at the pump P2 on the circulating path L4, and the pH regulator that will adjust liquid 3a is extremely smaller or equal to 2.In this case, if make concentrated phosphoric acid liquid circulation to be adjusted to smaller or equal to pH2, then adjust liquid 3a be adjusted to phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to 200mS/m.Need to prove, in Fig. 1,, also can use specific gravity hydrometer and Conductivity Meters to regulate phosphoric acid concentration and electric conductivity though be to utilize pH meter to adjust the pH of liquid 3a.
The phosphorous sour water of adjusting liquid bath 3 pressurizes through force (forcing) pump P, import the concentrated liquid chamber 4c of 1RO device 4 from pipeline L5, utilize RO film 4a to carry out membrane sepn (reverse osmosis processing), phosphoric acid such as nitric acid, acetic acid acid and water is in addition together seen through to seeing through liquid chamber 4b side, at concentrated liquid chamber 4c side concentrated phosphoric acid.The phosphorous sour water that neutralizes, when carrying out reverse osmosis handling under neutral state, the salt of the acid beyond the phosphoric acid such as nitric acid, acetic acid and the salt of phosphoric acid all do not see through RO film 4a, but are concentrated in concentrated liquid chamber 4c side.With respect to this, if do not neutralize phosphorous sour water, carry out RO in the RO device 4 and handle but it is imported under smaller or equal to 2 condition at pH, then phosphoric acid is seen through by RO film 4a prevention, be concentrated in concentrated liquid chamber 4c side, and acid beyond the phosphoric acid such as nitric acid, acetic acid and water are together through separated to seeing through liquid chamber 4b side.
Since supply with the phosphorous sour water of adjustment of 1RO device 4 be adjusted to smaller or equal to pH2, preferably smaller or equal to pH1.5, phosphoric acid concentration more than or equal to 600mg/L, preferably more than or equal to 1500mg/L and electric conductivity more than or equal to 200mS/m, preferably more than or equal to 1800mS/m, therefore handled to carry out membrane sepn by adjusting phosphoric acid water supply 1RO device 4, and can suppress harmful microorganisms such as fungi, yeast and on the face of reverse osmosis membrane, breed.Therefore, even do not use special medicine etc., the obstruction of the reverse osmosis membrane that the breeding by microorganism causes can not take place yet, the rising of intermembranous pressure reduction can not occur or see through the decline of the water yield, reverse osmosis equipment can steady running.To continue to a certain degree because harmful microorganism suppresses effect, adjust phosphorous sour water, adjust phosphorous sour water but preferably continue to supply with so can supply with discontinuously.
See through importing the after-treatment device 6 from pipeline L6 through liquid chamber 4b side through liquid to 1RO device 4, utilize ion exchange unit, biological treatment device, other impurities removing unit to remove negatively charged ion and other impurity, discharge from pipeline L7 through the nitric acid of RO film 4a, acetic acid etc.The pure water of having removed above-mentioned impurity is recovered to from pipeline L8 and reclaims the tank 7, has stored and has been used as recycle-water 7a, takes out from pipeline L9.
Carry out film when handling with the RO device of one-part form, to carrying out aftertreatment through the spissated concentrated solution of the concentrated liquid chamber 4c of 1RO device, can obtain reclaiming phosphoric acid, but carry out film when handling with the RO device of two-part, to import the concentrated liquid chamber 5c of 2RO device 5 from pipeline L11 through the spissated concentrated solution of the concentrated liquid chamber 4c of 1RO device, utilize RO film 5a to carry out membrane sepn (reverse osmosis processing), acid and water beyond the phosphoric acid such as acetic acid are together seen through to seeing through liquid chamber 5b side, at concentrated liquid chamber 5c side concentrated phosphoric acid.Whereby, the part in the concentrated solution that the purity of phosphoric acid and concentration have uprised imports adjustment with the phosphoric acid groove 9 from the concentrated liquid chamber 5c of 2RO device 5 through pipeline L12, has stored to be used as adjusting and has used phosphoric acid liquid 9a.
