WO2014104248A1 - Recovery method for dissolved salt, recovery device for dissolved salt, and production method for calcium chloride - Google Patents

Recovery method for dissolved salt, recovery device for dissolved salt, and production method for calcium chloride Download PDF

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Publication number
WO2014104248A1
WO2014104248A1 PCT/JP2013/084992 JP2013084992W WO2014104248A1 WO 2014104248 A1 WO2014104248 A1 WO 2014104248A1 JP 2013084992 W JP2013084992 W JP 2013084992W WO 2014104248 A1 WO2014104248 A1 WO 2014104248A1
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WIPO (PCT)
Prior art keywords
exchange resin
anion exchange
ion
solution
amount
Prior art date
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PCT/JP2013/084992
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French (fr)
Japanese (ja)
Inventor
清水　和彦
鳥羽　裕一郎
英二 今村
志村　光則
雅世 篠原
敏信 今濱
賢兒 金
Original Assignee
千代田化工建設株式会社
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Priority claimed from JP2012287988A external-priority patent/JP6159527B2/en
Priority claimed from JP2013048097A external-priority patent/JP6163326B2/en
Application filed by 千代田化工建設株式会社 filed Critical 千代田化工建設株式会社
Publication of WO2014104248A1 publication Critical patent/WO2014104248A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • 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
    • 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
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the present invention relates to a method and a recovery device for recovering dissolved salts from water associated with resource mining.
  • Patent Document 1 discloses a technique (Penrice method) for recovering salt in water as valuable salt Na 2 CO 3 for water associated with resource mining. This is a method in which C 12 amine and CO 2 dissolved in an oil phase are reacted with NaCl to convert them to NaHCO 3 and then converted to Na 2 CO 3 by applying heat.
  • Non-Patent Document 1 and Patent Document 2 disclose a method for producing NaHCO 3 from water containing NaCl using an ion exchange resin, as represented by Formula (1).
  • Patent Document 3 discloses a method using limestone (CaCO 3 ) as a CO 2 supply source. Further, in this method, CaCO 3 is burned to obtain CO 2 and, as represented by the formula (4), Ca (OH) 2 as a by-product is used as a regenerated alkali of the ion exchange resin. 2R 3 N—HCl + Ca (OH) 2 ⁇ 2R 3 N + CaCl 2 + 2H 2 O Formula (4)
  • Patent Document 3 uses CO 2 gas generated during the production of Ca (OH) 2 as a reaction raw material and is fixed as a carbonate, and as a system that emits almost no CO 2 gas to the atmosphere, global warming This is an effective technique from the viewpoint of prevention.
  • wastewater containing oil as a COD raw material is not generated.
  • the reaction of formula (3) proceeds almost completely, so there is no loss of carbonate recovery and a very high recovery rate can be obtained.
  • CaCl 2 is generated when the resin is regenerated, but in order to completely regenerate the ion exchange resin (R 3 N—HCl) combined with HCl (formula (4)).
  • a half amount of Ca (OH) 2 of HCl may be brought into contact with the ion-exchange resin, but in practice, a larger amount of Ca (OH) than half the amount of HCl. 2 must be brought into contact with the ion exchange resin.
  • the number of Ca (OH) 2 contained in the ion-exchange resin in the Ca (OH) 2 treatment solution obtained by contacting low even to obtain a CaCl 2 from the treatment liquid Only pure CaCl 2 is obtained, and the obtained CaCl 2 becomes waste.
  • the cost for disposing of this large amount of waste is high at the site of resource mining.
  • this CaCl 2 can be recovered with high purity, it can be used as an industrial raw material in the same way as carbonates, and thus can be a valuable resource.
  • this ion exchange method becomes extremely effective as a technique for recovering salts from the accompanying water generated by resource mining such as natural gas or crude oil such as CSG.
  • An object of the present invention is to recover the CaCl 2 from resource mining produced water, in particular, to provide a recovery method and recovery apparatus of dissolution salts makes it possible to recover the CaCl 2 that suppresses entry of impurities It is.
  • the method for recovering dissolved salts of the present invention includes a first recovery step of passing NaCl-containing resource mining associated water through an anion exchange resin and recovering NaHCO 3 , and after the resource mining accompanying water flowing.
  • a Ca (OH) 2 solution is passed through the anion exchange resin, and a regeneration process for regenerating the anion exchange resin, and a second recovery process for recovering the regenerated liquid after the regeneration process,
  • the pH of the regenerated reprocessing solution is monitored, and the regenerated processing solution recovered until the monitored pH value reaches a predetermined set value is concentrated and dried to recover CaCl 2 . .
  • the method for recovering dissolved salts of the present invention includes a first recovery step of passing NaCl-containing resource mining associated water through an anion exchange resin and recovering NaHCO 3 , and after the resource mining accompanying water flowing A Ca (OH) 2 solution is passed through the anion exchange resin, and a regeneration process for regenerating the anion exchange resin, and a second recovery process for recovering the regenerated liquid after the regeneration process,
  • the Cl ⁇ ion concentration of the regenerated reprocessing solution is monitored, and the amount of Cl ⁇ ion desorption of the anion exchange resin determined based on the monitored Cl ⁇ ion concentration is predetermined.
  • the regenerated solution collected until reaching the set value is concentrated and dried to recover CaCl 2 .
  • the regenerated treatment liquid recovered after the monitored pH value reaches a predetermined set value is used as the anion exchange resin. It is preferable to store as a regenerant for regenerating.
  • the regeneration treatment solution recovered after the Cl ⁇ ion desorption amount of the anion exchange resin has reached a predetermined set value Is preferably stored as a regenerant for regenerating the anion exchange resin.
  • the predetermined set value is the pH of the Ca (OH) 2 solution
  • the monitored pH is the pH of the Ca (OH) 2 solution.
  • the regenerated solution collected until reaching the concentration is concentrated and dried to collect CaCl 2
  • the regenerated solution collected after the monitored pH reaches the pH of the Ca (OH) 2 solution is converted into the anion exchange solution. It is preferable to store the resin as a regenerant for regenerating the resin.
  • the predetermined set value is set between pH 10 and 12, and the monitored pH reaches the set value set between pH 10 and 12.
  • the predetermined set value Cl of the anion-exchange resin in the first recovery step - as an ion adsorption amount, Cl of the anion exchange resin - The regenerated solution collected until the ion desorption amount reaches the Cl ⁇ ion adsorption amount of the anion exchange resin is concentrated and dried to recover CaCl 2, and the Cl ⁇ ion desorption amount of the anion exchange resin is recovered.
  • the predetermined set value is set between 85 and 96% of the Cl ⁇ ion desorption amount of the anion exchange resin, and the anion exchange is performed.
  • resins Cl - ion elimination amount, the anion exchange resin Cl - CaCl 2 was concentrated and dried playback processing liquid collected to reach a set value set between 85 to 96% of the ion adsorption Recovered after the Cl ⁇ ion desorption amount of the anion exchange resin reaches a set value set between 85 and 96% of the Cl ⁇ ion adsorption amount of the anion exchange resin.
  • the apparatus for recovering dissolved salts of the present invention includes a packed tower filled with an anion exchange resin and resource mining associated water containing NaCl through the packed tower to recover NaHCO 3 .
  • the dissolved salt recovery apparatus of the present invention includes a packed tower filled with an anion exchange resin, and resource mining associated water containing NaCl is passed through the packed tower to recover NaHCO 3 . and recovery means, and passed through a Ca (OH) 2 solution to the packed column, a reproducing means for the anion exchange resin regeneration process, Cl of the reproduction process reproduction processing solution - monitoring the ion concentration Cl - ions A second recovery means for recovering the regenerated processing solution until a Cl ⁇ ion desorption amount of the anion exchange resin determined based on the monitored Cl ⁇ ion concentration reaches a predetermined set value; Concentrating means for concentrating the recovered regeneration processing liquid and drying means for drying the concentrated regeneration processing liquid.
  • a calcium hydroxide solution is brought into contact with an ion exchange resin combined with hydrochloric acid to obtain a treatment solution containing calcium chloride, and the purity of the treatment solution is monitored.
  • a third step of obtaining calcium is obtained.
  • the method includes setting a specified value corresponding to the reference purity before the second step, and, based on the specified value in the second step, It is preferable to stop the acquisition.
  • the specified value is a pH of the treatment liquid when the calcium chloride purity is the reference purity.
  • the monitoring of the calcium chloride purity It is preferable to measure the pH of the treatment liquid.
  • the specified value is a chlorine ion desorption amount of the ion-exchange resin when the calcium chloride purity is the reference purity.
  • the calcium chloride purity Preferably, the monitoring includes measuring a chlorine ion concentration of the treatment liquid and calculating the chlorine ion desorption amount based on the measured chlorine ion concentration.
  • recovering the CaCl 2 from resource mining produced water in particular, it is possible to provide a recovery method and recovery apparatus of dissolution salts makes it possible to recover the CaCl 2 that suppresses entry of impurities .
  • PH of the reproduction processing solution for Ca (OH) 2 supply amount and Cl - is a diagram showing the relationship between ion desorption amount.
  • FIG.1 and FIG.2 is a schematic block diagram which shows an example of a structure of the dissolved salt collection
  • the dissolved salt recovery apparatus 1 includes a drainage storage tank 10, a drainage inflow line 12, a drainage pump 14, a packed tower 16 filled with an anion exchange resin, a treated water discharge line 18, a treated water tank 20,
  • the dissolved salt recovery device 1 includes a Ca (OH) 2 storage tank 22, a Ca (OH) 2 inflow line 24, a Ca (OH) 2 pump 26, and a blower 32.
  • the air inlet line 34, the regeneration processing liquid discharge lines 36a and 36b, and the regeneration processing liquid storage tanks 38a and 38b are further provided. As shown in FIG.
  • the waste water inlet line 12 Cl - ion sensor 31 is installed.
  • Ion sensor 21 is provided - Cl in waste water treatment line 18.
  • the Cl ⁇ ion sensor 21 may be installed in the treated water tank 20.
  • a Cl - ion sensor 21 is installed in the treated water tank 20, and a pH sensor 28 and a Cl - ion sensor 30 are installed in the packed tower 16 as shown in FIGS.
  • recovery apparatus 1 is equipped with the control part 40, and is electrically connected with each sensor and the integrating
  • the components shown in FIG. 1 are installed in the packed tower 16, and when recovering CaCl 2 described later, the packed tower 16 1 may be removed, and the components shown in FIG. 2 may be installed in the packed column 16, or the packed column 16 may be configured as shown in FIGS. 1 and 2 through the recovery of NaHCO 3 and the recovery of CaCl 2 . Parts may be installed.
  • one end of the drainage inflow line 12 is connected to the drainage storage tank 10, and the other end is connected to the upper part of the packed tower 16.
  • the wastewater inflow line 12, the drainage pump 14, the integrated flow meter 19, Cl - ions sensor 31 is installed.
  • One end of the treated water discharge line 18 is connected to the bottom of the packed tower 16, and the other end is connected to the treated water tank 20.
  • one end of the Ca (OH) 2 inflow line 24 is connected to the Ca (OH) 2 storage tank 22, and the other end is connected to the upper part of the packed tower 16.
  • the Ca (OH) 2 inlet line 24 Ca (OH) 2 pump 26 is installed.
  • One end of the air inflow line 34 is connected to the blower 32, and the other end is connected to the lower side surface of the packed tower 16.
  • One end of the regeneration processing liquid discharge line 36a is connected to the lower side surface of the packed tower 16, the other end is connected to the regeneration processing liquid storage tank 38a, and one end of the regeneration processing liquid discharge line 36b is connected to the regeneration processing liquid discharge line 36a. The other end is connected to the regeneration processing liquid storage tank 38b.
  • the drainage storage tank 10, the drainage inflow line 12, the drainage pump 14, the treated water discharge line 18, and the treated water tank 20 pass the resource mining associated water containing NaCl to the packed tower 16 and collect the NaHCO 3. It functions as a device.
  • the first recovery device if a configuration of recovering NaHCO 3 from resource mining produced water containing NaCl, but is not limited to the above structure.
  • the Ca (OH) 2 storage tank 22, the Ca (OH) 2 inflow line 24, and the Ca (OH) 2 pump 26 function as a regeneration device that regenerates the anion exchange resin in the packed tower 16.
  • the regenerating apparatus is not limited to the above structure as long as it has a structure for regenerating an anion exchange resin.
  • the second recovery device has a configuration for recovering the regeneration treatment solution until the pH of the regeneration treatment solution or the Cl ⁇ ion desorption amount of the anion exchange resin reaches a predetermined specified value,
  • the present invention is not limited to this configuration.
  • the concentrator 42 has a function of concentrating the regenerated liquid, and examples thereof include an evaporator and a liquid film descending evaporation concentrator.
  • the drying device 44 is for drying the concentrated regeneration treatment liquid, and examples thereof include an electric heating dryer and a vacuum drum dryer.
  • the wastewater to be treated in this embodiment is resource mining accompanying water containing NaCl.
  • the water associated with resource mining is water associated with resource mining such as natural gas such as CSG (Coal Seam Gas) or crude oil, and includes NaCl or the like.
  • the pretreatment step is a step of removing suspended substances, oils, and the like contained in the water associated with resource mining by coagulation sedimentation, coagulation flotation separation, membrane filtration using an MF membrane / UF membrane, or the like.
  • the concentration step is a step of concentrating water associated with resource mining with an RO membrane or the like to increase the NaCl concentration in the water.
  • the concentration of NaCl in the concentrated resource extraction accompanying water is preferably 0.1 mol / L or more from the viewpoint of shortening the subsequent treatment time and performing efficient operation.
  • the resource extraction produced water containing NaCl was passed through an anion exchange resin, the NaCl in the above reaction formula (3) is replaced with NaHCO 3, performing a first recovery step of recovering the NaHCO 3 .
  • the anion exchange resin is a H 2 CO 3 type weakly basic ion-exchange resin, and more preferably H 2 CO 3 type weakly basic acrylic ion exchange resin.
  • H 2 CO 3 type weakly basic acrylic ion exchange resin will be described as an example.
  • the H 2 CO 3 type weakly basic acrylic ion exchange resin is a carbonate-dissolved water obtained by dissolving carbonic acid in pure water or the like in a packed tower 16 filled with a weakly basic acrylic ion exchange resin before the first recovery step. It is necessary to pass water and convert it into H 2 CO 3 type.
  • Examples of the dissolution of carbonic acid include a method of dissolving CO 2 gas in pure water or the like using a gas absorption tower or the like.
  • As the CO 2 gas it is desirable to use CO 2 gas produced as a by-product when methane gas is burned or Ca (OH) 2 is produced from CaCO 3 .
  • the resource extraction accompanying water containing NaCl in the drainage storage tank 10 passes through the drainage inflow line 12 by the drainage pump 14, and is a weak base of H 2 CO 3 type. Is supplied to a packed tower 16 filled with a functional acrylic ion exchange resin. Within packed tower 16 by H 2 CO 3 type weakly basic acrylic ion exchange resin, Cl - is adsorbed, it is treated water containing NaHCO 3 is discharged from the treated water discharge line 18, stored in the processed water tank 20 The treated water containing NaHCO 3 stored in the treated water tank 20 is then concentrated by a concentrating device 42 such as an evaporator and dried by a drying device 44 such as a dryer.
  • a concentrating device 42 such as an evaporator
  • a drying device 44 such as a dryer.
  • Cl was placed in the treated water discharge line 18 - by the ion sensor 21, Cl in the treated water - monitoring the ion concentration, Cl - it is desirable that the ion concentration immediately terminated Once raised. For example, even if the measurement data of the Cl ⁇ ion sensor 21 is sent to the control unit 40 and the control unit 40 electronically controls to stop the operation of the drainage pump 14 and the like when the Cl ⁇ ion concentration increases. good to the worker Cl - checks the measurement data of the ion sensor 21, Cl - at the stage where the ion concentration is increased, may be stopped operation of such drainage pump 14 manually.
  • Cl H 2 CO 3 type weakly basic acrylic ion exchange resin is adsorbed - is that you calculate the ion adsorption amount desired. Specifically, Cl was placed in the drainage inlet line 12 - and the ion concentration, Cl installed in the treated water discharge line 18 - - Cl of resource extraction associated water detected by the ion sensor 31 is detected by the sensor 21 treatment water Cl - is determined by multiplying the flow rate of the resource extraction produced water detected by the integrating flowmeter in the difference between the ion concentration (through water).
  • Cl H 2 CO 3 type weakly basic acrylic ion exchange resin is adsorbed - ion adsorption amount, for example, the Cl - measurement data of the sensor and the integrated flow meter 19 is transmitted to the control unit 40, the control unit 40 It is calculated by.
  • the anion exchange resin used in this embodiment is a weakly basic anion exchange resin having an acrylic tertiary amine type functional group.
  • Amberlite IRA-67 is preferably used.
  • the water passing SV of the resource extraction accompanying water in the first recovery step is preferably about 0.5 to 10 (1 / h).
  • a Ca (OH) 2 solution (hereinafter sometimes referred to as Ca (OH) 2 slurry) is passed through the anion exchange resin to which HCl has been adsorbed in the first recovery step, and the above formula (4
  • a regeneration step is performed in which HCl is desorbed from the anion exchange resin to regenerate the anion exchange resin.
  • Such a regeneration step is a batch type in which the Ca (OH) 2 slurry is gradually added to a predetermined condition while stirring the resin in the packed tower 16 and the reaction solution is discharged from the packed tower 16 after a certain time of reaction. You can go.
  • the Ca (OH) 2 slurry may be passed through the packed tower 16 to continuously discharge the regeneration treatment liquid. From the viewpoint of more efficiently advancing the reaction of formula (4) on the anion exchange resin covered with the slurry, a batch of gradually adding the Ca (OH) 2 slurry to a predetermined amount while stirring the anion exchange resin. The formula is preferred.
  • the concentration of the Ca (OH) 2 slurry is preferably 5 to 10% when used in a batch system and 0.05 to 0.5% when used in a continuous system.
  • the fluid for supplying air to the packed column 16 and stirring the anion exchange resin in the packed column 16 is not limited to air, and any fluid that does not hinder the reaction of formula (4) may be used.
  • any fluid that does not hinder the reaction of formula (4) may be used.
  • methane gas etc. are mentioned.
  • undissolved Ca (OH) 2 is Ca 2+ and OH - from the dissolved, OH - because cause regeneration reaction with HCl on an anion exchange resin, the added Ca (OH) 2 is reproduced In some cases, it takes a time of several minutes to 10 minutes to be fully used in the process. Therefore, it is preferable that the addition of the Ca (OH) 2 slurry in a batch system is performed intermittently in consideration of the time.
  • the second recovery step of recovering the regeneration processing liquid discharged from the packed tower 16 is performed.
  • the pH of the regeneration treatment solution is monitored, and the recovered regeneration solution is concentrated and dried until the monitored pH value reaches a predetermined value.
  • reproduction processing liquid Cl - monitoring the ion concentration monitoring the Cl - Cl anion exchange resin obtained based on the ion concentration - ion elimination amount recovered to reach a predetermined default reproduction processing solution Is concentrated and dried.
  • pH and Cl reproduction process liquid to the supply amount of Ca (OH) 2 - is a diagram showing the relationship between ion desorption amount.
  • FIG. 3 when monitoring the pH of the regeneration treatment solution, before complete regeneration, the Ca (OH) 2 that has passed through the packed column 16 is consumed by the anion exchange resin, while the anion exchange resin. Since HCl is desorbed from the ion exchange resin, the pH of the regeneration treatment solution is lower than the pH 12.2 of the Ca (OH) 2 slurry (when the water temperature is 20 ° C.). The purity of CaCl 2 is high.
  • the pH of the regeneration treatment liquid discharged from the packed tower 16 is monitored by a pH sensor, and the monitored pH value is transmitted to the control unit 40. Then, for example, the control unit 40 compares the pH value of the regeneration processing solution with a predetermined pH value set in advance, and while the pH value does not reach the preset specified value, CaCl 2 in the regeneration processing solution. Therefore, the valve A provided in the regeneration processing liquid discharge line 36a is opened, and the valve B provided in the regeneration processing liquid discharge line 36b is closed. That is, while the pH value is less than the preset specified value, the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 36a to the regeneration processing liquid storage tank 38a.
  • the processing liquid stored in the regeneration processing liquid storage tank 38a is sent to a concentrating device 42 such as an evaporator and concentrated, and then sent to a drying device 44 such as a dryer and dried to recover high-purity CaCl 2. .
  • a concentrating device 42 such as an evaporator and concentrated
  • a drying device 44 such as a dryer and dried to recover high-purity CaCl 2.
  • the valve A is closed and the valve B is opened because the purity of the CaCl 2 in the regenerating solution is lowered.
  • the regeneration processing liquid is supplied from the regeneration processing discharge line 36b to the regeneration processing storage tank 38b.
  • the comparison between the pH value and the specified value, the opening / closing of the valve, and the like may be performed by electronic control by the control unit 40 or may be performed manually by an operator.
  • the pH value of the regeneration treatment liquid can be measured by the pH sensor 28 installed in the packed tower 16, but when it is a continuous type, the regeneration treatment liquid It is necessary to install a pH sensor in the discharge line 36a or the regeneration processing liquid storage tank 38a and measure the pH of the regeneration processing liquid.
  • the specified value to be set in advance is not particularly limited as long as it is a value capable of recovering high-purity CaCl 2 , but in the case of pH monitoring, it should be set to the pH value of the Ca (OH) 2 slurry. Is preferable, and it is more preferable to set between pH 10.0 and 12.0.
  • By setting the specified value to pH 12.0 or less it is possible to reliably transfer the regeneration treatment liquid containing high-purity CaCl 2 to the concentration / drying step.
  • by setting the specified value to pH 10.0 or more it is possible to suppress an increase in the regeneration processing liquid stored for regeneration, and it is possible to use a storage facility with a small capacity.
  • a prescribed value for example, pH of the regenerating solution
  • a calcium hydroxide solution is applied to the ion exchange resin combined with hydrochloric acid.
  • the contact is made to obtain a regeneration treatment liquid containing calcium chloride, and monitoring of the calcium chloride purity of the regeneration treatment liquid is started.
  • the acquisition of the regeneration treatment liquid is stopped until the calcium chloride purity is changed from a state higher than the reference purity to a state lower than the reference purity.
  • the acquisition of the regeneration treatment liquid was stopped until the calcium chloride purity of the regeneration treatment liquid became lower than the reference purity (for example, the calcium chloride purity of the regeneration treatment liquid when the pH of the regeneration treatment liquid was 12.0). Thereafter, by obtaining calcium chloride from the regeneration treatment solution, calcium chloride can be obtained from the regeneration treatment solution having a relatively high calcium chloride purity, and high purity calcium chloride can be produced.
  • the specified value is the pH of the regeneration treatment solution when the calcium chloride purity of the regeneration treatment solution is the reference purity (for example, pH 12.0), and when monitoring the calcium chloride purity, Measure the pH.
  • the specified value can be the chlorine ion desorption amount of the ion exchange resin when the calcium chloride purity of the regeneration treatment solution is the reference purity, instead of the above example which is the pH of the regeneration treatment solution.
  • Cl reproduction processing liquid - monitoring the ion concentration when monitoring calcium chloride purity, Cl reproduction processing liquid - monitoring the ion concentration.
  • Cl reproduction process liquid discharged from the packed tower 16 - ion concentration, Cl - is monitored by the ion sensor, the monitored Cl - ion concentration value is transmitted to the control unit 40 .
  • the desorption amount of Cl 2 ⁇ ions adsorbed on the anion exchange resin can be obtained by the product of the Cl 2 ⁇ ion concentration of the regeneration treatment solution and the regeneration treatment solution amount.
  • the control unit 40 If the flow rate of the regeneration process liquid is constant, the control unit 40, the monitored Cl - obtained by multiplying the constant ion density values, if the reproduction processing solution constant, integrating the reproduction processing liquid discharge line 36a the flowmeter is installed, it transmits a flow rate value of the measured playback processing solution by integrating flowmeter to the control unit 40, the control unit 40, the monitored Cl - measured ion concentration value reproduction processing solution flow rate value It is calculated by multiplying. Then, the control unit 40 compares, for example, the Cl ⁇ ion desorption amount adsorbed on the anion exchange resin with a preset specified value, and the Cl ⁇ ion desorption amount has reached the preset specified value.
  • the valve A is opened and the electromagnetic valve B is closed. That is, while the Cl 2 ⁇ ion desorption amount is less than a preset specified value, the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 36a to the regeneration processing liquid storage tank 38a.
  • the processing liquid stored in the regeneration processing liquid storage tank 38a is sent to a concentrating device 42 such as an evaporator and concentrated, and then sent to a drying device 44 such as a dryer and dried to recover high-purity CaCl 2. .
  • the Cl ⁇ ion concentration of the regenerated solution can be measured by a Cl ⁇ ion sensor 30 installed in the packed tower 16. , Cl playback processing liquid discharge line 36a or reproducing processing liquid reservoir 38a - installing an ion sensor, Cl reproduction processing solution - it is necessary to measure the ion concentration.
  • the specified value to be set in advance is not particularly limited as long as it is a value capable of recovering high-purity CaCl 2 , but in the case of Cl ⁇ ion concentration monitoring, the amount of Cl ⁇ ion adsorption of the anion exchange resin is not limited. preferably set to a value, Cl anion exchange resin - and more preferably set between 85 to 96% of the ion adsorption values.
  • the specified value Cl anion exchange resin - by 85% or more of the ion adsorption value it is possible to suppress the increased reproduction process liquid storing for playback, use a small storage facility capacity It becomes possible to do.
  • the calculation of the Cl ⁇ ion adsorption amount of the anion exchange resin is as described above.
  • Complete regeneration after regeneration treatment liquid i.e., reproduction processing liquid stored as reproduction processing liquid reservoir 38b playback processing liquid discharge line 36b as described above, Cl - somewhat containing ions, Cl - as compared with ion Since the content of Ca (OH) 2 is large, it is desirable to store it for use as a regenerant for regenerating the anion exchange resin in the next cycle. Further, when there are a plurality of packed columns 16 filled with an anion exchange resin, they may be used for regeneration of other series. By doing so, the number of storage facilities can be reduced.
  • this washing waste water is a dilute Ca (OH) 2 solution, it may be used as dissolved water for preparing a Ca (OH) 2 slurry.
  • FIG. 4 is a schematic configuration diagram illustrating an example of a configuration of a dissolved salt recovery apparatus according to a reference example.
