KR101621835B1 - 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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- KR101621835B1 KR101621835B1 KR1020107021133A KR20107021133A KR101621835B1 KR 101621835 B1 KR101621835 B1 KR 101621835B1 KR 1020107021133 A KR1020107021133 A KR 1020107021133A KR 20107021133 A KR20107021133 A KR 20107021133A KR 101621835 B1 KR101621835 B1 KR 101621835B1
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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- B01D61/025—Reverse osmosis; Hyperfiltration
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Abstract
It is possible to control the generation of microorganisms such as fungi and yeast from the phosphoric acid-containing water without using special medicines or the like and to recover the high-purity phosphoric acid useful as the recovered product in a liquid phase of high concentration at low cost or efficiently A phosphoric acid recovery method and a phosphoric acid recovery device are provided. The reverse osmosis treatment is carried out in the first reverse osmosis unit 4 by adjusting the pH of the phosphoric acid-containing water to not less than pH 2, not less than 600 mg / L, or the electric conductivity of not less than 200 mS / m, The concentrated liquid is supplied to the second reverse osmosis unit 5 and the second reverse osmosis unit 5 is returned to the second reverse osmosis unit 5 ) Is circulated as the adjusting phosphoric acid solution 9a and the remaining portion is recovered as the concentrated phosphoric acid solution 10a by removing the volatile components together with water with the evaporation concentrator 8. [
Description
The present invention relates to a method and apparatus for recovering phosphoric acid from a phosphoric acid-containing water by a reverse osmosis device and, more particularly, to a method and apparatus for recovering phosphoric acid from a phosphoric acid-containing water by washing a liquid crystal substrate, And recovering purified water, such as phosphoric acid, and purified water, which is treated water, into recoverable phosphoric acid, and a device therefor.
An etchant containing phosphoric acid is used for etching liquid crystal substrates, wafers and other electronic devices. The waste etching solution at a high concentration generated in the etching process is recovered and used for recycling. However, the electronic devices after etching are cleaned by pure water, and a large amount of low-concentration washing water is produced. Such rinse wastewater contains phosphoric acid, nitric acid, acetic acid and other acid components, which are the components of the etching solution, as well as metal ions and other impurities that have been eluted by etching, but most of them are pure water.
Such etching rinse wastewater has conventionally been mixed with other wastewater. Coagulation sedimentation treatment is a treatment technique of wastewater containing common phosphoric acid or hydrofluoric acid. However, in the case of flocculation and precipitation treatment of phosphoric acid or hydrofluoric acid, the use of a large amount of chemicals, an increase in treatment cost due to the generation of a large amount of sludge, and an increase in load on the environment become problems. In addition, the increase of water-soluble ions by a large amount of a chemical added during the flocculation and sedimentation treatment causes an increase in power cost due to an increase in the operating pressure of the reverse osmosis membrane process, deterioration of the treated water quality, generation of scale, Leading to an increase in the amount of regenerant used depending on use.
Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-75820) discloses a method of removing ions such as phosphoric acid and nitric acid with an ion exchange resin and recovering pure water and phosphate. However, since the phosphate is recovered in the form of sodium dihydrogenphosphate, there is almost no phos- phate pathway, and since the sodium salt of phosphoric acid has a low solubility, the content ratio of phosphoric acid in the liquid phase is low and it is difficult to carry have. On the other hand, there is a problem that caustic gauze (potassium hydroxide) is expensive when it is recovered as a potassium salt. Further, although a method of passing through an H-type cationic resin for recovering sodium dihydrogen phosphate has been disclosed, there is a problem that an acid such as hydrochloric acid is consumed by the regeneration of the cationic resin and sodium hydride used for regeneration of the anionic resin is unnecessarily There is a defect such as being discharged.
If a reverse osmosis (RO) membrane is used to replace the ion exchange resin and concentrate separation is carried out, harmful microorganisms such as fungi and yeast are proliferated on the surface of the membrane to increase the transmembrane pressure and decrease the permeation rate. The control of harmful microorganisms such as molds and yeasts includes physical control (proliferation control, sterilization, blocking, sterilization), physicochemical control (proliferation control), chemical control (proliferation control, pharmaceutical sterilization) and biological preparation. Among these, there are temperature control and chemical control (proliferation inhibitor) for the proliferation control. Examples of the sterilization include pasteurization, high temperature sterilization, electromagnetic wave sterilization (gamma ray, ultraviolet ray, microwave, etc.), high pressure sterilization (High-pressure pulse), sterilization of medicines includes solid disinfectants such as gas disinfectants (EO, formaldehyde, ozone, hydrogen peroxide), liquids, solution disinfectants (alcohol, hydrogen peroxide water, organic disinfectant, etc.) (Such as silicon-based quaternary ammonium).
