WO2014104248A1 - Procédé de récupération de sel dissous, dispositif de récupération de sel dissous, et procédé de production de chlorure de calcium - Google Patents

Procédé de récupération de sel dissous, dispositif de récupération de sel dissous, et procédé de production de chlorure de calcium 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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English (en)
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/ja
Priority claimed from JP2013048097A external-priority patent/JP6163326B2/ja
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/fr

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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

L'invention concerne un procédé de récupération d'un sel dissous dans lequel : une eau contenant du NaCl provenant de l'extraction de ressource est passée à travers une tour garnie (16) qui est remplie par une résine échangeuse d'anions de façon à récupérer NaHCO3 ; une solution de Ca(OH)2 est passée à travers la tour garnie (16) après que l'eau provenant de l'extraction de ressource a été passée à travers celle-ci ; le traitement de régénération est effectué sur la résine échangeuse d'anions à l'intérieur de la tour garnie (16) ; le pH d'un liquide de traitement de régénération utilisé dans le traitement de régénération est surveillé lors de la récupération dudit liquide de traitement de régénération ; et le liquide de traitement de régénération récupéré est concentré et séché de façon à récupérer CaCl2 jusqu'à ce que la valeur de pH surveillée atteigne une valeur de réglage préréglée. Comme résultat, il est possible de récupérer du CaCl2 contenant un minimum d'impuretés à partir de l'eau provenant de l'extraction de ressource.
PCT/JP2013/084992 2012-12-28 2013-12-26 Procédé de récupération de sel dissous, dispositif de récupération de sel dissous, et procédé de production de chlorure de calcium WO2014104248A1 (fr)

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JP2012-287988 2012-12-28
JP2012287988A JP6159527B2 (ja) 2012-12-28 2012-12-28 炭酸水素ナトリウムの製造方法及び炭酸水素ナトリウムの製造装置
JP2013-048097 2013-03-11
JP2013048097A JP6163326B2 (ja) 2013-03-11 2013-03-11 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

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (fr) * 2020-12-31 2022-07-07 Veolia (China) Environment Services Co., Ltd Procédé de traitement de composés organiques des eaux usées industrielles avec résines

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JPH07507032A (ja) * 1991-11-26 1995-08-03 ブルナー・モンド（ユーケイ）リミテッド アルカリ金属炭酸塩の製造
WO2006006497A1 (fr) * 2004-07-09 2006-01-19 Aquatech Corporation Agent absorbant l’indium et procede de separation d’indium

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Publication number Priority date Publication date Assignee Title
JPH07507032A (ja) * 1991-11-26 1995-08-03 ブルナー・モンド（ユーケイ）リミテッド アルカリ金属炭酸塩の製造
WO2006006497A1 (fr) * 2004-07-09 2006-01-19 Aquatech Corporation Agent absorbant l’indium et procede de separation d’indium

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (fr) * 2020-12-31 2022-07-07 Veolia (China) Environment Services Co., Ltd Procédé de traitement de composés organiques des eaux usées industrielles avec résines

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