The remainder of the concentrated solution of 2RO device 5 imports the evaporation concentration device 8 from pipeline L10, carries out evaporation concentration.The water of condensation that contains acetic acid that produces in the evaporation concentration device 8 imports the after-treatment device 6 to remove impurity, the recovery pure water from pipeline L14.Carry out evaporation concentration and removed the Phosphoric Acid Concentration water of acetic acid with evaporation concentration device 8, be recovered to from pipeline L15 and reclaim the phosphoric acid groove 10, but in this process, can remove the processing of nitric acid and other impurity.The recovery phosphoric acid liquid 10a that reclaims phosphoric acid groove 10 can also be circulated to a part wherein in the adjustment liquid bath 3 by circulating path L4, and remainder is taken out from pipeline L16 as reclaiming phosphoric acid.The RO film 5a that sees through 2RO device 5 arrives the liquid that sees through that sees through liquid chamber 5b side, to remove impurity, reclaims pure water from pipeline L13 importing after-treatment device 6.
The recovery phosphoric acid liquid 10a of Hui Shouing can be used as regenerant according to the method described above, and is recovered with the aqueous of high density, thus can transport on practical, and can be used as highly purified concentrated phosphoric acid and reclaim.In this case, with be adjusted to pH smaller or equal to 2, phosphoric acid concentration is more than or equal to 600mg/L and the electric conductivity adjustment phosphoric acid water supply RO device more than or equal to 200mS/m, handle to carry out membrane sepn, even do not use special medicine etc. whereby, also can suppress the generation of microorganisms such as fungi, yeast, handle to carry out membrane sepn.Whereby, the usage quantity of medicine and growing amount, the reduction processing cost of waste can be reduced, highly purified concentrated phosphoric acid and pure water can be reclaimed.
Embodiment
Below, embodiments of the invention are described.In each example, except that prevention rate and special instructions, % represents wt%.
(embodiment 1～6, comparative example 1～4):
Use the electric conductivity of acetic acid of nitric acid, the 1000mg/L of the phosphoric acid that contains 11000mg/L, 1000mg/L to be the phosphorous sour water of the standard of 1150mS/m, pH1.3, with its with the pure water dilution to regulate pH etc., obtain the former water (adjusting phosphorous sour water) of table 1.Need to prove that in the table 1, comparative example 1 is that the phosphorous sour water of standard is regulated pH with pure water dilution back with sodium hydroxide, thereby is adjusted to the former water of phosphoric acid concentration shown in the table 1 and pH.In addition, embodiment 6 is the examples that the phosphorous sour water of former water quality standard directly are used as former water.1～2 of embodiment is designed to: under enrichment stage, make pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L, electric conductivity more than or equal to 200mS/m.
Table 1
| pH | Phosphoric acid (mg/L) | Electric conductivity (mS/m) | |
| Comparative example 1 | 5.5 | 100 | 40 |
| Comparative example 2 | 3.3 | 100 | 62 |
| Comparative example 3 | 2.8 | 150 | 66 |
| Comparative example 4 | 2.4 | 280 | 102 |
| |
2.1 | 330 | 126 |
| Embodiment 2 | 1.9 | 600 | 170 |
| Embodiment 3 | 1.7 | 1600 | 355 |
| |
1.5 | 5000 | 612 |
| |
1.4 | 8500 | 795 |
| Embodiment 6 | 1.3 | 11000 | 1150 |
Flat membrane pilot unit contained as the reverse osmosis equipment of mimic diagram 1, use following apparatus: utilize sintered porous plate, with cutting into diameter is that the flat film of eastern electrician of day (thigh) system reverse osmosis membrane ES-20 of the circle of 32mm φ press directly 29mm φ support of effective film, be installed in the flat film unit of the stainless steel that internal diameter is 32mm φ (SUS304) system path, utilize pump to supply with former water to unitary concentrated liquid chamber, mix with the concentrated solution that is detained, utilize back pressure valve to discharge concentrated solution, to regulate the concentrated solution working pressure, stir at the indoor rotor of concentrated solution, make the concentrated solution circulation, the device of homogenizing.