However, the above method has a drawback that the energy consumption is large, the facility cost is high, the adverse effect on the reverse osmosis membrane (clogging due to oxidation, chemical adsorption or alteration) may occur, and the performance of the reverse osmosis membrane is deteriorated . In addition, toxic and environment-friendly chemicals are problematic for drugs such as gas disinfectants (EO, formaldehyde, etc.) and organic disinfectants used for chemical control. When the harmful microorganisms such as mold and yeast are propagated on the surface of the membrane, the resin and the eyes of the reverse osmosis membrane become clogged, making it impossible to perform stable operation and it is difficult to remove microorganisms such as fungi and yeast, There is no countermeasure against the use of oxidizing agents because the reverse osmosis membrane can not be used.
It is an object of the present invention to suppress the generation of microorganisms such as fungi and yeast from the phosphoric acid-containing water by a simple constitution and operation without using a special medicament or the like and to provide a high purity phosphoric acid useful as a recovered product in a liquid phase And to provide a method and apparatus for recovering phosphoric acid which can be recovered at low cost or efficiently.
The present invention relates to a method and apparatus for recovering phosphoric acid from a phosphate ion-containing water as described below.
(1) A method for recovering phosphoric acid by subjecting phosphoric acid-containing water to membrane separation treatment with a reverse osmosis device, wherein the adjusted phosphoric acid-containing water adjusted to
(2) A method for recovering phosphoric acid by subjecting a phosphoric acid-containing water to membrane separation treatment with a reverse osmosis device, wherein the adjusted phosphoric acid-containing water adjusted to a pH of 2 or lower, a phosphoric acid concentration of 600 mg / L or higher, or an electric conductivity of 200 mS / And then supplied to the permeating device to perform membrane separation treatment.
(3) The method according to the above (1) or (2), wherein the reverse osmosis device is constituted by two or more stages, the adjusted phosphorus-containing water is subjected to membrane separation treatment in the reverse osmosis device of the first stage, Wherein the phosphoric acid concentrate treated in the reverse osmosis unit is subjected to the membrane separation treatment after the second stage in the reverse osmosis unit after the second stage.
(4) The method of any one of (1) to (3) above, wherein the adjusted phosphoric acid-containing water to be supplied to the reverse osmosis device is adjusted to a predetermined value by adding phosphoric acid to the treated phosphoric acid- Recovery method.
(5) The method according to any one of (1) to (4) above, wherein the adjusted phosphoric acid-containing water supplied to the reverse osmosis device is the phosphoric acid-containing water of the reverse osmosis device and / Phosphoric acid liquid is added and adjusted to a predetermined value.
(6) An apparatus for recovering phosphoric acid from phosphoric acid-containing water is provided. The apparatus comprises a phosphoric acid-containing water adjuster for adjusting the pH of the treated phosphoric acid-containing water to
(7) In the apparatus described in (6) above, the reverse osmosis device is composed of two stages, and the first stage of supplying the first stage phosphoric acid concentrate of the first stage reverse osmosis device to the second stage reverse osmosis device And a phosphoric acid concentrated liquid supply unit. And the circulation path is configured to circulate a portion of the second stage phosphoric acid concentrate from the concentrated liquid side of the second stage reverse osmosis device to the phosphoric acid-containing water adjustment section. And the concentrated phosphoric acid liquid takeout portion is configured to extract the remaining portion of the second stage phosphoric acid concentrate from the concentrated liquid side of the second stage reverse osmosis device.
(8) The apparatus according to (7), further comprising an evaporation concentrator for concentrating the remaining portion of the second stage phosphoric acid concentrate extracted from the concentrated solution side of the second stage reverse osmosis device.
