KR20100127241A - 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
- Publication number
- KR20100127241A KR20100127241A KR1020107021133A KR20107021133A KR20100127241A KR 20100127241 A KR20100127241 A KR 20100127241A KR 1020107021133 A KR1020107021133 A KR 1020107021133A KR 20107021133 A KR20107021133 A KR 20107021133A KR 20100127241 A KR20100127241 A KR 20100127241A
- Authority
- KR
- South Korea
- Prior art keywords
- phosphoric acid
- reverse osmosis
- containing water
- concentrate
- adjusted
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
By simple construction and operation, it is possible to control the generation of microorganisms such as mold and yeast from phosphate-containing water without using a special medicine, and to recover high-purity phosphoric acid, which is useful as a recovered product, at low cost or efficiently in a high-concentration transportable liquid state. A phosphoric acid recovery method and a phosphoric acid recovery apparatus that can be provided are provided. Phosphoric acid-containing water is adjusted to pH2 or less, 600 mg / L or more, or the electrical conductivity is 200 mS / m or more and reverse osmosis treatment is carried out in the first reverse osmosis apparatus 4, and the acid other than phosphoric acid is permeated with water in the permeate chamber 4b. And the phosphoric acid is concentrated to the concentrate chamber 4c side, and the permeate is post-treated to recover the pure water 7a, the concentrate is supplied to the second reverse osmosis apparatus 5, and the second reverse osmosis apparatus 5 A part of the concentrated liquid of IXC is circulated as the adjusting phosphoric acid liquid 9a, and the remaining portion is removed by the evaporative concentrator 8 together with water to remove volatile components and recovered as the phosphoric acid concentrated liquid 10a.
Description
BACKGROUND OF THE
An etchant containing phosphoric acid is used for etching liquid crystal substrates, wafers and other electronic devices. The high concentration of the waste etchant generated during the etching process is recovered and used, but the electronic equipment after the etching is washed with pure water to generate a large amount of low-density washing drainage. Such washing drainage includes metal ions and other impurities eluted by etching in addition to phosphoric acid, nitric acid, acetic acid, and other acid components, which are components of the etching solution, but most of them are pure water.
Such etch cleaning wastewater has been conventionally mixed and treated with other wastewater. A coagulation-sedimentation process is mentioned as the wastewater processing technique containing general phosphoric acid and hydrofluoric acid. However, in the case of coagulation precipitation treatment of phosphoric acid or hydrofluoric acid, the use of a large amount of drugs, the increase of treatment costs due to the generation of a large amount of sludge, and the increase of environmental load are problems. In addition, the increase in the water-soluble ions by the drug added in a large amount during the flocculation precipitation treatment increases the operating cost by increasing the operating pressure of the reverse osmosis membrane process when water is recovered, deterioration of the treated water quality, generation of scale, and also the ion exchange method. It is leading to an increase in the amount of regenerant used.
Patent Document 1 (Patent 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, the phosphate is recovered in the form of sodium dihydrogen phosphate by the above method, but there is little market of phosphate, and the sodium salt of phosphate has a low solubility in liquid phase, so that it is difficult to transport. have. On the other hand, when recovering with potassium salt, there is a problem that caustic galley (potassium hydroxide) is expensive. In addition, although a method of passing through an H-type cation resin is disclosed to recover sodium dihydrogen phosphate, acid such as hydrochloric acid is consumed by regeneration of the cation resin, and sodium hydride used for regeneration of anionic resin is unnecessary. There was a defect such as discharge.
When attempting to concentrate separation using a reverse osmosis (RO) membrane in place of the ion exchange resin, harmful microorganisms such as mold and yeast multiply on the surface of the membrane to increase the interlayer differential pressure and lower the permeate yield. Control of harmful microorganisms such as mold and yeast include physical control (proliferation control, sterilization, blocking, sterilization), physicochemical control (proliferation control), chemical control (proliferation control, pharmaceutical sterilization), biological agents, and the like. Among these, the growth control includes temperature control, chemical control (proliferation inhibitor), etc., and the sterilization includes pasteurization, high temperature sterilization, electromagnetic sterilization (γ ray, ultraviolet ray, microwave, etc.), high pressure sterilization (pressure), and electro sterilization. (High pressure pulse), chemical sterilizers include gas sterilizers (EO, formaldehyde, ozone, hydrogen peroxide, etc.), liquids, solution disinfectants (alcohol, hydrogen peroxide, organic disinfectants, etc.) solid disinfectants (silver based disinfectants, photocatalyst disinfectants, etc.), immobilized disinfectants. (Such as silicon-based quaternary ammonium).
