CN101977849B - 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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- CN101977849B CN101977849B CN200980109247.4A CN200980109247A CN101977849B CN 101977849 B CN101977849 B CN 101977849B CN 200980109247 A CN200980109247 A CN 200980109247A CN 101977849 B CN101977849 B CN 101977849B
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- B01D61/025—Reverse osmosis; Hyperfiltration
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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 to conduct the permeation of acids other than phosphoric acid and water to a permeate chamber side and the concentration of phosphoric acid on a concentrate chamber side, subjecting the permeate to post treatment to recover pure water, feeding the concentrate into a second RO unit, circulating part of the concentrate formed in the second RO unit as a phosphoric acid solution for adjustment, and feeding the remainder of the concentrate into an evaporative concentration unit to remove volatile components and water and thus recover a concentrated phosphoric acid solution.
Description
Technical field
The invention relates to a kind of method and device that utilizes reverse osmosis equipment to reclaim phosphoric acid from phosphorous sour water, but and particularly relevant for the valuable material such as a kind of phosphoric acid of the generation that can from the washes that contains phosphoric acid behind etching crystal liquid substrate or wafer and other electronic equipments, reclaim the microorganisms such as Antifungi, yeast with as method and the device of the recovery phosphoric acid of the pure water of processing water.
Background technology
In the etching of crystal liquid substrate or wafer and other electronic equipments, use the etching solution that contains phosphoric acid.The spent etching solution of the high concentration that produces in the etch process is recovered with regeneration, but the electronic equipment after the etching washs through pure water, generates the washes of a large amount of low concentrations.Above-mentioned washes also contain by etching and metal ion and other impurity of stripping, but major part is pure water except containing phosphoric acid as liquid etching composition, nitric acid, acetic acid and other acid becomes to grade.
In the past, above-mentioned etching washes is mixed with other waste water process.As the treatment technology of the waste water of general phosphoric acid or fluoric acid, can enumerate coagulation sedimentation and process.But, phosphoric acid or fluoric acid are carried out coagulation sedimentation when processing, owing to use a large amount of medicines and produce a large amount of mud, thereby produce the problems such as processing cost rising, carrying capacity of environment increase.In addition, owing in coagulation sedimentation is processed, adding a large amount of medicines, therefore water soluble ion is increased, when this reclaims with water the operating pressure of reverse osmosis membrane technique rise that the power cost that causes increases, water quality treatment worsens, produce dirt (scale) and in ion-exchange the use amount increase of regenerative agent relevant.
In Japanese Patent Laid-Open 2006-75820 number, make spent ion exchange resin remove the ion of phosphoric acid, nitric acid etc., reclaim pure water and phosphate.But, although being form with phosphate (sodium dihydrogen phosphate etc.), the method reclaims, phosphate almost finds no market, the sodium salt of phosphoric acid is because solubility is little, therefore the containing ratio of phosphoric acid is low when aqueous, be difficult to transportation, the price of potassium hydroxide is high when forming sylvite.In addition, in order to form sodium dihydrogen phosphate, someone has showed in H shape resin cation and pass into the method for liquid, but has had following shortcoming: in the regeneration of resin cation, the acid such as hydrochloric acid are consumed; And in the regeneration of resin anion (R.A.), used NaOH 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 the harmful microorganism such as fungi, yeast is bred at face, and intermembranous pressure reduction rises, and sees through the water yield and descends.During the harmful microorganisms such as control fungi, yeast, physical 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.), liquid solution bactericide (alcohol, aquae hydrogenii dioxidi, organic system bactericide etc.), solid bactericide (silver is that bactericide, photochemical catalyst are bactericide etc.), immobilization bactericide (silicon is the 4th ammonium etc.) etc.
But there is following shortcoming in said method: energy consumption is large, and cost of equipment is high, and reverse osmosis membrane is caused harmful effect (oxidation, by chemisorbed or the rotten obstruction that causes), the hydraulic performance decline of reverse osmosis membrane etc.Need to prove, also there are the problem of toxicity or carrying capacity of environment in gaseous disinfectant (EO, formaldehyde etc.), organic system bactericide etc. for the medicine of Chemical Control.If the harmful microorganism such as fungi, yeast is bred at face, resin or reverse osmosis membrane are stopped up, can't steady running, and the 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 oxidant, 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, the method is not used special medicine etc., utilize simply to consist of and operation, can be low-cost and expeditiously from phosphorous sour water with the generations of the microorganisms such as the transportable aqueous recovery Antifungi of high concentration, yeast, 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 uses reverse osmosis equipment that phosphorous sour water is carried out membrane separation to reclaim phosphoric acid, and the method comprises:
In reverse osmosis equipment, to be adjusted to pH less than or equal to 2, phosphoric acid concentration carries out membrane separation more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of the adjustment of 200mS/m.
