WO2020013070A1 - 酸性液の再生装置および再生方法 - Google Patents

酸性液の再生装置および再生方法 Download PDF

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WO2020013070A1
WO2020013070A1 PCT/JP2019/026616 JP2019026616W WO2020013070A1 WO 2020013070 A1 WO2020013070 A1 WO 2020013070A1 JP 2019026616 W JP2019026616 W JP 2019026616W WO 2020013070 A1 WO2020013070 A1 WO 2020013070A1
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Prior art keywords
liquid
adsorbent
acidic
sulfuric acid
acidic liquid
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PCT/JP2019/026616
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English (en)
French (fr)
Japanese (ja)
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義信 鉢木
厚生 鈴木
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伸栄化学産業株式会社
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Priority to CN201980045928.2A priority Critical patent/CN112400039A/zh
Priority to JP2020530141A priority patent/JP7195649B2/ja
Publication of WO2020013070A1 publication Critical patent/WO2020013070A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon

Definitions

  • the present invention relates to an apparatus and a method for regenerating an acid solution.
  • alumite anodizing of aluminum
  • alumite anodizing of aluminum
  • aluminum ions are eluted into the bath solution in the sulfuric acid bath. It is known that an increase in the concentration of aluminum ions in the bath solution has an adverse effect on alumite. Therefore, in alumite, it is important to appropriately control the concentration of aluminum ions in the bath.
  • Known techniques for controlling the concentration of aluminum ions in the bath solution include a method using an ion exchange membrane and a method using a column of an ion exchange resin (chromatographic separation method).
  • a cathode or an anode is arranged on the back surface of an ion exchange membrane for positive or negative ions arranged facing a flow path for flowing a bath solution of a sulfuric acid bath. Then, the metal ions in the bath in the flow path and the anions to be paired with the metal are attracted to the cathode or the anode through the ion exchange membrane and removed from the bath. Anions are recovered as acids. Since the bath solution thus treated does not contain aluminum, the aluminum ion concentration in the bath solution of the sulfuric acid bath can be reduced by returning the bath solution to the sulfuric acid bath.
  • a bath solution of a sulfuric acid bath is intermittently supplied to a column filled with an ion exchange resin and developed with water.
  • Aluminum ions elute first as aluminum sulfate and sulfuric acid elutes later.
  • the recovered sulfuric acid is returned to the bath after adjusting the concentration with a higher concentration of sulfuric acid.
  • concentration of aluminum ions in the bath is reduced.
  • the bath liquid is regenerated by separating sulfuric acid or aluminum ions from the bath liquid.
  • various techniques are known as techniques for regenerating the bath liquid.
  • JP 2010-260009 A Japanese Unexamined Patent Publication
  • a separating agent that separates sulfuric acid or aluminum ions from a bath solution usually has a reduced separation ability with use, but can be regenerated, and such separation can restore the separation ability.
  • regeneration of the separating agent and wastewater treatment is not a small factor in determining the price of the product. For this reason, in alumite, a technique for efficiently and inexpensively regenerating an acidic liquid, such as a bath liquid, at low cost is required even if it includes regeneration of a separating agent and treatment of wastewater as well as alumite.
  • One object of one embodiment of the present invention is to realize a technique capable of reducing the amount of an acidic solution used for regeneration of an acidic solution including regeneration of an adsorbent.
  • an apparatus for regenerating an acidic liquid is an apparatus for regenerating an acidic liquid containing sulfuric acid, and a first acidic liquid containing sulfuric acid and aluminum ions.
  • an adsorption tower containing an adsorbent for adsorbing aluminum ions from the first acid solution, adsorbing and removing aluminum ions from the first acid solution, removing the first acid solution, and removing aluminum ions from the first acid solution.
  • the adsorbent is composed of a chelate resin having an aminophosphate group
  • the adsorbent regenerating device is an acidic liquid supply device for supplying a third acidic liquid serving as a supply source of the hydrogen ions to the adsorption tower.
  • the acidic liquid supply device is configured to supply a part of the second acidic liquid regenerated by the acidic liquid regenerating device to the adsorption tower as the third acidic liquid.
  • a method for regenerating an acidic solution is a method for regenerating an acidic solution containing sulfuric acid, and a first acidic solution containing sulfuric acid and aluminum ions. Is brought into contact with an adsorbent to adsorb the aluminum ions in the first acidic liquid to the adsorbent, and the first acidic liquid is regenerated into a second acidic liquid in which aluminum ions have been removed from the first acidic liquid.
  • a chelate resin having an aminophosphate group is used as the adsorbent, and a part of the second acidic liquid is used as the third acidic liquid.
  • the amount of the acidic solution used in the regeneration of the acidic solution including the regeneration of the adsorbent can be reduced.
  • FIG. 1 is a diagram schematically illustrating an example of the configuration of an acid liquid regenerating apparatus according to the present embodiment.
  • the regenerating device is a device for regenerating an alumite bath solution.
  • the regenerating apparatus includes an adsorption tower 11, an H-type conversion sulfuric acid tank (hereinafter, also simply referred to as "sulfuric acid tank”) 12, an alkaline tank 13, a storage tank 14, a solid-liquid And a separation device 15.
  • the adsorption tower 11 contains an adsorbent that adsorbs aluminum ions from the bath liquid.
  • the form of the adsorbent is, for example, particles, and the adsorbent is filled in the adsorption tower 11.
  • a fixed bed having liquid permeability is formed of the adsorbent in the adsorption tower 11. The adsorbent will be described later.
