WO2016157452A1 - 廃水の処理方法、廃水の処理システム - Google Patents

廃水の処理方法、廃水の処理システム Download PDF

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Publication number
WO2016157452A1
WO2016157452A1 PCT/JP2015/060249 JP2015060249W WO2016157452A1 WO 2016157452 A1 WO2016157452 A1 WO 2016157452A1 JP 2015060249 W JP2015060249 W JP 2015060249W WO 2016157452 A1 WO2016157452 A1 WO 2016157452A1
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Prior art keywords
concentration
wastewater
fluorine
waste water
decomposition
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PCT/JP2015/060249
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English (en)
French (fr)
Japanese (ja)
Inventor
治雄 柴山
務 村木
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住友金属鉱山エンジニアリング株式会社
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Priority to JP2017508959A priority Critical patent/JP6728546B2/ja
Priority to KR1020177029308A priority patent/KR102434086B1/ko
Priority to PCT/JP2015/060249 priority patent/WO2016157452A1/ja
Publication of WO2016157452A1 publication Critical patent/WO2016157452A1/ja

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    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment

Definitions

  • the present invention relates to a processing system processing method and wastewater wastewater containing a hardly decomposable compound, more particularly, with fluorine, BF 4 of persistent - implementing the method and method for processing waste water containing It relates to a processing system.
  • Patent Document 1 hardly degradable BF 4 - processing method of waste water containing is proposed. According to the method disclosed in Patent Document 1, BF 4 ⁇ contained in waste water can be treated easily, quickly and inexpensively with high decomposition efficiency. However, the concentration of BF 4 ⁇ in the wastewater changes with time. For this reason, it is preferable to continuously change the amount of the medicine to be used in accordance with this, and this makes it possible to control the amount of the medicine to be used and to perform the decomposition process more efficiently. .
  • the present invention has been proposed in view of such circumstances, BF 4 of persistent - in the process of wastewater containing, BF 4 included in the waste water - based on the concentration of more efficient and to provide a method of processing waste water that can degrade - BF 4 in.
  • the inventors of the present invention have made extensive studies in order to solve the above-described problems.
  • the free fluorine ions contained in the wastewater are removed, the concentration of BF 4 ⁇ contained in the wastewater from which the free fluorine ions have been removed is measured, and the amount of drug used determined based on the obtained concentration measurement results ( BF 4 was added to the polyvalent metal or polyvalent metal salts) - by performing the decomposition process of, found that it is possible to perform efficient processing, thereby completing the present invention. That is, the present invention is as follows.
  • a first invention of the present invention is a method for treating wastewater containing BF 4 - which is hardly decomposable together with fluorine, and a fluorine removing step for removing free fluorine ions contained in the wastewater; BF in the removal of the free fluorine ion wastewater 4 - measuring the concentration BF 4 - decomposition decompose - a measuring step, the BF 4 - the BF 4 based on the concentration of - BF 4 measured by the measuring step has a step, the BF 4 - in the measurement step, by adjusting the pH of the wastewater to 4 below BF 4 - to determine the concentration, in the decomposition step, the waste water, the BF 4 - to a concentration of
  • This is a wastewater treatment method in which a polyvalent metal or a metal salt thereof whose addition amount is determined based on the addition amount is added.
  • the wastewater BF 4 - is the waste water to determine the concentration processing method - into contact with the electrode BF 4 .
  • the waste water in the first or second aspect of the invention, in the fluorine removal step, is set so that the concentration of free fluorine ions in the waste water is less than 0.1 mol / L. It is a processing method.
  • waste water is generated and removed by generating a precipitate of free fluorine ions using a calcium salt. It is a processing method.
  • BF 4 of persistent - in the process of wastewater containing, BF 4 included in the waste water - based on the concentration of efficiently BF 4 - capable of degrading.
  • the waste water treatment method according to the present embodiment is a method for treating waste water containing BF 4 ⁇ which is hardly decomposable together with fluorine. Specifically, the processing method of the wastewater, the fluorine removal process S1 to remove free fluorine ions contained in waste water, BF 4 included in the waste water to remove fluoride ions - BF 4 for measuring the concentration - concentration measurement process S2 And a decomposition step S3 for decomposing BF 4 ⁇ based on the measured BF 4 ⁇ concentration.