However, the method has high drawbacks such as high energy consumption, high equipment cost, adverse effects on the reverse osmosis membrane (clogging due to oxidation, chemical adsorption, or alteration), and deterioration of the reverse osmosis membrane. . In addition, chemicals such as gas fungicides (EO, formaldehyde, etc.) and organic fungicides used for chemical control have problems with toxicity and environmental response. When harmful microorganisms such as mold and yeast propagate on the surface of the membrane, the eyes of the resin or the reverse osmosis membrane are clogged and stable operation is impossible, and it is difficult to remove microorganisms such as mold and yeast generated. Since the oxidizing agent cannot be used in the reverse osmosis membrane, there is no countermeasure.
The object of the present invention is to suppress the generation of microorganisms such as mold and yeast from phosphate-containing water by simple constitution and operation without using a special medicine, etc. The present invention provides 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 phosphate ion-containing water as follows.
(1) A method for recovering phosphoric acid by membrane separation treatment of phosphoric acid-containing water with a reverse osmosis device, and a reverse osmosis system for adjusting phosphoric acid-containing water adjusted to pH2, phosphoric acid concentration of 600 mg / L or higher, or electrical conductivity of 200 mS / m or higher. Phosphoric acid recovery method characterized in that the membrane separation treatment.
(2) A method of recovering phosphoric acid by membrane separation treatment of phosphoric acid-containing water with a reverse osmosis device, and intermittently reverses the adjusted phosphoric acid water adjusted to pH2, phosphoric acid concentration of 600 mg / L or higher, or electric conductivity of 200 mS / m or higher. It is a phosphoric acid recovery method characterized in that the membrane separation treatment by supplying to the permeation device.
(3) In the method described in the above (1) or (2), the reverse osmosis apparatus is configured in two or more stages, and the adjusted phosphoric acid-containing water is subjected to membrane separation treatment in the first stage reverse osmosis apparatus, and the first stage The phosphate concentrate treated in the reverse osmosis apparatus of the stage is a phosphoric acid recovery method for performing the membrane separation treatment after the second stage in the reverse osmosis apparatus after the second stage.
(4) Subsequent to the method described in (1) to (3), the adjusted phosphoric acid-containing water supplied to the reverse osmosis apparatus is adjusted to a predetermined value by adding phosphoric acid to the treated phosphoric acid-containing water. It is a recovery method.
(5) The method according to (1) to (4), wherein the adjusted phosphoric acid-containing water supplied to the reverse osmosis device is treated with the phosphoric acid concentrate of the reverse osmosis device and / or the evaporative concentration device. A phosphoric acid recovery method characterized by adding a phosphoric acid liquid and adjusting to a predetermined value.
(6) An apparatus for recovering phosphoric acid from phosphoric acid-containing water is provided. The apparatus includes a phosphoric acid water adjusting unit for adjusting the treated phosphoric acid water to be adjusted to phosphoric acid water having a pH of 2 or less, a phosphoric acid concentration of 600 mg / L or more, or an electrical conductivity of 200 mS / m or more, a
(7) The apparatus according to (6), wherein the reverse osmosis apparatus is composed of two stages, and the first stage supplies the first stage phosphoric acid concentrate of the first stage reverse osmosis apparatus to the second stage reverse osmosis apparatus. A phosphoric acid concentrate supply portion is provided. The circulation path is configured to circulate a portion of the second stage phosphoric acid concentrate from the concentrate chamber side of the second stage reverse osmosis apparatus to the phosphoric acid containing water adjusting unit. The concentrated phosphate extracting unit is configured to extract the remaining portion of the second stage phosphate concentrate from the concentrate chamber side of the second stage reverse osmosis device.
(8) The apparatus according to (7), further comprising an evaporation concentrator for evaporating and concentrating the remaining portion of the second stage phosphate concentrate extracted from the concentrate chamber side of the second stage reverse osmosis apparatus.
In the present invention, the phosphoric acid-containing water to be treated may be any object as long as it contains phosphoric acid. However, when the phosphoric acid concentration is 50 mg / L or more and less than 600 mg / L (adjusted phosphoric acid content is 1500 mg / L or more) , 50mg / L or more and less than 1500mg / L), pH is more than 2 and less than 3 (if the adjusted phosphoric acid content is less than pH1.5, it exceeds pH1.5 and less than pH3), or the electrical conductivity is less than 200mS / m (If the adjusted phosphorus content is 1800mS / m or more, less than 1800mS / m).