  • the dissolved salt recovery apparatus 2 includes a drainage storage tank 46, drainage inflow lines 48a and 48b, drainage pumps 50a and 50b, a pH adjusting tower 52, a blower 54, a gas inflow line 56, and an anion exchange resin.
  • a packed tower 58, a treated water discharge line 60, and a treated water tank 62 are provided.
  • the wastewater inflow line 48a Cl - ion sensor 64 and the alkalinity gauge 68 is installed, the waste water inlet line 48b is installed pH sensors 70, Cl is the treated water discharge line 60 - Ion A sensor 66 is installed.
  • the dissolved salt recovery apparatus 2 includes a control unit 72 and is electrically connected to each sensor and the alkalinity meter 68, and the measurement values of each sensor and the alkalinity meter 68 are transmitted. It is like that.
  • the dissolved salt recovery apparatus 2 includes a concentrating device 74 and a drying device 76.
  • one end of the drainage inflow line 48 a is connected to the drainage storage tank 46, and the other end is connected to the upper part of the pH adjustment tower 52.
  • a drainage pump 50a is installed in the drainage inflow line 48a.
  • One end of the gas inflow line 56 is connected to the blower 54, and the other end is connected to the side surface of the pH adjusting tower 52.
  • One end of the drainage inflow line 48 b is connected to the lower side surface of the pH adjusting tower 52, and the other end is connected to the upper part of the packed tower 58.
  • a drainage pump 50b is installed in the drainage inflow line 48b.
  • One end of the treated water discharge line 60 is connected to the bottom of the packed tower 58, and the other end is connected to the treated water tank 62.
  • the drainage inflow line 48a, the drainage pump 50a, the pH adjusting tower 52, the blower 54, and the gas inflow line 56 function as a pH adjusting device that adjusts the pH of the water associated with resource mining.
  • the pH adjusting device is not limited to the above configuration as long as it has a configuration for adjusting the pH of the resource mining accompanying water. It is preferable to fill the pH adjusting tower 52 with a filler such as Raschig ring from the viewpoint of suppressing the amount of the gas for adjusting the pH of the resource extraction accompanying water.
  • the concentrating device 74 has a function of concentrating the regeneration treatment liquid, and examples thereof include an evaporator and a liquid film descending evaporation concentrating device.
  • the drying device 76 is for drying the concentrated regeneration treatment liquid, and examples thereof include an electric heating dryer and a vacuum drum dryer.
  • the wastewater to be treated in the reference example is resource mining accompanying water containing NaCl and a carbonate substance.
  • the water associated with resource mining is water associated with resource mining such as natural gas such as CSG (Coal Seam Gas) or crude oil, and includes NaCl or the like.
  • the carbonate substance is bicarbonate ion (HCO 3 ⁇ ), carbonate ion (CO 3 2 ⁇ ), free carbonic acid (soluble CO 2 ) and the like.
  • the pretreatment step is a step of removing suspended substances, oils, and the like contained in the water associated with resource mining by coagulation sedimentation, coagulation flotation separation, membrane filtration using an MF membrane / UF membrane, or the like.
  • the concentration step is a step of concentrating water associated with resource mining with an RO membrane or the like to increase the NaCl concentration in the water.
  • the concentration of NaCl in the concentrated resource extraction accompanying water is preferably 0.1 mol / L or more from the viewpoint of shortening the subsequent treatment time and performing efficient operation.
  • the amount of Cl ⁇ ions (moles) relative to the amount (moles) of all carbonated substances (HCO 3 ⁇ , CO 3 2 ⁇ ) excluding free carbonic acid in the water associated with resource mining (after pretreatment and concentration steps) ) Is adjusted according to the ratio (molar ratio) of the source mining accompanying water.
  • the ratio of the amount of Cl ⁇ ions to the amount of all carbonates excluding free carbonic acid in the resources associated with resource mining is smaller. There is.
  • the treated water discharged from the packed column 58 includes NaHCO 3 in addition to NaHCO 3 . Since Na 2 CO 3 is contained, there is no problem with the purity of the dissolved salts, but the purity of NaHCO 3 alone is lowered. Further, when the water associated with resource mining with a pH of 9.5 or more is passed through the packed tower 58 at the subsequent stage, the regeneration reaction of the ion exchange resin by OH ⁇ ions occurs simultaneously with the reaction of the above formula (3).
  • the pH of the water associated with resource mining is set to 7.0 or more and 8.0 or less.
  • most of the total carbonic acid contained in the water associated with resource mining is HCO 3 ⁇ , so that more NaHCO 3 with high purity can be obtained from the treated water discharged from the packed column 58 at the subsequent stage. It can be recovered.
  • the pH of the water associated with resource mining is 6.5 to 8.5 It is adjusted to the range to become difficult to proceed the reaction of the above formula (3), Cl to treated water discharged from the packed tower 58 - incorporation of ions becomes large.
  • the amount of HCO 3 ⁇ with respect to Cl ⁇ ions can be reduced by lowering the pH of the water associated with resource mining from the above range and converting the carbon dioxide in the resource mining accompanying water to free carbonic acid. The reaction of the above formula (3) is likely to proceed.
  • the reaction of the above formula (3) can be promoted by the nature of the anion exchange resin that performs ion exchange at a low pH. Therefore, Cl to treated water - mixing of ions is reduced, can be recovered NaHCO 3 in high purity from the treated water.
  • the lower the ratio of the amount of Cl ⁇ ions to the amount of all carbonates excluding free carbonic acid in the resource extraction associated water the lower the pH of the resource extraction associated water.
  • the pH adjustment tower 52 sets the pH of the resource extraction associated water to 6.5 to 8 is preferably adjusted to .5 or less, more preferably adjusted to 7.0 or more and 8.0 or less, relative to the amount of substance of all carbon materials except for free carbon dioxide of resource extraction associated water Cl - of the amount of substance of ions If the ratio is less than 2, the pH adjustment tower 52 preferably adjusts the pH of the water associated with resource mining to a range of 5.6 or more and less than 6.5.
  • the pH adjustment tower 52 adjusts the pH of the water associated with resource mining to 6 It is preferable to adjust to a range of from 0.0 to less than 6.5, and if the ratio of the amount of Cl ⁇ ions to the amount of all carbonates excluding free carbonic acid in the water associated with resource mining is less than 1, pH adjustment It is preferable to adjust the pH of the water associated with resource mining to a range of 5.6 to less than 6.0 in the tower 52.
  • the pH adjustment process will be described in detail with reference to FIG. 4.
  • the resource mining accompanying water containing NaCl and carbonated material in the drainage storage tank 46 is sent to the drainage inflow line 48a by the drainage pump 50a.
  • Cl of resource extraction associated water through the drainage inlet line 48a - substance amount of ions (mol) of Cl - is measured by the ion sensor 64, the alkalinity of the resource extraction associated water is measured by the alkalinity meter 68.
  • Measured Cl - amount of substance and alkalinity ions are transmitted to the control unit 72.
  • the pH of the resource extraction accompanying water discharged from the pH adjustment tower 52 is measured by the pH sensor 70 installed in the drainage inflow line 48 b, and the measured value is transmitted to the control unit 72. Further, the pH of the water associated with resource mining discharged from the pH adjusting tower 52 is Cl ⁇ ion with respect to the amount (mole) of the total carbonic substances (HCO 3 ⁇ , CO 3 2 ⁇ ) excluding free carbonic acid in the water associated with resource mining.
  • the output of the blower 54 and the like is controlled by the control unit 72 so as to satisfy the pH range, and the CO 2 gas or air The supply amount is adjusted.
  • CO 2 gas when lowering the pH of the water associated with resource mining, CO 2 gas is supplied (or added with HCl or the like described later), and when increasing the pH of the water associated with resource mining, air is supplied (or later described). NaOH to be added).
  • a CO 2 gas a CO 2 that by-product produced when burning the lime to be used for regeneration of the ion exchange resin described later (Ca (OH) 2) and limestone (CaCO 3) It may be used, or CO 2 gas obtained by burning methane gas obtained locally.
  • the anion exchange resin is a H 2 CO 3 type weakly basic ion-exchange resin, and more preferably H 2 CO 3 type weakly basic acrylic ion exchange resin.
  • H 2 CO 3 type weakly basic acrylic ion exchange resin will be described as an example.
  • the H 2 CO 3 type weakly basic ion exchange resin is passed through a packed tower 58 filled with a weakly basic ion exchange resin before the recovery step, by passing carbonate-dissolved water in which carbonic acid is dissolved in pure water or the like. Obtained by conversion to 2 CO 3 type.
  • Examples of the dissolution of carbonic acid include a method of dissolving CO 2 gas in pure water or the like using a gas absorption tower or the like.
  • the CO 2 gas it is desirable to use CO 2 gas produced as a by-product when methane gas is burned or Ca (OH) 2 is produced from CaCO 3 .
  • the recovery process will be described in detail with reference to FIG. 4.
  • the resource extraction accompanying water containing NaCl and carbonated material flowing through the drainage inflow line 48 b and adjusted in pH is filled with anion exchange resin by the drainage pump 50 b.
  • Cl ⁇ is adsorbed by the anion exchange resin, and treated water containing NaHCO 3 is discharged from the treated water discharge line 60 and stored in the treated water tank 62.
  • the treated water containing NaHCO 3 stored in the treated water tank 62 is then concentrated by a concentrating device 74 such as an evaporator and dried by a drying device 76 such as a dryer.
  • Cl was placed in the treated water discharge line 60 or processed water tank 62 - by ion sensor 66, Cl in the treated water - monitoring the ion concentration, Cl - it is desirable that the ion concentration immediately terminated Once raised .
  • the measurement data of the Cl ⁇ ion sensor 66 may be sent to the control unit 72, and electronic control may be performed by the control unit 72 to stop the operation of the drainage pump 50b and the like when the Cl ⁇ ion concentration increases. and the worker Cl - checks the measurement data of the ion sensor 66, Cl - at the stage where the ion concentration is increased, may be stopped operation such as manual drainage pump 50b.
  • the anion exchange resin used in the Reference Example is preferably an anion exchange resin having an acrylic tertiary amine type functional group, and for example, Amberlite IRA-67 is preferably used. It is preferable that the water SV associated with resource mining in the recovery process is about 0.5 to 10 (1 / h).
  • the pH of the water associated with resource mining supplied to the packed tower 58 is adjusted in accordance with the ratio of the amount of Cl ⁇ ions to the amount of the total carbonaceous material excluding free carbonic acid in the water associated with resource mining.
  • Cl ⁇ is efficiently adsorbed by the anion exchange resin, and it becomes possible to recover NaHCO 3 with high purity.
  • FIG. 5 is a schematic configuration diagram showing another example of the configuration of the dissolved salt recovery apparatus according to the reference example.
  • the dissolved salt recovery apparatus 3 shown in FIG. 5 the same components as those of the dissolved salt recovery apparatus 2 shown in FIG.
  • the dissolved salt recovery apparatus 3 includes an HCl storage tank 78, an HCl addition line 80, an HCl pump 82, and a pH adjustment tank 84.
  • a pH sensor 70 is installed in the pH adjustment tank 84.
  • a stirring device (not shown) is installed in the pH adjustment tank 84.
  • one end of the drainage inflow line 48 a is connected to the drainage storage tank 46, and the other end is connected to the pH adjustment tank 84.
  • One end of the HCl addition line 80 is connected to the HCl storage tank 78, and the other end is connected to the pH adjustment tank 84.
  • One end of the drainage inflow line 48 b is connected to the pH adjustment tank 84, and the other end is connected to the upper part of the packed tower 58.
  • a drainage pump 50b is installed in the drainage inflow line 48b.
  • One end of the treated water discharge line 60 is connected to the bottom of the packed tower 58, and the other end is connected to the treated water tank 62.
  • the drainage inflow line 48a, the pH adjustment tank 84, the HCl storage tank 78, the HCl addition line 80, and the HCl pump 82 function as a pH adjustment device that adjusts the pH of the water associated with resource mining.
  • the pH adjusting device is not limited to the above configuration as long as it has a configuration for adjusting the pH of the resource mining accompanying water.
  • the pH sensor 70 installed in the pH adjusting tank 84 measures the pH of the water associated with resource mining and transmits the measured value to the control unit 72.
  • the pH of the water associated with resource mining in the pH adjustment tank 84 is such that the amount of Cl ⁇ ion relative to the amount (mole) of the total carbonic substances (HCO 3 ⁇ , CO 3 2 ⁇ ) excluding free carbonic acid in the resource mining accompanying water (
  • the output of the HCl pump 82 and the like are controlled by the controller 72 so as to satisfy the pH range, and the supply amount of HCl is adjusted.
  • Resource mining associated water adjusted according to the ratio of the mass (mol) of Cl ⁇ ions to the mass (mol) of all carbonic substances (HCO 3 ⁇ , CO 3 2 ⁇ ) excluding free carbonic acid in the resource mining associated water
  • the pH is as described above.
  • HCl is used for pH adjustment, but it is not limited to this as long as it adjusts the pH of water associated with resource mining.
  • an acid agent such as carbonated water can be used. is there.
  • the acid agent such as HCl is used for lowering the pH of the water associated with resource mining, and it is necessary to use an alkaline agent such as NaOH when the pH of the water associated with resource mining is increased.
  • the resource extraction accompanying water whose pH is adjusted in the pH adjusting tank 84 is supplied to the packed tower 58 filled with the anion exchange resin by the drain pump 50b.
  • Cl ⁇ is adsorbed by the anion exchange resin, and treated water containing NaHCO 3 is discharged from the treated water discharge line 60 and stored in the treated water tank 62.
  • the treated water containing NaHCO 3 stored in the treated water tank 62 is then concentrated by a concentrating device 74 such as an evaporator and dried by a drying device 76 such as a dryer.
  • the Cl ⁇ ion concentration in the treated water is monitored by the Cl 2 ⁇ ion sensor 66 installed in the treated water discharge line 60 or the treated water tank 62, and is immediately terminated when the Cl 2 ⁇ ion concentration increases. .
  • the control unit 72 is electronically controlled to stop the operation of the drain pump 50b and the like. good to the worker Cl - checks the measurement data of the ion sensor 66, Cl - at the stage where the ion concentration is increased, may be stopped operation such as manual drainage pump 50b.
  • FIG. 6 is a schematic configuration diagram illustrating an example of a configuration of a dissolved salt recovery apparatus when performing a regeneration process.
  • the dissolved salt recovery device (2, 3) includes a Ca (OH) 2 storage tank 86, a Ca (OH) 2 inflow line 88, a Ca (OH) 2 pump 90, a blower 92, and an air inflow line. 94, a regeneration processing liquid discharge line 98, and a regeneration processing liquid storage tank 38a.
  • a stirring device (not shown) is installed in the Ca (OH) 2 storage tank 86.
  • remove the components shown in FIG. 4 or 5 from the packed tower 58 may be equipped with components shown in FIG. 6 in the packed column 58, NaHCO 3
  • the components shown in FIG. 4 or 5 and FIG. 6 may be installed in the packed tower 58 through the recovery and regeneration process.
  • one end of the Ca (OH) 2 inflow line 88 is connected to the Ca (OH) 2 storage tank 86, and the other end is connected to the upper portion of the packed tower 58.
  • the Ca (OH) 2 inlet line 88 Ca (OH) 2 pump 90 is installed.
  • One end of the air inflow line 94 is connected to the blower 92, and the other end is connected to the lower side surface of the packed tower 58.
  • One end of the regeneration processing liquid discharge line 98 is connected to the lower side surface of the packed tower 58, and the other end is connected to the regeneration processing liquid storage tank 38a.
  • a Ca (OH) 2 solution (hereinafter sometimes referred to as Ca (OH) 2 slurry) is passed through the anion exchange resin to which HCl has been adsorbed in the recovery step, and the above formula (4)
  • a regeneration step is performed in which HCl is desorbed from the anion exchange resin to regenerate the anion exchange resin.
  • Ca (OH) operate the second pump 90
  • Ca (OH) 2 Ca in the storage tank 86 (OH) 2 slurry Ca (OH) 2 inlet line 88 Is supplied to the packed tower 58 and the blower 92 is operated, and the air is supplied to the packed tower 58 through the air inflow line 94.
  • HCl is desorbed from the anion exchange resin and CaCl 2 is generated by contacting the Ca (OH) 2 slurry with air while stirring the anion exchange resin.
  • the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 98 to the regeneration processing liquid storage tank 38a.
  • the regeneration treatment liquid contains CaCl 2 , Ca (OH) 2, etc., and is sent to the concentrating device 74 and the drying device 76 as necessary.
  • Such a regeneration step is a batch type in which the Ca (OH) 2 slurry is gradually added to a predetermined condition while stirring the resin in the packed column 58 and the reaction solution is discharged from the packed column 58 after a predetermined time of reaction. You can go.
  • the Ca (OH) 2 slurry may be passed through the packed tower 58 to continuously discharge the regeneration treatment liquid. From the viewpoint of more efficiently advancing the reaction of formula (4) on the anion exchange resin covered with the slurry, a batch of gradually adding the Ca (OH) 2 slurry to a predetermined amount while stirring the anion exchange resin. The formula is preferred.
  • the concentration of the Ca (OH) 2 slurry is preferably 5 to 10% when used in a batch system and 0.05 to 0.5% when used in a continuous system.
  • the fluid for stirring the anion exchange resin in the packed tower 58 is not limited to air, and may be any fluid that does not inhibit the reaction of the formula (4), and examples thereof include methane gas.
  • undissolved Ca (OH) 2 is Ca 2+ and OH - from the dissolved, OH - because cause regeneration reaction with HCl on an anion exchange resin, the added Ca (OH) 2 is reproduced In some cases, it takes a time of several minutes to 10 minutes to be fully used in the process. Therefore, it is preferable that the addition of the Ca (OH) 2 slurry in a batch system is performed intermittently in consideration of the time.
  • Example 1 CSG resources mining accompanying simulated water is subjected to coagulation pressure flotation separation for the purpose of SS removal and membrane filtration using a UF membrane as a pretreatment step, and further concentration using a reverse osmosis membrane (concentration by 10 times) Went.
  • Table 1 summarizes the water quality of CSG resource mining accompanying simulated water (hereinafter referred to as treated water) after the pretreatment process and the concentration process.
  • This treated water was concentrated under reduced pressure using an evaporator and evaporated to dryness using a hot plate (70 ° C.) to precipitate dissolved salts containing NaHCO 3 .
  • a small amount of the precipitate was dissolved again in pure water, and the Cl - ion concentration was measured to confirm the Cl - ion content in the precipitate. It was confirmed that NaHCO 3 was recovered.
  • Pure water of 5 times the amount of weakly basic anion exchange resin in the packed tower of each series was passed through the packed tower to wash the packed tower. After washing, aeration of air into the resin tower and in a state where the weakly basic anion exchange resin is flowed, 5 w / v% Ca (OH) 2 slurry is intermittently added to the packed tower. Installation was pH sensor and Cl - were measured ion concentration - pH and Cl regeneration treatment liquid ion sensor.
  • the pH of the regenerated solution is 9.8 (Example 1-1: 1st series), 10.0 (Example 1-2: 2nd series), 10.5 (Example) 1-3: Third series), 11.7 (Example 1-4: Fourth series), 12.0 (Example 1-5: Fifth series), and 12.2 Then, 0.018 mol of Ca (OH) 2 was added (comparative example: 6th series), and the regenerated waste liquid was taken out (hereinafter referred to as “first stage regenerated solution”), vacuum concentrated by an evaporator, and hot plate ( (70 ° C.) was evaporated to dryness, and dissolved salts containing CaCl 2 were precipitated.
  • Examples 1-1 to 1-5 pure water was introduced in an amount sufficient to allow the weakly basic anion exchange resin in the packed tower to be immersed (130 mL), and Ca (OH) was allowed to flow while the resin was flowing by air aeration. 2 Slurries were added. The addition of Ca (OH) 2 slurry from the start of regeneration was continued until the same amount as in the comparative example. Moreover, it confirmed that pH at this time was set to 12.2.
  • the regeneration treatment liquid after the additional addition of the Ca (OH) 2 slurry (hereinafter referred to as “second-stage regeneration treatment liquid”) is taken out, concentrated by vacuum distillation using an evaporator, and Evaporation to dryness by a hot plate was performed to precipitate dissolved salts containing Ca (OH) 2 . A small amount of the precipitate was dissolved again in pure water, and the Ca 2+ and Cl ⁇ concentrations were measured to confirm the molar ratio of both elements in the precipitate. The results are summarized in Table 2.
  • This Cl / Camol ratio of 1.86 has a CaCl 2 purity of 95.2% in terms of weight, and contains only 4.2% of Ca (OH) 2 as an impurity.
  • the Cl / Camol ratio is 1.95 or more.
  • This Cl / Camol ratio when converted to weight, has a CaCl 2 purity of 98.3%, and contains only 1.7% of Ca (OH) 2 as an impurity. That is, the lower the pH of the first stage regeneration treatment solution or the lower the Cl desorption rate, the higher the purity of CaCl 2 recovered from the regeneration treatment solution. However, the lower the pH of the first stage regeneration treatment liquid or the lower the Cl desorption rate, the more the amount of the second stage regeneration treatment liquid tends to increase when the second stage regeneration treatment liquid is recovered. Therefore, it is predicted that the storage facility will become large.
  • CaCl 2 can be obtained with high purity from water associated with resource mining containing NaCl.
  • the pH of the regeneration treatment solution is measured, or the Cl ⁇ ion concentration is measured to determine the amount of Cl desorption, and the regeneration recovered until they reach a predetermined set value. It has been found that it is necessary to concentrate and dry the treatment liquid, that is, to obtain CaCl 2 from a regeneration treatment liquid having a relatively high CaCl 2 purity.
  • the range of the set value is set between pH 10.0 and 12.0 in the case of pH measurement, and between 85 and 96% of the Cl ⁇ ion adsorption amount in the case of Cl ⁇ ion concentration measurement. It is preferable.
  • Example 2 In Example 2, the same operation as in Example 1 was performed until CSG resource mining accompanying water simulated water was passed through the resin tower, NaHCO 3 was collected, and washed with pure water. Thereafter, the packed column, pH and Cl regeneration treatment solution - while measuring the ion concentration, and the second stage regeneration process liquid obtained in Example 1-4 (purity CaCl 2 is low) intermittently added . After using all of the second stage regeneration solution, 5 w / v% Ca (OH) 2 slurry was added intermittently. Then, when the pH of the regeneration treatment solution reached 11.7, the regeneration treatment solution in the packed tower was taken out.
  • the reclaimed reprocessing solution (first stage regenerating solution) was concentrated by vacuum distillation with an evaporator and evaporated to dryness with a hot plate to precipitate dissolved salts containing CaCl 2 . A small amount of the precipitate was dissolved again in pure water, and the Ca 2+ and Cl ⁇ concentrations were measured to confirm the molar ratio of both elements in the precipitate.
  • Example 2 the Cl / Camol ratio of the precipitate obtained by concentrating and evaporating and drying the first stage regenerating solution taken out when the pH reached 11.7 was 1.96, and CaCl It was confirmed that 2 could be recovered with high purity.
  • new Ca (OH) 2 was further added, including Ca (OH) 2 added in the first stage regeneration.
  • [NaHCO 3 ] (g / L) [HCO 3 ⁇ ] (mol / L) ⁇ (84/61)
  • [HCO 3 ⁇ ] (mol / L) M alkalinity ⁇ P alkalinity (mol / L)
  • the NaHCO 3 concentration is determined from the CO 3 2- concentrations, CO 3 2- concentrations were determined from the M alkalinity and pH.
  • Reference Example 2 Reference Example 1 except that the simulated drainage was adjusted to pH 6.5 to 8.4 by blowing air into the simulated drainage at pH 6.0, and the simulated drainage at pH 6.0 was used without comparison. As well as. The results of Reference Example 2 are summarized in Table 5.
  • Reference Example 3 by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 6.4 ⁇ 8.0, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1.
  • the results of Reference Example 3 are summarized in Table 6.
  • Reference Example 4 by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 6.1 ⁇ 8.0, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1.
  • the results of Reference Example 4 are summarized in Table 7.
  • Reference Example 5 by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 5.8 ⁇ 6.5, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1. The results of Reference Example 5 are summarized in Table 8.
  • Dissolved salt recovery device 10,46 Drainage storage tank, 12, 48a, 48b Drainage inflow line, 14, 50a, 50b Drain pump, 16,58 Packing tower, 18,60 Treated water discharge line, 19 Integrated flow meter 20, 62 Treated water tank, 21, 30, 31, 64, 66 Cl - ion sensor, 22, 86 Ca (OH) 2 storage tank, 24, 88 Ca (OH) 2 inflow line, 26, 90 Ca (OH) 2 pump, 28, 70 pH sensor, 32, 54, 92 Blower, 34, 94 Air inflow line, 36a, 36b, 98 Regeneration liquid discharge line, 38a, 38b Regeneration liquid storage tank, 40, 72 Controller, 42 , 74 Concentrator, 44,76 Dryer, 52 pH adjustment tower, 56 Gas inflow line, 68 Alkali meter, 78 HCl reservoir, 80 HCl addition line, 82 Cl pump, 84 pH adjustment tank.

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Abstract

Provided is a recovery method for a dissolved salt in which: NaCl-containing water resulting from resource extraction is passed through a packed tower (16) that is packed with an anion exchange resin in order to recover NaHCO3; a Ca(OH)2 solution is passed through the packed tower (16) after the water resulting from resource extraction has passed therethrough; regeneration treatment is performed on the anion exchange resin within the packed tower (16); the pH of a regeneration treatment liquid used in the regeneration treatment is monitored when recovering said regeneration treatment liquid; and the recovered regeneration treatment liquid is concentrated and dried in order to recover CaCl2 until the monitored pH value reaches a preset setting value. As a result, it is possible to recover CaCl2 containing a minimum of impurities from the water resulting from resource extraction.

Description

溶解塩類の回収方法、溶解塩類の回収装置及び塩化カルシウムの製造方法Method for recovering dissolved salts, device for recovering dissolved salts, and method for producing calcium chloride
　本発明は、資源採掘随伴水から溶解塩類を回収する方法及び回収装置に関する。 The present invention relates to a method and a recovery device for recovering dissolved salts from water associated with resource mining.