(2) a kind of method that reclaims phosphoric acid uses reverse osmosis equipment that phosphorous sour water is carried out membrane separation to reclaim phosphoric acid, and the method comprises:
Be adjusted to pH less than or equal to 2, phosphoric acid concentration supplies with reverse osmosis equipment more than or equal to 600mg/L and conductance discontinuously more than or equal to the phosphorous sour water of the adjustment of 200mS/m, to carry out membrane separation.
(3) method of putting down in writing such as above-mentioned (1) or (2), wherein reverse osmosis equipment forms the formation more than or equal to two sections,
In the reverse osmosis equipment of first paragraph, carry out membrane separation to adjusting phosphoric acid water,
In the later reverse osmosis equipment of second segment, the Phosphoric Acid Concentration liquid of the reverse osmosis equipment of first paragraph is carried out the later membrane separation of second segment.
(4) such 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 predetermined value in processed phosphorous sour water.
(5) such 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 predetermined value.
(6) a kind of phosphoric acid retracting device 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 less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of the adjustment of 200mS/m;
Reverse osmosis equipment, its to be adjusted to pH less than or equal to 2, phosphoric acid concentration carries out membrane separation more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of the adjustment of 200mS/m, so that together seeing through, the acid beyond the phosphoric acid and water extremely sees through the liquid chamber side, and at concentrated liquid chamber side concentrated phosphoric acid;
Phosphorous sour water supply unit, its concentrated liquid chamber side to reverse osmosis equipment is supplied with and is adjusted phosphorous sour water;
See through liquid taking-up section, 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 section, it takes out the remainder from the concentrated liquid chamber side of reverse osmosis equipment.
(7) device of putting down in writing such as above-mentioned (6), wherein reverse osmosis equipment forms two sections formation,
Have first paragraph Phosphoric Acid Concentration liquid supply unit, above-mentioned supply unit is supplied with the first paragraph Phosphoric Acid Concentration liquid of first paragraph reverse osmosis equipment to the second segment reverse osmosis equipment;
Wherein the constituted mode of circulating path is: the part of second segment Phosphoric Acid Concentration liquid is circulated to phosphorous sour water adjustment part from the concentrated liquid chamber side of second segment reverse osmosis equipment;
The constituted mode of concentrated phosphoric acid liquid taking-up section is: the remainder that goes out second segment Phosphoric Acid Concentration liquid from the concentrated liquid chamber side-draw of second segment reverse osmosis equipment.
(8) device of putting down in writing such as above-mentioned (7), it has evaporation concentration device, the remainder of the second segment Phosphoric Acid Concentration liquid that above-mentioned evaporation concentration device evaporation and concentration goes out from the concentrated liquid chamber side-draw of second segment reverse osmosis equipment.
Among the present invention, as the phosphorous sour water of processing object so long as contain the water of phosphoric acid and get final product, not restriction, 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 (adjusts the pH of phosphorous sour water less than or equal to 1.5 o'clock above 2 less than or equal to 3, the pH of phosphorous sour water is above 1.5 and less than or equal to 3), and conductance is less than 200mS/m (conductance of adjusting phosphorous sour water more than or equal to 1800mS/m time, the conductance of phosphorous sour water is less than 1800mS/m).
In any situation, acid water is as processing object, preferably, except containing phosphate ion, all can contain cation and other impurity such as the sour composition such as nitrate ion, acetic acid ion, other anion and metal ion, but preferably, before processing, remove first decationizing.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 better phosphorous sour water of processing object, be included in the washes of the low 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 electronic equipments.
When above-mentioned processed phosphorous sour water and above-mentioned adjustment phosphoric acid water when high and concentration is low than pH, fungi, the 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 remove cationic phosphorous sour water and be adjusted to pH less than or equal to 2, preferably less than 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 conductance is more than or equal to 200mS/m, preferably carry out membrane separation more than or equal to the phosphorous sour water of the adjustment of 1800mS/m.As long as the phosphorous sour water of above-mentioned adjustment reaches above-mentioned pH, phosphoric acid concentration and conductance in the membrane separation stage, so in membrane separation, when concentrated by the enriched chamber of reverse osmosis equipment, as long as under enrichment stage, reach above-mentioned pH, phosphoric acid concentration and conductance.