  • An anodizing bath 20 is connected to the inlet side of the adsorption tower 11 via a flow path 31.
  • Bathtub 20 contains a bath liquid.
  • the bath solution contains sulfuric acid and aluminum ions generated from alumite.
  • the sulfuric acid tank 12 is connected to the outlet side of the adsorption tower 11 via a flow path 32.
  • the sulfuric acid tank 12 is a tank for accommodating a part of sulfuric acid recovered from the adsorption tower 11 described later. Connected to the side.
  • the regenerating apparatus of the present embodiment is configured so that a part of the sulfuric acid discharged from the adsorption tower 11 in the early stage of the regeneration of the adsorbent described later can be supplied to the adsorption tower 11 via the flow path 36. I have.
  • the adsorption tower 11 is connected to the bathtub 20 via a flow path 33 on the outlet side.
  • the alkaline tank 13 is a tank for containing an alkaline liquid, for example, an aqueous solution of sodium hydroxide.
  • the alkaline tank 13 is connected to the inlet side of the adsorption tower 11 via a flow path 34.
  • the storage tank 14 is connected to the outlet side of the adsorption tower 11 via the flow path 35.
  • the storage tank 14 is a tank for storing the liquid discharged from the adsorption tower 11.
  • the storage tank 14 has a stirring device (not shown) for stirring the stored fluid.
  • the storage tub 14 is connected to the bath tub 20 via a flow path 38.
  • the regenerating apparatus of the present embodiment is configured so that the bath liquid in the bathtub 20 can be directly supplied to the storage tank 14.
  • the solid-liquid separation device 15 is a device for separating a solid precipitated from the liquid in the storage tank 14 from the liquid.
  • the solid-liquid separation device 15 is connected to the storage tank 14 via the flow path 39 so that the fluid in the storage tank 14 is supplied.
  • Each of the flow paths 31 to 36, 38, and 39 is usually formed of a pipe, and includes appropriately arranged pumps and valves (not shown). As described above, each of the channels 31 to 36, 38, and 39 is configured to be able to send the fluid in the channel to a desired destination.
  • the regenerating device appropriately includes various detecting devices such as a flow meter, a pH sensor, and a thermometer, and is configured to be able to send a fluid at a desired flow rate according to a detection value of the detecting device. .
  • the adsorbent is composed of a chelating resin having an H ion type aminophosphate group.
  • the adsorbent may be one kind or more.
  • the H-ion type means that the cation in the phosphate group of the aminophosphate group is a hydrogen ion.
  • the form of the adsorbent may be any form as long as a fixed bed through which liquid can pass can be constructed.
  • the adsorbent may be in the form of particles filled in the adsorption tower, or may be a porous body having open cells that can be accommodated in the adsorption tower.
  • the chelating resin has a resin and an aminophosphate group.
  • the resin can have an aminophosphate group and can be appropriately selected within a range having properties required for the form of the adsorbent.
  • examples of the resin include a styrene resin, a phenol resin, an acrylic resin, and an epoxy resin.
  • the amino phosphate group is a functional group containing an amino group and a phosphate group.
  • the aminophosphate group has a property of capturing a polyvalent metal ion, and may further include another group such as a hydrocarbon group as long as such a property is exhibited.
  • Examples of the amino phosphate group include —CH 2 NHCH 2 PO (OH) 2 .
  • the aminophosphate group may be chemically bonded to the resin or may be physically supported within a range where it can be used to adsorb aluminum ions from an acidic solution containing sulfuric acid.
  • the aminophosphate group may be one of the substituents of a monomer constituting the resin, or may be bonded to the resin by being replaced with a specific functional group in the resin.
  • the aminophosphate group may be physically supported on the carrier by being contained in a coating layer that covers, for example, a particulate resin carrier.
  • the content of the aminophosphate group can be appropriately determined according to the desired total exchange capacity of the chelating resin.
  • the total exchange capacity is represented by the exchange capacity of aluminum ions per liter of resin.
  • the total exchange capacity is preferably as high as possible from the viewpoint of allowing a large amount of aluminum ions to be adsorbed from the acidic solution, and is appropriately determined according to the content of aminophosphate groups in the chelate resin or the type of aminophosphate groups.
  • the chelate resin is preferably a polymer of a monomer having an aminophosphate group.
  • the chelate resin may be a synthetic product or a commercial product.
  • the synthetic product is obtained by a known method, for example, by subjecting a styrene monomer having an aminophosphate group to a radical polymerization reaction.
  • examples of commercially available products include trade name: Purolite (manufactured by Purolite), trade name: Uniselec (manufactured by Unitika), trade name: rebatit (manufactured by LANXESS), and trade name: EPORAS (miyoshi oil and fat). Inc.).
  • the chelating resin is represented by the following structural formula.
  • This chelate resin has an H-type phosphate group.
  • H-type aminophosphoric acid-type chelating resins include Uniselec UR-3300S (trade name) manufactured by Unitika Ltd.
  • Regeneration method of acidic solution A method for regenerating a bath solution, which is an acidic liquid, using the regenerating apparatus of the present embodiment will be described below.
  • the bath contains sulfuric acid and aluminum ions.
  • the bath liquid is an alumite bath liquid as described above, and has a composition suitable for the alumite bath liquid.
  • the components in the bath solution may include components other than sulfuric acid and aluminum ions as long as the effects of the present embodiment can be obtained.
  • the concentration of sulfuric acid in the bath solution is preferably 140 g / L or more, and more preferably 150 g / L or more.