Acidic water is preferable for the treatment, and acid components such as phosphate and other nitrate and acetate ions, cation such as other anions and metal ions, and other impurities may be included. It is desirable to remove it. The present invention is particularly suitable for recovering phosphoric acid having high purity by removing other acid components such as nitrate ions and acetate ions from phosphate-containing water containing other acid components such as nitrate ions and acetate ions. In particular, the phosphoric acid-containing water, which is preferable as a treatment target, includes a low concentration of wash water generated when pure water is washed after etching with a phosphoric acid-containing etching liquid of a liquid crystal substrate, a wafer or other electronic device.
In the present invention, when the treated phosphoric acid content is higher than the adjusted phosphoric acid water and has a low concentration, harmful microorganisms such as mold and yeast may grow on the membrane surface of the reverse osmosis membrane and cause clogging. In order to recover the phosphate-containing water, in particular the phosphate-containing water from which cation has been removed, the pH is less than or equal to pH2, preferably less than or equal to pH1.5, greater than or equal to 600 mg / L of phosphoric acid, preferably greater than or equal to 1500 mg / L, or an electrical conductivity of 200 mS / m Above, preferably, the adjusted phosphoric acid-containing water adjusted to 1800 mS / m or more is subjected to membrane separation in a reverse osmosis apparatus. Since the adjusted phosphoric acid-containing water should be adjusted to the pH, phosphoric acid concentration, and electrical conductivity in the membrane separation step, when the membrane is concentrated in the concentration chamber of the reverse osmosis device during membrane separation, the pH, What is necessary is just to adjust with the phosphoric acid concentration and electrical conductivity.
The adjustment of the treated phosphoric acid-containing water is performed at a higher pH and lower concentration than the adjusted phosphoric acid-containing water in the step of feeding the reverse osmosis apparatus. The case where the reverse osmosis device is one stage or two or more stages is also a case where the treated phosphoric acid content supplied to the first stage reverse osmosis device is higher than the adjusted phosphoric acid water and has a low concentration. When the reverse osmosis apparatus is two or more stages, since the phosphate concentrate of the first stage reverse osmosis apparatus is low pH and high concentration, the phosphoric acid concentrate supplied after the second stage does not need to perform pH and concentration adjustment.
In order to adjust the high pH, low concentration of the treated phosphoric acid-containing water to a low pH, high concentration, it is preferable to inject an acid to adjust the pH and concentration of the treated phosphoric acid-containing water, in particular using phosphoric acid as the acid. It is preferable to adjust with the adjusted phosphoric acid containing water which has the value of. As phosphoric acid added to the treated phosphoric acid-containing water, a phosphoric acid concentrate of the reverse osmosis device and / or a phosphoric acid solution of the evaporative concentration device can be used. The phosphoric acid concentrate of the reverse osmosis device is preferably recycled because impurities such as nitric acid and acetic acid are removed and the phosphoric acid concentration is high. The phosphate solution of the evaporation concentrator is a concentrated phosphate solution obtained by evaporating and concentrating the concentrate of the reverse osmosis device, especially the second stage.
As described above, when the adjusted phosphate-containing water adjusted to low pH and high concentration is subjected to membrane separation in a reverse osmosis device, reproduction of harmful microorganisms such as mold and yeast on the membrane surface of the reverse osmosis membrane is inhibited. For this reason, even if a special chemical agent such as an oxidizing agent or a sterilizing means such as ultraviolet light is not used, clogging of the reverse osmosis membrane due to propagation of microorganisms does not occur, and a stable reverse osmosis device does not increase the intermembrane differential pressure or lower the permeate amount. It is possible to drive. Since the harmful microorganism inhibitory effect persists to some extent, the adjusted phosphoric acid-containing water may be intermittently supplied, but it is preferable to continuously supply the adjusted phosphoric acid-containing water.
That is, the adjusted phosphoric acid-containing water adjusted to low pH and high concentration is preferably continuously supplied to the reverse osmosis apparatus to perform the membrane separation treatment, but it may be intermittently supplied to perform the membrane separation treatment. In the latter case, usually, the treated phosphoric acid-containing water having a higher pH and lower concentration than the adjusted phosphoric acid-containing water is supplied to the reverse osmosis device as it is to perform membrane separation treatment intermittently, for example, once every 1 to 2 days, For example, the membrane separation treatment may be performed by supplying the adjusted phosphoric acid-containing water adjusted to low pH and high concentration for 1 to 2 hours. In this case, the treated phosphoric acid-containing water may be supplied to the reverse osmosis apparatus as it is to perform membrane separation treatment and intermittently injecting phosphoric acid to adjust the pH and concentration of the phosphoric acid-containing water.