In the present invention, the phosphoric acid-containing water to be treated is not limited if it is water containing phosphoric acid. However, if the phosphoric acid ion concentration is 50 mg / L or more and less than 600 mg / L (when the adjusted phosphoric acid- (PH below 1.5 and
The object to be treated is preferably an acidic water, and may contain phosphate ions and other nitrate ions, acid components such as nitric acid ions, other cationic substances such as anions and metal ions, and other impurities. However, It is preferable to remove the film. The present invention is particularly suitable for removing phosphoric acid-containing water containing nitric acid ions, nitric acid ions, and other acid components and other acid components such as nitric acid ions, acetic acid ions and the like and recovering high purity phosphoric acid. Particularly, the phosphoric acid-containing water preferable as the object to be treated includes low-rinsing rinsing water which is generated when pure cleaning is performed after etching with a phosphoric acid-containing etching solution of a liquid crystal substrate, wafer or other electronic equipment.
When the pH of the treated phosphoric acid-containing water is higher than that of the adjusted phosphoric acid-containing water, the harmful microorganisms such as mold and yeast may grow on the membrane surface of the reverse osmosis membrane to cause clogging. Therefore, The pH of the phosphoric acid-containing water from which the cationic water is removed is adjusted to
The adjustment of the treated phosphoric acid-containing water is performed at a higher pH and a lower concentration than the adjusted phosphoric acid-containing water in the step of supplying the treated phosphoric acid-containing water to the reverse osmosis device. In the case where the reverse osmosis device has one stage and two or more stages, the number of the treated phosphoric acid-containing water supplied to the reverse osmosis unit of the first stage is higher than that of the adjusted phosphorus-containing water. When the reverse osmosis device has two or more stages, the concentration of the phosphoric acid concentrate of the first-stage reverse osmosis device is low and the concentration is high. Therefore, it is not necessary to adjust the pH and concentration of the concentrated phosphoric acid supplied after the second stage.
In order to adjust the pH and the concentration of the low-concentration treated phosphoric acid-containing water to a low pH and a high concentration, it is preferable to inject an acid into the treated phosphoric acid-containing water for pH and concentration adjustment. Containing phosphorus-containing water having a value of "% " As the phosphoric acid added to the treated phosphoric acid-containing water, a phosphoric acid solution of the reverse osmosis device and / or a phosphoric acid solution of an evaporation concentration device may be used. The concentrated phosphoric acid solution of the reverse osmosis device is preferably circulated because impurities such as nitric acid and acetic acid are removed and the concentration of phosphoric acid is high. The phosphoric acid solution of the evaporation concentrator is a concentrated phosphoric acid solution obtained by concentrating the concentrate of the reverse osmosis device, especially the concentrate of the second stage by evaporation, and this can be circulated.
As described above, when the adjusted phosphoric acid-containing water adjusted to a low pH and a high concentration is subjected to membrane separation treatment in a reverse osmosis device, the propagation of harmful microorganisms such as fungi and yeast on the membrane surface of the reverse osmosis membrane is inhibited. Therefore, even if a special medicament such as an oxidizing agent, ultraviolet rays, or the like is not used, clogging of the reverse osmosis membrane due to the propagation of microorganisms does not occur and a stable reverse osmosis device Can be operated. Since the harmful microbial inhibitory effect lasts to some extent, it is preferable to continuously supply the adjusted phosphoric acid-containing water even though the adjusted phosphoric acid-containing water can be supplied intermittently.
That is, it is preferable that the adjusted phosphoric acid-containing water adjusted to a low pH and a high concentration is continuously supplied to the reverse osmosis device to perform the membrane separation treatment, but the membrane separation treatment may be performed intermittently. In the latter case, the treated phosphoric acid-containing water having a higher pH and a lower concentration than the above-mentioned adjusted phosphoric acid-containing water is usually supplied to the reverse osmosis device as it is and the membrane separation treatment is carried out, and intermittently, for example, The adjusted phosphoric acid-containing water adjusted to a low pH and a high concentration for 1 to 2 hours may be supplied to perform the membrane separation treatment. In this case, the treated phosphoric acid-containing water can be directly supplied to the reverse osmosis device to carry out the membrane separation treatment, and the pH and the concentration of the phosphoric acid-containing water can be adjusted by intermittently injecting phosphoric acid.