  • the concentration of sulfuric acid in the bath liquid is preferably 230 g / L or less, and more preferably 220 g / L or less.
  • the concentration of aluminum ions in the bath solution is preferably 3 g / L or more, more preferably 5 g / L or more.
  • the concentration of aluminum ions in the bath liquid is preferably 15 g / L or less, and more preferably 12 g / L or less.
  • the composition of the bath solution is, for example, 200 g / L sulfuric acid, 10 g / L aluminum ions, and water as the balance.
  • the composition of the bath can be controlled to a desired range, for example, by adding sulfuric acid or extracting the bath.
  • FIG. 2 is a diagram illustrating an outline of an example of a method for regenerating an acidic liquid according to the present embodiment.
  • the bath liquid in the bathtub 20 is supplied to the adsorption tower 11, and at least a part of the sulfuric acid discharged from the adsorption tower 11 (hereinafter, also referred to as “recovered sulfuric acid”) is returned to the bathtub 20. It is.
  • the recovered sulfuric acid is a liquid of the bath liquid after passing through the adsorption tower 11, and is a liquid in which aluminum ions in the bath liquid are adsorbed by the adsorbent and removed.
  • the recovered sulfuric acid is substantially free of aluminum ions or has a reduced aluminum ion content.
  • the above-mentioned chelate resin having an H ion type aminophosphate group is used as the adsorbent.
  • the adsorbent in the adsorption tower 11 adsorbs aluminum ions to a saturated state, regeneration of the adsorbent is performed. For example, by detecting that the aluminum ion concentration in the recovered sulfuric acid discharged from the adsorption tower 11 has become substantially the same as that in the bath liquid, it is possible to determine the above-mentioned saturated state.
  • an aqueous sodium hydroxide solution is supplied to the adsorption tower 11.
  • the desorption waste liquid which is a waste liquid when the aqueous sodium hydroxide solution is supplied to the adsorption tower 11 is introduced into the storage tank 14 and neutralized with an acid.
  • the storage tank 14 can also be called a neutralization tank.
  • the desorption waste liquid is an alkaline liquid containing aluminum ions desorbed from the adsorbent (chelating resin).
  • aluminum is contained (dissolved) as aluminum hydroxide.
  • a part of the bath liquid in the bathtub 20 is used for neutralizing the desorbed waste liquid.
  • Aluminum hydroxide precipitates from the waste liquid due to neutralization of the desorbed waste liquid.
  • the precipitate of aluminum hydroxide by the neutralization is separated by, for example, solid-liquid separation (not shown).
  • the bath liquid in the bathtub 20 is supplied to the adsorption tower 11 through the flow path 31.
  • the adsorption tower 11 is usually immersed in sulfuric acid (sulfuric acid having a concentration lower than that of the sulfuric acid in the bath liquid) for converting or maintaining the chelate resin in the H ion form.
  • sulfuric acid in the bath solution is also referred to as free sulfuric acid to distinguish it from aluminum sulfate in the bath solution from the viewpoint of sulfate ions.
  • the bath liquid comes into contact with the adsorbent while passing through the fixed bed.
  • the aluminum ion in the bath solution replaces the hydrogen of the phosphate group of the aminophosphate group in the chelating resin as the adsorbent.
  • the chelating resin captures aluminum ions and releases hydrogen ions.
  • Sulfate ions paired with aluminum ions in the bath solution and hydrogen ions released from the chelating resin are discharged from the adsorption tower 11 to become sulfuric acid, and together with sulfuric acid in the bath solution, become the above-mentioned recovered sulfuric acid. .
  • the flow path 31 and the adsorption tower 11 include the adsorption tower 11 containing the adsorbent that adsorbs aluminum ions from the bath liquid, and adsorb and remove aluminum ions from the bath liquid.
  • An acidic liquid regenerating device for regenerating the bath liquid into sulfuric acid (recovered sulfuric acid) from which aluminum ions have been removed from the bath liquid is configured.
  • a bath solution of an alumite bath is used as an acidic solution to be treated, and the bath solution is brought into contact with the adsorbent to adsorb aluminum ions in the bath solution to the adsorbent.
  • the bath solution is regenerated into recovered sulfuric acid from which aluminum ions have been removed from the bath solution.
  • the concentration of the recovered sulfuric acid discharged from the adsorption tower 11 at the start of the passage of the bath liquid is such that the sulfuric acid for converting or maintaining the H ion type initially contained in the adsorption tower 11 is discharged. Lower than the concentration.
  • the recovered sulfuric acid in the initial stage of the passage of the sulfuric acid having a lower sulfuric acid concentration than the bath liquid is stored in the sulfuric acid tank 12 through the flow path 32. Since the initially recovered sulfuric acid is a regenerated solution of the bath solution supplied at the start of use of the adsorption tower 11, the concentration of sulfuric acid may be lower than that of the bath solution, but aluminum ions are substantially removed. ing. The concentration of sulfuric acid in the initially recovered sulfuric acid increases as the liquid flows.
  • the “initial recovered sulfuric acid” means that the concentration of sulfuric acid in the recovered sulfuric acid discharged from the adsorption tower 11 when the treatment of the bath liquid with the new or regenerated adsorbent is started is lower than that of the bath liquid, It refers to recovered sulfuric acid substantially free of aluminum ions.
  • the initially recovered sulfuric acid is supplied to the adsorption tower 11 at an appropriate flow rate in the regeneration of the adsorbent described later.