In the present invention, before supplying the phosphate-containing water to the reverse osmosis device, it is possible to perform the removal of impurities including cation and / or anion as pretreatment, in particular, to treat the phosphoric acid-containing water from which cation has been removed. Furthermore, the separation effect of phosphoric acid and other acids can be enhanced by adjusting the phosphoric acid concentration and performing membrane separation treatment. In this case, as a pretreatment, solid matters may be removed by precipitation separation, filtration, and the like, and cation such as metal ions may be removed by cation exchange resins, and perchloric acid and organic acid complexes may be further removed by anion exchange resins. Removal of negative ions and the like. As a pretreatment apparatus used for such a pretreatment process, the general apparatus employ | adopted for the said objective is used.
Metal ions such as indium, iron, and aluminum contained in the washing drainage after etching cause clogging of the reverse osmosis (RO) membrane in the membrane separation process, and perchloric acid, etc., cause membrane damage when contained at high concentrations. By removing cation and anion, it is preferable because clogging or damage of the film can be prevented. As the cation exchange resin, a strong acid or weak acid cation exchange resin can be used. However, when the cation is removed by using an H-type strong acid cation exchange resin, it is necessary to adjust the treatment solution to pH3 or less due to an increase in acid content. It is preferable because it becomes easy. The cation exchange resin may be a chelate resin. Strong anionic or weakly basic anion exchange resin can be used as the anion exchange resin. Anion exchange resins are used in acid form such as phosphoric acid type and remove other impurity anions by passing phosphoric acid, nitric acid, acetic acid and the like.
The reverse osmosis apparatus in the membrane separation process of the present invention is also referred to as RO apparatus, and is divided into a permeate chamber and a concentrated chamber by a reverse osmosis (RO) membrane, and the phosphoric acid-containing water has a pH of 2 or less, a phosphoric acid concentration of 600 mg / L or more, or an electrical conductivity. The reverse osmosis membrane treatment is carried out by supplying to the concentrate chamber side under a condition of 200 mS / m or more, and permeate the phosphoric acid to the concentrate chamber side while permeating an acid other than phosphoric acid with water to the permeate chamber side. The concentrated liquid chamber side of the reverse osmosis apparatus is provided with a phosphoric acid-containing water supply portion for supplying the phosphoric acid-containing water and a concentrated phosphoric acid extracting portion for extracting the concentrated phosphoric acid liquid. The permeate extraction part which extracts permeate liquid is formed in the permeate chamber side of the said reverse osmosis apparatus. Between the concentrated phosphate extracting unit and the phosphate-containing water supply unit, a circulating path for circulating the concentrated phosphate extracted from the concentrated phosphate extracting unit to the concentrated liquid chamber side as adjustment phosphoric acid may be formed.
When the reverse osmosis apparatus is configured in two stages, the first stage phosphoric acid concentrate of the first stage reverse osmosis apparatus is provided to the second stage reverse osmosis apparatus. Configured to circulate a portion of the second stage phosphate concentrate to the concentrate chamber side of the first stage reverse osmosis apparatus at the concentrate chamber side of the two stage reverse osmosis apparatus, and the concentrated phosphate extracting unit is The remaining portion of the second stage phosphoric acid concentrate may be taken out. Thereby, the phosphate concentrate of the first stage reverse osmosis apparatus is supplied to the second stage reverse osmosis apparatus to perform membrane separation treatment, and a part of the phosphoric acid concentrate of the second stage reverse osmosis apparatus is used as the phosphoric acid for adjustment. The remaining part can be recovered while circulating to the concentrate chamber side of the single-stage reverse osmosis unit.
The reverse osmosis membrane is a semi-permeable membrane which permeates water by the infiltration pressure or, conversely, pressurizes it at a higher pressure than the penetration pressure to supply the liquid to be treated and permeates the water by reverse osmosis, while preventing salt and other solutes 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 permeable membrane, a polyimide permeable membrane, a cellulose permeable membrane, and the like. Composite reverse osmosis membranes are preferred in which an active skin layer having a substantially selective separation on a microporous support is formed.
The reverse osmosis device may be provided with such a reverse osmosis membrane, but it is preferable to include a membrane module in which the reverse osmosis membrane, the support mechanism, the collecting mechanism, and the like are integrated. The membrane module is not particularly limited, and examples thereof include a tubular membrane module, a planar membrane module, a spiral membrane module, a hollow membrane module, and the like. As the reverse osmosis device having these, generally known ones can be used, and those having high permeability to be operated at low pressure are preferable.