  • BF 4 - in concentration measurement step S2 by adjusting the pH of the wastewater to 4 below to determine the concentration, also in the decomposition step S3, the measured BF 4 - on the basis of the concentration added
  • a feature is that BF 4 - is decomposed by adding a polyvalent metal or a metal salt thereof (polyvalent metal salt) whose amount is determined to waste water.
  • the addition amount of the polyvalent metal or the metal salt as a chemical for decomposing the BF 4 ⁇ is determined. and for which, BF 4 varies with decomposition treatment - the amount of continuous drug based on the concentration can be controlled, it is possible to perform a more efficient treatment of wastewater as compared with the conventional.
  • BF 4 contained in the waste water - prior to measuring the concentration also with the addition of agents such as polyvalent metal salts in the waste water BF 4 - Prior to decompose, in advance, the By removing the free fluorine ions (free F ⁇ ) contained in the wastewater, the free F ⁇ contained in the wastewater can be prevented from becoming strong hydrofluoric acid, and the concentration of BF 4 ⁇ can be measured more accurately. Can do. Further, by removing free F 2 ⁇ from wastewater, waste of chemicals such as polyvalent metal salts added for the decomposition of BF 4 ⁇ can be suppressed, and an efficient decomposition process can be performed.
  • FIG. 1 is a diagram illustrating an example of a configuration of a wastewater treatment system for carrying out a wastewater treatment method according to the present embodiment.
  • a wastewater treatment system 1 is larger, free fluorine ions contained in the waste water to be processed BF contained in waste water to remove - - fluorine removal apparatus 10 for removing the free F (F) 4 - BF 4 for measuring the concentration of - the concentration measuring device 20, BF 4 of the waste water - and a decomposition treatment unit 30 for processing the degradation to the wastewater.
  • the fluorine removal apparatus 10 is an apparatus for performing the fluorine removal step S1 in the above-described wastewater treatment method, and is a place where wastewater to be treated is first introduced, and measures the concentration of BF 4 ⁇ and BF 4. - prior to decomposition treatment of the free F contained in the waste water - the removal.
  • Waste water to be processed is adapted to contain fluorine, BF 4 of hardly decomposable - it contains a.
  • BF 4 ⁇ contained in this waste water is decomposed over time as shown in the following reaction formula (v). If F ⁇ is present in the waste water as shown in this reaction formula, BF 4 ⁇ is stable. Will come to do. From this point of view, it is considered that the presence of F ⁇ in the wastewater is preferable from the viewpoint of measuring the concentration of BF 4 ⁇ over time and measuring the concentration accurately.
  • BF 4 - in a concentration measuring device 20 BF 4 by adjusting the pH of the wastewater to 4 below - performs the density measurement while suppressing the degradation of, F in its pH4 following waste - Is present, the F ⁇ becomes hydrogen fluoride and the wastewater becomes a strong hydrofluoric acid solution.
  • the decomposition of BF 4 ⁇ in the wastewater in the decomposition treatment apparatus 30 described later is performed by adding a chemical whose use amount is determined based on the measurement result of the BF 4 ⁇ concentration, specifically, a polyvalent metal salt or the like.
  • a chemical whose use amount is determined based on the measurement result of the BF 4 ⁇ concentration specifically, a polyvalent metal salt or the like.
  • F ⁇ is present in the wastewater
  • the polyvalent metal element constituting the added polyvalent metal salt reacts with F ⁇ in the wastewater, and the polyvalent metal salt is consumed. It will be.
  • the amount of the polyvalent metal salt to be used for decomposing BF 4 ⁇ is reduced, and BF 4 ⁇ cannot be effectively decomposed, and by-produced by the reaction between the polyvalent metal salt and F ⁇ .
  • Precipitates (AlF 3 ) and hydroxide precipitates of polyvalent metal salts added excessively for the decomposition of BF 4 ⁇ become flocs, resulting in enormous waste.
  • the fluorine removing device 10 prior to measuring the BF 4 ⁇ concentration in the wastewater, and prior to decomposing BF 4 ⁇ by adding a chemical such as a polyvalent metal salt to the wastewater, the fluorine removing device 10 Then, a treatment for removing free F 2 ⁇ in waste water is performed. In this way, by removing free F 2 ⁇ from waste water, corrosion of the pH electrode, such as a glass electrode, used when measuring the BF 4 ⁇ concentration is suppressed, and appropriate pH adjustment and accurate BF 4 ⁇ concentration measurement are performed. In addition, the waste of the polyvalent metal salt added to the decomposition of BF 4 ⁇ can be prevented, and the BF 4 ⁇ in the waste water can be decomposed effectively and efficiently.