  • the initial storage amount of sulfuric acid in the sulfuric acid tank 12 may be an amount sufficient to be used for regeneration of an adsorbent described later.
  • the intended amount of the recovered sulfuric acid to be stored in the sulfuric acid tank 12 may be an amount necessary for converting the chelate resin in the adsorption tower 11 into the H ion type in the regeneration of the adsorbent described later.
  • the concentration of the recovered sulfuric acid in the sulfuric acid tank 12 may be adjusted to a concentration suitable for application to regeneration of the adsorbent. For example, when the concentration of the recovered sulfuric acid in the sulfuric acid tank 12 is higher than an expected concentration, the recovered sulfuric acid may be diluted and used in the regeneration of the adsorbent.
  • the recovered sulfuric acid other than the initially recovered sulfuric acid is supplied from the adsorption tower 11 to the bathtub 20 through the flow path 33.
  • the sulfuric acid concentration of the bath solution is increased, and the concentration of aluminum ions is relatively lowered, so that the bath solution is controlled to have a desired composition.
  • the adsorption tower 11 and the flow path 33 supply a part of the recovered sulfuric acid to the bath 20 for generating aluminum ions in the bath to adjust the composition of the bath in the bath 20.
  • the composition of the bath liquid is adjusted by adding a part of the recovered sulfuric acid to the bath liquid.
  • the bath solution is extracted from the adsorption tower 11, and the inside (resin) of the adsorption tower 11 is washed with water, and then the aqueous sodium hydroxide solution is supplied to the adsorption tower 11 from the alkali tank 13 via the flow path 34.
  • the adsorbent in the adsorption tower 11 comes into contact with the aqueous sodium hydroxide solution, and the aluminum ions trapped by the phosphate groups of the chelating resin are replaced with sodium ions.
  • the alkaline tank 13 and the flow path 34 constitute an alkaline liquid supply device for supplying an alkaline liquid for replacing the aluminum ions adsorbed by the adsorbent with alkali-derived cations to the adsorption tower 11. are doing.
  • the aluminum ions desorbed from the chelate resin are discharged from the adsorption tower 11 as aluminum hydroxide.
  • the desorption waste liquid discharged from the adsorption tower 11 is an alkaline liquid containing aluminum hydroxide.
  • Aluminum hydroxide is dissolved in water when alkaline, and the desorbed waste liquid is stored as a liquid in the storage tank 14 through the flow path 35.
  • the storage tank 14 is a tank for storing the alkaline waste liquid (desorption waste liquid) discharged from the adsorption tower 11 to which the aqueous sodium hydroxide solution has been supplied.
  • sulfuric acid is supplied from the sulfuric acid tank 12 to the adsorption tower 11 via the flow path 36.
  • the sulfuric acid tank 12 contains the initially recovered sulfuric acid, and the adsorption tower 11 is supplied with the initially recovered sulfuric acid.
  • the adsorbent in the adsorption tower 11 comes into contact with sulfuric acid, and the sodium ions trapped by the phosphate groups of the chelating resin are replaced with hydrogen ions.
  • sulfuric acid is brought into contact with the adsorbent having sodium ions, and the sodium ions of the adsorbent are replaced with hydrogen ions.
  • the aluminum ions adsorbed by the adsorbent are replaced by hydrogen ions through replacement with sodium ions, and the adsorbent is regenerated.
  • the sulfuric acid tank 12 and the flow path 36 constitute an acidic liquid supply device for supplying sulfuric acid, which is a supply source of hydrogen ions, to the adsorption tower 11.
  • This apparatus is configured to be able to supply a part of the recovered sulfuric acid (initial recovered sulfuric acid) regenerated by the above-described acidic liquid regenerating apparatus to the adsorption tower 11 as sulfuric acid for replacing hydrogen ions.
  • the above-described alkaline liquid supply device and acidic liquid supply device that is, the sulfuric acid tank 12, the alkaline tank 13, and the flow paths 34 and 36 replace the aluminum ions adsorbed by the adsorbent with hydrogen ions to convert the adsorbent. It can also be said that it constitutes an adsorbent regeneration device for regeneration.
  • the waste liquid discharged from the adsorption tower 11 by the supply of the initially recovered sulfuric acid (hereinafter also referred to as “replacement waste liquid”) mainly contains sodium ions and sulfate ions, and is substantially neutral.
  • the end point of the replacement of hydrogen ions in the chelate resin can be determined by lowering the pH of the replacement waste liquid.
  • the replacement waste liquid is also stored in the storage tank 14 through the flow path 35.
  • the storage tank 14 stores an alkaline desorption waste liquid containing aluminum hydroxide and a neutral replacement waste liquid containing sodium sulfate. As a result, the waste liquid in the storage tank 14 is alkaline, and therefore, the aluminum ions in the waste liquid become aluminum hydroxide.
  • the alkaline waste liquid in the storage tank 14 is neutralized with a bath solution to precipitate aluminum hydroxide contained in the alkaline waste liquid.
  • the bath liquid is supplied from the bath 20 to the storage bath 14 through the flow path 38.
  • the bath liquid supplied to the storage tank 14 is used for neutralizing the waste liquid in the storage tank 14.
  • the bathtub 20 and the flow path 38 constitute a neutralization device for neutralizing the alkaline waste liquid in the storage tank 14 with the bath solution.
  • the bath solution contains 10 g / L of aluminum ions, and these aluminum ions also become aluminum hydroxide in the alkaline waste liquid when the waste liquid is neutralized. As described above, by using the bath solution for neutralizing the waste liquid, the content of aluminum hydroxide in the waste liquid increases. Further, by using the bath liquid for neutralizing the waste liquid, the content of aluminum ions in the bath liquid is reduced.