In stage from processed phosphorous sour water to reverse osmosis equipment that supply with, concentration is low than pH is high if processed phosphorous sour water is with above-mentioned adjustment phosphoric acid water, then processed phosphorous sour water is adjusted.In the situation that reverse osmosis equipment is one section and more than or equal to two sections, concentration is low than pH is high with above-mentioned adjustment phosphoric acid water to supply with the processed phosphorous sour water of reverse osmosis equipment of first paragraph.In the situation that reverse osmosis equipment is more than or equal to two sections, because the Phosphoric Acid Concentration liquid of the reverse osmosis equipment of first paragraph reaches low pH, high concentration, so needn't adjust pH and the concentration of the later Phosphoric Acid Concentration liquid of supplying with of second segment.
When the processed phosphorous sour water of high pH, low concentration is adjusted to low pH, high concentration, 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 predetermined 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 the impurity such as nitric acid, acetic acid is removed, and phosphoric acid concentration is high, therefore preferably recycles.Concentrated phosphoric acid solution when the phosphoric acid solution in the evaporation concentration device is the concentrate of the concentrate of reverse osmosis equipment, particularly evaporation and concentration second segment can recycle.
So be adjusted to the phosphorous sour water of adjustment of low pH, high concentration, if in reverse osmosis equipment it is carried out membrane separation, then the harmful microorganism such as fungi, yeast is inhibited in the breeding of the face of reverse osmosis membrane.Therefore, even do not use the sterilizing units such as the special medicine such as oxidant or ultraviolet ray etc., the obstruction of the reverse osmosis membrane that the breeding by microorganism causes can not occur 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.Because the harmful microorganism inhibition can continue to a certain degree, adjust phosphorous sour water so also can supply with discontinuously, adjust phosphorous sour water but preferably continue to supply with.
That is, be adjusted to the phosphorous sour water of adjustment of low pH, high concentration, usually preferably supply with reverse osmosis equipment carrying out membrane separation, but also can supply with discontinuously reverse osmosis equipment to carry out membrane separation.Under latter event, normally will be than the pH of the phosphorous sour water of above-mentioned adjustment high and processed phosphorous sour water that concentration is low is directly supplied with reverse osmosis equipment to carry out membrane separation, can supply with discontinuously the phosphorous sour water of adjustment that is adjusted to low pH, high concentration, for example supplied with in 1～2 day 1 time, for example supply with about 1～2 hour, to carry out membrane separation.In this case, processed phosphorous sour water is directly supplied with reverse osmosis equipment to carry out membrane separation, can inject discontinuously phosphoric acid, with pH and the concentration of adjusting phosphorous sour water.
Among the present invention, before phosphorous sour water is supplied with reverse osmosis equipment, can carry out pre-treatment, namely remove the impurity that comprises cation and/or anion, particularly by to have removed cationic phosphorous sour water as processing object, above-mentioned phosphoric acid concentration be can be adjusted to, phosphoric acid and other sour separating effects that membrane separation produces improved.In this case, can carry out preliminary treatment, namely remove solid matter by precipitate and separate, filtration etc., can also carry out pre-treatment, namely utilize cationic ion-exchange resin to remove the cations such as metal ion, can also utilize anion exchange resin to remove anion of perchloric acid, organic acid misfit thing etc. etc.As the pretreating device that uses in the above-mentioned pre-treating technology, the general device that uses above-mentioned purpose to adopt.
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 concentration, therefore by removing above-mentioned cation and anion, can prevent film obstruction and damage etc., therefore better.As cationic ion-exchange resin, can use highly acid or weakly acidic cationic ion-exchange resin, but exchange when removing above-mentioned cation with the storng-acid cation exchange resin of H shape, the sour composition for the treatment of fluid increases, easily be adjusted to less than or equal to pH3, therefore better.As cationic ion-exchange resin, it can be chelating resin.Anion exchange resin can use strong basicity or weakly alkaline anion exchange resin.Anion 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 anion.
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 less than or equal to 2, phosphoric acid concentration supplies with concentrated liquid chamber side more than or equal to 600mg/L and conductance under more than or equal to the condition of 200mS/m, process 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 phosphorous sour water supply unit of phosphorous sour water and the concentrated phosphoric acid liquid taking-up section 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 section that sees through that sees through liquid that takes out.Can form circulating path between concentrated phosphoric acid liquid taking-up section and phosphorous sour water supply unit, above-mentioned circulating path will extremely concentrate the liquid chamber side as the phosphoric acid circulation of adjusting usefulness from the concentrated phosphoric acid liquid that concentrated phosphoric acid liquid taking-up section takes out.