  • a chemical such as a polyvalent metal salt
  • the fluorine removing apparatus 10 it is preferable to remove free F ⁇ in the waste water so that the free F ⁇ concentration in the waste water is less than 0.1 mol / L. Further, it is more preferable to remove free F ⁇ from the waste water so that the free F ⁇ concentration is less than 0.01 mol / L.
  • the fluorine removal apparatus 10 for example, waste water is introduced free F - those with the fluorine removal reaction tank 11 to remove, and a sedimentation tank 12 for settling the precipitate containing fluorine It can be.
  • a method for removing free F 2 ⁇ from wastewater there is a method in which a chemical is added to wastewater to fix free F ⁇ as an insoluble substance (precipitate), and the precipitate is separated and removed from wastewater. Can do.
  • calcium salt can be added to waste water to make free F ⁇ into a CaF 2 precipitate, which can be separated and removed to remove free F ⁇ .
  • the calcium salt for example, inorganic calcium salts such as calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide, and calcium sulfate are preferably used.
  • the free F using calcium salt - when removing it is preferable to add an excess amount as the amount added.
  • the pH of the wastewater it is preferable to adjust the pH of the wastewater to 4 to 11.
  • a CaF 2 precipitate can be efficiently generated by adding a calcium salt.
  • a slurry containing a precipitate generated by adding calcium salt is transferred to a settling tank 12 or the like, and the generated precipitate such as CaF 2 is settled and separated from waste water from which F ⁇ is removed. (Solid-liquid separation).
  • the precipitate obtained was separated off waste water, i.e. free F - waste water was removed is then BF 4 - is transferred to the concentration measuring apparatus 20.
  • sediments such as sedimented CaF 2 are dispensed.
  • BF 4 - BF 4 for measuring the concentration - concentration measuring device > BF 4 - concentration measuring device 20 has been transferred from the fluorine removal apparatus 10, the free F - is introduced waste water was removed, BF 4 contained in the waste water - measuring the concentration of.
  • BF 4 - BF 4 in the concentration measuring device 20 - As a method for measuring the concentration is not particularly limited, and a method for example using an ion-selective electrode.
  • BF 4 indicated by a dotted line enclosing unit in the diagram of Figure 1 - concentration measuring device 20 is cited as an example a device for performing the density measurement by ion electrode.
  • BF 4 using an ion electrode - with respect to the concentration measurement it is possible to refer to the patent document 2.
  • BF 4 shows a part of Figure 1 - concentration measuring device 20, BF 4 - and the container 21 for accommodating the waste water is the concentration of the measurement target, BF 4 - ion electrode device portion having a reference electrode 22b and the electrode 22a and a concentration measuring unit 24 for measuring the concentration - 22, a liquid feed portion 23 for feeding the waste water from the container 21 to the ion electrode device unit 22, BF 4 - BF 4 contained in the waste water in contact with the electrode 22a.
  • BF 4 - is intended to accommodate the waste water is the concentration of the measuring object, the liquid supply unit 23 to be described later, the liquid feed portion of the waste water contained within the chamber 21 to the ion electrode device 22 Is done.
  • the container 21 is, BF 4 - is also possible to decomposition reactor 31, thereby, BF 4 in the wastewater in real time - - BF 4 of decomposition treating apparatus 30 for performing decomposition treatment while measuring the concentration, the Based on the concentration measurement result, the amount of the drug (polyvalent metal or a salt of the polyvalent metal) used for the decomposition of BF 4 ⁇ can be controlled.
  • Ion electrode unit Ion electrode device 22, BF 4 - and the electrode 22a, provided with a reference electrode 22b, the BF 4 - BF to the electrode 22a 4 - contacting the wastewater the concentration of the measurement target.
  • BF 4 - as the electrode 22a, it is possible to use an ion electrode of DKK-TOA Corporation.
  • BF 4 - By contacting the waste water with the electrode 22a, BF 4 in the wastewater in the concentration measuring unit 24 to be described later - the concentration is measured.
  • the ion electrode device unit 22 is provided with a pH electrode (pH meter) 22A made of a glass electrode or the like.
  • a pH electrode 22A made of a glass electrode or the like.