  • the waste liquid is neutralized to neutrality.
  • aluminum hydroxide precipitates from the waste liquid in the storage tank 14.
  • the alkaline waste liquid generated by replacing the aluminum ions with the sodium ions in the chelate resin is neutralized using the bath solution, and aluminum hydroxide contained in the alkaline waste liquid is precipitated.
  • the slurry generated by the neutralization in the storage tank 14 is supplied to the solid-liquid separator 15 through the flow path 39.
  • the solid-liquid separator 15 separates solid aluminum hydroxide from the slurry.
  • the solid-liquid separation device 15 is a device for separating a precipitate deposited by neutralization in the above-described neutralization device.
  • the aluminum hydroxide separated by the solid-liquid separation device 15 is carried out to the outside.
  • the liquid phase of the slurry is subjected to an appropriate treatment such as concentration or dilution as necessary.
  • the concentrate has a high concentration of sodium sulfate and is carried out.
  • the distilled water obtained by the concentration and the diluent are discharged to the outside as wastewater, provided that they satisfy environmental standards.
  • the bath solution contains 200 g / L of sulfuric acid and 10 g / L of aluminum ions.
  • a chelate resin having an aminophosphate group is used as the adsorbent.
  • the chelate resin adsorbs and removes aluminum ions in the acid solution from the acid solution containing sulfuric acid at a high concentration of 200 g / L, and releases hydrogen ions. Therefore, the sulfate ion, which has been an anion with respect to the aluminum ion in the bath liquid, receives the released hydrogen ion and becomes sulfuric acid.
  • the bath liquid that has become unnecessary due to the high concentration of aluminum ions is entirely neutralized and treated as a waste liquid.
  • a large amount of sulfuric acid to be added as a new solution is required.
  • the amount of sulfuric acid required for regenerating the bath liquid and the adsorbent may be the above-mentioned small amount. Therefore, according to the present embodiment, the amount of sulfuric acid used is significantly reduced as compared with the case where the entire amount of the bath liquid is discarded. Also, the amount of alkali required for neutralizing the bath liquid to be discarded is significantly smaller than when the entire amount of the bath liquid is discarded.
  • the cations captured by the phosphate groups of the chelating resin are once replaced by aluminum ions by sodium ions, and then by sodium ions by hydrogen ions. Since the waste liquid of alumite is acidic, alkali is usually essential in the treatment of the waste liquid. In the present embodiment, such an alkali is used for the regeneration of the adsorbent, and the cation of the chelate resin is efficiently used. Often replaced.
  • the amount of the alkali used is an amount required for exchanging cations of the chelate resin. Therefore, according to the present embodiment, even when the alkali is used for the regeneration (cation exchange) of the chelate resin, the use amount of the alkali is remarkably reduced as compared with the case where the entire amount of the bath solution is discarded.
  • a bath solution can be used for the neutralization treatment of the alkaline waste liquid after the aluminum ions are desorbed from the chelate resin. Therefore, in this embodiment, a part of the bath solution containing ions of a metal such as aluminum at a relatively high concentration can be effectively used for waste liquid treatment.
  • the apparatus for regenerating an acidic solution (sulfuric acid) is an adsorbent that adsorbs aluminum ions from a bath solution (first acidic solution) containing sulfuric acid and aluminum ions.
  • an adsorption tower 11 for adsorbing and removing aluminum ions from the bath solution to regenerate the bath solution into recovered sulfuric acid (second acid solution) from which aluminum ions have been removed from the bath solution. It has a liquid regenerating device and an adsorbent regenerating device for regenerating the adsorbent by replacing the aluminum ions adsorbed by the adsorbent with hydrogen ions.
  • the adsorbent is composed of a chelate resin having an aminophosphate group, and the adsorbent regenerating device is used to supply the sulfuric acid for hydrogen replacement (third acidic liquid) serving as a supply source of hydrogen ions to the adsorption tower 11. It has a liquid supply device.
  • the acidic liquid supply device is configured to supply a part of the recovered sulfuric acid (initial recovered sulfuric acid) regenerated by the acidic liquid regenerating device to the adsorption tower 11 as sulfuric acid for hydrogen replacement.
  • recovered sulfuric acid is used as the acid used for regenerating the adsorbent used for treating the bath solution. Therefore, the regeneration device of the first aspect can reduce the amount of sulfuric acid required for regeneration of the adsorbent. Therefore, in the regeneration device of the first aspect, the amount of sulfuric acid used in the regeneration of sulfuric acid including the regeneration of the adsorbent can be reduced.
  • the adsorbent regenerating apparatus uses an aqueous sodium hydroxide solution (alkaline liquid) for replacing aluminum ions adsorbed by the adsorbent with sodium ions (cations derived from alkali). It further has an alkaline liquid supply device for supplying to the adsorption tower 11.
  • alkaline liquid aqueous sodium hydroxide solution
  • the aluminum ions adsorbed by the adsorbent are easily desorbed by replacement with sodium ions. Therefore, the regeneration device of the second aspect is more effective from the viewpoint of performing the regeneration of the adsorbent with high efficiency.
  • the regenerating apparatus for sulfuric acid includes a storage tank 14 for storing desorption waste liquid (alkaline waste liquid) discharged from the adsorption tower 11 to which the aqueous sodium hydroxide solution is supplied, and a storage tank 14.