In the present invention, before the phosphoric acid-containing water is supplied to the above-described reverse osmosis device, impurities containing cations and / or anions can be removed as a pretreatment. Particularly, The separation efficiency between phosphoric acid and other acids can be increased by adjusting the concentration of phosphoric acid and performing film separation treatment. In this case, as a preliminary treatment, removal of solids by precipitation separation, filtration and the like and pretreatment can be carried out to remove cations such as metal ions by a cation exchange resin, and further, anion exchange resin such as perchloric acid, Removal of anions and the like can be performed. As a pretreatment apparatus used in such a pretreatment step, a general apparatus employed for the above purpose is used.
Metal ions such as indium, iron, and aluminum contained in the rinsing water after etching cause clogging of the reverse osmosis (RO) film in the membrane separation process, and perchloric acid or the like may cause film damage when the concentration is high. It is preferable to remove the cation or the anion of the film so that the film can be prevented from being clogged or damaged. As the cation exchange resin, a strongly acidic or weakly acidic cation exchange resin can be used, but when the strongly acidic cation exchange resin of the H type is used to exchange and remove the cation, the acidity of the treatment liquid increases to adjust the pH to 3 or less So that it is preferable. As the cation exchange resin, it may be a chelate resin. As the anion exchange resin, a strongly basic or weakly basic anion exchange resin can be used. The anion exchange resin is used as an acid type such as a phosphoric acid type and passes through phosphoric acid, nitric acid, acetic acid and the like to remove other impurity anions.
The reverse osmosis device in the membrane separation process of the present invention is also referred to as an RO device and is divided into a permeate chamber and a concentrate chamber by a reverse osmosis (RO) membrane, and the pH of the phosphate- Permeation membrane treatment is performed under the condition of 200 mS / m or more to conduct the reverse osmosis membrane treatment, and the acid other than the phosphoric acid is permeated to the permeated liquid side with water and the phosphoric acid is concentrated to the concentrated liquid side. In the reverse osmosis device of the reverse osmosis device, a phosphoric acid-containing water supply portion for supplying the phosphoric acid-containing water and a concentrated phosphoric acid solution outlet portion for extracting the concentrated phosphoric acid solution are formed. A permeate outlet portion for extracting the permeate is formed on the permeate side of the permeate of the reverse osmosis device. Between the concentrated phosphoric acid solution outflow portion and the phosphoric acid-containing water supply portion, a circulation path can be formed in which the concentrated phosphoric acid solution extracted from the concentrated phosphoric acid solution outflow portion is circulated as the adjustment phosphoric acid to the concentrated solution chamber side.
And a first stage phosphoric acid concentrate supply unit for supplying the first stage phosphoric acid concentrate of the first stage reverse osmosis device to the second stage reverse osmosis device when the reverse osmosis device has a two stage structure, Wherein a part of the second stage phosphoric acid concentrate is circulated to the concentrated liquid side of the first stage reverse osmosis device in the concentrated liquid side of the second stage reverse osmosis device and the concentrated phosphoric acid liquid take- The remaining portion of the second stage phosphoric acid concentrate can be taken out. As a result, the phosphoric acid concentrate of the first permeation device is supplied to the second permeation device to perform a membrane separation treatment, so that a part of the phosphoric acid concentrate of the second permeation device is used as the adjustment phosphoric acid It is possible to circulate the concentrate of the first stage reverse osmosis device and recover the remaining portion.
The reverse osmosis membrane is a semi-permeable membrane that permeates water by permeation pressure or conversely pressurizes to a higher pressure than osmotic pressure to feed the liquid to be treated, while permeating water through reverse osmosis while blocking salt and other solute from permeating. The material of the reverse osmosis membrane is not particularly limited as long as it has the above characteristics, and examples thereof include a polyamide-based permeable membrane, a polyimide-based permeable membrane, and a cellulose-based permeable membrane, and an asymmetric reverse osmosis membrane is also possible, A composite reverse osmosis membrane in which an active skin layer having substantially selective separation is formed on a microporous support is preferable.
The reverse osmosis device may be provided with such a reverse osmosis membrane, but it is preferable that the reverse osmosis membrane device is provided with a membrane module in which a reverse osmosis membrane, a supporting mechanism, a collecting mechanism, and the like are integrated. The membrane module is not particularly limited and includes, for example, a tubular membrane module, a flat membrane module, a spiral membrane module, and a hollow membrane module. As the reverse osmosis device having these, generally known ones can be used, and it is preferable that the reverse osmosis device is operated at a low pressure and has high permeability.