　ＣＳＧ（Ｃｏａｌ　Ｓｅａｍ　Ｇａｓ）のような天然ガスや原油などの資源採掘で発生する随伴水には、高濃度でＮａＣｌやＮａＨＣＯ３が含まれているため、脱塩処理をして水系環境に放流する必要がある。従来、除去された多量の塩は蒸発乾燥され、廃棄物処分されていた。一方でこれらの塩類を有価物として回収する試みもなされている。 The accompanying water generated by mining resources such as natural gas and crude oil such as CSG (Coal Seam Gas) contains NaCl and NaHCO 3 at high concentrations, so it is desalted and released into the aqueous environment. There is a need. Conventionally, a large amount of removed salt is evaporated to dryness and disposed of as waste. On the other hand, attempts have been made to recover these salts as valuable materials.
　例えば、特許文献１には、資源採掘随伴水を対象に水中の塩を有価塩であるＮａ２ＣＯ３として回収する技術が（Penrice法）開示されている。これは、油相中に溶解したＣ１２アミンとＣＯ２をＮａＣｌに反応させＮａＨＣＯ３に変換し、熱をかけてＮａ２ＣＯ３に転化する方法である。 For example, Patent Document 1 discloses a technique (Penrice method) for recovering salt in water as valuable salt Na 2 CO 3 for water associated with resource mining. This is a method in which C 12 amine and CO 2 dissolved in an oil phase are reacted with NaCl to convert them to NaHCO 3 and then converted to Na 2 CO 3 by applying heat.
　非特許文献１及び特許文献２には、式（１）で表されるように、ＮａＣｌを含む水からイオン交換樹脂を用いてＮａＨＣＯ３を製造する方法が開示されている。
　Ｒ３Ｎ＋ＣＯ２＋ＮａＣｌ＋Ｈ２Ｏ　→　Ｒ３Ｎ－ＨＣｌ＋ＮａＨＣＯ３　式（１） Non-Patent Document 1 and Patent Document 2 disclose a method for producing NaHCO 3 from water containing NaCl using an ion exchange resin, as represented by Formula (1).
R 3 N + CO 2 + NaCl + H 2 O → R 3 N—HCl + NaHCO 3 Formula (1)
　上記方法では反応効率を高めるため、式（２）で表されるように、イオン交換樹脂にＣＯ２溶解水を吹き込んで、樹枝上に重炭酸または炭酸が補足された型Ｒ３Ｎ－ＨＣＯ３（炭酸型）に変換してから、式（３）で表されるように、ＮａＣｌを含む被処理水を通水して、ＮａＨＣＯ３を製造する。
　Ｒ３Ｎ＋ＣＯ２＋Ｈ２Ｏ　→　Ｒ３Ｎ－Ｈ２ＣＯ３　　　　　　　　　　　式（２）
　Ｒ３Ｎ-Ｈ２ＣＯ３＋ＮａＣｌ　→　Ｒ３Ｎ-ＨＣｌ＋ＮａＨＣＯ３　　　　式（３） In the above method, in order to increase the reaction efficiency, as represented by the formula (2), CO 2 -dissolved water is blown into the ion exchange resin, and type R 3 N—HCO 3 in which bicarbonate or carbonic acid is supplemented on the tree branch is obtained. After being converted to (carbonic acid type), as shown by the formula (3), water to be treated containing NaCl is passed through to produce NaHCO 3 .
R 3 N + CO 2 + H 2 O → R 3 N—H 2 CO 3 formula (2)
R 3 N—H 2 CO 3 + NaCl → R 3 N—HCl + NaHCO 3 Formula (3)
　特許文献３には、ＣＯ２の供給源として石灰石（ＣａＣＯ３）を用いる方法が開示されている。また、この方法では、ＣａＣＯ３を燃やしてＣＯ２を得ると共に、式（４）で表されるように、副生物であるＣａ（ＯＨ）２をイオン交換樹脂の再生アルカリとして用いている。
　２Ｒ３Ｎ－ＨＣｌ＋Ｃａ（ＯＨ）２　→　２Ｒ３Ｎ＋ＣａＣｌ２＋２Ｈ２Ｏ　式（４） Patent Document 3 discloses a method using limestone (CaCO 3 ) as a CO 2 supply source. Further, in this method, CaCO 3 is burned to obtain CO 2 and, as represented by the formula (4), Ca (OH) 2 as a by-product is used as a regenerated alkali of the ion exchange resin.
2R 3 N—HCl + Ca (OH) 2 → 2R 3 N + CaCl 2 + 2H 2 O Formula (4)
　特許文献３の方法は、Ｃａ（ＯＨ）２製造時に発生するＣＯ２ガスを反応原料として用い、炭酸塩として固定化するものであり、ＣＯ２ガスをほとんど大気へ排出しないシステムとして、地球温暖化防止の観点から有効な技術である。また、油分を使用しないため、ＣＯＤ原となる油分を含んだ排水が発生することもない。さらに、通水条件が適切であれば、式（３）の反応がほぼ完全に進行するため、炭酸塩の回収ロスがなく、非常に高い回収率が得られる。 The method of Patent Document 3 uses CO 2 gas generated during the production of Ca (OH) 2 as a reaction raw material and is fixed as a carbonate, and as a system that emits almost no CO 2 gas to the atmosphere, global warming This is an effective technique from the viewpoint of prevention. In addition, since no oil is used, wastewater containing oil as a COD raw material is not generated. Furthermore, if the water flow conditions are appropriate, the reaction of formula (3) proceeds almost completely, so there is no loss of carbonate recovery and a very high recovery rate can be obtained.
オーストラリア特許第１０５３号Australian Patent No. 1053 南アフリカ特許第７８５９６２号South African Patent No. 785962 特許第３３７３５１２号公報Japanese Patent No. 3373512
　ところで、イオン交換樹脂法は、樹脂の再生の際に、ＣａＣｌ２が発生するが、ＨＣｌと結合したイオン交換樹脂（Ｒ３Ｎ－ＨＣｌ）を完全に再生する（式（４））ためには、理論上は前記ＨＣｌの１/２の量のＣａ（ＯＨ）２を前記イオン交換樹脂に接触させればよいが、実際には前記ＨＣｌの１/２の量より多い量のＣａ（ＯＨ）２を前記イオン交換樹脂に接触させる必要がある。このため、従来技術では、前記イオン交換樹脂にＣａ（ＯＨ）２を接触させて得られた処理液に多くのＣａ（ＯＨ）２が含まれ、前記処理液からＣａＣｌ２を得ようとしても低純度のＣａＣｌ２しか得られず、得られたＣａＣｌ２は廃棄物となる。一般に、資源採掘の現場において、この大量の廃棄物を処分するためのコストは高額となる。しかし、このＣａＣｌ２を高純度で回収することができれば、炭酸塩と同じく工業用原料などとして利用できるため、有価物となり得る。また、そうなることで、このイオン交換法がＣＳＧのような天然ガスや原油などの資源採掘で発生する随伴水から塩類を回収する技術として極めて有効なものとなる。 By the way, in the ion exchange resin method, CaCl 2 is generated when the resin is regenerated, but in order to completely regenerate the ion exchange resin (R 3 N—HCl) combined with HCl (formula (4)). Theoretically, a half amount of Ca (OH) 2 of HCl may be brought into contact with the ion-exchange resin, but in practice, a larger amount of Ca (OH) than half the amount of HCl. 2 must be brought into contact with the ion exchange resin. Therefore, in the prior art, the number of Ca (OH) 2 contained in the ion-exchange resin in the Ca (OH) 2 treatment solution obtained by contacting, low even to obtain a CaCl 2 from the treatment liquid Only pure CaCl 2 is obtained, and the obtained CaCl 2 becomes waste. In general, the cost for disposing of this large amount of waste is high at the site of resource mining. However, if this CaCl 2 can be recovered with high purity, it can be used as an industrial raw material in the same way as carbonates, and thus can be a valuable resource. In addition, by doing so, this ion exchange method becomes extremely effective as a technique for recovering salts from the accompanying water generated by resource mining such as natural gas or crude oil such as CSG.
　そこで、本発明の目的は、資源採掘随伴水からＣａＣｌ２を回収すること、特に、不純物の混入を抑制したＣａＣｌ２を回収することを可能とする溶解塩類の回収方法及び回収装置を提供することである。 An object of the present invention is to recover the CaCl 2 from resource mining produced water, in particular, to provide a recovery method and recovery apparatus of dissolution salts makes it possible to recover the CaCl 2 that suppresses entry of impurities It is.
　（１）本発明の溶解塩類の回収方法は、ＮａＣｌを含有する資源採掘随伴水を陰イオン交換樹脂に通水し、ＮａＨＣＯ３を回収する第１回収工程と、前記資源採掘随伴水通水後の陰イオン交換樹脂にＣａ（ＯＨ）２溶液を通水し、前記陰イオン交換樹脂を再生処理する再生工程と、前記再生処理した再生処理液を回収する第２回収工程と、を備え、前記第２回収工程では、前記再生処理した再生処理液のｐＨをモニタリングし、前記モニタリングしたｐＨ値が予め定めた設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収する。 (1) The method for recovering dissolved salts of the present invention includes a first recovery step of passing NaCl-containing resource mining associated water through an anion exchange resin and recovering NaHCO 3 , and after the resource mining accompanying water flowing. A Ca (OH) 2 solution is passed through the anion exchange resin, and a regeneration process for regenerating the anion exchange resin, and a second recovery process for recovering the regenerated liquid after the regeneration process, In the second recovery step, the pH of the regenerated reprocessing solution is monitored, and the regenerated processing solution recovered until the monitored pH value reaches a predetermined set value is concentrated and dried to recover CaCl 2 . .
　（２）本発明の溶解塩類の回収方法は、ＮａＣｌを含有する資源採掘随伴水を陰イオン交換樹脂に通水し、ＮａＨＣＯ３を回収する第１回収工程と、前記資源採掘随伴水通水後の陰イオン交換樹脂にＣａ（ＯＨ）２溶液を通水し、前記陰イオン交換樹脂を再生処理する再生工程と、前記再生処理した再生処理液を回収する第２回収工程と、を備え、前記第２回収工程では、前記再生処理した再生処理液のＣｌ－イオン濃度をモニタリングし、前記モニタリングしたＣｌ－イオン濃度に基づいて求められる前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収する。 (2) The method for recovering dissolved salts of the present invention includes a first recovery step of passing NaCl-containing resource mining associated water through an anion exchange resin and recovering NaHCO 3 , and after the resource mining accompanying water flowing A Ca (OH) 2 solution is passed through the anion exchange resin, and a regeneration process for regenerating the anion exchange resin, and a second recovery process for recovering the regenerated liquid after the regeneration process, In the second recovery step, the Cl − ion concentration of the regenerated reprocessing solution is monitored, and the amount of Cl − ion desorption of the anion exchange resin determined based on the monitored Cl − ion concentration is predetermined. The regenerated solution collected until reaching the set value is concentrated and dried to recover CaCl 2 .
　（３）上記（１）記載の溶解塩類の回収方法において、前記第２回収工程では、前記モニタリングしたｐＨ値が予め定めた設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (3) In the method for recovering dissolved salts according to (1) above, in the second recovery step, the regenerated treatment liquid recovered after the monitored pH value reaches a predetermined set value is used as the anion exchange resin. It is preferable to store as a regenerant for regenerating.
　（４）上記（２）記載の溶解塩類の回収方法において、前記第２回収工程では、前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (4) In the method for recovering a dissolved salt according to the above (2), in the second recovery step, the regeneration treatment solution recovered after the Cl − ion desorption amount of the anion exchange resin has reached a predetermined set value. Is preferably stored as a regenerant for regenerating the anion exchange resin.
　（５）上記（３）記載の溶解塩類の回収方法において、前記予め定めた設定値を前記Ｃａ（ＯＨ）２溶液のｐＨとし、前記モニタリングしたｐＨが、前記Ｃａ（ＯＨ）２溶液のｐＨに達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記モニタリングしたｐＨが、前記Ｃａ（ＯＨ）２溶液のｐＨに達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (5) In the method for recovering dissolved salts according to (3) above, the predetermined set value is the pH of the Ca (OH) 2 solution, and the monitored pH is the pH of the Ca (OH) 2 solution. The regenerated solution collected until reaching the concentration is concentrated and dried to collect CaCl 2 , and the regenerated solution collected after the monitored pH reaches the pH of the Ca (OH) 2 solution is converted into the anion exchange solution. It is preferable to store the resin as a regenerant for regenerating the resin.
　（６）上記（３）記載の溶解塩類の回収方法において、前記予め定めた設定値をｐＨ１０～１２の間に設定し、前記モニタリングしたｐＨが、ｐＨ１０～１２の間に設定した設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記モニタリングしたｐＨが、ｐＨ１０～１２の間に設定した設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (6) In the method for recovering dissolved salts according to (3) above, the predetermined set value is set between pH 10 and 12, and the monitored pH reaches the set value set between pH 10 and 12. Concentrate and dry the reclaimed treatment solution collected up to 1 to collect CaCl 2, and recover the regenerated treatment solution collected after the monitored pH reaches a set value set between pH 10-12. It is preferable to store the resin as a regenerant for regenerating the resin.
　（７）上記（４）記載の溶解塩類の回収方法において、前記予め定めた設定値を前記第１回収工程における前記陰イオン交換樹脂のＣｌ－イオン吸着量とし、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (7) In the above (4) a method of recovering soluble salts described, the predetermined set value Cl of the anion-exchange resin in the first recovery step - as an ion adsorption amount, Cl of the anion exchange resin - The regenerated solution collected until the ion desorption amount reaches the Cl − ion adsorption amount of the anion exchange resin is concentrated and dried to recover CaCl 2, and the Cl − ion desorption amount of the anion exchange resin is recovered. However, it is preferable to store the regenerating solution collected after reaching the Cl 2 − ion adsorption amount of the anion exchange resin as a regenerant for regenerating the anion exchange resin.
　（８）上記（４）記載の溶解塩類の回収方法において、前記予め定めた設定値を前記陰イオン交換樹脂のＣｌ－イオン脱離量の８５～９６％の間に設定し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量の８５～９６％の間に設定した設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量の８５～９６％の間に設定した設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することが好ましい。 (8) In the method for recovering dissolved salts according to the above (4), the predetermined set value is set between 85 and 96% of the Cl − ion desorption amount of the anion exchange resin, and the anion exchange is performed. resins Cl - ion elimination amount, the anion exchange resin Cl - CaCl 2 was concentrated and dried playback processing liquid collected to reach a set value set between 85 to 96% of the ion adsorption Recovered after the Cl − ion desorption amount of the anion exchange resin reaches a set value set between 85 and 96% of the Cl − ion adsorption amount of the anion exchange resin. Is preferably stored as a regenerant for regenerating the anion exchange resin.
　（９）また、本発明の溶解塩類の回収装置は、陰イオン交換樹脂を充填した充填塔と、ＮａＣｌを含有する資源採掘随伴水を前記充填塔に通水し、ＮａＨＣＯ３を回収する第１回収手段と、Ｃａ（ＯＨ）２溶液を前記充填塔に通水し、前記陰イオン交換樹脂を再生処理する再生手段と、前記再生処理した再生処理液のｐＨをモニタリングするｐＨセンサと、前記モニタリングしたｐＨ値が予め定めた設定値に達するまでの再生処理液を回収する第２回収手段と、前記回収した再生処理液を濃縮する濃縮手段と、前記濃縮した再生処理液を乾燥する乾燥手段と、を備える。 (9) Moreover, the apparatus for recovering dissolved salts of the present invention includes a packed tower filled with an anion exchange resin and resource mining associated water containing NaCl through the packed tower to recover NaHCO 3 . A recovery means; a regeneration means for allowing the Ca (OH) 2 solution to flow through the packed tower to regenerate the anion exchange resin; a pH sensor for monitoring the pH of the regenerated regenerated liquid; and the monitoring A second recovery means for recovering the regeneration treatment liquid until the pH value reaches a predetermined set value, a concentration means for concentrating the recovered regeneration treatment liquid, and a drying means for drying the concentrated regeneration treatment liquid. .
　（１０）また、本発明の溶解塩類の回収装置は、陰イオン交換樹脂を充填した充填塔と、ＮａＣｌを含有する資源採掘随伴水を前記充填塔に通水し、ＮａＨＣＯ３を回収する第１回収手段と、Ｃａ（ＯＨ）２溶液を前記充填塔に通水し、前記陰イオン交換樹脂を再生処理する再生手段と、前記再生処理した再生処理液のＣｌ－イオン濃度をモニタリングするＣｌ－イオンセンサと、前記モニタリングしたＣｌ－イオン濃度に基づいて求められる前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達するまでの再生処理液を回収する第２回収手段と、前記回収した再生処理液を濃縮する濃縮手段と、前記濃縮した再生処理液を乾燥する乾燥手段と、を備える。 (10) The dissolved salt recovery apparatus of the present invention includes a packed tower filled with an anion exchange resin, and resource mining associated water containing NaCl is passed through the packed tower to recover NaHCO 3 . and recovery means, and passed through a Ca (OH) 2 solution to the packed column, a reproducing means for the anion exchange resin regeneration process, Cl of the reproduction process reproduction processing solution - monitoring the ion concentration Cl - ions A second recovery means for recovering the regenerated processing solution until a Cl − ion desorption amount of the anion exchange resin determined based on the monitored Cl − ion concentration reaches a predetermined set value; Concentrating means for concentrating the recovered regeneration processing liquid and drying means for drying the concentrated regeneration processing liquid.
　（１１）本発明の塩化カルシウムの製造方法は、塩酸と結合したイオン交換樹脂に水酸化カルシウム溶液を接触させて塩化カルシウムを含む処理液を取得しつつ該処理液の塩化カルシウム純度を監視することを開始する第１ステップと、前記塩化カルシウム純度が予め決められた基準純度より高い状態から低い状態になるまでに前記処理液の取得を停止する第２ステップと、取得された処理液から前記塩化カルシウムを得る第３ステップとを含む。 (11) According to the method for producing calcium chloride of the present invention, a calcium hydroxide solution is brought into contact with an ion exchange resin combined with hydrochloric acid to obtain a treatment solution containing calcium chloride, and the purity of the treatment solution is monitored. A second step of stopping the acquisition of the treatment liquid until the calcium chloride purity is lowered from a state higher than a predetermined reference purity, and the chloride from the obtained treatment liquid. A third step of obtaining calcium.
　（１２）上記（１１）記載の製造方法において、前記第２ステップの前に前記基準純度に対応する規定値を設定することを含み、前記第２ステップにおいて前記規定値に基づいて前記処理液の取得を停止することが好ましい。 (12) In the manufacturing method according to the above (11), the method includes setting a specified value corresponding to the reference purity before the second step, and, based on the specified value in the second step, It is preferable to stop the acquisition.
　（１３）上記（１２）記載の製造方法において、前記規定値は、前記塩化カルシウム純度が前記基準純度であるときの前記処理液のｐＨであり、この場合、前記塩化カルシウム純度の監視は、前記処理液のｐＨを測定することであることが好ましい。 (13) In the manufacturing method according to (12), the specified value is a pH of the treatment liquid when the calcium chloride purity is the reference purity. In this case, the monitoring of the calcium chloride purity It is preferable to measure the pH of the treatment liquid.
　（１４）上記（１２）記載の製造方法において、前記規定値は、前記塩化カルシウム純度が前記基準純度であるときの前記イオン交換樹脂の塩素イオン脱離量であり、この場合、前記塩化カルシウム純度の監視は、前記処理液の塩素イオン濃度を測定すること、測定された塩素イオン濃度に基づいて前記塩素イオン脱離量を算出することを含むことが好ましい。 (14) In the manufacturing method according to (12), the specified value is a chlorine ion desorption amount of the ion-exchange resin when the calcium chloride purity is the reference purity. In this case, the calcium chloride purity Preferably, the monitoring includes measuring a chlorine ion concentration of the treatment liquid and calculating the chlorine ion desorption amount based on the measured chlorine ion concentration.
　本発明によれば、資源採掘随伴水からＣａＣｌ２を回収すること、特に、不純物の混入を抑制したＣａＣｌ２を回収することを可能とする溶解塩類の回収方法及び回収装置を提供することができる。 According to the present invention, recovering the CaCl 2 from resource mining produced water, in particular, it is possible to provide a recovery method and recovery apparatus of dissolution salts makes it possible to recover the CaCl 2 that suppresses entry of impurities .
本実施形態に係る溶解塩類回収装置の構成の一例を示す概略構成図である。It is a schematic block diagram which shows an example of a structure of the dissolved salt collection | recovery apparatus which concerns on this embodiment. 本実施形態に係る溶解塩類回収装置の構成の一例を示す概略構成図である。It is a schematic block diagram which shows an example of a structure of the dissolved salt collection | recovery apparatus which concerns on this embodiment. Ｃａ（ＯＨ）２の供給量に対する再生処理液のｐＨ及びＣｌ－イオン脱離量との関係を示す図である。PH of the reproduction processing solution for Ca (OH) 2 supply amount and Cl - is a diagram showing the relationship between ion desorption amount. 参考例に係る溶解塩類回収装置の構成の一例を示す概略構成図である。It is a schematic block diagram which shows an example of a structure of the dissolved salt collection | recovery apparatus concerning a reference example. 参考例に係る溶解塩類回収装置の構成の他の一例を示す概略構成図である。It is a schematic block diagram which shows another example of a structure of the dissolved salt collection | recovery apparatus which concerns on a reference example. 再生処理を行う際の溶解塩類回収装置の構成の一例を示す概略構成図である。It is a schematic block diagram which shows an example of a structure of the dissolved salt collection | recovery apparatus at the time of performing a reproduction | regeneration process.
　以下、本発明の実施の形態について説明する。なお、本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
　図１及び図２は、本実施形態に係る溶解塩類回収装置の構成の一例を示す概略構成図である。図１に示すように、溶解塩類回収装置１は、排水貯留槽１０、排水流入ライン１２、排水ポンプ１４、陰イオン交換樹脂が充填された充填塔１６、処理水排出ライン１８、処理水槽２０、積算流量計１９、を備え、図２に示すように、溶解塩類回収装置１は、Ｃａ（ＯＨ）２貯留槽２２、Ｃａ（ＯＨ）２流入ライン２４、Ｃａ（ＯＨ）２ポンプ２６、ブロワ３２、空気流入ライン３４、再生処理液排出ライン３６ａ，３６ｂ、再生処理液貯留槽３８ａ，３８ｂとをさらに備えるものである。図１に示すように、排水流入ライン１２にはＣｌ－イオンセンサ３１が設置されている。排水処理ライン１８にはＣｌ－イオンセンサ２１が設置されている。Ｃｌ－イオンセンサ２１は処理水槽２０内に設置されていてもよい。処理水槽２０内にはＣｌ－イオンセンサ２１が設置され、図１及び２に示すように、充填塔１６には、ｐＨセンサ２８、Ｃｌ－イオンセンサ３０が設置されている。Ｃｌ－イオンセンサ２１，３０，３１としては、Ｃｌ－イオン電極を用いたセンサを使用することが望ましい。また、図１及び図２に示すように、溶解塩類回収装置１は、制御部４０を備え、各センサ及び積算流量計１９と電気的に接続され、各センサ及び積算流量計１９の測定値が送信されるようになっている。また、溶解塩類回収装置１は濃縮装置４２及び乾燥装置４４を備えている。なお、Ｃａ（ＯＨ）２貯留槽２２内には攪拌装置（不図示）が設置されていることが望ましい。本実施形態の溶解塩類回収装置１では、後述するＮａＨＣＯ３を回収する際には、充填塔１６に図１に示す構成部品を設置し、後述するＣａＣｌ２を回収する際には、充填塔１６から図１に示す構成部品を取り外し、充填塔１６に図２に示す構成部品を設置してもよいし、ＮａＨＣＯ３の回収及びＣａＣｌ２の回収を通して、充填塔１６に図１及び２に示す構成部品を設置していてもよい。 FIG.1 and FIG.2 is a schematic block diagram which shows an example of a structure of the dissolved salt collection | recovery apparatus concerning this embodiment. As shown in FIG. 1, the dissolved salt recovery apparatus 1 includes a drainage storage tank 10, a drainage inflow line 12, a drainage pump 14, a packed tower 16 filled with an anion exchange resin, a treated water discharge line 18, a treated water tank 20, As shown in FIG. 2, the dissolved salt recovery device 1 includes a Ca (OH) 2 storage tank 22, a Ca (OH) 2 inflow line 24, a Ca (OH) 2 pump 26, and a blower 32. The air inlet line 34, the regeneration processing liquid discharge lines 36a and 36b, and the regeneration processing liquid storage tanks 38a and 38b are further provided. As shown in FIG. 1, the waste water inlet line 12 Cl - ion sensor 31 is installed. Ion sensor 21 is provided - Cl in waste water treatment line 18. The Cl − ion sensor 21 may be installed in the treated water tank 20. A Cl - ion sensor 21 is installed in the treated water tank 20, and a pH sensor 28 and a Cl - ion sensor 30 are installed in the packed tower 16 as shown in FIGS. As the Cl − ion sensors 21, 30, and 31, it is desirable to use sensors using Cl − ion electrodes. Moreover, as shown in FIG.1 and FIG.2, the dissolved salt collection | recovery apparatus 1 is equipped with the control part 40, and is electrically connected with each sensor and the integrating | accumulating flow meter 19, and the measured value of each sensor and the integrating | accumulating flow meter 19 is shown. It is supposed to be sent. Further, the dissolved salt recovery apparatus 1 includes a concentrating device 42 and a drying device 44. It is desirable that a stirring device (not shown) is installed in the Ca (OH) 2 storage tank 22. In the dissolved salt recovery apparatus 1 of the present embodiment, when recovering NaHCO 3 described later, the components shown in FIG. 1 are installed in the packed tower 16, and when recovering CaCl 2 described later, the packed tower 16 1 may be removed, and the components shown in FIG. 2 may be installed in the packed column 16, or the packed column 16 may be configured as shown in FIGS. 1 and 2 through the recovery of NaHCO 3 and the recovery of CaCl 2 . Parts may be installed.