  • the pH of the wastewater can be monitored as appropriate. This makes it possible to stably adjust the pH of the wastewater for measuring the BF 4 ⁇ concentration to 4 or less, and to accurately measure the BF 4 ⁇ concentration in the waste water.
  • BF 4 - will be described in detail later pH adjustment during concentration measurement.
  • the ion electrode device 22 the vessel 21 - may be a device incidental to (BF 4 decomposition reactor 31), this case may not be provided liquid feed section 23 to be described later.
  • the liquid feeding part 23 is for sending waste water accommodated in the container 21 to the ion electrode device part 22.
  • a liquid feeding pump capable of feeding waste water at a desired liquid feeding speed is configured.
  • the waste water may be returned to the container 21 through the liquid feeding section 23.
  • the concentration measuring unit 24 measures the BF 4 ⁇ concentration contained in the waste water in contact with the BF 4 ⁇ electrode 22a in the ion electrode device unit 22.
  • the concentration measuring unit 24, for example, BF 4 - can be made to measure by the AC electrical conductivity of the waste water in contact with the electrode 22a electrode method.
  • BF 4 - the density measuring device 20, BF 4 by adjusting the pH of the wastewater to 4 below - to measure the concentration.
  • BF 4 was adjusted to pH 2 ⁇ 3 - measuring the concentration. If the pH of the wastewater exceeds 4, the BF 4 ⁇ decomposition over time in the wastewater cannot be sufficiently suppressed, and accurate concentration measurement cannot be performed. As a result, the amount of the chemical used for decomposing BF 4 ⁇ added in the decomposition processing apparatus 30 cannot be appropriately controlled.
  • the pH adjustment of the wastewater is not particularly limited as long as the pH can be adjusted to 4 or less.
  • various inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, or various organic acids can be used. These acids for adjusting the pH can be added to the container 21.
  • the pH of the waste water can be measured by a pH electrode 22A provided in the ion electrode device unit 22. Further, a pH electrode may be further provided in the container 21 so that the pH can be measured.
  • Density measurement part 24, BF 4 in is connected to the control unit 32 constituting the decomposition treating apparatus 30 to be described later were measured wastewater - it is possible to transmit the information on the concentration. Thereby, the amount of the agent (polyvalent metal salt or the like) for decomposing BF 4 ⁇ used in the decomposition processing apparatus 30 can be controlled based on the measurement result of the BF 4 ⁇ concentration. In particular, in the present embodiment, prior to the measurement of the BF 4 ⁇ concentration, the fluorine removing apparatus 10 removes free F ⁇ from the wastewater.
  • the free F - According to, BF 4 - effective in determining the concentration - to prevent corrosion of the pH electrode 22A made of glass electrodes or the like to be used for the measurement of concentration, BF 4 it is possible to appropriately adjust the pH It is possible to control the amount of medicine used in the decomposition processing apparatus 30 appropriately.
  • BF 4 - decomposing decomposition treating apparatus In the decomposition treatment apparatus 30, BF 4 ⁇ contained in the waste water is decomposed. Specifically, in the decomposition processing apparatus 30, the addition amount of the chemical for decomposing BF 4 ⁇ is determined based on the measurement result of BF 4 ⁇ concentration measured by the BF 4 ⁇ concentration measuring apparatus 20, and BF 4 ⁇ concentration is measured. 4 - the decomposition process is performed of. As described above, in the present embodiment, the amount of drug is controlled based on the measurement result of the BF 4 ⁇ concentration, and the BF 4 ⁇ decomposition process is continuously performed. Therefore, efficient processing can be performed using an appropriate amount of medicine.
  • BF 4 constituting the decomposition treating apparatus 30 - decomposition reaction vessel BF 4 - is identical to the container 21 in the concentration measuring device 20. Therefore, the decomposition treating apparatus 30, BF 4 - BF in the wastewater that has been measured by the concentration measuring device 20 4 - concentration is sent periodically, BF 4 was measured by the real-time - continuously based on the density to determine the drug loading amounts, BF 4 - decomposition process can be performed in.
  • BF 4 - configuration for the degradation process of the [BF 4 - decomposition reactor] BF 4 - decomposition reactor 31 is housed wastewater to be processed is, BF 4 included in the waste water - the decomposing reaction field.
  • the BF 4 - in the decomposition reactor, BF of the contained waste water 4 - is added drug amount determined based on the concentration, BF 4 - performing the decomposition process.
  • BF 4 decomposition reaction tank 31 a polyvalent metal salt is added to the wastewater to cause a decomposition reaction of BF 4 ⁇ .