When the phosphate-containing water, in particular the phosphate-containing water from which cation is removed, is subjected to membrane separation in the reverse osmosis device under a condition of
Comparing the permeation rate of the ionic material and the nonionic material to the reverse osmosis membrane, even if the reverse osmosis membrane blocking rate is the same molecular weight, it is known that the ionic material is more easily blocked than the nonionic material. However, if the reverse osmosis membrane treatment is carried out under a condition of
If the concentration of phosphoric acid in the concentrate is too high, it becomes difficult to perform the membrane treatment in relation to the penetration pressure, so that the upper limit of the concentration of phosphoric acid in the concentrate is 15% by weight, preferably 10%. By adding the treated phosphoric acid-containing water to the concentrated solution circulating while circulating the concentrated solution of the phosphoric acid concentration, and extracting the concentrated solution as a phosphoric acid concentrate part by part to perform a daily food treatment, the membrane is efficiently treated while maintaining the phosphoric acid concentration. Can be performed.
When performing the membrane treatment while circulating the concentrate, the more the number of cycles of the concentrate is increased, the more the acid other than phosphoric acid is in contact with the reverse osmosis membrane and more permeate the membrane, thereby lowering the concentration of the acid other than phosphoric acid in the concentrate. can do. At this time, if the phosphoric acid concentration is more than 15% by weight, the membrane separation can not be carried out, by adding a dilution water to the concentrate and circulating the reverse osmosis treatment, it is possible to lower the concentration of acid other than phosphoric acid, High purity phosphoric acid concentrate can be recovered. As dilution water, the recovery water which removed the impurity from permeate water can be circulated and used.
Since the permeated water of the reverse osmosis device taken out from the permeate chamber contains acids such as permeated phosphoric acid, nitric acid, acetic acid, etc., by removing these acids and other impurities from the permeated water of the reverse osmosis device by an impurity removal device. Pure water can be recovered. In this case, as an impurity removal device, an ion exchange device using an ion exchange resin, a biological treatment device, or the like can be used.
On the other hand, the phosphoric acid concentrated liquid taken out from the concentrated liquid chamber side has been removed most of the acid other than phosphoric acid such as nitric acid or acetic acid, but can be further purified by post-treatment in order to increase the purity and concentration of the recovered phosphoric acid liquid. have. As purification by the post-treatment, an acid other than phosphoric acid can be removed and purified from the phosphoric acid concentrate by anion exchange. In this case, an anion exchange device may be provided as a purification device to pass the concentrate to the anion exchange resin layer, and high concentrations of phosphoric acid containing almost no strong acid ions such as nitric acid may be recovered by removing strong acid ions such as nitric acid from the concentrate. have.
When the reverse osmosis apparatus is composed of two or more stages, the adjusted phosphoric acid-containing water is supplied to the reverse osmosis apparatus of the first stage to perform membrane separation treatment, and the phosphoric acid concentrate of the reverse osmosis apparatus of the first stage is applied after the second stage. The membrane was subjected to the membrane separation process after the second stage by supplying to the reverse osmosis apparatus of. In this case, the reverse osmosis apparatus has a first stage phosphoric acid concentrate supply portion for supplying the first stage phosphoric acid concentrate of the first stage reverse osmosis apparatus to the second stage reverse osmosis apparatus, and the circulation path is the second stage reverse osmosis. Configured to circulate a portion of the second stage phosphoric acid concentrate from the concentrate chamber side of the apparatus to the phosphoric acid containing water adjusting unit, and the concentrated phosphoric acid extracting unit extracts the remaining portion of the second stage phosphoric acid concentrate from the concentrate chamber side of the second stage reverse osmosis apparatus. It is configured to. The extracted second stage phosphate concentrate is further evaporated by an evaporation concentrator and can be recovered as a phosphate concentrate. The said phosphoric acid concentrate concentrated by evaporation can be circulated to the said phosphoric acid containing water adjustment part, and can also be used for adjustment.
That is, when acetic acid remains in the phosphate liquid permeated by the second stage reverse osmosis device, acetic acid cannot be completely removed even by an anion exchange resin, so that volatile components such as acetic acid are removed to remove the purity and concentration of the recovered phosphate liquid. In order to increase the concentration, the phosphoric acid concentrate is evaporated and concentrated by an evaporation concentrator and concentrated by removing volatile components together with water, thereby recovering a high concentration of phosphoric acid containing almost no volatile components such as acetic acid. As the evaporation concentrator, generally known devices such as rotary evaporators can be used.