  • the apparatus further includes a neutralization device for neutralizing the desorbed waste liquid therein with a bath solution, and a solid-liquid separation device 15 for separating a precipitate deposited by the neutralization in the neutralization device.
  • the regenerating apparatus of the third aspect is capable of removing desorbed aluminum ions as solid aluminum hydroxide from wastewater generated by regeneration of the adsorbent, and neutralizing the aluminum hydroxide for precipitation.
  • a bath solution can be used. Therefore, the regenerating apparatus of the third aspect can reduce the amount of sulfuric acid used until the wastewater is treated.
  • the neutralization device is a device for neutralizing the desorbed waste liquid with the bath solution.
  • the regenerator of the fourth aspect in the neutralization of wastewater treatment, aluminum ions in the bath solution are supplied to the wastewater. Therefore, the regeneration device of the fourth aspect is more effective from the viewpoint of increasing the concentration of aluminum hydroxide in the wastewater.
  • the sulfuric acid regenerating apparatus supplies a part of the recovered sulfuric acid to a bathtub 20 (processing tank) that contains a bath liquid and generates aluminum ions in the bath liquid, It further has a composition adjusting device for adjusting the composition of the liquid.
  • the composition of the bath solution is adjusted by supplying the recovered sulfuric acid recovered from the bath solution. Therefore, the regenerating device of the fourth embodiment is more effective from the viewpoint of maintaining the composition of the bath solution in a desired range.
  • the treatment tank is an alumite bath 20, and the first acid solution is a bath of the bath 20.
  • the regeneration device of the sixth aspect it is possible to reduce the amount of sulfuric acid used in the alumite including regeneration of the bath solution. Therefore, the reproducing device of the sixth aspect can reduce the cost of the entire anodized aluminum.
  • the bath liquid is brought into contact with an adsorbent to adsorb aluminum ions in the bath liquid to the adsorbent, and the bath liquid is recovered by removing aluminum ions from the bath liquid.
  • a chelate resin having an aminophosphate group is used as the adsorbent, and a part of the recovered sulfuric acid is used as sulfuric acid for hydrogen replacement.
  • the reproducing method according to the seventh aspect has the same effect as the reproducing apparatus according to the first aspect.
  • the method for regenerating sulfuric acid in the adsorbent regenerating step, an aqueous solution of sodium hydroxide is brought into contact with the adsorbent having adsorbed aluminum ions, and the aluminum ions adsorbed by the adsorbent are converted into sodium ions.
  • the method includes a cation replacement step of replacing, and a hydrogen ion replacement step of bringing sulfuric acid for hydrogen replacement into contact with an adsorbent having sodium ions to replace sodium ions of the adsorbent with hydrogen ions.
  • the reproducing method according to the eighth aspect has the same effect as the reproducing apparatus according to the second aspect.
  • neutralization is performed by neutralizing an alkaline waste liquid generated in the cation displacement step with a bath liquid to precipitate aluminum hydroxide contained in the waste liquid.
  • the desorption waste liquid is neutralized using a bath solution.
  • the reproducing method according to the tenth aspect has the same effects as those of the reproducing apparatus according to the fourth aspect.
  • the method for regenerating sulfuric acid according to the eleventh aspect of the present invention further includes a composition adjusting step of adjusting the composition of the bath liquid by adding a part of the recovered sulfuric acid to the bath liquid.
  • the playback method of the eleventh aspect has the same effects as the playback apparatus of the fifth aspect.
  • a bath solution of an alumite bath is used as the first acidic solution.
  • the reproducing method of the twelfth aspect has the same effects as the reproducing apparatus of the sixth aspect.
  • the playback device according to the present invention may further have a configuration other than the above-described configuration and device as long as the above-described effects are obtained.
  • the regenerator according to the present invention may include two or more adsorption towers 11 arranged in parallel. Such a configuration is preferable from the viewpoint that the regeneration of the bath liquid and the regeneration of the adsorbent can be performed simultaneously in the regeneration device.
  • the playback device according to the present invention may further include a control device that can control various devices included in the playback device to execute at least various steps in the playback method according to the present invention.
  • a control device can be realized using a known control device for controlling a waste liquid treatment facility in a business establishment.
  • the playback device having the control device can automatically execute the playback method according to the present invention.
  • the reproducing method according to the present invention may be executed continuously or intermittently. For example, when the concentration of aluminum ions in the bath liquid exceeds the allowable numerical range, the above-mentioned bath liquid is regenerated, and when the concentration falls within the allowable numerical range, the above-mentioned bath liquid may not be regenerated. Good.
  • the sulfuric acid in the sulfuric acid tank 12 contains only the initially recovered sulfuric acid, but may include both the initially recovered sulfuric acid and the new sulfuric acid.
  • the bath solution is used as the acid solution for neutralizing the alkaline waste solution generated in the cation substitution step, but the bath solution may be used in combination with the recovered sulfuric acid as the acid solution, Alternatively, only the recovered sulfuric acid may be used as the acid solution.
  • the regeneration of the adsorbent in the regeneration method according to the present invention may be performed before the adsorption amount of aluminum ions in the chelate resin is saturated.
  • the regeneration of the adsorbent may be performed at regular intervals of alumite treatment within a range in which the amount of adsorption is not saturated.
  • the alkaline solution contained in the alkaline bath 13 may be an alkaline solution having a cation capable of replacing the aluminum ion captured by the chelate resin.
  • Examples of the alkaline liquid include potassium hydroxide and lithium hydroxide.