  • BF 4 the following reaction formula (i) ⁇ (iv) progresses - are decomposed.
  • the polyvalent metal salt is an agent for decomposing BF 4 ⁇ , and more specifically, free hydrogen fluoride, which is a final decomposition product of BF 4 ⁇ , is removed from the system to decompose BF 4 ⁇ . It is a drug for promoting (the above reaction formulas (i) to (iv)).
  • the polyvalent metal element constituting the polyvalent metal salt is at least one selected from aluminum, iron, titanium and the like.
  • the polyvalent metal salt is not particularly limited as long as it reacts with free hydrogen fluoride.
  • aluminum salts such as aluminum sulfate, ferric salts such as ferric chloride and ferric sulfate.
  • a second titanium salt such as titanium chloride.
  • Polyvalent metal salt when the polyvalent metal element is aluminum or iron which constitutes it, BF 4 contained in wastewater - relative to 1 mole of aluminum ions or iron ions of 0.8 to 5 moles Are added as follows. Further, when the polyvalent metal elements constituting the polyvalent metal salt is Titanium, BF 4 contained in wastewater - relative to 1 mol of titanium ions are added so that 0.4 to 3 moles.
  • the amount of the polyvalent metal salt, BF 4 - BF was measured by the concentration measuring device 20 4 - is characterized by determining based on the concentration of the measurement results.
  • BF 4 - in a concentration measuring device 20 BF 4 - decomposition reactor 31 BF 4 contained in the contained wastewater (vessel 21) - BF 4 concentration is provided in the ion electrode device 22 of the - as measured by contact with the electrodes 22a, the density measurement part 24 BF 4 - the transmitted information related to the measurement result of the concentration of the control unit 32, the BF 4 in the control unit 32 - polyvalent metal salts based on concentration Is added. Details will be described later.
  • the polyvalent metal ion BF 4 - reacts with generated by decomposing the free hydrogen fluoride, for example, AlF n 3 -N , FeF n 3-n and TiF n 4-n are generated. Thereby, the decomposition reaction of BF 4 ⁇ shown in the above reaction formulas (i) to (iv) is promoted.
  • the following general formula (v) is a reaction formula in which aluminum is added as a polyvalent metal element.
  • the agent for promoting the decomposition reaction of BF 4 ⁇ is not limited to the polyvalent metal salt, and a polyvalent metal composed of the same kind of polyvalent metal element can also be added. That is, for example, aluminum, iron, can be added a polyvalent metal such as titanium, in this case, BF 4 - may be added in amount based on the concentration.
  • BF 4 - for the waste water containing, by adding a pH adjusting agent with the addition of a polyvalent metal salt it is preferable to adjust the pH conditions of the waste water under acidic conditions.
  • the pH is preferably 4 or less, more preferably 3 or less, and particularly preferably adjusted to 2 or less.
  • a pH adjuster for example, acid agents such as sulfuric acid, hydrochloric acid, and nitric acid, and alkali agents such as sodium hydroxide, potassium hydroxide, and calcium hydroxide can be used.
  • BF 4 contained in the waste water - the decomposition process is preferably performed by ultraviolet irradiation of the waste water.
  • the bond between fluorine (F) and boron (B) in BF 4 ⁇ is easily broken by the strong energy of the ultraviolet rays, and the decomposition reaction efficiency can be improved.
  • a mechanical stirrer such as a vertical stirrer, a turbine stirrer, a propeller stirrer, a jet stirrer using a pump or the like, a gas blowing stirrer, or the like can be used.
  • Control unit The control unit 32, BF 4 - BF in the wastewater that has been measured by the density measurement part 24 in the concentration measuring device 20 4 - receives the information on the concentration, the BF 4 - on the basis of the concentration, BF 4 decomposition reactor 31 The amount of the polyvalent metal salt added to.
  • the decomposition processing unit 30 definitive BF 4 - the amount of the polyvalent metal salt used in the decomposition treatment, BF 4 - BF 4 was measured by the concentration measuring device 20 - the concentration of It is characterized by being determined based on the measurement result.
  • the decomposition treating apparatus 30, BF 4 contained in the waste water - recognizes the concentration in real time, the time-varying BF 4 - to determine continuously the drug amount based on the concentration, BF 4 - allow disassembly process. Therefore, changing BF 4 - in accordance with the concentration can control the drug amount, it can be performed more appropriately and efficient processing.