When reverse osmosis equipment is two sections formations, has first paragraph Phosphoric Acid Concentration liquid supply unit, this supply unit is supplied with the second segment reverse osmosis equipment with the first paragraph Phosphoric Acid Concentration liquid of first paragraph reverse osmosis equipment, and the constituted mode of circulating path is: the concentrated liquid chamber side that the part of second segment Phosphoric Acid Concentration liquid is circulated to the reverse osmosis equipment of first paragraph from the concentrated liquid chamber side of second segment reverse osmosis equipment; And the constituted mode of concentrated phosphoric acid liquid taking-up section can be: the remainder that goes out second segment Phosphoric Acid Concentration liquid from the concentrated liquid chamber side-draw of second segment reverse osmosis equipment.Whereby, the Phosphoric Acid Concentration liquid of first paragraph reverse osmosis equipment can be supplied with the second segment reverse osmosis equipment to carry out membrane separation, and with the part of the Phosphoric Acid Concentration liquid of second segment reverse osmosis equipment as adjusting with the concentrated liquid chamber side of phosphoric acid circulation to the first paragraph reverse osmosis equipment, reclaim simultaneously remainder.
Reverse osmosis membrane is a kind of pellicle, 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, such as polyamide-based film, the polyimides system of seeing through being arranged through film, the cellulose-based film etc. that sees through, also can be asymmetric reverse osmosis membrane, have in fact the compound reverse osmosis membrane of selecting active surface separatory but preferably on little porous 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 integrated membrane modules (module) such as mechanism that catchment.Membrane module is not particularly limited, such as tubular film assembly, planar film assembly, spiral membrane assembly, hollow fiber membrane module etc. are arranged.The reverse osmosis equipment that possesses above-mentioned membrane module can use known reverse osmosis equipment, the reverse osmosis equipment of the high-permeability that preferably under low pressure operates.
With phosphorous sour water, particularly removed cationic phosphorous sour water when pH carries out membrane separation under less than or equal to 2 condition in reverse osmosis equipment, 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 concentrated liquid chamber side.At this moment, although there is a small amount of acid except phosphoric acid to remain in the concentrate, but when phosphoric acid concentration carried out membrane separation under more than or equal to the condition of 600mg/L, 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, can say that ionic substance easily is prevented from utterly than the nonionic material.But, be difficult for dissociating at phosphoric acid, pH is less than or equal to carrying out reverse osmosis membrane when processing under 2 the condition, the prevention rate of phosphoric acid uprises utterly than nitric acid and acetic acid, can reclaim respectively acid and phosphoric acid beyond the phosphoric acid such as nitric acid and acetic acid.
If the phosphoric acid concentration of concentrate is too high, then can't carry out film owing to soaking into the relation of pressure and process, so the phosphoric acid concentration of concentrate on be limited to 15 percentage by weights (wt%), preferably 10wt%.The concentrate of above-mentioned phosphoric acid concentration if circulate in the limit, the limit adds processed phosphorous sour water in the concentrate of circulation, the concentrate piecemeal is taken out as Phosphoric Acid Concentration liquid, then can keep above-mentioned phosphoric acid concentration and process expeditiously to carry out a processing of crossing formula.
Film is carried out when processing in circulation concentrate limit, limit, and the cycle-index of concentrate is more, and the acid beyond the phosphoric acid contact with reverse osmosis membrane and to see through the chance of film just more, can further reduce the concentration of phosphoric acid acid in addition in the concentrate.At this moment, if phosphoric acid concentration surpasses 15wt%, then can't carry out film and process, so adding dilution water in concentrate dilutes, circulate afterwards and carry out reverse osmosis and process, 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 see through water, having removed impurity.
From seeing through the water that sees through of reverse osmosis equipment that the liquid chamber side-draw goes out, owing to wherein contain the acid such as the phosphoric acid that sees through, nitric acid, acetic acid, so by utilizing impurities removing unit to remove above-mentioned acid and other impurity from seeing through of reverse osmosis equipment the water, can reclaim pure water.In this case, impurities removing unit can adopt the ion interchange unit that makes spent ion exchange resin, biological treatment device etc.