When the phosphoric acid-containing water, particularly the phosphoric acid-containing water from which the cation is removed, is subjected to membrane separation treatment in the reverse osmosis device under the condition of
Comparing the permeation of ionic and nonionic materials to the reverse osmosis membrane, it is known that the reverse osmosis membrane blocking rate is overwhelmingly inhibited by the ionic material as compared with the nonionic material, even with the same molecular weight. However, when the reverse osmosis membrane treatment is performed under the condition of
If the concentration of phosphoric acid in the concentrate is too high, it becomes difficult to carry out the membrane treatment in relation to the osmotic pressure, so that the upper limit of the concentration of phosphoric acid in the concentrate is 15% by weight, preferably 10%. When the concentrated phosphoric acid-containing water is added to the circulating concentrate while circulating the concentrate of phosphoric acid concentration and the concentrate is partially taken out into the phosphoric acid concentrate to perform the single-pass treatment, the membrane treatment Can be performed.
As the number of cycles of the concentrate is increased, the acid other than phosphoric acid is in contact with the reverse osmosis membrane and has a greater chance of permeating through the membrane, so that the concentration of the acid other than phosphoric acid in the concentrate becomes lower can do. At this time, if the concentration of phosphoric acid exceeds 15% by weight, it becomes impossible to perform the membrane separation. Therefore, concentration of acid other than phosphoric acid can be further lowered by adding diluted water to the concentrate and circulating it, A high-purity phosphoric acid concentrate can be recovered. As the diluted water, it is possible to circulate the recovered water from which the impurities are removed from the permeated water.
Since the permeated water of the reverse osmosis device taken out from the side of the permeated liquid contains an acid such as permeated phosphoric acid, nitric acid or acetic acid, these impurities are removed from the permeated water of the reverse osmosis device by the impurity removing device , Pure water can be recovered. In this case, as the impurity removing device, an ion exchange device using an ion exchange resin, a biological treatment device, or the like can be used.
On the other hand, most of the acids other than phosphoric acid such as nitric acid and acetic acid are removed from the concentrate of phosphoric acid taken out from the concentrate solution side, but purification can be carried out by post treatment in order to remove them and increase the purity and concentration of the recovered phosphoric acid solution have. As the purification by the above-mentioned post-treatment, purification can be performed by removing an acid other than phosphoric acid from the phosphoric acid concentrate by anion exchange. In this case, an anion exchange apparatus is provided as a refining apparatus, the concentrate is passed through an anion-exchange resin layer, and strong acid ions such as nitric acid are removed from the concentrate, whereby a high concentration of phosphoric acid have.
In the case where the reverse osmosis device has two or more stages, the adjusted phosphorus-containing water is supplied to the reverse osmosis device of the first stage to perform the membrane separation treatment, and the phosphate concentrate of the reverse osmosis device To the reverse osmosis device of the second stage to perform the membrane separation process after the second stage. In this case, the reverse osmosis device has a first stage phosphate concentrate feeder for feeding the first stage phosphoric acid concentrate of the first stage reverse osmosis device to the second stage reverse osmosis device, The concentrated phosphoric acid solution take-out part is configured to take out the remaining portion of the second stage phosphate concentrate from the concentrated solution side of the second stage reverse osmosis device . The second stage phosphoric acid concentrate taken out is further concentrated by evaporation using an evaporation concentrator and recovered as a phosphoric acid concentrate. The concentrated phosphoric acid concentrate may be circulated to the phosphoric acid-containing water regulating portion and used for regulating.
That is, when acetic acid remains in the phosphoric acid solution permeated from the second permeation device, acetic acid can not be completely removed even by the anion exchange resin. Therefore, volatile components such as acetic acid are removed and the purity and concentration The concentrated phosphoric acid can be recovered by concentrating the concentrated phosphoric acid by evaporation using an evaporation and concentration apparatus and removing volatile components with water to concentrate the concentrated phosphoric acid containing substantially no volatile components such as acetic acid. As the evaporation concentrator, generally known apparatuses such as a rotary evaporator can be used.