　図１に示すように、排水流入ライン１２の一端は排水貯留槽１０に接続され、他端は充填塔１６の上部に接続されている。排水流入ライン１２には、排水ポンプ１４、積算流量計１９、Ｃｌ－イオンセンサ３１が設置されている。処理水排出ライン１８の一端は、充填塔１６の底部に接続され、他端は処理水槽２０に接続されている。また、図２に示すように、Ｃａ（ＯＨ）２流入ライン２４の一端はＣａ（ＯＨ）２貯留槽２２に接続され、他端は充填塔１６の上部に接続されている。Ｃａ（ＯＨ）２流入ライン２４にはＣａ（ＯＨ）２ポンプ２６が設置されている。空気流入ライン３４の一端は、ブロワ３２に接続され、他端は充填塔１６の下部側面に接続されている。再生処理液排出ライン３６ａの一端は充填塔１６の下部側面に接続され、他端は再生処理液貯留槽３８ａに接続され、再生処理液排出ライン３６ｂの一端は再生処理液排出ライン３６ａに接続され、他端は再生処理液貯留槽３８ｂに接続されている。 As shown in FIG. 1, one end of the drainage inflow line 12 is connected to the drainage storage tank 10, and the other end is connected to the upper part of the packed tower 16. The wastewater inflow line 12, the drainage pump 14, the integrated flow meter 19, Cl - ions sensor 31 is installed. One end of the treated water discharge line 18 is connected to the bottom of the packed tower 16, and the other end is connected to the treated water tank 20. As shown in FIG. 2, one end of the Ca (OH) 2 inflow line 24 is connected to the Ca (OH) 2 storage tank 22, and the other end is connected to the upper part of the packed tower 16. The Ca (OH) 2 inlet line 24 Ca (OH) 2 pump 26 is installed. One end of the air inflow line 34 is connected to the blower 32, and the other end is connected to the lower side surface of the packed tower 16. One end of the regeneration processing liquid discharge line 36a is connected to the lower side surface of the packed tower 16, the other end is connected to the regeneration processing liquid storage tank 38a, and one end of the regeneration processing liquid discharge line 36b is connected to the regeneration processing liquid discharge line 36a. The other end is connected to the regeneration processing liquid storage tank 38b.
　排水貯留槽１０、排水流入ライン１２、排水ポンプ１４、処理水排出ライン１８及び処理水槽２０は、ＮａＣｌを含有する資源採掘随伴水を充填塔１６に通水し、ＮａＨＣＯ３を回収する第１回収装置として機能するものである。但し、第１回収装置は、ＮａＣｌを含有する資源採掘随伴水からＮａＨＣＯ３を回収する構成を備えていれば、上記の構成に制限されるものではない。 The drainage storage tank 10, the drainage inflow line 12, the drainage pump 14, the treated water discharge line 18, and the treated water tank 20 pass the resource mining associated water containing NaCl to the packed tower 16 and collect the NaHCO 3. It functions as a device. However, the first recovery device, if a configuration of recovering NaHCO 3 from resource mining produced water containing NaCl, but is not limited to the above structure.
　Ｃａ（ＯＨ）２貯留槽２２、Ｃａ（ＯＨ）２流入ライン２４及びＣａ（ＯＨ）２ポンプ２６は、充填塔１６内の陰イオン交換樹脂を再生処理する再生装置として機能するものである。但し、再生装置は、陰イオン交換樹脂を再生処理する構成を備えていれば、上記の構成に制限されるものではない。 The Ca (OH) 2 storage tank 22, the Ca (OH) 2 inflow line 24, and the Ca (OH) 2 pump 26 function as a regeneration device that regenerates the anion exchange resin in the packed tower 16. However, the regenerating apparatus is not limited to the above structure as long as it has a structure for regenerating an anion exchange resin.
　再生処理液排出ライン３６ａ、再生処理液貯留槽３８ａは、後述するように、再生処理液のｐＨ、又は再生処理液のＣｌ－イオン濃度に基づいて求められる陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた規定値に達するまでの再生処理液を回収する第２回収装置として機能するものである。但し、第２回収装置は、再生処理液のｐＨ、又は陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた規定値に達するまでの再生処理液を回収する構成を備えていれば、上記の構成に制限されるものではない。 Reproduction processing liquid discharge line 36a, the reproduction processing liquid reservoir 38a, as described later, pH of the reproduction processing solution, or the reproduction process liquid Cl - anion exchange resin obtained based on the ion concentration Cl - ion desorption It functions as a second recovery device that recovers the regenerated processing liquid until the amount reaches a predetermined specified value. However, if the second recovery device has a configuration for recovering the regeneration treatment solution until the pH of the regeneration treatment solution or the Cl − ion desorption amount of the anion exchange resin reaches a predetermined specified value, However, the present invention is not limited to this configuration.
　濃縮装置４２は、再生処理液を濃縮する機能を有するものであり、例えば、エバポレータ、液膜降下式蒸発濃縮装置等が挙げられる。また、乾燥装置４４は、濃縮した再生処理液を乾燥させるものであり、例えば、電熱加熱型ドライヤーや真空ドラム式ドライヤー等が挙げられる。 The concentrator 42 has a function of concentrating the regenerated liquid, and examples thereof include an evaporator and a liquid film descending evaporation concentrator. The drying device 44 is for drying the concentrated regeneration treatment liquid, and examples thereof include an electric heating dryer and a vacuum drum dryer.
　以下、本実施形態の溶解塩類回収装置１の動作について説明する。 Hereinafter, the operation of the dissolved salt recovery apparatus 1 of the present embodiment will be described.
　本実施形態の処理対象となる排水は、ＮａＣｌを含む資源採掘随伴水である。資源採掘随伴水とは、例えば、ＣＳＧ（Ｃｏａｌ　Ｓｅａｍ　Ｇａｓ）のような天然ガスや原油などの資源採掘で発生する随伴水であり、ＮａＣｌ等を含むものである。 The wastewater to be treated in this embodiment is resource mining accompanying water containing NaCl. The water associated with resource mining is water associated with resource mining such as natural gas such as CSG (Coal Seam Gas) or crude oil, and includes NaCl or the like.
　まず、ＮａＣｌを含む資源採掘随伴水は、排水貯留槽１０に供給される前に、前処理工程、濃縮工程を行うことが望ましい。前処理工程は、凝集沈殿、凝集浮上分離やＭＦ膜・ＵＦ膜などを用いた膜ろ過等により、資源採掘随伴水に含まれる懸濁物質や油分等を除去する工程である。濃縮工程は、ＲＯ膜等により資源採掘随伴水を濃縮し、水中のＮａＣｌ濃度を高める工程である。濃縮された資源採掘随伴水中のＮａＣｌ濃度は、その後の処理時間を短くし効率的な運転を行う観点等から、０．１ｍｏｌ／Ｌ以上であることが望ましい。 First, it is desirable that the resource extraction accompanying water containing NaCl is subjected to a pretreatment step and a concentration step before being supplied to the drainage storage tank 10. The pretreatment step is a step of removing suspended substances, oils, and the like contained in the water associated with resource mining by coagulation sedimentation, coagulation flotation separation, membrane filtration using an MF membrane / UF membrane, or the like. The concentration step is a step of concentrating water associated with resource mining with an RO membrane or the like to increase the NaCl concentration in the water. The concentration of NaCl in the concentrated resource extraction accompanying water is preferably 0.1 mol / L or more from the viewpoint of shortening the subsequent treatment time and performing efficient operation.
＜ＮａＨＣＯ３を回収する第１回収工程＞
　本実施形態では、ＮａＣｌを含む資源採掘随伴水を陰イオン交換樹脂に通水し、上記式（３）の反応でＮａＣｌをＮａＨＣＯ３に交換し、ＮａＨＣＯ３を回収する第１回収工程を実施する。陰イオン交換樹脂はＨ２ＣＯ３型の弱塩基性イオン交換樹脂であることが好ましく、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂であることがより好ましい。以下、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂を例として説明する。Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂は、第１回収工程前に、弱塩基性アクリル系イオン交換樹脂を充填した充填塔１６に、純水等に炭酸を溶解した炭酸溶解水を通水し、Ｈ２ＣＯ３型に変換しておく必要がある。炭酸の溶解については、ガス吸収塔などを用いて、純水等にＣＯ２ガスを溶解させる方法等が挙げられる。ＣＯ２ガスは、メタンガスの燃焼や、ＣａＣＯ３からＣａ（ＯＨ）２を製造する際に副生したＣＯ２ガスを使用することが望ましい。 <First recovery step for recovering NaHCO 3 >
In the present embodiment, the resource extraction produced water containing NaCl was passed through an anion exchange resin, the NaCl in the above reaction formula (3) is replaced with NaHCO 3, performing a first recovery step of recovering the NaHCO 3 . Preferably the anion exchange resin is a H 2 CO 3 type weakly basic ion-exchange resin, and more preferably H 2 CO 3 type weakly basic acrylic ion exchange resin. Hereinafter, an H 2 CO 3 type weakly basic acrylic ion exchange resin will be described as an example. The H 2 CO 3 type weakly basic acrylic ion exchange resin is a carbonate-dissolved water obtained by dissolving carbonic acid in pure water or the like in a packed tower 16 filled with a weakly basic acrylic ion exchange resin before the first recovery step. It is necessary to pass water and convert it into H 2 CO 3 type. Examples of the dissolution of carbonic acid include a method of dissolving CO 2 gas in pure water or the like using a gas absorption tower or the like. As the CO 2 gas, it is desirable to use CO 2 gas produced as a by-product when methane gas is burned or Ca (OH) 2 is produced from CaCO 3 .
　図１を用いて第１回収工程を具体的に説明すると、排水貯留槽１０内のＮａＣｌを含む資源採掘随伴水が、排水ポンプ１４により排水流入ライン１２を通り、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂を充填した充填塔１６に供給される。充填塔１６内では、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂により、Ｃｌ－が吸着され、処理水排出ライン１８からＮａＨＣＯ３を含む処理水が排出され、処理水槽２０に貯留される。処理水槽２０に貯留されたＮａＨＣＯ３を含む処理水は、その後、エバポレータ等による濃縮装置４２により濃縮され、ドライヤー等の乾燥装置４４により乾燥処理される。本実施形態における第１回収工程では、処理水排出ライン１８に設置したＣｌ－イオンセンサ２１により、処理水中のＣｌ－イオン濃度をモニタリングし、Ｃｌ－イオン濃度が上昇したら直ちに終了することが望ましい。例えば、Ｃｌ－イオンセンサ２１の測定データが制御部４０に送られ、Ｃｌ－イオン濃度が上昇した段階で、制御部４０により、排水ポンプ１４等の稼働を停止するように電子制御されていてもよいし、作業者がＣｌ－イオンセンサ２１の測定データをチェックして、Ｃｌ－イオン濃度が上昇した段階で、手動で排水ポンプ１４等の稼働を停止してもよい。 The first recovery process will be described in detail with reference to FIG. 1. The resource extraction accompanying water containing NaCl in the drainage storage tank 10 passes through the drainage inflow line 12 by the drainage pump 14, and is a weak base of H 2 CO 3 type. Is supplied to a packed tower 16 filled with a functional acrylic ion exchange resin. Within packed tower 16 by H 2 CO 3 type weakly basic acrylic ion exchange resin, Cl - is adsorbed, it is treated water containing NaHCO 3 is discharged from the treated water discharge line 18, stored in the processed water tank 20 The The treated water containing NaHCO 3 stored in the treated water tank 20 is then concentrated by a concentrating device 42 such as an evaporator and dried by a drying device 44 such as a dryer. In the first recovery step in the present embodiment, Cl was placed in the treated water discharge line 18 - by the ion sensor 21, Cl in the treated water - monitoring the ion concentration, Cl - it is desirable that the ion concentration immediately terminated Once raised. For example, even if the measurement data of the Cl − ion sensor 21 is sent to the control unit 40 and the control unit 40 electronically controls to stop the operation of the drainage pump 14 and the like when the Cl − ion concentration increases. good to the worker Cl - checks the measurement data of the ion sensor 21, Cl - at the stage where the ion concentration is increased, may be stopped operation of such drainage pump 14 manually.
　また、本実施形態では、第１回収工程の開始から終了までに、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂が吸着したＣｌ－イオン吸着量を算出しておくことが望ましい。具体的には、排水流入ライン１２に設置したＣｌ－イオンセンサ３１により検出される資源採掘随伴水のＣｌ－イオン濃度と、処理水排出ライン１８に設置されたＣｌ－センサ２１により検出される処理水のＣｌ－イオン濃度との差に積算流量計により検出した資源採掘随伴水の流量（通水量）を乗じることにより求められる。Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂が吸着したＣｌ－イオン吸着量は、例えば、各Ｃｌ－センサ及び積算流量計１９の測定データが、制御部４０に送信され、制御部４０により求められる。 Further, in the present embodiment, from the start to the end of the first recovery step, Cl H 2 CO 3 type weakly basic acrylic ion exchange resin is adsorbed - is that you calculate the ion adsorption amount desired. Specifically, Cl was placed in the drainage inlet line 12 - and the ion concentration, Cl installed in the treated water discharge line 18 - - Cl of resource extraction associated water detected by the ion sensor 31 is detected by the sensor 21 treatment water Cl - is determined by multiplying the flow rate of the resource extraction produced water detected by the integrating flowmeter in the difference between the ion concentration (through water). Cl H 2 CO 3 type weakly basic acrylic ion exchange resin is adsorbed - ion adsorption amount, for example, the Cl - measurement data of the sensor and the integrated flow meter 19 is transmitted to the control unit 40, the control unit 40 It is calculated by.
　本実施形態において使用する陰イオン交換樹脂はアクリル系の第三アミン形の官能基を持った弱塩基性陰イオン交換樹脂であり、例えば、アンバーライトＩＲＡ－６７を使用するのが好適である。第１回収工程における資源採掘随伴水の通水ＳＶは、０．５～１０（１／ｈ）程度とすることが好適である。 The anion exchange resin used in this embodiment is a weakly basic anion exchange resin having an acrylic tertiary amine type functional group. For example, Amberlite IRA-67 is preferably used. The water passing SV of the resource extraction accompanying water in the first recovery step is preferably about 0.5 to 10 (1 / h).
＜再生工程＞
　本実施形態では、第１回収工程においてＨＣｌが吸着した陰イオン交換樹脂にＣａ（ＯＨ）２溶液（以下、Ｃａ（ＯＨ）２スラリーと呼ぶ場合がある）を通水して、上記式（４）の反応で、陰イオン交換樹脂からＨＣｌを脱離させ、陰イオン交換樹脂を再生する再生工程を実施する。なお、再生工程前には、充填塔１６に純水を通水し、陰イオン交換樹脂間の間隙に滞留している資源採掘随伴水を洗い流すことが望ましい。 <Regeneration process>
In the present embodiment, a Ca (OH) 2 solution (hereinafter sometimes referred to as Ca (OH) 2 slurry) is passed through the anion exchange resin to which HCl has been adsorbed in the first recovery step, and the above formula (4 In the reaction (1), a regeneration step is performed in which HCl is desorbed from the anion exchange resin to regenerate the anion exchange resin. Prior to the regeneration step, it is desirable to pass pure water through the packed tower 16 and wash away the water associated with resource mining that is retained in the gap between the anion exchange resins.
　図２を用いて再生工程を具体的に説明すると、Ｃａ（ＯＨ）２ポンプ２６を稼働させ、Ｃａ（ＯＨ）２貯留槽２２内のＣａ（ＯＨ）２スラリーがＣａ（ＯＨ）２流入ライン２４から充填塔１６に供給されると共に、ブロワ３２を稼働させ、空気が空気流入ライン３４を通り、充填塔１６に供給される。充填塔１６内では、空気により、陰イオン交換樹脂が攪拌されながらＣａ（ＯＨ）２スラリーと接触することにより、陰イオン交換樹脂からＨＣｌが脱離され、有価物であるＣａＣｌ２が生成される。このような再生工程は、充填塔１６内の樹脂を攪拌しながらＣａ（ＯＨ）２スラリーを所定条件まで徐々に添加し、一定時間反応後、再生処理液を充填塔１６から排出させる回分式で行っても良い。また、Ｃａ（ＯＨ）２スラリーを充填塔１６に通水し再生処理液を連続的に排出させる連続式で行っても良い。スラリーに覆われた陰イオン交換樹脂上で式（４）の反応をより効率的に進める観点等から、陰イオン交換樹脂を攪拌しながらＣａ（ＯＨ）２スラリーを所定量まで徐々に添加する回分式のほうが望ましい。 Specifically explaining a reproduction process with reference to FIG. 2, operate the Ca (OH) 2 pumps 26, Ca (OH) 2 Ca in the storage tank 22 (OH) 2 slurry Ca (OH) 2 inlet line 24 Is supplied to the packed tower 16, and the blower 32 is operated, and air is supplied to the packed tower 16 through the air inflow line 34. Within packed tower 16, the air, by anion exchange resin is contacted with Ca (OH) 2 slurry with stirring, HCl is desorbed from the anion-exchange resin, CaCl 2 is produced a valuable . Such a regeneration step is a batch type in which the Ca (OH) 2 slurry is gradually added to a predetermined condition while stirring the resin in the packed tower 16 and the reaction solution is discharged from the packed tower 16 after a certain time of reaction. You can go. Alternatively, the Ca (OH) 2 slurry may be passed through the packed tower 16 to continuously discharge the regeneration treatment liquid. From the viewpoint of more efficiently advancing the reaction of formula (4) on the anion exchange resin covered with the slurry, a batch of gradually adding the Ca (OH) 2 slurry to a predetermined amount while stirring the anion exchange resin. The formula is preferred.
　Ｃａ（ＯＨ）２スラリーの濃度は、回分式で使用する場合は５～１０％が好適であり、連続式で使用する場合は、０．０５～０．５％が好適である。 The concentration of the Ca (OH) 2 slurry is preferably 5 to 10% when used in a batch system and 0.05 to 0.5% when used in a continuous system.
　充填塔１６に空気を供給して、充填塔１６内の陰イオン交換樹脂を攪拌するための流体は、空気に限定されるものではなく、式（４）の反応を阻害しない流体であればよく、例えばメタンガス等が挙げられる。 The fluid for supplying air to the packed column 16 and stirring the anion exchange resin in the packed column 16 is not limited to air, and any fluid that does not hinder the reaction of formula (4) may be used. For example, methane gas etc. are mentioned.
　再生工程では、未溶解のＣａ（ＯＨ）２がＣａ２＋とＯＨ－に溶解してから、ＯＨ－が陰イオン交換樹脂上のＨＣｌと再生反応を起こすので、添加したＣａ（ＯＨ）２が再生に十分に使われるのに数分～１０分程度の時間を要する場合があるため、回分式でのＣａ（ＯＨ）２スラリーの添加はその時間を見込んで間欠的に行うことが好ましい。 In the regeneration step, undissolved Ca (OH) 2 is Ca 2+ and OH - from the dissolved, OH - because cause regeneration reaction with HCl on an anion exchange resin, the added Ca (OH) 2 is reproduced In some cases, it takes a time of several minutes to 10 minutes to be fully used in the process. Therefore, it is preferable that the addition of the Ca (OH) 2 slurry in a batch system is performed intermittently in consideration of the time.
＜第２回収工程＞
　本実施形態では、充填塔１６から排出される再生処理液を回収する第２回回収工程を実施する。この際、再生処理液のｐＨをモニタリングし、モニタリングしたｐＨ値が予め定めた既定値に達するまでに回収した再生処理液を濃縮及び乾燥する。又は再生処理液のＣｌ－イオン濃度をモニタリングし、モニタリングしたＣｌ－イオン濃度に基づいて求められる陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた既定値に達するまでに回収した再生処理液を濃縮及び乾燥する。 <Second recovery process>
In the present embodiment, the second recovery step of recovering the regeneration processing liquid discharged from the packed tower 16 is performed. At this time, the pH of the regeneration treatment solution is monitored, and the recovered regeneration solution is concentrated and dried until the monitored pH value reaches a predetermined value. Or reproduction processing liquid Cl - monitoring the ion concentration, monitoring the Cl - Cl anion exchange resin obtained based on the ion concentration - ion elimination amount recovered to reach a predetermined default reproduction processing solution Is concentrated and dried.
　図３は、Ｃａ（ＯＨ）２の供給量に対する再生処理液のｐＨ及びＣｌ－イオン脱離量との関係を示す図である。図３に示すように、再生処理液のｐＨをモニタリングする場合、完全再生前であれば、充填塔１６に通水したＣａ（ＯＨ）２は、陰イオン交換樹脂により消費され、その一方で陰イオン交換樹脂からＨＣｌが脱離していく段階であるので、再生処理液のｐＨは、Ｃａ（ＯＨ）２スラリーのｐＨ１２．２（水温２０℃の場合）よりも低いｐＨであり、再生処理液中のＣａＣｌ２の純度は高い状態である。一方、完全再生後であれば、ＨＣｌの脱離が終了し、充填塔１６に通水したＣａ（ＯＨ）２スラリーが充填塔１６から再生処理液として排出される段階であるので、再生処理液のｐＨは、Ｃａ（ＯＨ）２スラリーのｐＨ１２．２（水温２０℃の場合）に達し、再生処理液中のＣａＣｌ２の純度が低下していく状態である。 3, pH and Cl reproduction process liquid to the supply amount of Ca (OH) 2 - is a diagram showing the relationship between ion desorption amount. As shown in FIG. 3, when monitoring the pH of the regeneration treatment solution, before complete regeneration, the Ca (OH) 2 that has passed through the packed column 16 is consumed by the anion exchange resin, while the anion exchange resin. Since HCl is desorbed from the ion exchange resin, the pH of the regeneration treatment solution is lower than the pH 12.2 of the Ca (OH) 2 slurry (when the water temperature is 20 ° C.). The purity of CaCl 2 is high. On the other hand, if it is after complete regeneration, desorption of HCl is completed, and the Ca (OH) 2 slurry that has passed through the packed tower 16 is discharged from the packed tower 16 as a regenerated process liquid. The pH of the slurry reaches pH 12.2 (when the water temperature is 20 ° C.) of the Ca (OH) 2 slurry, and the purity of CaCl 2 in the regeneration treatment liquid is in a state of decreasing.
　そこで、本実施形態では、充填塔１６から排出される再生処理液のｐＨが、ｐＨセンサによりモニタリングされ、モニタリングされたｐＨ値が制御部４０に送信される。そして、制御部４０により、例えば、再生処理液のｐＨ値と予め設定した規定のｐＨ値とが比較され、ｐＨ値が予め設定した規定値に達していない間は、再生処理液中のＣａＣｌ２の純度が高いため、再生処理液排出ライン３６ａに設けられたバルブＡを開放し、再生処理液排出ライン３６ｂに設けられたバルブＢを閉じる。すなわち、ｐＨ値が予め設定した規定値未満の間は、再生処理液は、再生処理液排出ライン３６ａから再生処理液貯留槽３８ａに供給される。再生処理液貯留槽３８ａに貯留された処理液は、エバポレータ等の濃縮装置４２に送られて濃縮された後、ドライヤー等の乾燥装置４４に送られて乾燥され、高純度ＣａＣｌ２が回収される。また、制御部４０により、ｐＨ値が予め設定した規定値に達した場合には、再生処理液中のＣａＣｌ２の純度が低下していく段階に入るため、バルブＡを閉じ、バルブＢを開放する。すなわち、ｐＨ値が予め設定した規定値に達した後は、再生処理液は、再生処理排出ライン３６ｂから再生処理貯留槽３８ｂに供給される。なお、本実施形態では、ｐＨ値と規定値の比較及びバルブの開閉等を制御部４０による電子制御により実施しても良いし、作業者による手動により実施してもよい。なお、充填塔１６を回分式とした場合には、充填塔１６内に設置したｐＨセンサ２８により再生処理液のｐＨ値を測定することができるが、連続式とした場合には、再生処理液排出ライン３６ａ又は再生処理液貯留槽３８ａにｐＨセンサを設置し、再生処理液のｐＨを測定する必要がある。 Therefore, in the present embodiment, the pH of the regeneration treatment liquid discharged from the packed tower 16 is monitored by a pH sensor, and the monitored pH value is transmitted to the control unit 40. Then, for example, the control unit 40 compares the pH value of the regeneration processing solution with a predetermined pH value set in advance, and while the pH value does not reach the preset specified value, CaCl 2 in the regeneration processing solution. Therefore, the valve A provided in the regeneration processing liquid discharge line 36a is opened, and the valve B provided in the regeneration processing liquid discharge line 36b is closed. That is, while the pH value is less than the preset specified value, the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 36a to the regeneration processing liquid storage tank 38a. The processing liquid stored in the regeneration processing liquid storage tank 38a is sent to a concentrating device 42 such as an evaporator and concentrated, and then sent to a drying device 44 such as a dryer and dried to recover high-purity CaCl 2. . In addition, when the pH value reaches a preset specified value by the control unit 40, the valve A is closed and the valve B is opened because the purity of the CaCl 2 in the regenerating solution is lowered. To do. That is, after the pH value reaches a preset specified value, the regeneration processing liquid is supplied from the regeneration processing discharge line 36b to the regeneration processing storage tank 38b. In the present embodiment, the comparison between the pH value and the specified value, the opening / closing of the valve, and the like may be performed by electronic control by the control unit 40 or may be performed manually by an operator. When the packed tower 16 is a batch type, the pH value of the regeneration treatment liquid can be measured by the pH sensor 28 installed in the packed tower 16, but when it is a continuous type, the regeneration treatment liquid It is necessary to install a pH sensor in the discharge line 36a or the regeneration processing liquid storage tank 38a and measure the pH of the regeneration processing liquid.