By the above-described process, it is possible to recover phosphoric acid which is useful as a recovered matter or is transportable in a high concentration liquid phase, and which is concentrated in high purity. In the present invention, the reverse osmosis treatment can be performed under the condition of
By adjusting the pH, the phosphoric acid concentration, and the electrical conductivity as described above, by supplying the adjusted phosphate concentrate and reverse osmosis treatment, it is possible to suppress the generation of microorganisms such as mold and yeast, and to recover high purity phosphoric acid. As a result, the amount of chemicals used and the amount of waste generated can be reduced, thereby lowering the treatment cost and recovering high-purity concentrated phosphoric acid and pure water useful as a recovered product. The recovered phosphoric acid may be used for the adjustment of phosphoric acid-containing water, or for immersing the reverse osmosis module taken out from the reverse osmosis apparatus, for suppressing the generation of microorganisms such as mold and yeast.
As described above, according to the present invention, ionic acid-containing water, in particular, phosphate-containing water from which cation has been removed, is reversely penetrated with adjusted ion-containing water adjusted to
1 is a flowchart of a phosphoric acid recovery method and a phosphoric acid recovery apparatus 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 illustrating a phosphoric acid recovery method and a phosphoric acid recovery apparatus according to an embodiment of the present invention. The
In FIG. 1, the pressurizing pump P1 comprises the raw water supply part which supplies the adjustment liquid (adjusted phosphoric acid containing water) 3a to the
In the above-described phosphoric acid recovery device, raw water (phosphate-containing water) 1a in which impurities are removed by precipitation separation, filtration, or the like is introduced into the
The raw water (phosphate-containing water) 1a can be obtained in an acidic state of pH3 or lower in general, but the
The phosphoric acid-containing water of the
The adjusted phosphoric acid-containing water supplied to the first
The permeate that has permeated to the
In case of membrane treatment with a single stage reverse osmosis device, the concentrated solution concentrated in the
The remaining portion of the concentrate of the second
The recovered
In the following, embodiments of the present invention will be described. In each example,% represents the blocking rate and, unless otherwise indicated,% by weight.
(Examples 1 to 6 and Comparative Examples 1 to 4)
Dilute this with pure water using an electric conductivity of 1150 mS / m, pH 1.3 containing 11,000 mg / L phosphoric acid, 1,000 mg / L nitric acid, and 1,000 mg / L acetic acid, and pH 1.3. Raw water (adjusted phosphoric acid-containing water) was obtained. In Table 1, Comparative Example 1 was adjusted to raw water having a phosphoric acid concentration and pH shown in Table 1 by diluting the standard phosphoric acid-containing water with pure water, and then pH adjustment with sodium hydride. In addition, Example 6 is an example which used the standard phosphoric acid containing water as raw water. Examples 1 to 2 are concentrated and designed to have a pH of 2 or less, a phosphoric acid of 600 mg / L or more, and an electrical conductivity of 200 mS / m or more.
TABLE 1
As a flat membrane test apparatus that simulates the reverse osmosis apparatus shown in FIG. 1, a reverse osmosis membrane (ES) manufactured by Ildong Electronics Co., Ltd., cut into small diameter flat membrane cells made of stainless steel (SUS304) having an inner diameter of 32 mmØ in a diameter of 32 mmØ. -20) is supported by a sintered perforated plate with an effective membrane diameter of 29 mm Ø, and the raw water is fed to the concentrate chamber of the cell by a pump, mixed with the stagnant concentrate, and the concentrate is discharged by a back pressure valve to operate the concentrate. The pressure was adjusted, and the apparatus which circulated and homogenized the concentrated liquid by stirring with a rotor in the concentrated liquid chamber was used.
The raw water (adjusted phosphate-containing water) shown in Table 1 was supplied to the concentration chamber of the flat membrane test apparatus at a flow rate of 1 mL / min, the liquid in the cell was stirred with a rotor, mixed with the stagnant concentrate, and the back pressure valve was adjusted. The membrane separation was carried out by adjusting the amount of permeate and the amount of concentrated water to be the same amount (0.5 mL / min). The pressure at the time of adjustment is shown in Table 2 as the operating pressure. Thereafter, the membrane separation process is continued while the operation pressure is maintained. The change according to the water passage time of the permeation flux at this time is shown in FIG. In addition, the concentration of each component of the concentrated water and the blocking rate of each component at the end of the operation (Comparative Example 1 is 20 hours for water supply time, Comparative Example 2 is 40 hours for water supply time, and other examples are terminated with 60 hours for water supply time). Although shown in Table 2, about 1 hour after the start of operation, it became the numerical value equivalent to Table 2, and the value was hold | maintained until completion | finish of operation. In addition, the blocking rate was calculated by the formula of [(1- concentration of permeate / 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. incubator using an antibiotic-added PDA medium. As a result of the chalet culture test, the yellow mold Penicillium chrysogeum produced a large number of colonies in the neutral region. The fungal species which occurred below pH3 was fusarium spp . As a result of the chalet culture test, the number of days until colony of mold was observed visually is shown in Table 3. In Table 3, 'more than 10 days' indicates that no colonies were observed in the 10-day culture test.