By the above-described process, it is possible to recover phosphoric acid which is useful as a recovered product or can be carried in a liquid phase in a high concentration, and which is further concentrated in high purity. In the present invention, reverse osmosis treatment can be carried out under the condition of
By adjusting the pH, the phosphoric acid concentration, and the electric conductivity as described above, a regulated phosphoric acid concentrate is supplied and the reverse osmosis treatment is performed, whereby the generation of microorganisms such as fungi and yeast can be suppressed and high purity phosphoric acid can be recovered. This makes it possible to reduce the amount of medicines used and the amount of waste produced, thereby lowering the treatment cost and recovering high purity concentrated phosphoric acid and pure water useful as recovered products. The recovered phosphoric acid may be used for the adjustment of the phosphoric acid-containing water, or the reverse osmosis module taken out from the reverse osmosis unit may be immersed for treatment of inhibiting generation of microorganisms such as fungi and yeast.
As described above, according to the present invention, the adjusted ion-containing water in which the ionic acid-containing water, especially the cationic water-free phosphoric acid-containing water, is adjusted to
1 is a flowchart of a phosphoric acid recovery method and a phosphoric acid recovery device according to an embodiment of the present invention.
2 is a graph showing the results of an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. 1 is a flowchart showing a phosphoric acid recovery method and a phosphoric acid recovery device according to an embodiment of the present invention. The
1, the pressurizing pump P1 constitutes a raw water supply portion for supplying the adjustment liquid (adjusted phosphorus-containing water) 3a to the concentrated
In the above-described phosphoric acid recovery apparatus, raw water (phosphoric acid-containing water) 1a that has been subjected to removal of impurities by precipitation separation, filtration or the like is introduced into the
The raw water (the phosphoric acid-containing water) 1a is usually obtained in an acidic state at a pH of 3 or less. However, in order to perform a reverse osmosis treatment under the condition of
The phosphoric acid-containing water in the adjusting
The adjusted phosphoric acid-containing water to be supplied to the first
The permeated liquid permeating to the permeate
In the case of membrane treatment using the one-stage reverse osmosis device, the concentrated solution concentrated in the concentrated
The remaining portion of the concentrate of the second reverse
The recovered
Hereinafter, an embodiment of the present invention will be described. In each example,% represents the percent rejection and represents% by weight unless otherwise indicated.
(Examples 1 to 6 and Comparative Examples 1 to 4)
The pH and the like were adjusted by adjusting the pH and the like by using a standard phosphoric acid-containing water having an electric conductivity of 1150 mS / m and a pH of 1.3 containing 11,000 mg / L phosphoric acid, 1,000 mg / L nitric acid and 1,000 mg / L acetic acid, (Adjusted phosphoric acid-containing water). In Table 1, in Comparative Example 1, the standard phosphoric acid-containing water was diluted with pure water and then the pH was adjusted with sodium hydride to adjust the raw water having the phosphoric acid concentration and pH shown in Table 1. In addition, Example 6 is an example in which standard phosphoric acid-containing water is used as raw water as it is. Examples 1 and 2 are designed to be in a concentrated state at
[Table 1]
A flat membrane test apparatus simulating a reverse osmosis device shown in Fig. 1 was constructed by using a reverse osmosis membrane (ES (trade name) manufactured by Ildong Electronics Co., Ltd.) cut into a circle having a diameter of 32 mm in a small diameter flat cell made of stainless steel (SUS304) -20) was supported by a sintered porous plate at an effective membrane diameter of 29 mm, and the raw water was supplied to the concentrate chamber of the cell by a pump to mix it with the concentrating liquid to be stagnated. The concentrated liquid was discharged by the back- And a device for circulating and homogenizing the concentrate by stirring with a rotor in the concentrate chamber was used.
The raw water (adjusted phosphoric acid-containing water) shown in Table 1 was supplied to the concentrating chamber of the above-mentioned flat membrane testing apparatus at a flow rate of 1 mL / min, mixed with a concentrate to stir the liquid in the cell with the rotor, And the permeate and condensed water were adjusted to the same volume (0.5 mL / min) to perform membrane separation. The pressure during the adjustment is shown in Table 2 as the operating pressure. Thereafter, the membrane separation process is continued while maintaining the operating pressure. The change of the permeate flow rate with the passage time is shown in Fig. The concentration of each component of the concentrated water and the inhibition rate of each component at the time of termination of the operation (the operation time is 20 hours for Comparative Example 1, the operation time is 40 hours for Comparative Example 2 and the operation time is 60 hours for the other Examples) Is shown in Table 2. However, after about one hour from the commencement of operation, the same value as in Table 2 was obtained, and the value was maintained until the end of operation. Also, the inhibition rate was calculated by the formula [(1 - concentration of permeated water / concentration of concentrated water) × 100].