　予め設定する規定値としては、高純度のＣａＣｌ２を回収することができる値であれば特に制限されるものではないが、ｐＨモニタリングの場合、Ｃａ（ＯＨ）２スラリーのｐＨ値に設定することが好ましく、ｐＨ１０．０～１２．０の間で設定することがより好ましい。規定値をｐＨ１２．０以下とすることにより、確実に高純度のＣａＣｌ２を含有する再生処理液を濃縮・乾燥工程に移行することが可能となる。また、規定値をｐＨ１０．０以上とすることにより、再生用として貯留する再生処理液が多くなることを抑制することができ、容量の小さな貯留設備を使用することが可能となる。このようにして、まず、塩化カルシウムの予め決められた基準純度に対応する規定値（例えば、再生処理液のｐＨ）を設定し、次に、塩酸と結合したイオン交換樹脂に水酸化カルシウム溶液を接触させて塩化カルシウムを含む再生処理液を取得するとともに再生処理液の塩化カルシウム純度の監視を開始する。その後、規定値に基づいて、塩化カルシウム純度が基準純度より高い状態から低い状態になるまでに再生処理液の取得を停止する。このように、再生処理液の塩化カルシウム純度が基準純度（例えば、再生処理液のｐＨが１２．０のときの再生処理液の塩化カルシウム純度）より低くなるまでに再生処理液の取得を停止した後、再生処理液から塩化カルシウムを得ることにより、塩化カルシウム純度が比較的高い状態の再生処理液から塩化カルシウムを得ることができ、高純度の塩化カルシウムを製造することができる。上記の例では、規定値は、再生処理液の塩化カルシウム純度が基準純度であるときの再生処理液のｐＨ（例えば、ｐＨ１２．０）であり、塩化カルシウム純度を監視するとき、再生処理液のｐＨを測定する。規定値は、再生処理液のｐＨである上記の例に代え、再生処理液の塩化カルシウム純度が基準純度であるときのイオン交換樹脂の塩素イオン脱離量とすることができる。この場合、塩化カルシウム純度を監視するとき、再生処理液のＣｌ－イオン濃度をモニタリングする。 The specified value to be set in advance is not particularly limited as long as it is a value capable of recovering high-purity CaCl 2 , but in the case of pH monitoring, it should be set to the pH value of the Ca (OH) 2 slurry. Is preferable, and it is more preferable to set between pH 10.0 and 12.0. By setting the specified value to pH 12.0 or less, it is possible to reliably transfer the regeneration treatment liquid containing high-purity CaCl 2 to the concentration / drying step. In addition, by setting the specified value to pH 10.0 or more, it is possible to suppress an increase in the regeneration processing liquid stored for regeneration, and it is possible to use a storage facility with a small capacity. In this way, first, a prescribed value (for example, pH of the regenerating solution) corresponding to a predetermined standard purity of calcium chloride is set, and then a calcium hydroxide solution is applied to the ion exchange resin combined with hydrochloric acid. The contact is made to obtain a regeneration treatment liquid containing calcium chloride, and monitoring of the calcium chloride purity of the regeneration treatment liquid is started. Then, based on the specified value, the acquisition of the regeneration treatment liquid is stopped until the calcium chloride purity is changed from a state higher than the reference purity to a state lower than the reference purity. Thus, the acquisition of the regeneration treatment liquid was stopped until the calcium chloride purity of the regeneration treatment liquid became lower than the reference purity (for example, the calcium chloride purity of the regeneration treatment liquid when the pH of the regeneration treatment liquid was 12.0). Thereafter, by obtaining calcium chloride from the regeneration treatment solution, calcium chloride can be obtained from the regeneration treatment solution having a relatively high calcium chloride purity, and high purity calcium chloride can be produced. In the above example, the specified value is the pH of the regeneration treatment solution when the calcium chloride purity of the regeneration treatment solution is the reference purity (for example, pH 12.0), and when monitoring the calcium chloride purity, Measure the pH. The specified value can be the chlorine ion desorption amount of the ion exchange resin when the calcium chloride purity of the regeneration treatment solution is the reference purity, instead of the above example which is the pH of the regeneration treatment solution. In this case, when monitoring calcium chloride purity, Cl reproduction processing liquid - monitoring the ion concentration.
　図２に示すように、再生処理液のＣｌ－イオン濃度をモニタリングする場合、完全再生前であれば、陰イオン交換樹脂に吸着していたＨＣｌが脱離していく段階であるので、再生処理液中のＣｌ－イオン濃度に基づいて求められる陰イオン交換樹脂のＣｌ－イオン脱離量は、陰イオン交換樹脂のＣｌ－イオン吸着量より低く、再生処理液中のＣａＣｌ２の純度は高い状態である。一方、完全再生後であれば、ＨＣｌの脱離が終了し、充填塔１６に通水したＣａ（ＯＨ）２スラリーが充填塔１６から再生処理液として排出される段階であるので、陰イオン交換樹脂のＣｌ－イオン脱離量は、陰イオン交換樹脂のＣｌ－イオン吸着量に達し、再生処理液中のＣａＣｌ２の純度が低下していく状態である。 As shown in FIG. 2, Cl reproduction processing liquid - when monitoring the ion concentration, if complete regeneration before, because at the stage where HCl adsorbed on the anion exchange resin is gradually desorbed, reproduction processing liquid Cl anion exchange resin obtained based on the ion concentration - - Cl in the ion desorption amount is, Cl anion exchange resin - lower than the ion adsorption amount, the purity of CaCl 2 in the regeneration process liquid is in a state of high is there. On the other hand, if it is after complete regeneration, desorption of HCl is completed, and the Ca (OH) 2 slurry that has passed through the packed tower 16 is discharged from the packed tower 16 as a regeneration treatment liquid. The Cl − ion desorption amount of the resin reaches the Cl − ion adsorption amount of the anion exchange resin, and the purity of CaCl 2 in the regeneration treatment liquid is in a state of decreasing.
　そこで、他の本実施形態では、充填塔１６から排出される再生処理液のＣｌ－イオン濃度が、Ｃｌ－イオンセンサによりモニタリングされ、モニタリングされたＣｌ－イオン濃度値が制御部４０に送信される。ここで、陰イオン交換樹脂に吸着していたＣｌ－イオンの脱離量は、再生処理液のＣｌ－イオン濃度と再生処理液量との積により求められる。再生処理液の流量が一定であれば、制御部４０で、モニタリングされたＣｌ－イオン濃度値に定数を乗じることにより求められ、再生処理液が一定でなければ、再生処理液排出ライン３６ａに積算流量計を設置し、積算流量計により測定された再生処理液の流量値を制御部４０に送信し、制御部４０で、モニタリングされたＣｌ－イオン濃度値に測定された再生処理液の流量値を乗じることにより求められる。そして、制御部４０により、例えば、陰イオン交換樹脂に吸着していたＣｌ－イオン脱離量と予め設定した規定値とが比較され、Ｃｌ－イオン脱離量が予め設定した規定値に達していない間は、再生処理液中のＣａＣｌ２の純度が高いため、バルブＡを開放し、電磁バルブＢを閉じる。すなわち、Ｃｌ－イオン脱離量が予め設定した規定値未満の間は、再生処理液は、再生処理液排出ライン３６ａから再生処理液貯留槽３８ａに供給される。再生処理液貯留槽３８ａに貯留された処理液は、エバポレータ等の濃縮装置４２に送られて濃縮された後、ドライヤー等の乾燥装置４４に送られて乾燥され、高純度ＣａＣｌ２が回収される。また、制御部４０により、Ｃｌ－イオン脱離量が予め設定した規定値に達した場合には、再生処理液中のＣａＣｌ２の純度が低下していく段階に入るため、バルブＡを閉じ、バルブＢを開放する。すなわち、Ｃｌ－イオン脱離量が予め設定した規定値に達した後は、再生処理液は、再生処理排出ラインｂから再生処理貯留槽ｂに供給される。なお、本実施形態では、Ｃｌ－イオン脱離量と規定値の比較及びバルブの開閉等を制御部４０による電子制御により実施しても良いし、作業者による手動により実施してもよい。なお、充填塔１６を回分式とした場合には、充填塔１６内に設置したＣｌ－イオンセンサ３０により再生処理液のＣｌ－イオン濃度を測定することができるが、連続式とした場合には、再生処理液排出ライン３６ａ又は再生処理液貯留槽３８ａにＣｌ－イオンセンサを設置し、再生処理液のＣｌ－イオン濃度を測定する必要がある。 Therefore, in another embodiment, Cl reproduction process liquid discharged from the packed tower 16 - ion concentration, Cl - is monitored by the ion sensor, the monitored Cl - ion concentration value is transmitted to the control unit 40 . Here, the desorption amount of Cl 2 − ions adsorbed on the anion exchange resin can be obtained by the product of the Cl 2 − ion concentration of the regeneration treatment solution and the regeneration treatment solution amount. If the flow rate of the regeneration process liquid is constant, the control unit 40, the monitored Cl - obtained by multiplying the constant ion density values, if the reproduction processing solution constant, integrating the reproduction processing liquid discharge line 36a the flowmeter is installed, it transmits a flow rate value of the measured playback processing solution by integrating flowmeter to the control unit 40, the control unit 40, the monitored Cl - measured ion concentration value reproduction processing solution flow rate value It is calculated by multiplying. Then, the control unit 40 compares, for example, the Cl − ion desorption amount adsorbed on the anion exchange resin with a preset specified value, and the Cl − ion desorption amount has reached the preset specified value. During the absence, since the purity of CaCl 2 in the regeneration processing solution is high, the valve A is opened and the electromagnetic valve B is closed. That is, while the Cl 2 − ion desorption amount is less than a preset specified value, the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 36a to the regeneration processing liquid storage tank 38a. The processing liquid stored in the regeneration processing liquid storage tank 38a is sent to a concentrating device 42 such as an evaporator and concentrated, and then sent to a drying device 44 such as a dryer and dried to recover high-purity CaCl 2. . Further, when the amount of Cl − ion desorption reaches a predetermined value set in advance by the control unit 40, since the purity of CaCl 2 in the regeneration processing solution is lowered, the valve A is closed, Open valve B. That is, after the Cl − ion desorption amount reaches a predetermined value set in advance, the regeneration processing liquid is supplied from the regeneration processing discharge line b to the regeneration processing storage tank b. In the present embodiment, Cl - Comparison of ion desorption amount a specified value and may be implemented by the electronic control of the control unit 40 of the opening and closing of the valve may be performed manually by an operator. When the packed tower 16 is a batch type, the Cl − ion concentration of the regenerated solution can be measured by a Cl − ion sensor 30 installed in the packed tower 16. , Cl playback processing liquid discharge line 36a or reproducing processing liquid reservoir 38a - installing an ion sensor, Cl reproduction processing solution - it is necessary to measure the ion concentration.
　予め設定する規定値としては、高純度のＣａＣｌ２を回収することができる値であれば特に制限されるものではないが、Ｃｌ－イオン濃度モニタリングの場合、陰イオン交換樹脂のＣｌ－イオン吸着量の値に設定することが好ましく、陰イオン交換樹脂のＣｌ－イオン吸着量の値の８５～９６％の間に設定することがより好ましい。規定値を陰イオン交換樹脂のＣｌ－イオン吸着量の値の９６％以下とすることにより、確実に高純度のＣａＣｌ２を含有する再生処理液を濃縮・乾燥工程に移行することが可能となる。規定値を陰イオン交換樹脂のＣｌ－イオン吸着量の値の８５％以上とすることにより、再生用として貯留する再生処理液が多くなることを抑制することができ、容量の小さな貯留設備を使用することが可能となる。陰イオン交換樹脂のＣｌ－イオン吸着量の算出については、前述の通りである。 The specified value to be set in advance is not particularly limited as long as it is a value capable of recovering high-purity CaCl 2 , but in the case of Cl − ion concentration monitoring, the amount of Cl − ion adsorption of the anion exchange resin is not limited. preferably set to a value, Cl anion exchange resin - and more preferably set between 85 to 96% of the ion adsorption values. By setting the specified value to 96% or less of the value of the Cl − ion adsorption amount of the anion exchange resin, it becomes possible to reliably transfer the regeneration treatment liquid containing high-purity CaCl 2 to the concentration / drying process. . The specified value Cl anion exchange resin - by 85% or more of the ion adsorption value, it is possible to suppress the increased reproduction process liquid storing for playback, use a small storage facility capacity It becomes possible to do. The calculation of the Cl − ion adsorption amount of the anion exchange resin is as described above.
　本実施形態では、再生処理液のｐＨ又はＣｌ－イオン脱離量が既定値に達した後、充填塔１６に、Ｃａ（ＯＨ）２スラリーをさらに導入し、陰イオン交換樹脂の完全再生を行うことが好ましい。完全再生後の再生処理液、すなわち、前述したように再生処理液排出ライン３６ｂを通り再生処理液貯留槽３８ｂに貯留した再生処理液は、Ｃｌ－イオンを多少含むが、Ｃｌ－イオンに比べてＣａ（ＯＨ）２含有量が多いので、次のサイクルにおける陰イオン交換樹脂を再生するための再生剤として使用するために貯留しておくことが望ましい。また、陰イオン交換樹脂を充填した充填塔１６が複数ある場合は、他の系列の再生に使用しても良い。そうすることにより、貯留設備の数を減らすことが可能となる。 In the present embodiment, pH or Cl reproduction processing solution - after ion desorption amount reaches the predetermined value, the packed tower 16, Ca (OH) further introduced 2 slurry, a complete regeneration of the anion exchange resin It is preferable. Complete regeneration after regeneration treatment liquid, i.e., reproduction processing liquid stored as reproduction processing liquid reservoir 38b playback processing liquid discharge line 36b as described above, Cl - somewhat containing ions, Cl - as compared with ion Since the content of Ca (OH) 2 is large, it is desirable to store it for use as a regenerant for regenerating the anion exchange resin in the next cycle. Further, when there are a plurality of packed columns 16 filled with an anion exchange resin, they may be used for regeneration of other series. By doing so, the number of storage facilities can be reduced.
　第２回収工程終了後には、充填塔１６に純水を通水して、陰イオン交換樹脂を洗浄することが望ましい。この洗浄排水は、希薄なＣａ（ＯＨ）２溶液であるので、Ｃａ（ＯＨ）２スラリーを調製するための、溶解水として使用してもよい。 After completion of the second recovery step, it is desirable to wash the anion exchange resin by passing pure water through the packed tower 16. Since this washing waste water is a dilute Ca (OH) 2 solution, it may be used as dissolved water for preparing a Ca (OH) 2 slurry.
　図４は、参考例に係る溶解塩類回収装置の構成の一例を示す概略構成図である。図４に示すように、溶解塩類回収装置２は、排水貯留槽４６、排水流入ライン４８ａ，４８ｂ、排水ポンプ５０ａ，５０ｂ、ｐＨ調整塔５２、ブロワ５４、ガス流入ライン５６、陰イオン交換樹脂が充填された充填塔５８、処理水排出ライン６０、処理水槽６２を備えるものである。図４に示すように、排水流入ライン４８ａにはＣｌ－イオンセンサ６４及びアルカリ度計６８が設置され、排水流入ライン４８ｂにはｐＨセンサ７０が設置され、処理水排出ライン６０にはＣｌ－イオンセンサ６６が設置されている。Ｃｌ－イオンセンサ６４，６６としては、Ｃｌ－イオン電極を用いたセンサを使用することが望ましい。また、図４に示すように、溶解塩類回収装置２は、制御部７２を備え、各センサ、アルカリ度計６８と電気的に接続され、各センサ及びアルカリ度計６８の測定値が送信されるようになっている。また、溶解塩類回収装置２は濃縮装置７４及び乾燥装置７６を備えている。 FIG. 4 is a schematic configuration diagram illustrating an example of a configuration of a dissolved salt recovery apparatus according to a reference example. As shown in FIG. 4, the dissolved salt recovery apparatus 2 includes a drainage storage tank 46, drainage inflow lines 48a and 48b, drainage pumps 50a and 50b, a pH adjusting tower 52, a blower 54, a gas inflow line 56, and an anion exchange resin. A packed tower 58, a treated water discharge line 60, and a treated water tank 62 are provided. As shown in FIG. 4, the wastewater inflow line 48a Cl - ion sensor 64 and the alkalinity gauge 68 is installed, the waste water inlet line 48b is installed pH sensors 70, Cl is the treated water discharge line 60 - Ion A sensor 66 is installed. As the Cl - ion sensors 64 and 66, it is desirable to use sensors using Cl - ion electrodes. As shown in FIG. 4, the dissolved salt recovery apparatus 2 includes a control unit 72 and is electrically connected to each sensor and the alkalinity meter 68, and the measurement values of each sensor and the alkalinity meter 68 are transmitted. It is like that. The dissolved salt recovery apparatus 2 includes a concentrating device 74 and a drying device 76.
　図４に示すように、排水流入ライン４８ａの一端は排水貯留槽４６に接続され、他端はｐＨ調整塔５２の上部に接続されている。排水流入ライン４８ａには、排水ポンプ５０ａが設置されている。ガス流入ライン５６の一端はブロワ５４に接続され、他端はｐＨ調整塔５２の側面に接続されている。排水流入ライン４８ｂの一端はｐＨ調整塔５２の下部側面に接続され、他端は充填塔５８の上部に接続されている。排水流入ライン４８ｂには、排水ポンプ５０ｂが設置されている。処理水排出ライン６０の一端は、充填塔５８の底部に接続され、他端は処理水槽６２に接続されている。 As shown in FIG. 4, one end of the drainage inflow line 48 a is connected to the drainage storage tank 46, and the other end is connected to the upper part of the pH adjustment tower 52. A drainage pump 50a is installed in the drainage inflow line 48a. One end of the gas inflow line 56 is connected to the blower 54, and the other end is connected to the side surface of the pH adjusting tower 52. One end of the drainage inflow line 48 b is connected to the lower side surface of the pH adjusting tower 52, and the other end is connected to the upper part of the packed tower 58. A drainage pump 50b is installed in the drainage inflow line 48b. One end of the treated water discharge line 60 is connected to the bottom of the packed tower 58, and the other end is connected to the treated water tank 62.
　排水流入ライン４８ａ、排水ポンプ５０ａ、ｐＨ調整塔５２、ブロワ５４、ガス流入ライン５６は、資源採掘随伴水のｐＨを調整するｐＨ調整装置として機能するものである。ｐＨ調整装置は、資源採掘随伴水のｐＨを調整する構成を備えていれば、上記の構成に制限されるものではない。ｐＨ調整塔５２内には、資源採掘随伴水のｐＨ調整用ガスの使用量を抑制する等の観点から、ラシヒリング等の充填剤を充填することが好ましい。 The drainage inflow line 48a, the drainage pump 50a, the pH adjusting tower 52, the blower 54, and the gas inflow line 56 function as a pH adjusting device that adjusts the pH of the water associated with resource mining. The pH adjusting device is not limited to the above configuration as long as it has a configuration for adjusting the pH of the resource mining accompanying water. It is preferable to fill the pH adjusting tower 52 with a filler such as Raschig ring from the viewpoint of suppressing the amount of the gas for adjusting the pH of the resource extraction accompanying water.
　濃縮装置７４は、再生処理液を濃縮する機能を有するものであり、例えば、エバポレータ、液膜降下式蒸発濃縮装置等が挙げられる。また、乾燥装置７６は、濃縮した再生処理液を乾燥させるものであり、例えば、電熱加熱式ドライヤーや真空ドラムドライヤー等が挙げられる。 The concentrating device 74 has a function of concentrating the regeneration treatment liquid, and examples thereof include an evaporator and a liquid film descending evaporation concentrating device. The drying device 76 is for drying the concentrated regeneration treatment liquid, and examples thereof include an electric heating dryer and a vacuum drum dryer.
　以下、参考例の溶解塩類回収装置２の動作について説明する。 Hereinafter, the operation of the dissolved salt recovery apparatus 2 of the reference example will be described.
　参考例の処理対象となる排水は、ＮａＣｌ及び炭酸物質を含む資源採掘随伴水である。資源採掘随伴水とは、例えば、ＣＳＧ（Ｃｏａｌ　Ｓｅａｍ　Ｇａｓ）のような天然ガスや原油などの資源採掘で発生する随伴水であり、ＮａＣｌ等を含むものである。ここで、炭酸物質とは、重炭酸イオン（ＨＣＯ３ －）、炭酸イオン（ＣＯ３ ２－）、遊離炭酸（溶解性ＣＯ２）等である。 The wastewater to be treated in the reference example is resource mining accompanying water containing NaCl and a carbonate substance. The water associated with resource mining is water associated with resource mining such as natural gas such as CSG (Coal Seam Gas) or crude oil, and includes NaCl or the like. Here, the carbonate substance is bicarbonate ion (HCO 3 − ), carbonate ion (CO 3 2− ), free carbonic acid (soluble CO 2 ) and the like.
　まず、ＮａＣｌ及び炭酸物質を含む資源採掘随伴水は、排水貯留槽４６に供給される前に、前処理工程、濃縮工程を行うことが望ましい。前処理工程は、凝集沈殿、凝集浮上分離やＭＦ膜・ＵＦ膜などを用いた膜ろ過等により、資源採掘随伴水に含まれる懸濁物質や油分等を除去する工程である。濃縮工程は、ＲＯ膜等により資源採掘随伴水を濃縮し、水中のＮａＣｌ濃度を高める工程である。濃縮された資源採掘随伴水中のＮａＣｌ濃度は、その後の処理時間を短くし効率的な運転を行う観点等から、０．１ｍｏｌ／Ｌ以上であることが望ましい。 First, it is desirable that the resource mining accompanying water containing NaCl and carbonate material is subjected to a pretreatment step and a concentration step before being supplied to the drainage storage tank 46. The pretreatment step is a step of removing suspended substances, oils, and the like contained in the water associated with resource mining by coagulation sedimentation, coagulation flotation separation, membrane filtration using an MF membrane / UF membrane, or the like. The concentration step is a step of concentrating water associated with resource mining with an RO membrane or the like to increase the NaCl concentration in the water. The concentration of NaCl in the concentrated resource extraction accompanying water is preferably 0.1 mol / L or more from the viewpoint of shortening the subsequent treatment time and performing efficient operation.
＜ｐＨ調整工程＞
　参考例では、（前処理・濃縮工程後）の資源採掘随伴水中の遊離炭酸を除く全炭酸物質（ＨＣＯ３ －、ＣＯ３ ２－）の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比（モル比）に応じて、源採掘随伴水のｐＨを調整するｐＨ調整工程を実施する。高純度のＮａＨＣＯ３を回収するためには、資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が小さいほど、資源採掘随伴水のｐＨを低くする必要がある。 <PH adjustment step>
In the reference example, the amount of Cl − ions (moles) relative to the amount (moles) of all carbonated substances (HCO 3 − , CO 3 2− ) excluding free carbonic acid in the water associated with resource mining (after pretreatment and concentration steps) ) Is adjusted according to the ratio (molar ratio) of the source mining accompanying water. In order to recover high-purity NaHCO 3 , it is necessary to lower the pH of the resources associated with resource mining as the ratio of the amount of Cl − ions to the amount of all carbonates excluding free carbonic acid in the resources associated with resource mining is smaller. There is.
　通常、モル比に関わらず、ｐＨ８．５以上の資源採掘随伴水を後段の充填塔５８に通水して処理を行うと、充填塔５８から排出される処理水には、ＮａＨＣＯ３の他にＮａ２ＣＯ３が含まれる状態となるため、溶解塩類の純度としては問題ないが、ＮａＨＣＯ３単体の純度としては低下する。更にｐＨ９．５以上の資源採掘随伴水を後段の充填塔５８に通水して処理を行うと、上記式（３）の反応と同時に、ＯＨ－イオンによるイオン交換樹脂の再生反応が生じ、充填塔５８から排出される処理水にはＣｌ－イオンが混入するため、充填塔５８から排出される処理水中のＮａＨＣＯ３純度は更に低下する。しかし、遊離炭酸を除く全炭酸物質の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比が２以上の場合、資源採掘随伴水のｐＨを６．５以上～８．５以下にすると、上記式（３）の反応が十分進行するとともに、資源採掘随伴水中に含まれる全炭酸物質の多くがＨＣＯ３ －となっているため、後段の充填塔５８から排出される処理水から高純度のＮａＨＣＯ３を回収することができる。遊離炭酸を除く全炭酸物質の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比が２以上の場合、特に、資源採掘随伴水のｐＨを７．０以上～８．０以下に調整することにより、資源採掘随伴水中に含まれる全炭酸物質の大部分がＨＣＯ３ －となっているため、後段の充填塔５８から排出される処理水から、高純度でより多くのＮａＨＣＯ３を回収することができる。一方、遊離炭酸を除く全炭酸物質の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比が２より小さくなるにつれ、資源採掘随伴水のｐＨを６．５以上～８．５以下の範囲に調整しても上記式（３）の反応が進みにくくなるため、充填塔５８から排出される処理水にＣｌ－イオンの混入が多くなってしまう。しかし、資源採掘随伴水のｐＨを上記範囲より下げ、資源採掘随伴水中の炭酸を遊離炭酸にすることで、Ｃｌ－イオンに対するＨＣＯ３ －の量を低減させることができるため、充填塔５８内では上記式（３）の反応が進み易くなる。また、資源採掘随伴水のｐＨを上記範囲に設定することにより、低ｐＨでイオン交換する陰イオン交換樹脂の性質により上記式（３）の反応を促進することができる。このため、処理水へのＣｌ－イオンの混入が少なくなり、処理水から高純度のＮａＨＣＯ３を回収することができる。 Normally, regardless of the molar ratio, when processing is performed by passing water associated with resource mining at a pH of 8.5 or more through the packed column 58 at the subsequent stage, the treated water discharged from the packed column 58 includes NaHCO 3 in addition to NaHCO 3 . Since Na 2 CO 3 is contained, there is no problem with the purity of the dissolved salts, but the purity of NaHCO 3 alone is lowered. Further, when the water associated with resource mining with a pH of 9.5 or more is passed through the packed tower 58 at the subsequent stage, the regeneration reaction of the ion exchange resin by OH − ions occurs simultaneously with the reaction of the above formula (3). Since Cl - ions are mixed in the treated water discharged from the column 58, the purity of NaHCO 3 in the treated water discharged from the packed column 58 is further lowered. However, when the ratio of the mass (mol) of Cl − ions to the mass (mol) of all carbonic substances excluding free carbonic acid is 2 or more, the pH of the water associated with resource mining should be 6.5 to 8.5. Then, the reaction of the above formula (3) proceeds sufficiently, and most of the total carbonic acid contained in the resource extraction accompanying water is HCO 3 − , so that the amount of water from the treated water discharged from the packed tower 58 in the subsequent stage is high. Purity NaHCO 3 can be recovered. When the ratio of the mass (mol) of Cl − ions to the mass (mol) of all carbonates excluding free carbonic acid is 2 or more, the pH of the water associated with resource mining is set to 7.0 or more and 8.0 or less. By adjusting, most of the total carbonic acid contained in the water associated with resource mining is HCO 3 − , so that more NaHCO 3 with high purity can be obtained from the treated water discharged from the packed column 58 at the subsequent stage. It can be recovered. On the other hand, as the ratio of the substance amount (mole) of Cl − ions to the substance amount (mole) of all carbonic substances excluding free carbonic acid becomes smaller than 2, the pH of the water associated with resource mining is 6.5 to 8.5 It is adjusted to the range to become difficult to proceed the reaction of the above formula (3), Cl to treated water discharged from the packed tower 58 - incorporation of ions becomes large. However, the amount of HCO 3 − with respect to Cl − ions can be reduced by lowering the pH of the water associated with resource mining from the above range and converting the carbon dioxide in the resource mining accompanying water to free carbonic acid. The reaction of the above formula (3) is likely to proceed. In addition, by setting the pH of the water associated with resource mining within the above range, the reaction of the above formula (3) can be promoted by the nature of the anion exchange resin that performs ion exchange at a low pH. Therefore, Cl to treated water - mixing of ions is reduced, can be recovered NaHCO 3 in high purity from the treated water.