  • the first acidic liquid to be regenerated with the adsorbent may further contain components other than sulfuric acid and aluminum ions as long as aluminum ions can be adsorbed by the adsorbent and removed from the first acidic liquid.
  • components other than sulfuric acid and aluminum ions include ions of metals other than aluminum, phosphoric acid, nitric acid, and oxalic acid generated with the use of the first acidic liquid.
  • examples of the metal of the metal ion generated by using the first acidic liquid include copper and magnesium.
  • the content of other components in the first acidic solution can be appropriately determined as long as aluminum ions are adsorbed by the adsorbent and can be removed from the first acidic solution. Metal ions other than aluminum ions may or may not be captured by the chelating resin.
  • Examples of such a first acidic liquid include a bath liquid (chemical polishing liquid) in chemical polishing of aluminum products, a cleaning waste liquid after chemical polishing, and a secondary waste liquid related to regeneration of the chemical polishing liquid.
  • Chemical polishing for example, dissolves fine protrusions on the surface of an aluminum product to provide a mirror-like surface.
  • the regeneration of the acidic solution from the chemical polishing liquid and the cleaning waste liquid related thereto will be described as a second embodiment
  • the regeneration of the acidic liquid from the secondary waste liquid according to the regeneration of the chemical polishing liquid will be described as a third embodiment. I do.
  • a phosphoric acid / nitric acid based chemical polishing liquid which is an aqueous solution containing phosphoric acid and nitric acid
  • a phosphoric acid / sulfuric acid based chemical polishing liquid which is an aqueous solution containing phosphoric acid and sulfuric acid
  • These chemical polishing liquids and their cleaning waste liquids usually contain aluminum ions eluted from aluminum products as aluminum phosphate and aluminum nitrate, or aluminum phosphate and aluminum sulfate.
  • the chemical polishing liquid is preferably a phosphoric acid / sulfuric acid-based chemical polishing liquid, since the technique for regenerating an acidic liquid according to the present invention is advantageous for recovering aluminum ions when sulfuric acid is contained.
  • the ratio of phosphoric acid and sulfuric acid in the phosphoric acid / sulfuric acid-based chemical polishing solution can be appropriately determined from the range in which chemical polishing can be performed. From such a viewpoint, the ratio of phosphoric acid in the phosphoric acid / sulfuric acid-based chemical polishing liquid is preferably 20 to 95% by mass, and more preferably 30 to 90% by mass. Further, the ratio of sulfuric acid in the phosphoric acid / sulfuric acid-based chemical polishing liquid is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 70% by mass or less.
  • the collected chemical polishing liquid is reused as the original use, that is, the chemical polishing liquid, like the recovered sulfuric acid in the above-described embodiment.
  • the washing waste liquid is concentrated as necessary and reused as a chemical polishing liquid.
  • FIG. 3 is a diagram schematically illustrating a configuration of a main part of an example of an apparatus for regenerating a chemical polishing liquid and a cleaning waste liquid related thereto.
  • the regenerating apparatus has a bath 40, a washing tank 41, an adsorption tower 11, and a concentrator 42.
  • the bathtub 40 is connected to the inlet side of the adsorption tower 11 via a flow path 51.
  • the cleaning tank 41 is connected to the inlet side of the adsorption tower 11 via a flow path 52.
  • the concentration device 42 is connected to the outlet side of the adsorption tower 11 via a flow path 53, and connected to the bathtub 40 via a flow path 54.
  • the bathtub 40 is a bathtub for chemical polishing and contains a chemical polishing liquid.
  • the cleaning tank 41 is a tank for washing the aluminum product chemically polished in the bath 40 with water.
  • the chemical polishing liquid adheres to the aluminum product.
  • the concentrating device 42 is a device for condensing the liquid to be treated by distilling off water in the liquid to be treated.
  • the regeneration of the chemical polishing liquid and the cleaning waste liquid relating to the chemical polishing liquid will be described by taking the regeneration of the phosphoric acid / sulfuric acid chemical polishing liquid as an example.
  • the phosphoric acid / sulfuric acid-based chemical polishing liquid in the bath 40 is diluted with water as required, and supplied to the adsorption tower 11 through the flow path 51.
  • the cleaning waste liquid in the cleaning tank 41 is supplied to the adsorption tower 11 through the flow path 52.
  • the acidic solution containing phosphoric acid, sulfuric acid, and aluminum ions is supplied to the adsorption tower 11, and the aluminum ions are adsorbed and removed from the acidic solution by the chelate resin as described above.
  • the acidic liquid from which the aluminum ions have been removed is supplied to the concentrator 42 through the channel 53.
  • the concentrating device 42 concentrates water by distilling water from the supplied acidic liquid. This concentration produces an acidic solution containing the desired concentrations of phosphoric acid and sulfuric acid.
  • the acid liquid thus regenerated is supplied to the bath 40 through the flow path 54 as a chemical polishing liquid or a raw material thereof, and is reused.
  • the regeneration of the chelate resin in the adsorption tower 11 is performed in the same manner as in the first embodiment.
  • the phosphoric acid / sulfuric acid-based chemical polishing liquid for aluminum products and the cleaning waste liquid related thereto can be easily regenerated. Further, according to the present embodiment, it is possible to reduce the amount of the acidic liquid used in the regeneration of the phosphoric acid / sulfuric acid-based chemical polishing liquid and the cleaning waste liquid related thereto.
  • the regenerating apparatus according to the present embodiment can also be used to remove aluminum ions in the phosphoric acid / nitric acid based chemical polishing liquid and the cleaning waste liquid related thereto. Therefore, the regenerating apparatus according to the present embodiment may be applied to chemical polishing using a phosphoric acid / nitric acid-based chemical polishing liquid.