On the other hand, the Phosphoric Acid Concentration liquid that goes out from concentrating the liquid chamber side-draw, although the major part of the acid beyond the phosphoric acid such as nitric acid wherein and acetic acid has been removed, in order further to remove mentioned component to improve purity and the concentration that reclaims phosphoric acid liquid, can carry out purifying by post processing.As the purifying that is undertaken by post processing, can from Phosphoric Acid Concentration liquid, remove phosphoric acid acid in addition by anion exchange and carry out purifying.In this case, the anion exchange device is set as purification devices, concentrate is passed in the anion exchange resin layer, from concentrate, remove the strong acid ion of nitric acid etc., can reclaim the phosphoric acid of the high concentration of the strong acid ion that contains hardly nitric acid etc.
When reverse osmosis equipment is during more than or equal to two sections formation, to adjust reverse osmosis equipment that phosphorous sour water supplies with first paragraph carrying out membrane separation, the Phosphoric Acid Concentration liquid of the reverse osmosis equipment of first paragraph is supplied with the later reverse osmosis equipment of second segment to carry out the later membrane separation of second segment.In this case, reverse osmosis equipment has first paragraph Phosphoric Acid Concentration liquid supply unit, this supply unit is supplied with the second segment reverse osmosis equipment with the first paragraph Phosphoric Acid Concentration liquid of first paragraph reverse osmosis equipment, and the constituted mode of circulating path is: the part of second segment Phosphoric Acid Concentration liquid is circulated to phosphorous sour water adjustment part from the concentrated liquid chamber side of second segment reverse osmosis equipment; And the constituted mode of concentrated phosphoric acid liquid taking-up section is: the remainder of the second segment Phosphoric Acid Concentration liquid concentrated liquid chamber side-draw from the second segment reverse osmosis equipment is gone out.The above-mentioned second segment Phosphoric Acid Concentration liquid that has taken out further carries out evaporation and concentration with evaporation concentration device, can reclaim as Phosphoric Acid Concentration liquid.The Phosphoric Acid Concentration liquid of evaporation and concentration can also be circulated to phosphorous sour water adjustment part, use phosphoric acid with adjusting.
Namely, when in the phosphoric acid liquid that sees through with the second segment reverse osmosis equipment during residual acetic acid, namely use anion exchange resin acetic acid can not be removed fully, therefore reclaim purity and the concentration of phosphoric acid liquid with raising in order to remove the volatile ingredients such as acetic acid, carry out evaporation and concentration with evaporation concentration device, water and volatile ingredient are together removed with concentrated phosphoric acid liquid, thereby can be reclaimed the phosphoric acid that contains hardly the high concentration of the volatile ingredients such as acetic acid.Evaporation concentration device can use the 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 concentration, and can be used as highly purified concentrated phosphoric acid and reclaim.In the present invention, although be under less than or equal to the condition of pH2, to carry out the reverse osmosis processing, but processed phosphorous sour water is usually obtaining less than or equal to the acid state of pH3, therefore by injecting the phosphoric acid that reclaims as pH adjusting agent, can easily regulate.In addition, utilize to be used for reclaim method and the device of phosphoric acid, by simple formation and operation, phosphorous sour water can be adjusted to pH less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and conductance more than or equal to 200mS/m.
The effect of invention
Regulate pH, phosphoric acid concentration and conductance by aforesaid operations, supply with to adjust Phosphoric Acid Concentration liquid, and carry out reverse osmosis and process, thereby the generation of the microorganisms such as Antifungi, yeast can be reclaimed high-purity phosphoric acid.Whereby, reduce the use amount of medicine and the growing amount of discarded object, 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 for adjusting phosphorous sour water, can also flood the reverse osmosis assembly that takes out from reverse osmosis equipment, the generation that is used for the microorganisms such as fungi, yeast suppresses to process 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 remove cationic phosphorous sour water and be adjusted to pH less than or equal to 2, phosphoric acid concentration is more than or equal to 600mg/L, and conductance is carried out membrane separation more than or equal to the phosphorous sour water of the adjustment of 200mS/m, so do not use special medicine etc., utilize simply to consist of and operation, can be low-cost and expeditiously from phosphorous sour water with the transportable aqueous recovery Antifungi of high concentration, the generation of the microorganisms such as yeast, can be used as the highly purified phosphoric acid of regenerant.
Description of drawings
Fig. 1 is phosphoric acid recovery method in the embodiment and the flow chart of device.