  • control unit 32 BF 4 - on the basis of the density measurement results, determined as follows the amount of the polyvalent metal salt.
  • the control unit 32, BF 4 - receives the information on the concentration, the BF 4 - - from the density measuring unit 24 in the concentration measuring device 20 BF 4 measurements and concentrations, also was controlled to less than 0.1 mol / L
  • the value obtained by multiplying the free F ⁇ concentration and the like by a predetermined coefficient is taken as the addition amount of the polyvalent metal salt.
  • the medicated portion 33 receives the information about the amount of the polyvalent metal salt from the control unit 32, the addition amount thereof, i.e. BF 4 - a polyvalent metal salt of the addition amount based on the concentration of the measurement results, BF 4 - It adds to the wastewater accommodated in the decomposition reaction tank 31.
  • the drug addition unit 33 is connected to, for example, a polyvalent metal salt supply tank that supplies a polyvalent metal salt. A predetermined ratio of the polyvalent metal salt is supplied from the polyvalent metal salt supply tank, and the predetermined amount is supplied. Store.
  • the medicated portion 33 on the basis of information about the amount of the control unit 32, a polyvalent metal salt which stores the partial multivalent metal salt of the amount added BF 4 - is added to the decomposition reaction vessel 31.
  • BF 4 - BF by adjusting the pH of the wastewater to 4 below in a concentration measuring device 20 4 - concentration were measured, and sends the measurement result to the decomposition treating apparatus 30 , BF 4 in the decomposition processor 30 - so that to determine the amount of drug based on the concentration.
  • the wastewater treatment method since the amount of the chemical used can be controlled continuously based on the BF 4 ⁇ concentration in the wastewater that varies with time, the wastewater can be treated more efficiently. be able to.
  • the wastewater prior to measuring the BF 4 ⁇ concentration contained in the wastewater, and before decomposing BF 4 ⁇ by adding a chemical such as a polyvalent metal salt to the wastewater, the wastewater By removing the free F ⁇ contained in the water, it is possible to suppress the free F ⁇ contained in the wastewater from becoming strong hydrofluoric acid, and to measure the concentration of BF 4 ⁇ more accurately. Further, by removing free F 2 ⁇ from wastewater, waste of chemicals such as polyvalent metal salts added for the decomposition of BF 4 ⁇ can be suppressed, and an efficient decomposition process can be performed.
  • the decomposition treatment apparatus 30 can perform a defluorination treatment that removes fluorine obtained by decomposing BF 4 ⁇ contained in wastewater. As shown in the block diagram of FIG. 1, this defluorination treatment can be performed in a defluorination (F) treatment tank.
  • F defluorination
  • a calcium salt such as slaked lime and a pH adjuster are added to wastewater obtained by decomposing BF 4 ⁇ to insolubilize fluorine contained in the wastewater ( Fluorine insolubilization treatment). That is, fluorine ions generated by the decomposition of BF 4 ⁇ are insolubilized.
  • the calcium salt is added to convert fluorine ions into an insoluble substance.
  • the preceding stage of BF 4 - aluminum salts in the decomposition reaction vessel 31 as polyvalent metal salts, ferric salts, BF 4 with a second titanium salt such as - when degrade, AlF n 3-n soluble , FeF n 3-n and TiF n 4-n complexes are formed.
  • a second titanium salt such as - when degrade, AlF n 3-n soluble , FeF n 3-n and TiF n 4-n complexes
  • fluorine ions can be converted to CaF 2 and insolubilized by an adsorption reaction of fluorine ions to calcium hydroxide of a hydrolysis product of solid calcium hydroxide or calcium salt.
  • fluorine component By converting the fluorine component into insoluble CaF 2 and insolubilizing in this way, the fluorine component can be easily flocated and removed in the agglomeration tank 36 described later.
  • inorganic calcium salts such as calcium chloride, calcium hydroxide, calcium carbonate, calcium oxide, and calcium sulfate.
  • the pH adjuster is added to adjust the pH condition of the wastewater in the defluorination treatment tank 34, but it is adjusted to a pH condition that can precipitate the reaction product generated by the addition of the calcium salt described above.
  • the pH is preferably adjusted to 4 to 8
  • a ferric salt and a second titanium salt are used, the pH is preferably adjusted to 4 or more.
  • acid agents such as sulfuric acid, hydrochloric acid and nitric acid, and alkali agents such as sodium hydroxide, potassium hydroxide and calcium hydroxide can be used.