  • the secondary waste liquid related to the regeneration of the chemical polishing liquid is a waste liquid generated by regenerating the adsorbent obtained by regenerating the chemical polishing liquid.
  • the secondary waste liquid is a sulfuric acid aqueous solution in which a phosphoric acid / nitric acid-based chemical polishing liquid containing aluminum ions or a cleaning waste liquid relating thereto is brought into contact with an ion exchange resin treated.
  • FIG. 4 is a diagram schematically illustrating a configuration of a main part of an example of an apparatus for regenerating a phosphoric acid / nitric acid-based chemical polishing liquid and a cleaning waste liquid related thereto.
  • the same components as those of the playback device of the above-described embodiment are denoted by the same reference numerals, and description thereof will not be repeated.
  • the regenerating apparatus has a bath 40, a washing tank 41, an adsorption tower 45, a concentrator 42, an adsorption tower 11, and a sulfuric acid tank 12, as shown in FIG.
  • the bath 40 has the same configuration as that of the third embodiment except that it contains a phosphoric acid / nitric acid-based chemical polishing liquid.
  • the phosphoric acid / nitric acid chemical polishing liquid is, for example, an aqueous phosphoric acid solution containing 3 to 5% by mass of nitric acid.
  • the adsorption tower 45 has a liquid-permeable fixed bed, and the fixed bed is configured by filling the adsorption tower 45 with ion exchange resin particles.
  • the ion exchange resin is a strongly acidic cation exchange resin, for example, a resin having an acidic functional group such as a sulfonic acid group, which is stronger than phosphoric acid.
  • the bath 40 is connected to the inlet side of the adsorption tower 45 via the flow path 61.
  • the cleaning tank 41 is connected to the inlet side of the adsorption tower 45 via a flow path 62.
  • the concentrating device 42 is connected to the outlet side of the adsorption tower 45 via the channel 63.
  • the inlet side of the adsorption tower 11 is connected to the outlet side of the adsorption tower 45 via a flow path 64.
  • the sulfuric acid tank 12 is connected to the inlet side of the adsorption tower 45 via a flow path 65.
  • the phosphoric acid / nitric acid-based chemical polishing solution containing aluminum ions in the bath 40 is diluted with water as required, and supplied to the adsorption tower 45 through the flow channel 61.
  • the cleaning waste liquid containing aluminum ions, phosphoric acid and nitric acid in the cleaning tank 41 is supplied to the adsorption tower 45 through the flow path 62.
  • the acidic liquid containing phosphoric acid, nitric acid, and aluminum ions supplied to the adsorption tower 45 comes into contact with the particles of the ion exchange resin contained in the adsorption tower 45.
  • the aluminum ions in the acidic liquid are replaced with hydrogen ions of strongly acidic functional groups in the ion exchange resin.
  • the aluminum ions in the acidic solution are adsorbed by the ion exchange resin and removed from the acidic solution.
  • the acidic solution from which the aluminum ions have been removed is supplied to the concentrating device 42 through the flow channel 63, concentrated by the concentrating device 42 to contain phosphoric acid of a desired concentration, and reused as the chemical polishing liquid.
  • the adsorption of the aluminum ion by the ion exchange resin in the adsorption tower 45 reaches saturation, the supply of the acidic liquid containing aluminum to the adsorption tower 45 is stopped, and the H-type conversion is performed from the sulfuric acid tank 12 through the flow path 65. Is supplied to the adsorption tower 45.
  • the ion exchange resin comes into contact with the aqueous sulfuric acid solution in the adsorption tower 45, the aluminum ions adsorbed by the ion exchange resin are replaced with hydrogen ions in the aqueous sulfuric acid solution.
  • the ion exchange resin is regenerated into an H type ion exchange resin.
  • the aluminum ions desorbed from the ion exchange resin are discharged from the adsorption tower 45 together with the aqueous sulfuric acid solution.
  • the liquid discharged from the adsorption tower 45 contains aluminum ions and sulfuric acid that has not been used for regenerating the ion exchange resin, and corresponds to a secondary waste liquid.
  • the secondary waste liquid is supplied to the adsorption tower 11 through the flow path 64.
  • Aluminum ions in the secondary waste liquid are adsorbed by the chelate resin in the adsorption tower 11 and removed from the secondary waste liquid.
  • the secondary waste liquid from which aluminum ions have been removed is supplied to the sulfuric acid tank 12 through the flow path 32 as recovered sulfuric acid, and is reused in the regeneration of the ion exchange resin in the adsorption tower 45 as described above.
  • the regeneration of the chelate resin in the adsorption tower 11 is performed in the same manner as in the first embodiment.
  • the secondary waste liquid related to the phosphoric acid / nitric acid-based chemical polishing liquid for aluminum products can be easily regenerated. Further, according to the present embodiment, it is possible to reduce the amount of the acidic liquid used in the regeneration of the secondary waste liquid.
  • the present invention can be used for a technique for regenerating an acidic solution containing sulfuric acid by adsorbing and removing aluminum ions from the acidic solution.
PCT/JP2019/026616 2018-07-11 2019-07-04 酸性液の再生装置および再生方法 WO2020013070A1 (ja)

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JP7429178B2 (ja) 2020-10-12 2024-02-07 クボタ環境エンジニアリング株式会社 アルミニウムイオン含有硝酸溶液の処理方法

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