Fig. 2 is the curve map 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: concentrated 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
The specific embodiment
Below, utilize diagram that embodiments of the present invention are described.Fig. 1 is phosphoric acid recovery method in the embodiment and the flow chart of device.1 is former tank, stores former water (processed phosphorous sour water) 1a.2 is pretreating device, is made of cation exchange device, anion exchange device and other impurities removing unit, but preferably, consists of according to being provided with at least the cation exchange device and removing cationic mode.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 interchange 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 force (forcing) pump, and its formation will be adjusted the former water supply unit 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 consist of concentrated phosphoric acid liquid taking-up section.The pump P2, adjustment liquid bath 3 and the pH meter pH that are arranged on the circulating path L4 consist of phosphorous sour water adjustment part.
In above-mentioned phosphoric acid retracting device, will carry out former water 1a (phosphoric acid ionized water) pretreating process, that namely removed impurity by precipitate and separate, filtration etc. and import the former tank 1 from pipeline L1.The former water 1a of former tank 1 imports the pretreating device 2 from pipeline L2, removes the cations such as indium contained in the former water, other metal ions, but preferably, further removes the impurity such as anion of perchloric acid, organic acid misfit thing etc.Pre-treatment water imports from pipeline L3 and adjusts the liquid bath 3.
Usually obtain less than or equal to 3 acid state with pH as the phosphorous sour water of former water, but when pH carries out reverse osmosis under less than or equal to 2 condition and processes, 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, survey the pH that adjusts the adjustment liquid 3a in the liquid bath 3 with the pH meter pH meter, control is arranged at the pump P2 on the circulating path L4, and the pH that adjusts liquid 3a is adjusted to less than or equal to 2.In this case, if make concentrated phosphoric acid liquid circulate to be adjusted to less than or equal to pH2, then adjust liquid 3a be adjusted to phosphoric acid concentration more than or equal to 600mg/L and conductance more than or equal to 200mS/m.Need to prove, in Fig. 1, although be to utilize pH meter to adjust the pH of liquid 3a, also can regulate phosphoric acid concentration and conductance with densimeter and conductivity meter.
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 film and separate (reverse osmosis processing), the 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 processing 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 process but it is imported under less than 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 the 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 less than or equal to pH2, preferably less than or equal to pH1.5, phosphoric acid concentration more than or equal to 600mg/L, preferably more than or equal to 1500mg/L and conductance more than or equal to 200mS/m, preferably more than or equal to 1800mS/m, therefore supplied with 1RO device 4 carrying out membrane separation by adjusting phosphorous sour water, but the harmful microorganisms such as Antifungi, yeast are bred at the face of reverse osmosis membrane.Therefore, even do not use special medicine etc., the obstruction of the reverse osmosis membrane that the breeding by microorganism causes can not occur 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.Because the harmful microorganism inhibition will continue to a certain degree, adjust phosphorous sour water so can supply with discontinuously, adjust phosphorous sour water but preferably continue to supply with.
See through the importing the after-treatment device 6 from pipeline L6 through liquid through liquid chamber 4b side to 1RO device 4, utilize ion interchange unit, biological treatment device, other impurities removing unit to remove anion and other impurity through the nitric acid of RO film 4a, acetic acid etc., discharge from pipeline L7.The pure water of having removed above-mentioned impurity is recovered to from pipeline L8 and reclaims the tank 7, is stored up as recycle-water 7a, takes out from pipeline L9.
Carry out film when processing with the RO device of one-part form, to carrying out post processing through the concentrated concentrate of the concentrated liquid chamber 4c of 1RO device, can be recycled phosphoric acid, but carry out film when processing with the RO device of two-part, to import the concentrated liquid chamber 5c of 2RO device 5 from pipeline L11 through the concentrated concentrate of the concentrated liquid chamber 4c of 1RO device, utilize RO film 5a to carry out film and separate (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 concentrate 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, is stored up as adjusting and uses phosphoric acid liquid 9a.
The remainder of the concentrate of 2RO device 5 imports the evaporation concentration device 8 from pipeline L10, carries out evaporation and concentration.The condensed water 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 and 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 that reclaims according to the method described above can be used as regenerant, and is recovered with the aqueous of high concentration, 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 less than or equal to 2, phosphoric acid concentration supplies with the RO device more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of the adjustment of 200mS/m, to carry out membrane separation, even do not use whereby special medicine etc., also can Antifungi, the generation of the microorganism such as yeast, to carry out membrane separation.Whereby, the use amount of medicine and growing amount, the reduction processing cost of discarded object 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 prevention rate and special instructions, % represents wt%.