[Table 3]
As a single-stage reverse osmosis membrane water permeation test apparatus simulating the reverse osmosis apparatus of FIG. 1, an ultra low pressure aromatic polyamide type reverse osmosis membrane 'ES20-D2' manufactured by Ildong Electric Co., Ltd. (vessel is an S2 vessel for seawater desalination) The raw water (adjusted phosphoric acid-containing water) of Examples 1 and 4 was breached to 5 L / min in the brine quantity at 5 L / min, using a device configured to circulate some of the concentrate into the concentrate chamber and the adjustment tank of the 4-inch new membrane module. Membrane separation treatment by supplying to the concentration chamber of, and the other portion of the concentrate and the permeate was circulated to the raw water tank to circulate in the crude water tank of a part of the concentrate solution was performed for 1 month. Table 4 shows the results of treatments after one month of treatment.
[Table 4]
Referring to Table 4, no significant difference was observed in the treatment performance after the treatment for the raw water of Examples 1 and 4 for one month. However, when the adhesion state of the slime after the treatment for one month was examined, in the raw water treatment of Example 1, a small amount of slime was applied to the electrode of the liquid level meter installed in the adjusting liquid tank, but in the raw water treatment of Example 4, the slime was still after one month. Was not observed.
As a result, the phosphoric acid-containing water containing no cation is
The present invention provides a method and apparatus for recovering phosphoric acid and pure water from phosphoric acid-containing water, in particular, recovering phosphoric acid suitable for recovering valuables such as phosphoric acid and pure water, which is treated water, from a washing drainage after etching a liquid crystal substrate, a wafer or other electronic device. It can be used for the method and the phosphate recovery device.
1: raw water tank 1a: raw water
2: Pretreatment device 3: Adjustment liquid tank
3a: adjusting liquid 4: first reverse osmosis device
4a, 5a:
4c, 5c: concentrate chamber 5: second reverse osmosis device
6: aftertreatment device 7: recovery water tank
8: evaporative concentration device 9: phosphate tank for adjustment
9a: phosphate for adjustment 10: recovered phosphate tank
10a: recovered phosphate
Claims (8)
A phosphoric acid recovery method characterized by subjecting the adjusted phosphoric acid-containing water adjusted to pH 2 or less, the phosphoric acid concentration 600 mg / L or more, or the electrical conductivity 200 mS / m or more with a reverse osmosis apparatus.
A method for recovering phosphoric acid, wherein the adjusted phosphoric acid-containing water adjusted to pH 2 or less, phosphorus concentration 600 mg / L or more, or electrical conductivity 200 mS / m or more is intermittently supplied to the reverse osmosis device to perform membrane separation.
The reverse osmosis device is composed of two or more stages,
The adjusted phosphoric acid-containing water is subjected to membrane separation by the first stage reverse osmosis apparatus, and the phosphate concentrate of the first stage of reverse osmosis apparatus is separated by the second stage subsequent reverse osmosis apparatus. Phosphoric acid recovery method to carry out.
And the adjusted phosphoric acid-containing water supplied to the reverse osmosis device is adjusted to a predetermined value by adding phosphoric acid to the treated phosphoric acid-containing water.
And the adjusted phosphoric acid-containing water supplied to the reverse osmosis apparatus is adjusted to a predetermined value by adding the phosphoric acid concentrate of the reverse osmosis apparatus and / or the phosphoric acid solution of the evaporation concentration apparatus to the treated phosphoric acid-containing water.
A phosphoric acid-containing water adjusting unit for adjusting the treated phosphoric acid-containing water to an adjusted phosphoric acid-containing water having a pH of 2 or less, a phosphoric acid concentration of 600 mg / L or more, or an electrical conductivity of 200 mS / m or more;
Membrane treatment of the adjusted phosphoric acid-containing water adjusted to pH 2 or less, phosphorus concentration 600 mg / L or more, or electrical conductivity 200 mS / m or more to permeate the non-phosphoric acid with water to the permeate chamber to concentrate the phosphoric acid in the concentrate chamber side. Reverse osmosis devices;
A phosphoric acid-containing water supply unit for supplying the adjusted phosphoric acid-containing water to the concentrate chamber side of the reverse osmosis apparatus;
A permeate extracting unit for extracting a permeate from the permeate chamber side of the reverse osmosis apparatus;
A circulation path for circulating a portion of the concentrated phosphoric acid solution to the phosphoric acid-containing water adjusting unit at the concentrate chamber side of the reverse osmosis unit; And
And a concentrated phosphate extracting unit for extracting the remaining portion from the concentrate chamber side of the reverse osmosis unit.