[Table 2]
The concentrated water obtained in Examples 1 and 4 and Comparative Examples 1 to 3 was subjected to a culture test in a chalet. The medium was cultured in a 30 ° C. thermostat using PDA medium supplemented with antibiotics. As a result of the above culture test, Penicillium chrysogeum, which is a yellow mold in the neutral region, produced a large number of colonies. In addition, the fungus of the fungus that occurred under
[Table 3]
ES20-D2 '(Bessel is an S2 vessel for seawater desalination), which is a low-pressure aromatic polyamide type reverse osmosis membrane made by Ildong Co., Ltd., as a one-stage reverse osmosis membrane water tank testing apparatus simulating the reverse osmosis device of Fig. Raw water (adjusted phosphoric acid-containing water) of Examples 1 and 4 was supplied from the adjustment liquid tank to the reverse osmosis device at a flow rate of 5 L / min by using a device configured to circulate a part of the concentrate with the concentrate chamber of the 4-inch- And a part of the concentrate was circulated to the adjustment liquid bath to circulate the other part of the concentrate and the permeate liquid to the water quality of Table 2 for one month. Table 4 shows the treatment results after one month of treatment.
[Table 4]
Referring to Table 4, there was no significant difference in the treatment performance after treating the raw water of Examples 1 and 4 for one month. However, in the raw water treatment of Example 1, a small amount of slime was applied to the electrode of the level gauge provided in the adjustment liquid water tank. In the raw water treatment of Example 4, however, Was not observed.
The above results show that the pH of the phosphoric acid-containing water containing no cation is adjusted to
The present invention relates to a method and an apparatus for recovering phosphoric acid and pure water from phosphoric acid-containing water, and more particularly to a method and apparatus for recovering phosphoric acid and pure water from phosphoric acid-containing water, Method and a phosphoric acid recovery device.
1: raw water tank 1a: raw water
2: Pretreatment device 3: Adjustment liquid tank
3a: Adjustment amount 4: First reverse osmosis device
4a, 5a:
4c, 5c: concentrated liquid chamber 5: second reverse osmosis device
6: Post-treatment apparatus 7:
8: Evaporation concentrator 9: Adjustable phosphoric acid tank
9a: Phosphoric acid solution for adjustment 10: Recovery phosphoric acid tank
10a: Recovery phosphorus
Claims (14)
The adjusted phosphoric acid-containing water adjusted to pH 2 or less, the phosphoric acid concentration of 600 mg / L or more, or the electric conductivity of 200 mS / m or more by removing the cationic water is subjected to membrane separation treatment with a reverse osmosis device to remove acids other than phosphoric acid To permeate the permeated liquid side, and concentrate the phosphoric acid to the concentrated liquid side to recover the phosphoric acid.
Wherein the reverse osmosis device has two or more stages,
The adjusted phosphoric acid-containing water was subjected to membrane separation treatment by a reverse osmosis device of the first stage, and the phosphoric acid concentrate of the reverse osmosis device of the first stage was subjected to membrane separation treatment after the second stage Of phosphoric acid.
Wherein the adjusted phosphorus-containing water to be supplied to the reverse osmosis device is adjusted to a predetermined value by adding phosphoric acid to the treated phosphoric acid-containing water.
Wherein the adjusted phosphorus-containing water to be supplied to the reverse osmosis device is adjusted to a predetermined value by adding at least one of the phosphoric acid solution of the reverse osmosis device and the phosphoric acid solution of the evaporation concentrator to the treated phosphoric acid-containing water.