　参考例では、高純度のＮａＨＣＯ３を回収するためには、資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が小さいほど、資源採掘随伴水のｐＨを低くすればよいが、以下の基準でｐＨ調整することが好ましい。資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が２以上であれば、ｐＨ調整塔５２にて資源採掘随伴水のｐＨを６．５以上～８．５以下に調整することが好ましく、７．０以上～８．０以下に調整することがより好ましく、資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が２未満であれば、ｐＨ調整塔５２にて資源採掘随伴水のｐＨを５．６以上～６．５未満の範囲に調整することが好ましい。さらに、資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が２未満～１以上であれば、ｐＨ調整塔５２にて資源採掘随伴水のｐＨを６．０以上～６．５未満の範囲に調整することが好ましく、資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が１未満であれば、ｐＨ調整塔５２にて資源採掘随伴水のｐＨを５．６以上～６．０未満の範囲に調整することが好ましい。 In the reference example, in order to recover high-purity NaHCO 3 , the lower the ratio of the amount of Cl − ions to the amount of all carbonates excluding free carbonic acid in the resource extraction associated water, the lower the pH of the resource extraction associated water. However, it is preferable to adjust the pH based on the following criteria. If the ratio of the amount of Cl − ions to the total amount of carbonic acid material excluding free carbonic acid in the resource extraction associated water is 2 or more, the pH adjustment tower 52 sets the pH of the resource extraction associated water to 6.5 to 8 is preferably adjusted to .5 or less, more preferably adjusted to 7.0 or more and 8.0 or less, relative to the amount of substance of all carbon materials except for free carbon dioxide of resource extraction associated water Cl - of the amount of substance of ions If the ratio is less than 2, the pH adjustment tower 52 preferably adjusts the pH of the water associated with resource mining to a range of 5.6 or more and less than 6.5. Further, if the ratio of the amount of Cl 2 − ions to the amount of all carbonates excluding free carbonic acid in the water associated with resource mining is less than 2 to 1 or more, the pH adjustment tower 52 adjusts the pH of the water associated with resource mining to 6 It is preferable to adjust to a range of from 0.0 to less than 6.5, and if the ratio of the amount of Cl − ions to the amount of all carbonates excluding free carbonic acid in the water associated with resource mining is less than 1, pH adjustment It is preferable to adjust the pH of the water associated with resource mining to a range of 5.6 to less than 6.0 in the tower 52.
　図４を用いてｐＨ調整工程を具体的に説明すると、排水貯留槽４６内のＮａＣｌ及び炭酸物質を含む資源採掘随伴水が、排水ポンプ５０ａにより排水流入ライン４８ａに送液される。排水流入ライン４８ａを通る資源採掘随伴水中のＣｌ－イオンの物質量（モル）がＣｌ－イオンセンサ６４により測定され、資源採掘随伴水中のアルカリ度がアルカリ度計６８により測定される。測定されたＣｌ－イオンの物質量及びアルカリ度が制御部７２に送信される。制御部７２では、アルカリ度とｐＨに基づいて、遊離炭酸を除く全炭酸物質の物質量（ｍｏｌ／Ｌ）が算出される（＝Ｍアルカリ度／１００，０００－１０（ｐＨ－１４））。そして、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比（Ｃｌ－イオン／遊離炭酸を除く全炭酸物質）が求められる。そして、ｐＨ調整塔５２に供給された資源採掘随伴水に、ブロワ５４からガス流入ライン５６を通してｐＨ調整塔５２に供給されたＣＯ２ガス又は空気を接触させ、資源採掘随伴水のｐＨが調整される。参考例では、ｐＨ調整塔５２から排出される資源採掘随伴水のｐＨが、排水流入ライン４８ｂに設置されたｐＨセンサ７０により測定され、その測定値が制御部７２に送信される。そして、ｐＨ調整塔５２から排出された資源採掘随伴水のｐＨが、資源採掘随伴水中の遊離炭酸を除く全炭酸物質（ＨＣＯ３ －、ＣＯ３ ２－）の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比に応じて調整されるｐＨを満たしていない場合は、そのｐＨ範囲を満たすように、制御部７２によりブロワ５４等の出力等が制御され、ＣＯ２ガス又は空気の供給量が調節される。参考例では、資源採掘随伴水のｐＨを下げる場合には、ＣＯ２ガスを供給し（又は後述するＨＣｌ等を添加）、資源採掘随伴水のｐＨを上げる場合には、空気を供給（又は後述するＮａＯＨ等を添加）する。なお、ＣＯ２ガスを用いる場合には、後述するイオン交換樹脂の再生に利用する消石灰（Ｃａ（ＯＨ）２）や石灰石（ＣａＣＯ３）を燃焼して製造する際に副生されるＣＯ２を利用しても良いし、現地で得られるメタンガスなどを燃焼して得られるＣＯ２ガスを利用してもよい。 The pH adjustment process will be described in detail with reference to FIG. 4. The resource mining accompanying water containing NaCl and carbonated material in the drainage storage tank 46 is sent to the drainage inflow line 48a by the drainage pump 50a. Cl of resource extraction associated water through the drainage inlet line 48a - substance amount of ions (mol) of Cl - is measured by the ion sensor 64, the alkalinity of the resource extraction associated water is measured by the alkalinity meter 68. Measured Cl - amount of substance and alkalinity ions are transmitted to the control unit 72. Based on the alkalinity and pH, the control unit 72 calculates the amount (mol / L) of the total carbonic acid substance excluding free carbonic acid (= M alkalinity / 100,000-10 (pH-14) ). Then, the ratio of the substance amount of Cl − ions to the substance amount of the total carbonic substances excluding free carbonic acid (Cl − ions / total carbonic acid substances excluding free carbonic acid) is obtained. Then, CO 2 gas or air supplied from the blower 54 to the pH adjusting tower 52 through the gas inflow line 56 is brought into contact with the resource mining accompanying water supplied to the pH adjusting tower 52 to adjust the pH of the resource mining accompanying water. The In the reference example, the pH of the resource extraction accompanying water discharged from the pH adjustment tower 52 is measured by the pH sensor 70 installed in the drainage inflow line 48 b, and the measured value is transmitted to the control unit 72. Further, the pH of the water associated with resource mining discharged from the pH adjusting tower 52 is Cl − ion with respect to the amount (mole) of the total carbonic substances (HCO 3 − , CO 3 2− ) excluding free carbonic acid in the water associated with resource mining. When the pH adjusted according to the ratio of the amount of substance (mol) is not satisfied, the output of the blower 54 and the like is controlled by the control unit 72 so as to satisfy the pH range, and the CO 2 gas or air The supply amount is adjusted. In the reference example, when lowering the pH of the water associated with resource mining, CO 2 gas is supplied (or added with HCl or the like described later), and when increasing the pH of the water associated with resource mining, air is supplied (or later described). NaOH to be added). In the case of using a CO 2 gas, a CO 2 that by-product produced when burning the lime to be used for regeneration of the ion exchange resin described later (Ca (OH) 2) and limestone (CaCO 3) It may be used, or CO 2 gas obtained by burning methane gas obtained locally.
＜ＮａＨＣＯ３を回収する回収工程＞
　参考例では、前述したようにｐＨ調整されたＮａＣｌ及び炭酸物質を含む資源採掘随伴水を陰イオン交換樹脂に通水し、上記式（３）の反応でＮａＣｌをＮａＨＣＯ３に交換し、ＮａＨＣＯ３を回収する回収工程を実施する。陰イオン交換樹脂はＨ２ＣＯ３型の弱塩基性イオン交換樹脂であることが好ましく、Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂であることがより好ましい。以下Ｈ２ＣＯ３型の弱塩基性アクリル系イオン交換樹脂を例として説明する。Ｈ２ＣＯ３型の弱塩基性イオン交換樹脂は、回収工程前に、弱塩基性イオン交換樹脂を充填した充填塔５８に、純水等に炭酸を溶解した炭酸溶解水を通水し、Ｈ２ＣＯ３型に変換することによって得られる。炭酸の溶解については、ガス吸収塔などを用いて、純水等にＣＯ２ガスを溶解させる方法等が挙げられる。ＣＯ２ガスは、メタンガスの燃焼や、ＣａＣＯ３からＣａ（ＯＨ）２を製造する際に副生したＣＯ２ガスを使用することが望ましい。 <Recovery process for recovering NaHCO 3 >
In the reference example, as described above, pH-adjusted NaCl and carbonated water containing resource mining accompanying water is passed through an anion exchange resin, NaCl is exchanged for NaHCO 3 by the reaction of the above formula (3), and NaHCO 3 A recovery process is performed to recover the. Preferably the anion exchange resin is a H 2 CO 3 type weakly basic ion-exchange resin, and more preferably H 2 CO 3 type weakly basic acrylic ion exchange resin. Hereinafter, an H 2 CO 3 type weakly basic acrylic ion exchange resin will be described as an example. The H 2 CO 3 type weakly basic ion exchange resin is passed through a packed tower 58 filled with a weakly basic ion exchange resin before the recovery step, by passing carbonate-dissolved water in which carbonic acid is dissolved in pure water or the like. Obtained by conversion to 2 CO 3 type. Examples of the dissolution of carbonic acid include a method of dissolving CO 2 gas in pure water or the like using a gas absorption tower or the like. As the CO 2 gas, it is desirable to use CO 2 gas produced as a by-product when methane gas is burned or Ca (OH) 2 is produced from CaCO 3 .
　図４を用いて回収工程を具体的に説明すると、排水流入ライン４８ｂを流れるＮａＣｌ及び炭酸物質を含み、ｐＨ調整された資源採掘随伴水が、排水ポンプ５０ｂにより、陰イオン交換樹脂を充填した充填塔５８に供給される。充填塔５８内では、陰イオン交換樹脂により、Ｃｌ－が吸着され、処理水排出ライン６０からＮａＨＣＯ３を含む処理水が排出され、処理水槽６２に貯留される。処理水槽６２に貯留されたＮａＨＣＯ３を含む処理水は、その後、エバポレータ等による濃縮装置７４により濃縮され、ドライヤー等の乾燥装置７６により乾燥処理される。参考例における回収工程では、処理水排出ライン６０または処理水槽６２に設置したＣｌ－イオンセンサ６６により、処理水中のＣｌ－イオン濃度をモニタリングし、Ｃｌ－イオン濃度が上昇したら直ちに終了することが望ましい。例えば、Ｃｌ－イオンセンサ６６の測定データが制御部７２に送られ、Ｃｌ－イオン濃度が上昇した段階で、制御部７２により、排水ポンプ５０ｂ等の稼働停止するように電子制御されていてもよいし、作業者がＣｌ－イオンセンサ６６の測定データをチェックして、Ｃｌ－イオン濃度が上昇した段階で、手動で排水ポンプ５０ｂ等の稼働を停止してもよい。 The recovery process will be described in detail with reference to FIG. 4. The resource extraction accompanying water containing NaCl and carbonated material flowing through the drainage inflow line 48 b and adjusted in pH is filled with anion exchange resin by the drainage pump 50 b. Feeded to column 58. In the packed column 58, Cl − is adsorbed by the anion exchange resin, and treated water containing NaHCO 3 is discharged from the treated water discharge line 60 and stored in the treated water tank 62. The treated water containing NaHCO 3 stored in the treated water tank 62 is then concentrated by a concentrating device 74 such as an evaporator and dried by a drying device 76 such as a dryer. The recovery process in the reference example, Cl was placed in the treated water discharge line 60 or processed water tank 62 - by ion sensor 66, Cl in the treated water - monitoring the ion concentration, Cl - it is desirable that the ion concentration immediately terminated Once raised . For example, the measurement data of the Cl − ion sensor 66 may be sent to the control unit 72, and electronic control may be performed by the control unit 72 to stop the operation of the drainage pump 50b and the like when the Cl − ion concentration increases. and the worker Cl - checks the measurement data of the ion sensor 66, Cl - at the stage where the ion concentration is increased, may be stopped operation such as manual drainage pump 50b.
　参考例において使用する陰イオン交換樹脂はアクリル系の第三アミン形の官能基を持った陰イオン交換樹脂であることが好ましく、例えば、アンバーライトＩＲＡ－６７を使用するのが好適である。回収工程における資源採掘随伴水の通水ＳＶは、０．５～１０（１／ｈ）程度とすることが好適である。 The anion exchange resin used in the Reference Example is preferably an anion exchange resin having an acrylic tertiary amine type functional group, and for example, Amberlite IRA-67 is preferably used. It is preferable that the water SV associated with resource mining in the recovery process is about 0.5 to 10 (1 / h).
　参考例では、充填塔５８に供給される資源採掘随伴水のｐＨを資源採掘随伴水中の遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比に応じて調整しているため、充填塔５８内では、陰イオン交換樹脂により効率よくＣｌ－が吸着され、高い純度のＮａＨＣＯ３を回収することが可能となる。 In the reference example, the pH of the water associated with resource mining supplied to the packed tower 58 is adjusted in accordance with the ratio of the amount of Cl − ions to the amount of the total carbonaceous material excluding free carbonic acid in the water associated with resource mining. In the packed column 58, Cl − is efficiently adsorbed by the anion exchange resin, and it becomes possible to recover NaHCO 3 with high purity.
　図５は、参考例に係る溶解塩類回収装置の構成の他の一例を示す概略構成図である。図５に示す溶解塩類回収装置３において、図４に示す溶解塩類回収装置２と同様の構成については同一の符号を付し、その説明を省略する。図５に示すように、溶解塩類回収装置３は、ＨＣｌ貯留槽７８、ＨＣｌ添加ライン８０、ＨＣｌポンプ８２、ｐＨ調整槽８４、を備える。図５に示すように、ｐＨ調整槽８４内にはｐＨセンサ７０が設置されている。また、ｐＨ調整槽８４内には、攪拌装置（不図示）が設置されることが望ましい。 FIG. 5 is a schematic configuration diagram showing another example of the configuration of the dissolved salt recovery apparatus according to the reference example. In the dissolved salt recovery apparatus 3 shown in FIG. 5, the same components as those of the dissolved salt recovery apparatus 2 shown in FIG. As shown in FIG. 5, the dissolved salt recovery apparatus 3 includes an HCl storage tank 78, an HCl addition line 80, an HCl pump 82, and a pH adjustment tank 84. As shown in FIG. 5, a pH sensor 70 is installed in the pH adjustment tank 84. In addition, it is desirable that a stirring device (not shown) is installed in the pH adjustment tank 84.
　図５に示すように、排水流入ライン４８ａの一端は排水貯留槽４６に接続され、他端はｐＨ調整槽８４に接続されている。また、ＨＣｌ添加ライン８０の一端はＨＣｌ貯留槽７８に接続され、他端はｐＨ調整槽８４に接続されている。また、排水流入ライン４８ｂの一端はｐＨ調整槽８４に接続され、他端は充填塔５８の上部に接続されている。排水流入ライン４８ｂには、排水ポンプ５０ｂが設置されている。処理水排出ライン６０の一端は、充填塔５８の底部に接続され、他端は処理水槽６２に接続されている。 As shown in FIG. 5, one end of the drainage inflow line 48 a is connected to the drainage storage tank 46, and the other end is connected to the pH adjustment tank 84. One end of the HCl addition line 80 is connected to the HCl storage tank 78, and the other end is connected to the pH adjustment tank 84. One end of the drainage inflow line 48 b is connected to the pH adjustment tank 84, and the other end is connected to the upper part of the packed tower 58. A drainage pump 50b is installed in the drainage inflow line 48b. One end of the treated water discharge line 60 is connected to the bottom of the packed tower 58, and the other end is connected to the treated water tank 62.
　排水流入ライン４８ａ、ｐＨ調整槽８４、ＨＣｌ貯留槽７８、ＨＣｌ添加ライン８０、ＨＣｌポンプ８２は、資源採掘随伴水のｐＨを調整するｐＨ調整装置として機能するものである。ｐＨ調整装置は、資源採掘随伴水のｐＨを調整する構成を備えていれば、上記の構成に制限されるものではない。 The drainage inflow line 48a, the pH adjustment tank 84, the HCl storage tank 78, the HCl addition line 80, and the HCl pump 82 function as a pH adjustment device that adjusts the pH of the water associated with resource mining. The pH adjusting device is not limited to the above configuration as long as it has a configuration for adjusting the pH of the resource mining accompanying water.
　以下、参考例の溶解塩類回収装置３の動作について説明する。 Hereinafter, the operation of the dissolved salt recovery apparatus 3 of the reference example will be described.
　ＮａＣｌ及び炭酸物質を含む資源採掘随伴水は、前述したように、排水貯留槽４６に供給される前に前処理工程、濃縮工程を行うことが望ましい。そして、排水貯留槽４６内のＮａＣｌ及び炭酸物質を含む資源採掘随伴水が、排水流入ライン４８ａを通る際に、資源採掘随伴水中のＣｌ－イオンの物質量（モル）がＣｌ－イオンセンサ６４により測定され、資源採掘随伴水中のアルカリ度がアルカリ度計６８により測定される。測定されたＣｌ－イオンの物質量及びアルカリ度が制御部７２に送信される。制御部７２では、アルカリ度とｐＨに基づいて、遊離炭酸を除く全炭酸物質の物質量（ｍｏｌ／Ｌ）が算出される（＝Ｍアルカリ度／１００，０００－１０（ｐＨ－１４））。そして、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比（Ｃｌ－イオン／遊離炭酸を除く全炭酸物質）が求められる。そして、資源採掘随伴水がｐＨ調整槽８４に供給されると共に、ＨＣｌポンプ８２によりＨＣｌ貯留槽７８内のＨＣｌ溶液がＨＣｌ添加ライン８０からｐＨ調整槽８４に供給され、資源採掘随伴水のｐＨが調整される。参考例では、ｐＨ調整槽８４内に設置されたｐＨセンサ７０により、資源採掘随伴水のｐＨが測定され、その測定値が制御部７２に送信される。ｐＨ調整槽８４内の資源採掘随伴水のｐＨが、資源採掘随伴水中の遊離炭酸を除く全炭酸物質（ＨＣＯ３ －、ＣＯ３ ２－）の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比に応じて調整されるｐＨを満たしていない場合は、そのｐＨ範囲を満たすように、制御部７２によりＨＣｌポンプ８２等の出力等が制御され、ＨＣｌの供給量が調節される。資源採掘随伴水中の遊離炭酸を除く全炭酸物質（ＨＣＯ３ －、ＣＯ３ ２－）の物質量（モル）に対するＣｌ－イオンの物質量（モル）の比に応じて調整される資源採掘随伴水のｐＨについては前述した通りである。 As described above, it is desirable to perform the pretreatment process and the concentration process on the resource extraction accompanying water containing NaCl and the carbonate substance before being supplied to the drainage storage tank 46. Then, resource extraction produced water containing NaCl and carbonate material in the waste water storage tank 46, it passes through the drainage inlet line 48a, Cl of resource extraction accompanying water - the amount of substance of ions (mol) of Cl - by ion sensor 64 The alkalinity in the water associated with resource mining is measured by an alkalinometer 68. Measured Cl - amount of substance and alkalinity ions are transmitted to the control unit 72. Based on the alkalinity and pH, the control unit 72 calculates the amount (mol / L) of the total carbonic acid substance excluding free carbonic acid (= M alkalinity / 100,000-10 (pH-14) ). Then, the ratio of the substance amount of Cl − ions to the substance amount of the total carbonic substances excluding free carbonic acid (Cl − ions / total carbonic acid substances excluding free carbonic acid) is obtained. Then, the resource mining accompanying water is supplied to the pH adjusting tank 84, and the HCl solution in the HCl storage tank 78 is supplied from the HCl addition line 80 to the pH adjusting tank 84 by the HCl pump 82, and the pH of the resource mining accompanying water is set. Adjusted. In the reference example, the pH sensor 70 installed in the pH adjusting tank 84 measures the pH of the water associated with resource mining and transmits the measured value to the control unit 72. The pH of the water associated with resource mining in the pH adjustment tank 84 is such that the amount of Cl − ion relative to the amount (mole) of the total carbonic substances (HCO 3 − , CO 3 2− ) excluding free carbonic acid in the resource mining accompanying water ( When the pH adjusted according to the ratio of (mol) is not satisfied, the output of the HCl pump 82 and the like are controlled by the controller 72 so as to satisfy the pH range, and the supply amount of HCl is adjusted. Resource mining associated water adjusted according to the ratio of the mass (mol) of Cl − ions to the mass (mol) of all carbonic substances (HCO 3 − , CO 3 2− ) excluding free carbonic acid in the resource mining associated water The pH is as described above.
　参考例では、ｐＨ調整にＨＣｌを用いているが、資源採掘随伴水のｐＨを調整するものであればこれに制限されるものではなく、例えば、炭酸水等の酸剤を用いることも可能である。また、ＨＣｌ等の酸剤は、資源採掘随伴水のｐＨを下げるために用いるものであって、資源採掘随伴水のｐＨを上げる場合には、ＮａＯＨ等のアルカリ剤を用いることが必要である。 In the reference example, HCl is used for pH adjustment, but it is not limited to this as long as it adjusts the pH of water associated with resource mining. For example, an acid agent such as carbonated water can be used. is there. The acid agent such as HCl is used for lowering the pH of the water associated with resource mining, and it is necessary to use an alkaline agent such as NaOH when the pH of the water associated with resource mining is increased.
　ｐＨ調整槽８４内でｐＨ調整された資源採掘随伴水は、排水ポンプ５０ｂにより、陰イオン交換樹脂を充填した充填塔５８に供給される。充填塔５８内では、陰イオン交換樹脂により、Ｃｌ－が吸着され、処理水排出ライン６０からＮａＨＣＯ３を含む処理水が排出され、処理水槽６２に貯留される。処理水槽６２に貯留されたＮａＨＣＯ３を含む処理水は、その後、エバポレータ等による濃縮装置７４により濃縮され、ドライヤー等の乾燥装置７６により乾燥処理される。参考例における回収工程では、処理水排出ライン６０あるいは処理水槽６２に設置したＣｌ－イオンセンサ６６により、処理水中のＣｌ－イオン濃度をモニタリングし、Ｃｌ－イオン濃度が上昇したら直ちに終了することが望ましい。例えば、Ｃｌ－イオンセンサ６６の測定データが制御部７２に送られ、Ｃｌ－イオン濃度が上昇した段階で、制御部７２により、排水ポンプ５０ｂ等の稼働を停止するように電子制御されていてもよいし、作業者がＣｌ－イオンセンサ６６の測定データをチェックして、Ｃｌ－イオン濃度が上昇した段階で、手動で排水ポンプ５０ｂ等の稼働を停止してもよい。 The resource extraction accompanying water whose pH is adjusted in the pH adjusting tank 84 is supplied to the packed tower 58 filled with the anion exchange resin by the drain pump 50b. In the packed column 58, Cl − is adsorbed by the anion exchange resin, and treated water containing NaHCO 3 is discharged from the treated water discharge line 60 and stored in the treated water tank 62. The treated water containing NaHCO 3 stored in the treated water tank 62 is then concentrated by a concentrating device 74 such as an evaporator and dried by a drying device 76 such as a dryer. In the recovery process in the reference example, it is desirable that the Cl − ion concentration in the treated water is monitored by the Cl 2 − ion sensor 66 installed in the treated water discharge line 60 or the treated water tank 62, and is immediately terminated when the Cl 2 − ion concentration increases. . For example, even if the measurement data of the Cl − ion sensor 66 is sent to the control unit 72 and the Cl − ion concentration is increased, the control unit 72 is electronically controlled to stop the operation of the drain pump 50b and the like. good to the worker Cl - checks the measurement data of the ion sensor 66, Cl - at the stage where the ion concentration is increased, may be stopped operation such as manual drainage pump 50b.
　次に、ＮａＨＣＯ３を回収した後における、陰イオン交換樹脂の再生処理について説明する。 Next, the anion exchange resin regeneration process after the recovery of NaHCO 3 will be described.
　図６は、再生処理を行う際の溶解塩類回収装置の構成の一例を示す概略構成図である。図６に示すように、溶解塩類回収装置（２，３）は、Ｃａ（ＯＨ）２貯留槽８６、Ｃａ（ＯＨ）２流入ライン８８、Ｃａ（ＯＨ）２ポンプ９０、ブロワ９２、空気流入ライン９４、再生処理液排出ライン９８、再生処理液貯留槽３８ａ、を備えるものである。なお、Ｃａ（ＯＨ）２貯留槽８６内には攪拌装置（不図示）が設置されていることが望ましい。参考例では、後述する再生処理を実施する際には、充填塔５８から図４又は５に示す構成部品を取り外し、充填塔５８に図６に示す構成部品を設置してもよいし、ＮａＨＣＯ３の回収及び再生処理を通して、充填塔５８に図４又は５、及び図６に示す構成部品を充填塔５８に設置していてもよい。 FIG. 6 is a schematic configuration diagram illustrating an example of a configuration of a dissolved salt recovery apparatus when performing a regeneration process. As shown in FIG. 6, the dissolved salt recovery device (2, 3) includes a Ca (OH) 2 storage tank 86, a Ca (OH) 2 inflow line 88, a Ca (OH) 2 pump 90, a blower 92, and an air inflow line. 94, a regeneration processing liquid discharge line 98, and a regeneration processing liquid storage tank 38a. It is desirable that a stirring device (not shown) is installed in the Ca (OH) 2 storage tank 86. In the reference example, in practicing the regeneration process described below, remove the components shown in FIG. 4 or 5 from the packed tower 58, may be equipped with components shown in FIG. 6 in the packed column 58, NaHCO 3 The components shown in FIG. 4 or 5 and FIG. 6 may be installed in the packed tower 58 through the recovery and regeneration process.