With the former water (adjust phosphorous sour water) of 1mL/ minute flow to the concentration compartments of above-mentioned flat membrane pilot unit contained supply schedule 1, with the liquid in the rotor agitating unit, mix with the concentrated solution that is detained, regulate back pressure valve simultaneously, make through the water yield to equate (0.5mL/ minute) with the concentrated water yield, carry out membrane sepn.Pressure during with aforesaid operations is as working pressure, and is as shown in table 2.Afterwards, keep this working pressure constant, proceed membrane sepn.This moment see through a fluid stream over time as shown in Figure 2.In addition, (comparative example 1 was to finish running after 20 hours in water flowing when running finished, comparative example 2 is to finish running after 40 hours in water flowing, other each examples finish running in water flowing after 60 hours) concentration of each composition of condensed water and the prevention rate of each composition be as shown in table 2, in running beginning back about 1 hour identical with the numerical value of table 2, this value is maintained to the running end.Need to prove that the prevention rate utilizes formula ((concentration of the concentration/condensed water of 1-permeate water) * 100) to calculate.
Table 2
The condensed water of embodiment 1,4 and comparative example 1～3 gained is carried out culture experiment with culture dish.Substratum is for adding antibiotic PDA substratum, cultivates in thermostatic bath under 30 ℃.The result of above-mentioned culture dish culture experiment, yellow fungi penicillium chrysogenum (Penicillium chrysogenum) forms a plurality of bacterium colonies in the neutral zone.In addition, pH is sickle-like bacteria (fusariumspp.) smaller or equal to the fungi strain of generation in 3 o'clock.The result of culture dish culture experiment, promptly as shown in table 3 until the fate that is observed visually fungal colony.In the table 3, " more than or equal to 10 days " are illustrated in 10 days the culture experiment and do not observe bacterium colony.
Table 3
One-part form RO film flushing test device as the reverse osmosis equipment of mimic diagram 1, use the device that constitutes day concentrated liquid chamber of 4 inches new product membrane modules of eastern electrician (thigh) system ultralow pressure aromatic polyamide type RO film " ES20-D2 " (container is seawater fresh waterization S2 container) and adjustment liquid bath according to a part of concentrated solution round-robin mode, the former water (adjusting phosphorous sour water) of embodiment 1 and 4 was supplied with the concentration compartments of RO device in 5L/ minute from the adjustment liquid bath with the salt solution water yield, carry out membrane sepn, a part of concentrated solution is circulated to the adjustment liquid bath, be circulated to former tank with another part concentrated solution and through liquid, handled 1 month, and made the water quality that reaches table 2.The result of handling after 1 month is as shown in table 4.
Table 4
As shown in Table 4: the former water treatment of embodiment 1 and 4 after 1 month, is not confirmed big difference on handling property.But, glutinous mud (slime) after research is handled 1 month adhere to situation the time, in the former water treatment of embodiment 1, on the electrode that is arranged at the liquid level meter of adjusting liquid bath, hang with a little thread glutinous mud, and in the former water treatment of embodiment 4, do not find thread glutinous mud after 1 month yet.
By above result as can be known: by in reverse osmosis equipment to will be not the phosphorous sour water of cation be adjusted to smaller or equal to pH2, particularly smaller or equal to pH1.5, phosphoric acid concentration more than or equal to 600mg/L, particularly more than or equal to 1500mg/L and electric conductivity more than or equal to 200mS/m, particularly carry out membrane sepn and handle more than or equal to the phosphorous sour water of the adjustment of 1800mS/m, under the situation of not using special medicine etc., utilize simple formation and operation, can from phosphorous sour water, reclaim the generation of microorganisms such as suppressing fungi, yeast, useful highly purified phosphoric acid.
Utilizability on the industry
In sum, the present invention can be applicable to reclaim the method and apparatus of phosphoric acid and pure water, particularly be suitable for reclaiming the valuable material such as phosphoric acid and as the method and apparatus of the recovery phosphoric acid of the pure water of processing water from the washes behind etching crystal liquid substrate and wafer and other electronic equipments from phosphorous sour water.
Claims (8)
1. a method that reclaims phosphoric acid is used reverse osmosis equipment that phosphorous sour water is carried out membrane sepn and is handled to reclaim phosphoric acid, it is characterized in that:
In reverse osmosis equipment, carry out membrane sepn and handle adjusting phosphoric acid water, the phosphorous sour water of above-mentioned adjustment be adjusted to pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to 200mS/m.