A phosphoric acid-containing water adjuster for adjusting the pH of the treated phosphoric acid-containing water from which the cation is removed to a pH of not more than 2, a phosphoric acid concentration of 600 mg / L or more, or an adjusted conductivity of 200 mS /
the adjusted phosphoric acid-containing water adjusted to a pH of not more than 2, a phosphoric acid concentration of not less than 600 mg / L, or an electric conductivity of not less than 200 mS / m is subjected to a membrane separation treatment to transmit an acid other than phosphoric acid to the side of the permeate chamber together with water to concentrate the phosphoric acid Reverse osmosis equipment;
A phosphoric acid-containing water supply unit for supplying the adjusted phosphoric acid-containing water to the concentrate chamber side of the reverse osmosis device;
A permeated liquid outlet portion for extracting the permeated liquid from the permeated liquid chamber side of the reverse osmosis device; And
And a concentrated phosphoric acid liquid takeout portion for taking out the concentrated phosphoric acid solution from the concentrated liquid side of the reverse osmosis device.
The reverse osmosis device comprises two stages,
A first stage phosphate concentrate feeder for feeding the first stage phosphoric acid concentrate of the first stage reverse osmosis device to the second stage reverse osmosis device,
And the concentrated phosphoric acid liquid takeout portion is configured to take out the concentrated phosphoric acid solution from the concentrated liquid chamber side of the second stage reverse osmosis device.
Further comprising an evaporation concentrator for concentrating the concentrated phosphoric acid liquid taken out from the concentrate liquid side of at least one of the first permeation device and the second permeation device.
And a circulation path for circulating a part of the concentrated phosphoric acid solution from the concentrated liquid chamber side of the reverse osmosis device to the phosphoric acid-containing water adjustment section.
And a circulation path for circulating a part of the concentrated phosphoric acid solution from the concentrated liquid chamber side of at least one of the first permeation device and the second permeation device to the phosphoric acid-containing water adjustment section.
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| JP (1) | JP5413192B2 (en) |
| KR (1) | KR101621835B1 (en) |
| CN (1) | CN101977849B (en) |
| TW (1) | TWI424964B (en) |
| WO (1) | WO2009119684A1 (en) |
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| CN111591966B (en) * | 2020-04-20 | 2021-08-06 | 同济大学 | Device and method for recovering phosphoric acid in aluminum etching waste liquid |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164389A (en) * | 1999-12-09 | 2001-06-19 | Toyota Motor Corp | Method for recovering washing water of phosphate film chemical conversion treatment and metal surface treating device |
| JP2002332583A (en) * | 2001-05-07 | 2002-11-22 | Nippon Paint Co Ltd | Method and apparatus for treating cleaning water for phosphate film chemical conversion |
| JP2004353007A (en) * | 2003-05-27 | 2004-12-16 | Nippon Parkerizing Co Ltd | Method for recovering and reusing phosphate chemical processing liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0663362A (en) * | 1992-08-24 | 1994-03-08 | Kurita Water Ind Ltd | Membrane separator |
| JP4490565B2 (en) * | 2000-09-19 | 2010-06-30 | 日本ペイント株式会社 | Method for recovering treatment agent components in metal surface treated rinse water |
| JP2002370088A (en) * | 2001-06-13 | 2002-12-24 | Nippon Parkerizing Co Ltd | Method for recovering washing water discharged from coating pretreatment line |
| 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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- 2009-03-25 WO PCT/JP2009/055996 patent/WO2009119684A1/en active Application Filing
- 2009-03-25 KR KR1020107021133A patent/KR101621835B1/en active IP Right Grant
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- 2009-03-25 JP JP2009513910A patent/JP5413192B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164389A (en) * | 1999-12-09 | 2001-06-19 | Toyota Motor Corp | Method for recovering washing water of phosphate film chemical conversion treatment and metal surface treating device |
| JP2002332583A (en) * | 2001-05-07 | 2002-11-22 | Nippon Paint Co Ltd | Method and apparatus for treating cleaning water for phosphate film chemical conversion |
| JP2004353007A (en) * | 2003-05-27 | 2004-12-16 | Nippon Parkerizing Co Ltd | Method for recovering and reusing phosphate chemical processing liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101977849A (en) | 2011-02-16 |
| WO2009119684A1 (en) | 2009-10-01 |
| JPWO2009119684A1 (en) | 2011-07-28 |
| CN101977849B (en) | 2013-01-30 |
| JP5413192B2 (en) | 2014-02-12 |
| TW201002627A (en) | 2010-01-16 |
| TWI424964B (en) | 2014-02-01 |
| KR20100127241A (en) | 2010-12-03 |
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