　また、図６に示すように、Ｃａ（ＯＨ）２流入ライン８８の一端はＣａ（ＯＨ）２貯留槽８６に接続され、他端は充填塔５８の上部に接続されている。Ｃａ（ＯＨ）２流入ライン８８にはＣａ（ＯＨ）２ポンプ９０が設置されている。空気流入ライン９４の一端は、ブロワ９２に接続され、他端は充填塔５８の下部側面に接続されている。再生処理液排出ライン９８の一端は充填塔５８の下部側面に接続され、他端は再生処理液貯留槽３８ａに接続されている。 As shown in FIG. 6, one end of the Ca (OH) 2 inflow line 88 is connected to the Ca (OH) 2 storage tank 86, and the other end is connected to the upper portion of the packed tower 58. The Ca (OH) 2 inlet line 88 Ca (OH) 2 pump 90 is installed. One end of the air inflow line 94 is connected to the blower 92, and the other end is connected to the lower side surface of the packed tower 58. One end of the regeneration processing liquid discharge line 98 is connected to the lower side surface of the packed tower 58, and the other end is connected to the regeneration processing liquid storage tank 38a.
　図６に示す再生処理を行う際の溶解塩類回収装置（２，３）の動作について説明する。 The operation of the dissolved salt recovery apparatus (2, 3) when performing the regeneration process shown in FIG. 6 will be described.
＜再生工程＞
　参考例では、上記回収工程においてＨＣｌが吸着した陰イオン交換樹脂にＣａ（ＯＨ）２溶液（以下、Ｃａ（ＯＨ）２スラリーと呼ぶ場合がある）を通水して、上記式（４）の反応で、陰イオン交換樹脂からＨＣｌを脱離させ、陰イオン交換樹脂を再生する再生工程を実施する。なお、再生工程前には、充填塔５８に純水を通水し、陰イオン交換樹脂間の間隙に滞留している資源採掘随伴水を洗い流すことが望ましい。 <Regeneration process>
In the reference example, a Ca (OH) 2 solution (hereinafter sometimes referred to as Ca (OH) 2 slurry) is passed through the anion exchange resin to which HCl has been adsorbed in the recovery step, and the above formula (4) In the reaction, a regeneration step is performed in which HCl is desorbed from the anion exchange resin to regenerate the anion exchange resin. Prior to the regeneration step, it is desirable to pass pure water through the packed tower 58 and wash away the water associated with resource mining that is retained in the gap between the anion exchange resins.
　図６を用いて再生工程を具体的に説明すると、Ｃａ（ＯＨ）２ポンプ９０を稼働させ、Ｃａ（ＯＨ）２貯留槽８６内のＣａ（ＯＨ）２スラリーがＣａ（ＯＨ）２流入ライン８８から充填塔５８に供給されると共に、ブロワ９２を稼働させ、空気が空気流入ライン９４を通り、充填塔５８に供給される。充填塔５８内では、空気により、陰イオン交換樹脂が攪拌されながらＣａ（ＯＨ）２スラリーと接触することにより、陰イオン交換樹脂からＨＣｌが脱離され、ＣａＣｌ２が生成される。そして、再生処理液が再生処理液排出ライン９８から再生処理液貯留槽３８ａに供給される。再生処理液中には、ＣａＣｌ２やＣａ（ＯＨ）２等が含まれており、必要に応じて、濃縮装置７４及び乾燥装置７６に送られる。 Specifically explaining a reproduction process with reference to FIG. 6, Ca (OH) operate the second pump 90, Ca (OH) 2 Ca in the storage tank 86 (OH) 2 slurry Ca (OH) 2 inlet line 88 Is supplied to the packed tower 58 and the blower 92 is operated, and the air is supplied to the packed tower 58 through the air inflow line 94. In the packed tower 58, HCl is desorbed from the anion exchange resin and CaCl 2 is generated by contacting the Ca (OH) 2 slurry with air while stirring the anion exchange resin. Then, the regeneration processing liquid is supplied from the regeneration processing liquid discharge line 98 to the regeneration processing liquid storage tank 38a. The regeneration treatment liquid contains CaCl 2 , Ca (OH) 2, etc., and is sent to the concentrating device 74 and the drying device 76 as necessary.
　このような再生工程は、充填塔５８内の樹脂を攪拌しながらＣａ（ＯＨ）２スラリーを所定条件まで徐々に添加し、一定時間反応後、再生処理液を充填塔５８から排出させる回分式で行っても良い。また、Ｃａ（ＯＨ）２スラリーを充填塔５８に通水し再生処理液を連続的に排出させる連続式で行っても良い。スラリーに覆われた陰イオン交換樹脂上で式（４）の反応をより効率的に進める観点等から、陰イオン交換樹脂を攪拌しながらＣａ（ＯＨ）２スラリーを所定量まで徐々に添加する回分式のほうが望ましい。 Such a regeneration step is a batch type in which the Ca (OH) 2 slurry is gradually added to a predetermined condition while stirring the resin in the packed column 58 and the reaction solution is discharged from the packed column 58 after a predetermined time of reaction. You can go. Alternatively, the Ca (OH) 2 slurry may be passed through the packed tower 58 to continuously discharge the regeneration treatment liquid. From the viewpoint of more efficiently advancing the reaction of formula (4) on the anion exchange resin covered with the slurry, a batch of gradually adding the Ca (OH) 2 slurry to a predetermined amount while stirring the anion exchange resin. The formula is preferred.
　Ｃａ（ＯＨ）２スラリーの濃度は、回分式で使用する場合は５～１０％が好適であり、連続式で使用する場合は、０．０５～０．５％が好適である。 The concentration of the Ca (OH) 2 slurry is preferably 5 to 10% when used in a batch system and 0.05 to 0.5% when used in a continuous system.
　充填塔５８内の陰イオン交換樹脂を攪拌するための流体は、空気に限定されるものではなく、式（４）の反応を阻害しない流体であればよく、例えばメタンガス等が挙げられる。 The fluid for stirring the anion exchange resin in the packed tower 58 is not limited to air, and may be any fluid that does not inhibit the reaction of the formula (4), and examples thereof include methane gas.
　再生工程では、未溶解のＣａ（ＯＨ）２がＣａ２＋とＯＨ－に溶解してから、ＯＨ－が陰イオン交換樹脂上のＨＣｌと再生反応を起こすので、添加したＣａ（ＯＨ）２が再生に十分に使われるのに数分～１０分程度の時間を要する場合があるため、回分式でのＣａ（ＯＨ）２スラリーの添加はその時間を見込んで間欠的に行うことが好ましい。 In the regeneration step, undissolved Ca (OH) 2 is Ca 2+ and OH - from the dissolved, OH - because cause regeneration reaction with HCl on an anion exchange resin, the added Ca (OH) 2 is reproduced In some cases, it takes a time of several minutes to 10 minutes to be fully used in the process. Therefore, it is preferable that the addition of the Ca (OH) 2 slurry in a batch system is performed intermittently in consideration of the time.
　以下、実施例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
（実施例１及び比較例）
　ＣＳＧ資源採掘随伴水模擬水に、前処理工程としてＳＳ除去を目的とした凝集加圧浮上分離とＵＦ膜を用いた膜ろ過を行い、さらに、濃縮工程として逆浸透膜による濃縮（１０倍濃縮）を行った。前処理工程及び濃縮工程後のＣＳＧ資源採掘随伴水模擬水（以下、被処理水と呼ぶ）の水質を表１にまとめた。 (Example 1 and comparative example)
CSG resources mining accompanying simulated water is subjected to coagulation pressure flotation separation for the purpose of SS removal and membrane filtration using a UF membrane as a pretreatment step, and further concentration using a reverse osmosis membrane (concentration by 10 times) Went. Table 1 summarizes the water quality of CSG resource mining accompanying simulated water (hereinafter referred to as treated water) after the pretreatment process and the concentration process.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　弱塩基性アクリル系陰イオン交換樹脂（オルガノ社製、アンバーライトＩＲＡ－６７）を０．２Ｌ充填した充填塔に、ＣＯ２ガス曝気塔で調製したＣＯ２溶解水を通水し、弱塩基性陰イオン交換樹脂をＨ２ＣＯ３型に変換した（上記式（２）の反応を参照）。ここで、充填塔に流入する前のＣＯ２溶解水の無機炭素濃度、充填塔から流出した流出水の無機炭素濃度を測定し、流出水の無機炭素濃度が流入前のＣＯ２溶解水の無機炭素濃度と同等になるまで、ＣＯ２溶解水の通水を継続し、０．２ＬのＩＲＡ－６７が有する交換容量０．３２ｍｏｌ全量をＨ２ＣＯ３型（Ｒ３Ｎ－Ｈ２ＣＯ３）に変換させた。このＨ２ＣＯ３型に変換した弱塩基性陰イオン交換樹脂を充填した充填塔を６つ（以下、６系列）準備した。 Weakly basic acrylic anion exchange resin (manufactured by Organo Corporation, Amberlite IRA-67) to a packed tower filled 0.2 L, it was passed through the CO CO 2 dissolved water prepared with 2 gas aeration tower, weakly basic The anion exchange resin was converted to H 2 CO 3 type (see reaction of formula (2) above). Here, the inorganic carbon concentration of the CO 2 -dissolved water before flowing into the packed tower and the inorganic carbon concentration of the effluent discharged from the packed tower are measured, and the inorganic carbon concentration of the effluent water is the inorganic concentration of CO 2 -dissolved water before flowing in. Continue to pass the CO 2 -dissolved water until it becomes equal to the carbon concentration, and 0.2 L of IRA-67 has a total exchange capacity of 0.32 mol of H 2 CO 3 type (R 3 N—H 2 CO 3 ). Converted to. Six packed towers (hereinafter referred to as 6 series) packed with the weakly basic anion exchange resin converted into H 2 CO 3 type were prepared.
　各系列の充填塔への被処理水（２１℃）の通水を開始し、通水中の被処理水と、充填塔から排出された処理水のＣｌ－イオン濃度を計測した。通水初期から処理水のＣｌ－イオン濃度は１８０ｍｇ／Ｌ（０．００５ｍｏｌ／Ｌ）以下であったが、通水量３６０ｍＬの時に処理水のＣｌ－イオン濃度が２００ｍｇ／Ｌ（０．００６ｍｏｌ／Ｌ）に上昇し、その時点で通水を停止した。このときＣｌ－イオン吸着量は０．１４０ｍｏｌと推定された。この処理水をエバポレータによる減圧濃縮及びホットプレート（７０℃）による蒸発乾固を行ってＮａＨＣＯ３を含む溶解塩類を析出させた。ここで、析出物を再度純水に微量溶解し、Ｃｌ－イオン濃度を測定して、析出物中のＣｌ－イオン含有量を確認したところ、重量で０．１％未満であり、高純度のＮａＨＣＯ３が回収できていることを確認した。 Start the water flow of the water to be treated (21 ° C.) to a packed column of each series, the water to be treated passing water, Cl of the treated water discharged from the packed tower - ion concentration was measured. Cl from passing water early in the treated water - ion the concentration was less than 180mg / L (0.005mol / L) , the treated water at the time of passing water 360 mL Cl - ion concentration of 200mg / L (0.006mol / L The water flow stopped at that time. In this case Cl - ion adsorption amount was estimated to be 0.140 mol. This treated water was concentrated under reduced pressure using an evaporator and evaporated to dryness using a hot plate (70 ° C.) to precipitate dissolved salts containing NaHCO 3 . Here, a small amount of the precipitate was dissolved again in pure water, and the Cl - ion concentration was measured to confirm the Cl - ion content in the precipitate. It was confirmed that NaHCO 3 was recovered.
　各系列の充填塔内の弱塩基性陰イオン交換樹脂量の５倍量の純水を充填塔に通水し、充填塔内を洗浄した。洗浄後、樹脂塔内に空気を曝気して、弱塩基性陰イオン交換樹脂を流動させた状態で、５ｗ／ｖ％のＣａ（ＯＨ）２スラリーを間欠的に添加しながら、充填塔内に設置したｐＨセンサ及びＣｌ－イオンセンサで再生処理液のｐＨ及びＣｌ－イオン濃度を測定した。 Pure water of 5 times the amount of weakly basic anion exchange resin in the packed tower of each series was passed through the packed tower to wash the packed tower. After washing, aeration of air into the resin tower and in a state where the weakly basic anion exchange resin is flowed, 5 w / v% Ca (OH) 2 slurry is intermittently added to the packed tower. installation was pH sensor and Cl - were measured ion concentration - pH and Cl regeneration treatment liquid ion sensor.
　６系列の充填塔を用い、再生処理液のｐＨが９．８（実施例１－１：第１系列）、１０．０（実施例１－２：第２系列）、１０．５（実施例１－３：第３系列）、１１．７（実施例１－４：第４系列）、１２．０（実施例１－５：第５系列）に達した時点、及び１２．２に達してから更にＣａ（ＯＨ）２を０．０１８ｍｏｌ添加（比較例：第６系列）して、再生廃液を取り出し（以下、「第一段階再生処理液」と称する）、エバポレータによる減圧濃縮及びホットプレート（７０℃）による蒸発乾固を行って、ＣａＣｌ２を含む溶解塩類を析出させた。析出物を再度純水に微量溶解し、Ｃａ２＋とＣｌ－濃度を測定して、析出物中の両元素のモル比を確認した。その結果を表２にまとめた。なお、比較例はこの時点で既に完全に再生されている状態である。 Using 6 series packed towers, the pH of the regenerated solution is 9.8 (Example 1-1: 1st series), 10.0 (Example 1-2: 2nd series), 10.5 (Example) 1-3: Third series), 11.7 (Example 1-4: Fourth series), 12.0 (Example 1-5: Fifth series), and 12.2 Then, 0.018 mol of Ca (OH) 2 was added (comparative example: 6th series), and the regenerated waste liquid was taken out (hereinafter referred to as “first stage regenerated solution”), vacuum concentrated by an evaporator, and hot plate ( (70 ° C.) was evaporated to dryness, and dissolved salts containing CaCl 2 were precipitated. A small amount of the precipitate was dissolved again in pure water, and the Ca 2+ and Cl − concentrations were measured to confirm the molar ratio of both elements in the precipitate. The results are summarized in Table 2. Note that the comparative example is already completely reproduced at this point.
　その後、実施例１－１～１－５には、充填塔内の弱塩基性陰イオン交換樹脂が十分浸る量（１３０ｍＬ）の純水を導入し、空気曝気で樹脂を流動させながらＣａ（ＯＨ）２スラリーを添加した。再生開始からのＣａ（ＯＨ）２スラリー添加量が比較例と同じ量になるまで添加した。また、このときのｐＨが１２．２になっていることを確認した。 Thereafter, in Examples 1-1 to 1-5, pure water was introduced in an amount sufficient to allow the weakly basic anion exchange resin in the packed tower to be immersed (130 mL), and Ca (OH) was allowed to flow while the resin was flowing by air aeration. 2 Slurries were added. The addition of Ca (OH) 2 slurry from the start of regeneration was continued until the same amount as in the comparative example. Moreover, it confirmed that pH at this time was set to 12.2.
　実施例１－１～１－５では、Ｃａ（ＯＨ）２スラリーを追加添加した後の再生処理液（以下、「第二段階再生処理液」と称する）を取り出し、エバポレータによる減圧蒸留による濃縮及びホットプレートによる蒸発乾固を行って、Ｃａ（ＯＨ）２を含む溶解塩類を析出させた。析出物を再度純水に微量溶解し、Ｃａ２＋とＣｌ－濃度を測定して、析出物中の両元素のモル比を確認した。その結果を表２にまとめた。 In Examples 1-1 to 1-5, the regeneration treatment liquid after the additional addition of the Ca (OH) 2 slurry (hereinafter referred to as “second-stage regeneration treatment liquid”) is taken out, concentrated by vacuum distillation using an evaporator, and Evaporation to dryness by a hot plate was performed to precipitate dissolved salts containing Ca (OH) 2 . A small amount of the precipitate was dissolved again in pure water, and the Ca 2+ and Cl − concentrations were measured to confirm the molar ratio of both elements in the precipitate. The results are summarized in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　ＣａＣｌ２のＣａ２＋とＣｌ－のモル比は１：２であるので、実施例１－１～１－５及び比較例の析出物のＣｌ／Ｃａｍｏｌ比が２に近いほど再生処理液中のＣａＣｌ２の純度が高く、値が小さいほどＣａＣｌ２の純度が低いことになる。そこで、表２の結果を見ると、比較例では、析出物のＣｌ／Ｃａｍｏｌ比が１．４６と低かったのに対し、完全再生前で一旦Ｃａ（ＯＨ）２添加を停止し、第一段階再生処理液として再生処理液を取り出した実施例１－１～１－５では、Ｃｌ／Ｃａｍｏｌ比が１．８６以上であった。このＣｌ／Ｃａｍｏｌ比１．８６は、重量換算すると、ＣａＣｌ２純度９５．２％であり、不純物としてＣａ（ＯＨ）２を４．２％しか含まないことになる。また、ｐＨ１１．７以下（Ｃｌ脱離率９５％）の実施例１－１～１－４では、Ｃｌ／Ｃａｍｏｌ比が１．９５以上となっている。このＣｌ／Ｃａｍｏｌ比は、重量換算すると、ＣａＣｌ２純度９８．３％であり、不純物としてＣａ（ＯＨ）２を１．７％しか含まないことになる。すなわち、第一段階再生処理液のｐＨが低いほど、あるいはＣｌ脱離率が低いほど、再生処理液から回収されるＣａＣｌ２の純度は高くなる傾向にある。但し、第一段階再生処理液のｐＨが低いほど、あるいはＣｌ脱離率が低いほど、第二段階再生処理液を回収する場合には、第二段階再生処理液の量が多くなる傾向にあるため、貯留設備が大きくなることが予測される。 Ca 2+ of CaCl 2 and Cl - molar ratio of 1: since it is 2, Cl / Camol ratio of Examples 1-1 to 1-5 and Comparative Examples precipitates in more reproduction processing solution near 2 CaCl The higher the purity of 2 and the lower the value, the lower the purity of CaCl 2 . Therefore, looking at the results in Table 2, in the comparative example, the Cl / Camol ratio of the precipitate was as low as 1.46, whereas the addition of Ca (OH) 2 was temporarily stopped before the complete regeneration. In Examples 1-1 to 1-5 in which the regeneration treatment solution was taken out as the regeneration treatment solution, the Cl / Camol ratio was 1.86 or more. This Cl / Camol ratio of 1.86 has a CaCl 2 purity of 95.2% in terms of weight, and contains only 4.2% of Ca (OH) 2 as an impurity. In Examples 1-1 to 1-4 having a pH of 11.7 or less (Cl desorption rate of 95%), the Cl / Camol ratio is 1.95 or more. This Cl / Camol ratio, when converted to weight, has a CaCl 2 purity of 98.3%, and contains only 1.7% of Ca (OH) 2 as an impurity. That is, the lower the pH of the first stage regeneration treatment solution or the lower the Cl desorption rate, the higher the purity of CaCl 2 recovered from the regeneration treatment solution. However, the lower the pH of the first stage regeneration treatment liquid or the lower the Cl desorption rate, the more the amount of the second stage regeneration treatment liquid tends to increase when the second stage regeneration treatment liquid is recovered. Therefore, it is predicted that the storage facility will become large.
　以上の結果から、ＮａＣｌを含有する資源採掘随伴水から、ＣａＣｌ２を高純度で得ることができることが確認された。ＣａＣｌ２を高純度で回収するためには、再生処理液のｐＨを計測、またはＣｌ－イオン濃度を計測してＣｌ脱離量を求め、それらが予め定めた設定値に達するまでに回収した再生処理液を濃縮・乾燥させる、すなわちＣａＣｌ２純度が比較的高い再生処理液からＣａＣｌ２を得られるようにする必要があることがわかった。その設定値の範囲としては、ｐＨ計測の場合、ｐＨ１０．０～１２．０の間に設定すること、Ｃｌ－イオン濃度計測の場合、Ｃｌ－イオン吸着量の８５～９６％の間に設定することが好ましい。 From the above results, it was confirmed that CaCl 2 can be obtained with high purity from water associated with resource mining containing NaCl. In order to recover CaCl 2 with high purity, the pH of the regeneration treatment solution is measured, or the Cl − ion concentration is measured to determine the amount of Cl desorption, and the regeneration recovered until they reach a predetermined set value. It has been found that it is necessary to concentrate and dry the treatment liquid, that is, to obtain CaCl 2 from a regeneration treatment liquid having a relatively high CaCl 2 purity. The range of the set value is set between pH 10.0 and 12.0 in the case of pH measurement, and between 85 and 96% of the Cl − ion adsorption amount in the case of Cl − ion concentration measurement. It is preferable.
（実施例２）
　実施例２では、ＣＳＧ資源採掘随伴水模擬水を樹脂塔に通水しＮａＨＣＯ３を回収し、純水で洗浄するまで実施例１と同様の操作を行った。その後、充填塔に、再生処理液のｐＨ及びＣｌ－イオン濃度を測定しながら、実施例１－４で得られた第二段階再生処理液（ＣａＣｌ２の純度は低い）を間欠的に添加した。第二段階再生処理液を全て使用した後、５ｗ／ｖ％のＣａ（ＯＨ）２スラリーを間欠的に添加した。そして、再生処理液のｐＨが１１．７に達した時点で、充填塔内の再生処理液を取り出した。取り出した再生処理液（第一段階再生処理液）は、エバポレータによる減圧蒸留による濃縮及びホットプレートによる蒸発乾固を行って、ＣａＣｌ２を含む溶解塩類を析出させた。析出物を再度純水に微量溶解しＣａ２＋とＣｌ－濃度を測定して、析出物中の両元素のモル比を確認した。 (Example 2)
In Example 2, the same operation as in Example 1 was performed until CSG resource mining accompanying water simulated water was passed through the resin tower, NaHCO 3 was collected, and washed with pure water. Thereafter, the packed column, pH and Cl regeneration treatment solution - while measuring the ion concentration, and the second stage regeneration process liquid obtained in Example 1-4 (purity CaCl 2 is low) intermittently added . After using all of the second stage regeneration solution, 5 w / v% Ca (OH) 2 slurry was added intermittently. Then, when the pH of the regeneration treatment solution reached 11.7, the regeneration treatment solution in the packed tower was taken out. The reclaimed reprocessing solution (first stage regenerating solution) was concentrated by vacuum distillation with an evaporator and evaporated to dryness with a hot plate to precipitate dissolved salts containing CaCl 2 . A small amount of the precipitate was dissolved again in pure water, and the Ca 2+ and Cl − concentrations were measured to confirm the molar ratio of both elements in the precipitate.
　次に、充填塔内に純水を導入し、Ｃａ（ＯＨ）２スラリーを間欠的に添加し、再生処理液のｐＨを測定し、Ｃａ（ＯＨ）２スラリーを加えてもｐＨが１２．２以上に上がらない状態とした。この段階の再生処理液（第二段階再生処理液）を充填塔から取り出し、第二段階再生処理液中のＣｌ－イオンを計測した。そして、第一段階再生処理液のＣｌ－イオン脱離量と合わせた総Ｃｌ脱離率を算出し、完全に再生できたことを確認した。 Next, pure water is introduced into the packed tower, Ca (OH) 2 slurry is added intermittently, the pH of the regenerated solution is measured, and even if Ca (OH) 2 slurry is added, the pH is 12.2. It was set as the state which does not go up more. The regeneration solution at this stage (second stage regeneration solution) was taken out from the packed tower, and Cl 2 − ions in the second stage regeneration solution were measured. Then, Cl in the first stage regeneration treatment liquid - was confirmed that calculates the total Cl desorption rate combined with ion desorption amount, it could be completely reproduced.
　実施例２の結果としては、ｐＨ１１．７に達した時点で取り出した第一段階再生処理液を濃縮・蒸発乾固させて得られた析出物のＣｌ／Ｃａｍｏｌ比は１．９６であり、ＣａＣｌ２を高純度で回収できることが確認できた。第一段階再生後、完全再生まで（再生処理液のｐＨが１２．２になるまで）更に新規のＣａ（ＯＨ）２を添加したが、第一段階再生で添加したＣａ（ＯＨ）２も含め完全再生までに添加した新規のＣａ（ＯＨ）２量は０．０７１ｍｏｌ（０．１４２ｅｑ）であり、被処理水の通水で吸着したＣｌ－イオン量(０．１４０ｍｏｌ＝０．１４０ｅｑ)とほぼ等量であった。完全再生には、表２の比較例でＣａ（ＯＨ）２０．１００ｍｏｌを要しているように、本来Ｃｌ－イオン吸着量よりも多いＣａ（ＯＨ）２が必要だが、前のサイクルの再生における第二段階再生処理液を再生剤として使用することにより、１回の再生当たりに使用する新規のＣａ（ＯＨ）２量は、Ｃｌ－イオンの吸着量とほぼ等量で済むことが確認できた。 As a result of Example 2, the Cl / Camol ratio of the precipitate obtained by concentrating and evaporating and drying the first stage regenerating solution taken out when the pH reached 11.7 was 1.96, and CaCl It was confirmed that 2 could be recovered with high purity. After the first stage regeneration, until complete regeneration (until the pH of the regeneration treatment solution reaches 12.2), new Ca (OH) 2 was further added, including Ca (OH) 2 added in the first stage regeneration. The amount of new Ca (OH) 2 added until complete regeneration is 0.071 mol (0.142 eq), which is almost equal to the amount of Cl 2 − ion (0.140 mol = 0.140 eq) adsorbed by passing water to be treated. It was equivalent. The complete regeneration, as required Ca (OH) 2 0.100 mol in Comparative Example in Table 2, originally Cl - but must often Ca (OH) 2 than ion adsorption amount, regeneration of the previous cycle By using the second-stage regeneration treatment solution in Fig. 2 as a regenerant, it can be confirmed that the amount of new Ca (OH) 2 used per regeneration is almost equal to the adsorption amount of Cl - ions. It was.
　また、Ｃａ（ＯＨ）２とともに、第二段階再生処理液を再生剤として使用しても、ＣａＣｌ２を高純度で回収することができることが確認できた。その結果、必要最小限のＣａ（ＯＨ）２の添加で、弱塩基性陰イオン交換樹脂の再生が可能であり、Ｃａ（ＯＨ）２のロス・廃棄がほとんどなく、再生に関わるランニングコストを低減できることが示された。 Further, it was confirmed that CaCl 2 can be recovered with high purity even when the second stage regeneration treatment liquid is used as a regenerant together with Ca (OH) 2 . As a result, it is possible to regenerate weakly basic anion exchange resin with the minimum amount of Ca (OH) 2 added, and there is almost no loss or disposal of Ca (OH) 2 , reducing the running cost related to regeneration. It was shown that it can be done.