2. a method that reclaims phosphoric acid is used reverse osmosis equipment that phosphorous sour water is carried out membrane sepn and is handled to reclaim phosphoric acid, it is characterized in that:
To adjust phosphorous sour water and supply with reverse osmosis equipment discontinuously and handle to carry out membrane sepn, the phosphorous sour water of above-mentioned adjustment be adjusted to pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to 200mS/m.
3. the method for recovery phosphoric acid according to claim 1 and 2 is characterized in that, with the formation of above-mentioned reverse osmosis equipment formation more than or equal to two sections,
In first section above-mentioned reverse osmosis equipment, the phosphorous sour water of above-mentioned adjustment is carried out membrane sepn and handles,
In second section later above-mentioned reverse osmosis equipment, the Phosphoric Acid Concentration liquid of first section above-mentioned reverse osmosis equipment is carried out second section later membrane sepn handle.
4. according to the method for each the described recovery phosphoric acid in the claim 1 to 3, it is characterized in that the phosphorous sour water of above-mentioned adjustment of supplying with above-mentioned reverse osmosis equipment is to add phosphoric acid with the phosphorous sour water of the adjustment that is adjusted to preset value in processed phosphorous sour water.
5. according to the method for each the described recovery phosphoric acid in the claim 1 to 4, it is characterized in that, the phosphorous sour water of above-mentioned adjustment of supplying with above-mentioned reverse osmosis equipment is to add the Phosphoric Acid Concentration liquid of above-mentioned reverse osmosis equipment and/or the phosphoric acid solution of evaporation concentration device in processed phosphorous sour water, with the phosphorous sour water of the adjustment that is adjusted to preset value.
6. a phosphoric acid retrieving arrangement reclaims phosphoric acid from phosphorous sour water, it is characterized in that, above-mentioned phosphoric acid retrieving arrangement comprises:
Phosphorous sour water adjustment part, its with processed phosphorous sour water be adjusted to pH smaller or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and electric conductivity more than or equal to the phosphorous sour water of the adjustment of 200mS/m;
Reverse osmosis equipment, its to be adjusted to pH smaller or equal to 2, phosphoric acid concentration carries out membrane sepn more than or equal to 600mg/L and electric conductivity more than or equal to the phosphorous sour water of above-mentioned adjustment of 200mS/m and handles, so that together seeing through, acid beyond the phosphoric acid and water extremely sees through the liquid chamber side, and at concentrated liquid chamber side concentrated phosphoric acid;
Phosphoric acid water supply portion, its above-mentioned concentrated liquid chamber side to above-mentioned reverse osmosis equipment is supplied with the phosphorous sour water of above-mentioned adjustment;
See through liquid taking-up portion, its above-mentioned liquid chamber side-draw that sees through from above-mentioned reverse osmosis equipment goes out through liquid;
Circulating path, it is circulated to above-mentioned phosphorous sour water adjustment part with a part of concentrated phosphoric acid liquid from the above-mentioned concentrated liquid chamber side of above-mentioned reverse osmosis equipment; And
Concentrated phosphoric acid liquid taking-up portion, it takes out the remainder from the above-mentioned concentrated liquid chamber side of above-mentioned reverse osmosis equipment.
7. phosphoric acid retrieving arrangement according to claim 6 is characterized in that, above-mentioned reverse osmosis equipment is formed two sections formation,
Comprise first section Phosphoric Acid Concentration liquid supply unit, above-mentioned first section Phosphoric Acid Concentration liquid supply unit supplied with first section Phosphoric Acid Concentration liquid of first section reverse osmosis equipment to second section reverse osmosis equipment;
Wherein, the constituted mode of above-mentioned circulating path is: the part of second section Phosphoric Acid Concentration liquid is circulated to above-mentioned phosphorous sour water adjustment part from the above-mentioned concentrated liquid chamber side of second section reverse osmosis equipment;
The constituted mode of above-mentioned concentrated phosphoric acid liquid taking-up portion is: the remainder that goes out above-mentioned second section Phosphoric Acid Concentration liquid from the above-mentioned concentrated liquid chamber side-draw of above-mentioned second section reverse osmosis equipment.