(embodiment 1～6, comparative example 1～4):
Use the conductance of acetic acid of nitric acid, 1000mg/L of the phosphoric acid that contains 11000mg/L, 1000mg/L as the phosphorous sour water of the standard of 1150mS/m, pH1.3, it is diluted to regulate pH etc. with pure water, obtain the former water (adjusting phosphorous sour water) of table 1.Need to prove, in the table 1, comparative example 1 is that the phosphorous sour water of standard is regulated pH with the pure water dilution is rear with NaOH, thereby is adjusted to the former water of the 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 less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L, conductance more than or equal to 200mS/m.
Table 1
| pH | Phosphoric acid (mg/L) | Conductance (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 |
| |
1.7 | 1600 | 355 |
| Embodiment 4 | 1.5 | 5000 | 612 |
| Embodiment 5 | 1.4 | 8500 | 795 |
| Embodiment 6 | 1.3 | 11000 | 1150 |
Flat membrane pilot unit contained as the reverse osmosis equipment of simulation drawing 1, use following apparatus: utilize sintered porous plate, be that the flat film of day eastern electrician (thigh) reverse osmosis membrane ES-20 processed of the circle of 32mm φ is pressed directly 29mm φ support of effective film with cutting into diameter, be installed in the flat film unit of the stainless steel that internal diameter is 32mm φ (SUS304) path processed, utilize pump to supply with former water to the concentrated liquid chamber of unit, mix with the concentrate that is detained, utilize counterbalance valve to discharge concentrate, to regulate the concentrate operating pressure, stir at the indoor rotor of concentrate, make the concentrate circulation, the device of homogenising.
With the former water (adjust phosphorous sour water) of 1mL/ minute flow to enriched chamber's supply schedule 1 of above-mentioned flat membrane pilot unit contained, with the liquid in the rotor agitating unit, mix with the concentrate that is detained, regulate simultaneously counterbalance valve, make through the water yield to equate (0.5mL/ minute) with the concentrated water yield, carry out film and separate.Pressure during with aforesaid operations is as operating pressure, and is as shown in table 2.Afterwards, keep this operating pressure constant, proceed film and separate.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, after running beginning approximately 1 hour identical with the numerical value of table 2, this value is maintained to the running end.Need to prove, the prevention rate utilizes formula ((1-sees through the concentration of the concentration/condensed water of water) * 100) to calculate.
Table 2
With embodiment 1,4 and the condensed water of comparative example 1～3 gained carry out culture experiment with culture dish.Culture medium is for adding antibiotic PDA culture medium, cultivates in thermostat 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 differential gap.In addition, pH is sickle-like bacteria (fusariumspp.) less than or equal to the fungi strain of generation in 3 o'clock.The result of culture dish culture experiment, namely until to be observed visually the fate of fungus colony as shown in table 3.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 water test device as the reverse osmosis equipment of simulation drawing 1, use the device that consists of day concentrated liquid chamber of 4 inches new product membrane modules of eastern electrician (thigh) ultralow pressure aromatic polyamide processed type RO film " ES20-D2 " (container is seawater desalination S2 container) and adjustment liquid bath according to the mode of a part of concentrate circulation, the former water (adjusting phosphorous sour water) of embodiment 1 and 4 was supplied with the enriched chamber of RO device in 5L/ minute from adjusting liquid bath with the salt solution water yield, carrying out film separates, a part of concentrate is circulated to the adjustment liquid bath, be circulated to former tank with another part concentrate and through liquid, processed 1 month, and made the water quality that reaches table 2.The result of processing 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 large difference on handling property.But, when studying the attachment of the glutinous mud (slime) after processing 1 month, in the former water treatment of embodiment 1, hang with a little thread glutinous mud at the electrode that is arranged at the liquid level meter of adjusting liquid bath, 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 less than or equal to pH2, particularly less than or equal to pH1.5, phosphoric acid concentration more than or equal to 600mg/L, particularly more than or equal to 1500mg/L and conductance more than or equal to 200mS/m, particularly carry out membrane separation more than or equal to the phosphorous sour water of the adjustment of 1800mS/m, in the situation that do not use special medicine etc., utilize simple formation and operation, can from phosphorous sour water, reclaim the generation of the microorganisms such as Antifungi, 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 (10)
1. method that reclaims phosphoric acid uses reverse osmosis equipment to carrying out reverse osmosis and process to reclaim phosphoric acid through removing cationic phosphorous sour water, it is characterized in that:
In reverse osmosis equipment, carry out reverse osmosis and process adjusting phosphoric acid water, the phosphorous sour water of above-mentioned adjustment be adjusted to pH less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and conductance more than or equal to 200mS/m.