  • a calcium salt such as slaked lime and a pH adjuster are further added to the wastewater to insolubilize boron contained in the wastewater (boron insolubilization treatment). That is, boron ions generated by the decomposition of BF 4 ⁇ are insolubilized.
  • the calcium salt, a boron ion (borate ion), a reaction product of a calcium salt in defluorination treatment tank 34 described above and BF 4 - is added in decomposition reactor 31 the hydroxides of polyvalent metal ions Acts to encapsulate the boron ions, thereby insolubilizing the boron ions.
  • the boron component is encapsulated by the calcium salt reaction product or polyvalent metal ion hydroxide and insolubilized, whereby the boron component can be easily flocked and removed in the agglomeration tank 36 described later. It becomes like this.
  • the thing similar to what was added in the defluorination processing tank 34 can be used for a calcium salt and a pH adjuster.
  • the defluorination treatment tank 34 and the deboronation treatment tank 35 described above may be integrated, and the defluorination treatment and the deboronation treatment may be performed together.
  • a flocculant such as an anionic polymer flocculant is added to the wastewater to coarsen (flocculate) the particles of the reaction product in the wastewater. That, BF 4 - decomposition produced in the decomposition reaction vessel 31, to flock the fluorine ions or boron ions insolubilized by defluorination treatment tank 34 and the deboronation treatment tank 35.
  • the flocculant is added to flock the particles of the insoluble material generated in the defluorination treatment tank 34 and the deboronation treatment tank 35.
  • a nonionic polymer flocculant is used in the acidic region
  • a weak anionic polymer flocculant is used in the acidic to weakly acidic region
  • a neutral anionic high concentration agent is used in the weakly acidic to weakly alkaline region.
  • a flocculant may be used individually by 1 type, or may use 2 or more types together.
  • the flocculant is not limited to a polymer flocculant, and an inorganic flocculant may be used as long as it can flock insoluble substances.
  • the addition amount of the flocculant is, for example, a concentration range of 0.5 mg / L to 15 mg / L with respect to the wastewater to be treated.
  • the flocculation tank 36 after adding the flocculant, it is preferable to treat the waste water with stirring with, for example, a turbine stirrer or a propeller stirrer. By stirring in this way, flocking by the flocculant can be promoted.
  • a turbine stirrer or a propeller stirrer By stirring in this way, flocking by the flocculant can be promoted.
  • the fluorine contained in the wastewater is separated as CaF 2 and boron is precipitated and separated as boric acid, and the fluorine and boron in the supernatant water are treated to a low concentration, and after the treatment Water can be obtained.
  • the solid component separated by solid-liquid separation that is, floc containing fluorine or boron is discharged from the settling tank 37 as a precipitate.

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PCT/JP2015/060249 2015-03-31 2015-03-31 廃水の処理方法、廃水の処理システム WO2016157452A1 (ja)

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CN106348503A (zh) * 2016-10-10 2017-01-25 昆明理工大学 一种超声波强化脱除高氟废水的方法
JP2019143530A (ja) * 2018-02-20 2019-08-29 いすゞ自動車株式会社 燃料タンク

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JP2011027722A (ja) * 2009-06-24 2011-02-10 Central Res Inst Of Electric Power Ind Ｂｆ４−及びｆ−の同時計測方法及びシステム
JP2011104459A (ja) * 2009-11-12 2011-06-02 Sumitomo Metal Mining Engineering Co Ltd 廃水の処理方法
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JP2009233605A (ja) * 2008-03-27 2009-10-15 Eco System Akita Kk ホウフッ化物含有水の処理方法
JP2011027722A (ja) * 2009-06-24 2011-02-10 Central Res Inst Of Electric Power Ind Ｂｆ４−及びｆ−の同時計測方法及びシステム
JP2011104459A (ja) * 2009-11-12 2011-06-02 Sumitomo Metal Mining Engineering Co Ltd 廃水の処理方法
JP2014200745A (ja) * 2013-04-05 2014-10-27 オルガノ株式会社 フッ素含有排水の処理方法およびフッ素含有排水の処理装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106348503A (zh) * 2016-10-10 2017-01-25 昆明理工大学 一种超声波强化脱除高氟废水的方法
JP2019143530A (ja) * 2018-02-20 2019-08-29 いすゞ自動車株式会社 燃料タンク

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