8. phosphoric acid retrieving arrangement according to claim 7, it is characterized in that, described device comprises evaporation concentration device, the remainder of above-mentioned second section Phosphoric Acid Concentration liquid that above-mentioned evaporation concentration device evaporation concentration goes out from the above-mentioned concentrated liquid chamber side-draw of above-mentioned second section reverse osmosis equipment.
Applications Claiming Priority (3)
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| JP2008080696 | 2008-03-26 | ||
| JP2008-080696 | 2008-03-26 | ||
| PCT/JP2009/055996 WO2009119684A1 (en) | 2008-03-26 | 2009-03-25 | Process and equipment for recovering phosphoric acid from phosphoric acid-containing water |
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| CN101977849B CN101977849B (en) | 2013-01-30 |
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| JP (1) | JP5413192B2 (en) |
| KR (1) | KR101621835B1 (en) |
| CN (1) | CN101977849B (en) |
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| WO (1) | WO2009119684A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591966A (en) * | 2020-04-20 | 2020-08-28 | 同济大学 | Device and method for recovering phosphoric acid in aluminum etching waste liquid |
| CN116621136A (en) * | 2023-07-25 | 2023-08-22 | 杭州永洁达净化科技有限公司 | Phosphoric acid recovery process and system for phosphorus-containing polishing waste acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113816350A (en) * | 2021-09-02 | 2021-12-21 | 四川中雅科技有限公司 | Phosphoric acid recovery treatment process and system |
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| JP4098669B2 (en) * | 2003-05-27 | 2008-06-11 | 日本パーカライジング株式会社 | Recovery and reuse of phosphate chemical conversion solution |
| JP5135749B2 (en) * | 2006-09-28 | 2013-02-06 | 栗田工業株式会社 | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water |
-
2009
- 2009-03-25 KR KR1020107021133A patent/KR101621835B1/en active IP Right Grant
- 2009-03-25 TW TW98109731A patent/TWI424964B/en active
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Patent Citations (5)
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| JPH0663362A (en) * | 1992-08-24 | 1994-03-08 | Kurita Water Ind Ltd | Membrane separator |
| CN1309193A (en) * | 1999-12-09 | 2001-08-22 | 日本油漆株式会社 | Method for recovery of water lotion from chemical conversion of phosphate and device for surface treatment of metal |
| JP2002086147A (en) * | 2000-09-19 | 2002-03-26 | Nippon Paint Co Ltd | Method for recovering processing agent component in washing water of metallic surface treatment |
| JP2002332583A (en) * | 2001-05-07 | 2002-11-22 | Nippon Paint Co Ltd | Method and apparatus for treating cleaning water for phosphate film chemical conversion |
| JP2002370088A (en) * | 2001-06-13 | 2002-12-24 | Nippon Parkerizing Co Ltd | Method for recovering washing water discharged from coating pretreatment line |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111591966A (en) * | 2020-04-20 | 2020-08-28 | 同济大学 | Device and method for recovering phosphoric acid in aluminum etching waste liquid |
| CN111591966B (en) * | 2020-04-20 | 2021-08-06 | 同济大学 | Device and method for recovering phosphoric acid in aluminum etching waste liquid |
| CN116621136A (en) * | 2023-07-25 | 2023-08-22 | 杭州永洁达净化科技有限公司 | Phosphoric acid recovery process and system for phosphorus-containing polishing waste acid |
| CN116621136B (en) * | 2023-07-25 | 2023-10-20 | 杭州永洁达净化科技有限公司 | Phosphoric acid recovery process and system for phosphorus-containing polishing waste acid |
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| Publication number | Publication date |
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| TW201002627A (en) | 2010-01-16 |
| KR20100127241A (en) | 2010-12-03 |
| CN101977849B (en) | 2013-01-30 |
| JPWO2009119684A1 (en) | 2011-07-28 |
| TWI424964B (en) | 2014-02-01 |
| KR101621835B1 (en) | 2016-05-31 |
| JP5413192B2 (en) | 2014-02-12 |
| WO2009119684A1 (en) | 2009-10-01 |
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