2. method that reclaims phosphoric acid uses reverse osmosis equipment to carrying out reverse osmosis and process to reclaim phosphoric acid through removing cationic phosphorous sour water, it is characterized in that:
To adjust phosphorous sour water and supply with discontinuously reverse osmosis equipment and process to carry out reverse osmosis, the phosphorous sour water of above-mentioned adjustment be adjusted to pH less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and conductance 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 the above-mentioned reverse osmosis equipment of first paragraph, the phosphorous sour water of above-mentioned adjustment is carried out reverse osmosis and processes,
In the later above-mentioned reverse osmosis equipment of second segment, the Phosphoric Acid Concentration liquid of the above-mentioned reverse osmosis equipment of first paragraph is carried out the later reverse osmosis of second segment process.
4. the method for recovery phosphoric acid according to claim 1 and 2 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 predetermined value in processed phosphorous sour water.
5. the method for recovery phosphoric acid according to claim 1 and 2, 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 predetermined value.
6. the method for recovery phosphoric acid according to claim 3 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 predetermined value in processed phosphorous sour water.
7. the method for recovery phosphoric acid according to claim 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 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 predetermined value.
8. a phosphoric acid retracting device from reclaim phosphoric acid through removing cationic phosphorous sour water, is characterized in that, above-mentioned phosphoric acid retracting device comprises:
Phosphorous sour water adjustment part, its with processed phosphorous sour water be adjusted to pH less than or equal to 2, phosphoric acid concentration more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of the adjustment of 200mS/m;
Reverse osmosis equipment, its to be adjusted to pH less than or equal to 2, phosphoric acid concentration carries out reverse osmosis more than or equal to 600mg/L and conductance more than or equal to the phosphorous sour water of above-mentioned adjustment of 200mS/m and processes, so that together seeing through, the acid beyond the phosphoric acid and water extremely sees through the liquid chamber side, and at concentrated liquid chamber side concentrated phosphoric acid;
Phosphorous sour water supply unit, 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 section, 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 section, it takes out the remainder from the above-mentioned concentrated liquid chamber side of above-mentioned reverse osmosis equipment.
9. phosphoric acid retracting device according to claim 8 is characterized in that, above-mentioned reverse osmosis equipment is formed two sections formation,
Comprise first paragraph Phosphoric Acid Concentration liquid supply unit, above-mentioned first paragraph Phosphoric Acid Concentration liquid supply unit is supplied with the first paragraph Phosphoric Acid Concentration liquid of first paragraph reverse osmosis equipment to the second segment reverse osmosis equipment;
Wherein, the constituted mode of above-mentioned circulating path is: the part of second segment Phosphoric Acid Concentration liquid is circulated to above-mentioned phosphorous sour water adjustment part from the above-mentioned concentrated liquid chamber side of second segment reverse osmosis equipment;
The constituted mode of above-mentioned concentrated phosphoric acid liquid taking-up section is: the remainder that goes out above-mentioned second segment Phosphoric Acid Concentration liquid from the above-mentioned concentrated liquid chamber side-draw of above-mentioned second segment reverse osmosis equipment.
10. phosphoric acid retracting device according to claim 9, it is characterized in that, described device comprises evaporation concentration device, the remainder of the above-mentioned second segment Phosphoric Acid Concentration liquid that above-mentioned evaporation concentration device evaporation and concentration goes out from the above-mentioned concentrated liquid chamber side-draw of above-mentioned second segment reverse osmosis equipment.
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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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| 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 |
| 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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| 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 |
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| JP4728503B2 (en) * | 2001-05-07 | 2011-07-20 | 日本ペイント株式会社 | Washing water treatment method and treatment apparatus for phosphate film chemical conversion treatment |
| JP2002370088A (en) * | 2001-06-13 | 2002-12-24 | Nippon Parkerizing Co Ltd | Method for recovering washing water discharged from coating pretreatment line |
| 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 |
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| JP特开2002-332583A 2002.11.22 |
| JP特开2002-370088A 2002.12.24 |
| JP特开2002-86147A 2002.03.26 |
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| KR101621835B1 (en) | 2016-05-31 |
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