（参考例１～５の模擬排水）
　参考例１～５では、表３に示す組成の模擬排水を調整した。模擬排水中のＣｌ－濃度、各炭酸濃度は、実際の資源採掘随伴水に前処理・濃縮工程を実施したあとの濃度として想定される範囲内の値とした。 (Simulated drainage of Reference Examples 1-5)
In Reference Examples 1 to 5, simulated waste water having the composition shown in Table 3 was prepared. The Cl − concentration and each carbonic acid concentration in the simulated waste water were values within the range assumed as the concentration after the pretreatment / concentration process was performed on the actual resource extraction accompanying water.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（参考例１）
　ｐＨ９．５の模擬排水にＣＯ２ガスを吹き込んで、ｐＨ６．７～９に調整した模擬排水、及び比較のためＣＯ２ガスを吹き込まず、ｐＨ９．５の模擬排水を、弱塩基性アクリル系イオン交換樹脂（オルガノ社製、アンバーライトＩＲＡ－６７、交換容量１．６ｅｑ／Ｌ－Ｒ）を２００ｍＬ充填した充填塔に通水した。なお、充填塔の弱酸性アクリル系イオン交換樹脂は、あらかじめＣＯ２溶解水を通水して、弱塩基性イオン交換樹脂の全量をＨ２ＣＯ３型に変換した状態にしてから、上記模擬排水をＳＶ１．０（１／ｈ）で通水した。充填塔から排出された処理水のＨＣＯ３ －、ＣＯ３ ２－、Ｃｌ－の濃度を測定し、これら合計アニオンの総量が延べ０．２当量になった時点で、模擬排水の通水を停止した。Ｎａ＋イオン濃度、処理水ｐＨを確認し、得られた処理水のＮａＨＣＯ３、Ｎａ２ＣＯ３、ＮａＣｌ、ＮａＯＨ濃度をもとに、濃縮・乾燥で固形物として析出させた場合のＮａＨＣＯ３の純度及び回収量を求めた。その結果を表４にまとめた。ここで、処理水中に含有されるＮａＨＣＯ３濃度はＨＣＯ３ －濃度（ｍｏｌ／Ｌ）から求めた。ＨＣＯ３ －濃度はＭアルカリ度とＰアルカリ度を測定して求めた。
［ＮａＨＣＯ３］（ｇ／Ｌ）＝［ＨＣＯ３ －］（ｍｏｌ／Ｌ）×（８４／６１）
［ＨＣＯ３ －］（ｍｏｌ／Ｌ）＝Ｍアルカリ度－Ｐアルカリ度（ｍｏｌ／Ｌ）
　またＮａＨＣＯ３濃度は、ＣＯ３ ２－濃度から求め、ＣＯ３ ２－濃度はＭアルカリ度とｐＨから求めた。
［Ｎａ２ＣＯ３］（ｇ／Ｌ）＝［ＣＯ３ ２－］（ｍｏｌ／Ｌ）×（１０６／６０）
［ＣＯ３ ２－］＝２×（Ｍアルカリ度－１０（ｐＨ－１４））（ｍｏｌ／Ｌ）
　また、模擬排水１ＬあたりのＮａＨＣＯ３回収量（ｇ／Ｌ）は、濃縮乾燥後の析出物量×純度（％）で算出した。 (Reference Example 1)
by blowing CO 2 gas into the simulated wastewater pH 9.5, adjusted simulated wastewater in pH 6.7 ~ 9, and not blown CO 2 gas for comparison, the simulated wastewater pH 9.5, weakly basic acrylic ion Water was passed through a packed tower packed with 200 mL of an exchange resin (Amberlite IRA-67, manufactured by Organo Corporation, exchange capacity 1.6 eq / LR). The weakly acidic acrylic ion exchange resin in the packed tower is preliminarily supplied with CO 2 dissolved water so that the entire amount of the weak basic ion exchange resin is converted to H 2 CO 3 type. Was passed through with SV1.0 (1 / h). Measure the concentration of HCO 3 − , CO 3 2− , and Cl − in the treated water discharged from the packed tower, and stop the simulated waste water flow when the total amount of these total anions reaches 0.2 equivalents. did. The Na + ion concentration and the pH of the treated water were confirmed. Based on the NaHCO 3 , Na 2 CO 3 , NaCl, and NaOH concentrations of the obtained treated water, the concentration of NaHCO 3 when precipitated as a solid by concentration and drying. Purity and recovery were determined. The results are summarized in Table 4. Here, NaHCO 3 concentration contained in the treated water HCO 3 - were determined from the concentration (mol / L). HCO 3 - concentration was determined by measuring the M alkalinity and P alkalinity.
[NaHCO 3 ] (g / L) = [HCO 3 − ] (mol / L) × (84/61)
[HCO 3 − ] (mol / L) = M alkalinity−P alkalinity (mol / L)
The NaHCO 3 concentration is determined from the CO 3 2- concentrations, CO 3 2- concentrations were determined from the M alkalinity and pH.
[Na 2 CO 3 ] (g / L) = [CO 3 2− ] (mol / L) × (106/60)
[CO 3 2− ] = 2 × (M alkalinity−10 (pH−14)) (mol / L)
Moreover, the amount of NaHCO 3 recovered per liter of simulated waste water (g / L) was calculated by the amount of precipitate after concentration and drying × purity (%).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３及び表４から分かるように、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が６．０の模擬排水では、ＣＯ２ガスでｐＨを６．７～８．５の範囲で調整することにより、純度の高いＮａＨＣＯ３を高収量で回収できた。特に、ｐＨ６．７～８．０ではより純度が高く、より高収量でＮａＨＣＯ３を回収することができた。 Table 3 and as can be seen from Table 4, Cl to substances of total carbonate material except free carbon dioxide - in the simulated wastewater in the ratio of the amount of substance of ions 6.0, 6.7 pH with CO 2 gas to 8. By adjusting in the range of 5, high-purity NaHCO 3 could be recovered in high yield. In particular, at a pH of 6.7 to 8.0, the purity was higher and NaHCO 3 could be recovered with a higher yield.
（参考例２）
　ｐＨ６．０の模擬排水に空気を吹き込んで、ｐＨ６．５～８．４に調整した模擬排水、及び比較のため空気を吹き込まず、ｐＨ６．０の模擬排水を用いたこと以外は、参考例１と同様に行った。参考例２の結果を表５にまとめた。 (Reference Example 2)
Reference Example 1 except that the simulated drainage was adjusted to pH 6.5 to 8.4 by blowing air into the simulated drainage at pH 6.0, and the simulated drainage at pH 6.0 was used without comparison. As well as. The results of Reference Example 2 are summarized in Table 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表３及び表５から分かるように、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が６．０の模擬排水では、空気でｐＨを６．５～８．４の範囲で調整することにより、純度の高いＮａＨＣＯ３を高収量で回収できた。特に、ｐＨ６．５～８．０ではより純度が高く、より高収量でＮａＨＣＯ３を回収することができた。 As can be seen from Tables 3 and 5, in the simulated waste water in which the ratio of the amount of Cl − ions to the amount of all carbonates excluding free carbonic acid is 6.0, the pH is 6.5 to 8.4 with air. By adjusting within the range, NaHCO 3 with high purity could be recovered in high yield. In particular, at a pH of 6.5 to 8.0, the purity was higher and NaHCO 3 could be recovered with a higher yield.
（参考例３）
　ｐＨ９．５の模擬排水にＣＯ２ガスを吹き込んで、ｐＨ６．４～８．０に調整した模擬排水、及び比較のためＣＯ２ガスを吹き込まず、ｐＨ９．５の模擬排水を用いたこと以外は、参考例１と同様に行った。参考例３の結果を表６にまとめた。 (Reference Example 3)
by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 6.4 ~ 8.0, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1. The results of Reference Example 3 are summarized in Table 6.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表３及び表６から分かるように、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオの物質量の比が２．０の模擬排水では、ＣＯ２ガスでｐＨを６．４～８．０の範囲で調整することにより、純度の高いＮａＨＣＯ３を高収量で回収できた。特に、ｐＨ６．７～８．０ではより純度が高く、より高収量でＮａＨＣＯ３を回収することができた。 Table 3 and as can be seen from Table 6, Cl to substances of total carbonate material except free carbon dioxide - Io in the simulated wastewater in the ratio of amount of substance is 2.0, 6.4 pH with CO 2 gas to 8. By adjusting within the range of 0, highly pure NaHCO 3 could be recovered in high yield. In particular, at a pH of 6.7 to 8.0, the purity was higher and NaHCO 3 could be recovered with a higher yield.
（参考例４）
　ｐＨ９．５の模擬排水にＣＯ２ガスを吹き込んで、ｐＨ６．１～８．０に調整した模擬排水、及び比較のためＣＯ２ガスを吹き込まず、ｐＨ９．５の模擬排水を用いたこと以外は、参考例１と同様に行った。参考例４の結果を表７にまとめた。 (Reference Example 4)
by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 6.1 ~ 8.0, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1. The results of Reference Example 4 are summarized in Table 7.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表３及び表７から分かるように、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が１．５の模擬排水では、ＣＯ２ガスでｐＨを６．１～６．７の範囲で調整することにより、純度の高いＮａＨＣＯ３を高収量で回収できた。特に、ｐＨ６．１で、より純度の高いＮａＨＣＯ３を回収できた。 As can be seen from Tables 3 and 7, in the simulated waste water in which the ratio of the amount of Cl 2 − ions to the amount of all carbonates excluding free carbonic acid is 1.5, the pH is adjusted to 6.1 to 6. with CO 2 gas. By adjusting within the range of 7, high purity NaHCO 3 could be recovered in high yield. In particular, NaHCO 3 with higher purity could be recovered at pH 6.1.
（参考例５）
　ｐＨ９．５の模擬排水にＣＯ２ガスを吹き込んで、ｐＨ５．８～６．５に調整した模擬排水、及び比較のためＣＯ２ガスを吹き込まず、ｐＨ９．５の模擬排水を用いたこと以外は、参考例１と同様に行った。参考例５の結果を表８にまとめた。 (Reference Example 5)
by blowing CO 2 gas into the simulated wastewater pH9.5, adjusted simulated wastewater in pH 5.8 ~ 6.5, and not blown CO 2 gas for comparison, except for using simulated waste water pH9.5 This was carried out in the same manner as in Reference Example 1. The results of Reference Example 5 are summarized in Table 8.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表３及び表８から分かるように、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオンの物質量の比が０．９の模擬排水では、ＣＯ２ガスでｐＨを５．８～６．５の範囲で調整することにより、純度の高いＮａＨＣＯ３を高収量で回収できた。特に、ｐＨ５．８で、より純度の高いＮａＨＣＯ３を回収できた。 As can be seen from Tables 3 and 8, in the simulated waste water in which the ratio of the amount of Cl 2 − ions to the amount of all carbonates excluding free carbonic acid is 0.9, the pH is 5.8 to 6.5 with CO 2 gas. By adjusting in the range of 5, high-purity NaHCO 3 could be recovered in high yield. In particular, NaHCO 3 with higher purity could be recovered at pH 5.8.
　以上、参考例１～５の結果から、資源採掘随伴水にＮａＣｌと炭酸イオン・重炭酸イオンが共存し、その含有量・存在比率が様々に変化しても、遊離炭酸を除く全炭酸物質の物質量に対するＣｌ－イオン物質量の比に応じて、資源採掘随伴水のｐＨを調整することにより、純度の高いＮａＨＣＯ３を安定的に取り出せることが確認できた。 As described above, from the results of Reference Examples 1 to 5, NaCl and carbonate ions / bicarbonate ions coexist in the water associated with resource mining, and even if the content and abundance change variously, Cl to a substance quantity - in accordance with the ratio of the ionic material quantity, by adjusting the pH of the resource extraction produced water, it was confirmed that retrieve high purity NaHCO 3 stably.
　１～３　溶解塩類回収装置、１０，４６　排水貯留槽、１２，４８ａ，４８ｂ　排水流入ライン、１４，５０ａ，５０ｂ　排水ポンプ、１６，５８　充填塔、１８，６０　処理水排出ライン、１９　積算流量計、２０，６２　処理水槽、２１，３０，３１，６４，６６　Ｃｌ－イオンセンサ、２２，８６　Ｃａ（ＯＨ）２貯留槽、２４，８８　Ｃａ（ＯＨ）２流入ライン、２６，９０　Ｃａ（ＯＨ）２ポンプ、２８，７０　ｐＨセンサ、３２，５４，９２　ブロワ、３４，９４　空気流入ライン、３６ａ，３６ｂ，９８　再生処理液排出ライン、３８ａ，３８ｂ　再生処理液貯留槽、４０，７２　制御部、４２，７４　濃縮装置、４４，７６　乾燥装置、５２　ｐＨ調整塔、５６　ガス流入ライン、６８　アルカリ度計、７８　ＨＣｌ貯留槽、８０　ＨＣｌ添加ライン、８２　ＨＣｌポンプ、８４　ｐＨ調整槽。 1 to 3 Dissolved salt recovery device, 10,46 Drainage storage tank, 12, 48a, 48b Drainage inflow line, 14, 50a, 50b Drain pump, 16,58 Packing tower, 18,60 Treated water discharge line, 19 Integrated flow meter 20, 62 Treated water tank, 21, 30, 31, 64, 66 Cl - ion sensor, 22, 86 Ca (OH) 2 storage tank, 24, 88 Ca (OH) 2 inflow line, 26, 90 Ca (OH) 2 pump, 28, 70 pH sensor, 32, 54, 92 Blower, 34, 94 Air inflow line, 36a, 36b, 98 Regeneration liquid discharge line, 38a, 38b Regeneration liquid storage tank, 40, 72 Controller, 42 , 74 Concentrator, 44,76 Dryer, 52 pH adjustment tower, 56 Gas inflow line, 68 Alkali meter, 78 HCl reservoir, 80 HCl addition line, 82 Cl pump, 84 pH adjustment tank.

Claims (14)

  1. 　ＮａＣｌを含有する資源採掘随伴水を陰イオン交換樹脂に通水し、ＮａＨＣＯ３を回収する第１回収工程と、
    　前記資源採掘随伴水通水後の陰イオン交換樹脂にＣａ（ＯＨ）２溶液を通水し、前記陰イオン交換樹脂を再生処理する再生工程と、
    　前記再生処理した再生処理液を回収する第２回収工程と、を備え、
    　前記第２回収工程では、前記再生処理した再生処理液のｐＨをモニタリングし、前記モニタリングしたｐＨ値が予め定めた設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収することを特徴とする溶解塩類の回収方法。     A first recovery step of passing water associated with resource mining containing NaCl through an anion exchange resin and recovering NaHCO 3 ;
    A regeneration step of passing the Ca (OH) 2 solution through the anion exchange resin after passing water through the resource mining and regenerating the anion exchange resin;
    A second recovery step of recovering the regenerated reprocessing solution,
    In the second recovery step, the pH of the regenerated reprocessing solution is monitored, and the regenerated processing solution recovered until the monitored pH value reaches a preset value is concentrated and dried to recover CaCl 2 . A method for recovering dissolved salts.
  2. 　ＮａＣｌを含有する資源採掘随伴水を陰イオン交換樹脂に通水し、ＮａＨＣＯ３を回収する第１回収工程と、
    　前記資源採掘随伴水通水後の陰イオン交換樹脂にＣａ（ＯＨ）２溶液を通水し、前記陰イオン交換樹脂を再生処理する再生工程と、
    　前記再生処理した再生処理液を回収する第２回収工程と、を備え、
    　前記第２回収工程では、前記再生処理した再生処理液のＣｌ－イオン濃度をモニタリングし、前記モニタリングしたＣｌ－イオン濃度に基づいて求められる前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収することを特徴とする溶解塩類の回収方法。     A first recovery step of passing water associated with resource mining containing NaCl through an anion exchange resin and recovering NaHCO 3 ;
    A regeneration step of passing the Ca (OH) 2 solution through the anion exchange resin after passing water through the resource mining and regenerating the anion exchange resin;
    A second recovery step of recovering the regenerated reprocessing solution,
    In the second recovery step, the Cl − ion concentration of the regenerated reprocessing solution is monitored, and the amount of Cl − ion desorption of the anion exchange resin determined based on the monitored Cl − ion concentration is determined in advance. A method for recovering dissolved salts, comprising recovering CaCl 2 by concentrating and drying the regenerated solution recovered until the set value is reached.
  3. 　前記第２回収工程では、前記モニタリングしたｐＨ値が予め定めた設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することを特徴とする請求項１記載の溶解塩類の回収方法。 In the second recovery step, the regenerated liquid collected after the monitored pH value reaches a predetermined set value is stored as a regenerant for regenerating the anion exchange resin. The method for recovering dissolved salts according to claim 1.
  4. 　前記第２回収工程では、前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留することを特徴とする請求項２記載の溶解塩類の回収方法。 In the second recovery step, a reprocessing solution recovered after the amount of Cl − ion desorption of the anion exchange resin reaches a predetermined set value is used as a regenerant for regenerating the anion exchange resin. The method for recovering dissolved salts according to claim 2, wherein the method is stored.
  5. 　前記予め定めた設定値を前記Ｃａ（ＯＨ）２溶液のｐＨとし、前記モニタリングしたｐＨが、前記Ｃａ（ＯＨ）２溶液のｐＨに達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記モニタリングしたｐＨが、前記Ｃａ（ＯＨ）２溶液のｐＨに達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留する請求項３記載の溶解塩類の回収方法。 The predetermined set value as the pH of the Ca (OH) 2 solution, pH was the monitoring, the Ca (OH) 2 concentration of the regeneration process liquid collected to reach the pH of the solution and dried CaCl 2 The reprocessing solution collected after the monitored pH reaches the pH of the Ca (OH) 2 solution is stored as a regenerant for regenerating the anion exchange resin. Method for recovering dissolved salts.
  6. 　前記予め定めた設定値をｐＨ１０～１２の間に設定し、前記モニタリングしたｐＨが、ｐＨ１０～１２の間に設定した設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記モニタリングしたｐＨが、ｐＨ１０～１２の間に設定した設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留する請求項３記載の溶解塩類の回収方法。 The preset set value is set between pH 10 and 12, and the regenerated solution collected until the monitored pH reaches the set value set between pH 10 and 12 is concentrated and dried to obtain CaCl 2 . The reclaimed treatment liquid collected and collected after the monitored pH reaches a set value set between pH 10 and 12 is stored as a regenerant for regenerating the anion exchange resin. Method for recovering dissolved salts.
  7. 　前記予め定めた設定値を前記第１回収工程における前記陰イオン交換樹脂のＣｌ－イオン吸着量とし、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留する請求項４記載の溶解塩類の回収方法。 Wherein said anion exchange resin a predetermined set value in the first collecting step Cl - ion adsorption amount and then, Cl of the anion exchange resin - ion elimination amount, the anion exchange resin of the Cl - ion adsorption The regenerated solution collected until reaching the amount was concentrated and dried to recover CaCl 2, and the amount of Cl − ion desorption of the anion exchange resin reached the amount of Cl − ion adsorption of the anion exchange resin. The method for recovering a dissolved salt according to claim 4, wherein a reprocessing solution recovered later is stored as a regenerating agent for regenerating the anion exchange resin.
  8. 　前記予め定めた設定値を前記陰イオン交換樹脂のＣｌ－イオン脱離量の８５～９６％の間に設定し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量の８５～９６％の間に設定した設定値に達するまでに回収した再生処理液を濃縮及び乾燥してＣａＣｌ２を回収し、前記陰イオン交換樹脂のＣｌ－イオン脱離量が、前記陰イオン交換樹脂のＣｌ－イオン吸着量の８５～９６％の間に設定した設定値に達した後に回収した再生処理液を、前記陰イオン交換樹脂を再生処理するための再生剤として貯留する請求項４記載の溶解塩類の回収方法。 The predetermined set value is set between 85 and 96% of the Cl − ion desorption amount of the anion exchange resin, and the Cl − ion desorption amount of the anion exchange resin is The regenerated solution collected until reaching a set value set between 85 and 96% of the Cl − ion adsorption amount is concentrated and dried to recover CaCl 2, and the Cl − ion desorption amount of the anion exchange resin is recovered. Is used as a regenerating agent for regenerating the anion exchange resin, after the recovery solution recovered after reaching a set value set between 85 and 96% of the Cl − ion adsorption amount of the anion exchange resin. The method for recovering a dissolved salt according to claim 4 to be stored.
  9. 　陰イオン交換樹脂を充填した充填塔と、
    　ＮａＣｌを含有する資源採掘随伴水を前記充填塔に通水し、ＮａＨＣＯ３を回収する第１回収手段と、
    　Ｃａ（ＯＨ）２溶液を前記充填塔に通水し、前記陰イオン交換樹脂を再生処理する再生手段と、
    　前記再生処理した再生処理液のｐＨをモニタリングするｐＨセンサと、
    　前記モニタリングしたｐＨ値が予め定めた設定値に達するまでの再生処理液を回収する第２回収手段と、
    　前記回収した再生処理液を濃縮する濃縮手段と、
    　前記濃縮した再生処理液を乾燥する乾燥手段と、を備えることを特徴とする溶解塩類の回収装置。     A packed tower filled with an anion exchange resin;
    A first recovery means for recovering NaHCO 3 by passing water associated with resource mining containing NaCl through the packed tower;
    A regeneration means for passing the Ca (OH) 2 solution through the packed tower and regenerating the anion exchange resin;
    A pH sensor for monitoring the pH of the regenerated reprocessing solution;
    A second recovery means for recovering the regeneration treatment liquid until the monitored pH value reaches a predetermined set value;
    A concentration means for concentrating the recovered regeneration treatment solution;
    And a drying means for drying the concentrated reclaimed processing solution.
  10. 　　陰イオン交換樹脂を充填した充填塔と、
    　ＮａＣｌを含有する資源採掘随伴水を前記充填塔に通水し、ＮａＨＣＯ３を回収する第１回収手段と、
    　Ｃａ（ＯＨ）２溶液を前記充填塔に通水し、前記陰イオン交換樹脂を再生処理する再生手段と、
    　前記再生処理した再生処理液のＣｌ－イオン濃度をモニタリングするＣｌ－イオンセンサと、
    　前記モニタリングしたＣｌ－イオン濃度に基づいて求められる前記陰イオン交換樹脂のＣｌ－イオン脱離量が予め定めた設定値に達するまでの再生処理液を回収する第２回収手段と、
    　前記回収した再生処理液を濃縮する濃縮手段と、
    　前記濃縮した再生処理液を乾燥する乾燥手段と、を備えることを特徴とする溶解塩類の回収装置。     A packed tower filled with an anion exchange resin;
    A first recovery means for recovering NaHCO 3 by passing water associated with resource mining containing NaCl through the packed tower;
    A regeneration means for passing the Ca (OH) 2 solution through the packed tower and regenerating the anion exchange resin;
    An ion sensor, - Cl monitoring the ion concentration - Cl of the reproduction process reproduction processing solution
    A second recovery means for recovering the regenerated liquid until a Cl − ion desorption amount of the anion exchange resin determined based on the monitored Cl − ion concentration reaches a predetermined set value;
    A concentration means for concentrating the recovered regeneration treatment solution;
    And a drying means for drying the concentrated reclaimed processing solution.
  11. 　塩酸と結合したイオン交換樹脂に水酸化カルシウム溶液を接触させて塩化カルシウムを含む処理液を取得しつつ該処理液の塩化カルシウム純度を監視することを開始する第１ステップと、
    前記塩化カルシウム純度が予め決められた基準純度より高い状態から低い状態になるまでに前記処理液の取得を停止する第２ステップと、
    　取得された処理液から前記塩化カルシウムを得る第３ステップとを含む、塩化カルシウムの製造方法。     A first step of starting monitoring the calcium chloride purity of the treatment liquid while obtaining a treatment liquid containing calcium chloride by contacting a calcium hydroxide solution with an ion exchange resin combined with hydrochloric acid;
    A second step of stopping the acquisition of the treatment liquid until the calcium chloride purity is lowered from a state higher than a predetermined reference purity;
    And a third step of obtaining the calcium chloride from the obtained treatment liquid.
  12. 　前記第２ステップの前に前記基準純度に対応する規定値を設定することを含み、
    　前記第２ステップにおいて前記規定値に基づいて前記処理液の取得を停止する、請求項１１に記載の塩化カルシウムの製造方法。     Setting a specified value corresponding to the reference purity before the second step,
    The method for producing calcium chloride according to claim 11, wherein acquisition of the treatment liquid is stopped based on the specified value in the second step.
  13. 　前記規定値は、前記塩化カルシウム純度が前記基準純度であるときの前記処理液のｐＨであり、
    　前記塩化カルシウム純度の監視は、前記処理液のｐＨを測定することである、請求項１２に記載の塩化カルシウムの製造方法。     The specified value is the pH of the treatment liquid when the calcium chloride purity is the reference purity,
    The method for producing calcium chloride according to claim 12, wherein the calcium chloride purity is monitored by measuring a pH of the treatment liquid.
  14. 　前記規定値は、前記塩化カルシウム純度が前記基準純度であるときの前記イオン交換樹脂の塩素イオン脱離量であり、
    　前記塩化カルシウム純度の監視は、前記処理液の塩素イオン濃度を測定すること、測定された塩素イオン濃度に基づいて前記塩素イオン脱離量を算出することを含む、請求項１２に記載の塩化カルシウムの製造方法。     The specified value is a chlorine ion desorption amount of the ion exchange resin when the calcium chloride purity is the reference purity,
    The calcium chloride purity monitoring according to claim 12, wherein the monitoring of the calcium chloride purity includes measuring a chlorine ion concentration of the treatment liquid and calculating the chlorine ion desorption amount based on the measured chlorine ion concentration. Manufacturing method.
PCT/JP2013/084992 2012-12-28 2013-12-26 Recovery method for dissolved salt, recovery device for dissolved salt, and production method for calcium chloride WO2014104248A1 (en)

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WO2022141423A1 (en) * 2020-12-31 2022-07-07 Veolia (China) Environment Services Co., Ltd Method for treating organic compounds from industrial wastewaters with resins

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US20220119295A1 (en) * 2019-02-05 2022-04-21 Arizona Board Of Regents On Behalfof Arizona State University System and method of water rejuvenation for the regeneration of sorbent filters
WO2022141423A1 (en) * 2020-12-31 2022-07-07 Veolia (China) Environment Services Co., Ltd Method for treating organic compounds from industrial wastewaters with resins

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