The reverse osmosis device is composed of two stages,
It has a first stage phosphate concentrate supply unit for supplying the first stage phosphate concentrate of the first stage reverse osmosis apparatus,
The circulation path is configured to circulate a portion of the second stage phosphate concentrate on the phosphoric acid-containing water adjusting portion at the concentrate chamber side of the second stage reverse osmosis device,
And the concentrated phosphate extracting unit is configured to extract the remaining portion of the second stage phosphate concentrate from the concentrate chamber side of the second stage reverse osmosis apparatus.
And an evaporation concentrating device for evaporating and concentrating the remaining portion of the second stage phosphate concentrate taken out from the concentrate chamber side of the second stage reverse osmosis device.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2008-080696 | 2008-03-26 | ||
| JP2008080696 | 2008-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20100127241A true KR20100127241A (en) | 2010-12-03 |
| KR101621835B1 KR101621835B1 (en) | 2016-05-31 |
Family
ID=41113874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020107021133A KR101621835B1 (en) | 2008-03-26 | 2009-03-25 | Process and equipment for recovering phosphoric acid from phosphoric acid-containing water |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5413192B2 (en) |
| KR (1) | KR101621835B1 (en) |
| CN (1) | CN101977849B (en) |
| TW (1) | TWI424964B (en) |
| WO (1) | WO2009119684A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0663362A (en) * | 1992-08-24 | 1994-03-08 | Kurita Water Ind Ltd | Membrane separator |
| JP3742264B2 (en) * | 1999-12-09 | 2006-02-01 | 日本ペイント株式会社 | Flushing water recovery method and metal surface treatment apparatus for phosphate coating conversion treatment |
| 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 |
| 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 |
-
2009
- 2009-03-25 TW TW98109731A patent/TWI424964B/en active
- 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
- 2009-03-25 CN CN200980109247.4A patent/CN101977849B/en active Active
- 2009-03-25 JP JP2009513910A patent/JP5413192B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2009119684A1 (en) | 2011-07-28 |
| TWI424964B (en) | 2014-02-01 |
| WO2009119684A1 (en) | 2009-10-01 |
| KR101621835B1 (en) | 2016-05-31 |
| TW201002627A (en) | 2010-01-16 |
| JP5413192B2 (en) | 2014-02-12 |
| CN101977849A (en) | 2011-02-16 |
| CN101977849B (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8119008B2 (en) | Fluid purification methods and devices | |
| EP2367613B1 (en) | Membrane based solvent separation process | |
| JP5135749B2 (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| WO2013005369A1 (en) | Water purification system and water purification method | |
| US20150274541A1 (en) | Methods for treating bioreactor wastewater streams | |
| TWI428293B (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| JP4478996B2 (en) | Treatment method of polarizing plate manufacturing waste liquid | |
| US11565959B2 (en) | Cooling pond water treatment system | |
| KR101840896B1 (en) | Ultrapure water production process | |
| JPH10272495A (en) | Treatment of organic waste water containing salts of high concentration | |
| JP3800449B2 (en) | Method and apparatus for treating organic wastewater containing high concentrations of salts | |
| JP2009028724A (en) | Method for water treatment and apparatus for water treatment | |
| KR20100127241A (en) | Process and equipment for recovering phosphoric acid from phosphoric acid-containing water | |
| JP5277559B2 (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| KR100971499B1 (en) | Apparatus for seawater desalinating with reverse osmosis | |
| JP3137831B2 (en) | Membrane processing equipment | |
| JP5115271B2 (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| EP3240622B1 (en) | Multifunctional method for membrane protection and biofouling control | |
| JPS6336890A (en) | Apparatus for producing high-purity water | |
| JP2000317457A (en) | Production of pure water | |
| JP2010036160A (en) | Method and device for recovering water from discharged water | |
| JP5245596B2 (en) | Reverse osmosis membrane performance recovery method and membrane separation treatment method | |
| TWI337982B (en) | ||
| JPS6242787A (en) | Apparatus for producing high-purity water | |
| JPS60264314A (en) | Method for concentrating phosphoric acid or nitric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| AMND | Amendment | ||
| B701 | Decision to grant | ||
| GRNT | Written decision to grant |