WO2014064754A1 - ホウ素含有溶液の脱塩方法 - Google Patents
ホウ素含有溶液の脱塩方法 Download PDFInfo
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- WO2014064754A1 WO2014064754A1 PCT/JP2012/077263 JP2012077263W WO2014064754A1 WO 2014064754 A1 WO2014064754 A1 WO 2014064754A1 JP 2012077263 W JP2012077263 W JP 2012077263W WO 2014064754 A1 WO2014064754 A1 WO 2014064754A1
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- Prior art keywords
- exchange resin
- packed tower
- anion exchange
- boron
- ion
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/14—Controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/08—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic and anionic exchangers in separate beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/108—Boron compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
-
- 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 for reducing salts other than boron by using an ion exchange resin from a boron-containing solution containing anions such as chloride ions.
- boron compounds such as boric acid are contained in the plating solution and metal surface treatment solution, and cleaning wastewater containing boron is generated in factories that handle these solutions.
- the environmental standard for boron is set to 1 mg / L or less, and it is desirable to remove boron from wastewater containing boron, or to recover and purify and reuse it.
- the main impurity is a salt such as chloride ion
- the salt concentration that is, to perform a desalting treatment.
- the boron-containing wastewater has at least one of chloride ions, sulfate ions, nitrate ions, sulfite ions, and nitrite ions as anions. It is common that more than species are included.
- an ion exchange treatment that is, a method using an ion exchange resin is effective.
- an ion exchange resin for example, an H-type cation exchange resin that removes cations and an OH-type anion exchange resin that removes anions are combined to reduce the salt concentration in waste water.
- Patent Document 1 in order to treat and reuse boron-containing water having a high boron concentration, after filtering the boron-containing water, the cation exchange tower having a cation exchange resin and the anion exchange tower having an anion exchange resin are in this order. And passing through a cation exchange column, an anion exchange column and an ion exchange column having a mixed bed ion exchange resin in this order.
- Patent Document 2 describes a method for purifying a boron eluent as a type I strongly basic anion exchange resin adjusted to OH type, a type II strongly basic anion exchange resin adjusted to OH type, and a weakly basic type adjusted to OH type.
- Patent Document 3 discloses that a boron eluent is purified by connecting two stages of ion exchange towers filled with an anion exchange resin in series as a method for purifying the boron eluent.
- the boron concentration in the waste liquid generated by the regeneration treatment of the ion exchange resin that is, the boron concentration in the recycled waste liquid is preferably lower considering the influence on the environment. In short, it is desirable that boron is not adsorbed by the ion exchange resin in the desalting treatment of the boric acid-containing solution.
- boron is generally present in the form of boric acid molecules in acidic solutions, it has the property of being partially dissociated as anions (for example, borate ions) in neutral and alkaline solutions. It is adsorbed by the ion exchange resin (anion exchange resin).
- anion exchange resin anion exchange resin
- the solution is in a neutral or alkaline atmosphere near the interface with the OH type strongly basic anion exchange resin.
- boron is adsorbed on the functional group of the OH type strongly basic anion exchange resin and the boron concentration in the treated water is lowered.
- the boron concentration in the recycled waste liquid becomes high due to the adsorption of boron to the OH type strongly basic anion exchange resin.
- an object of the present invention is a desalting method for reducing salts other than boron by using an ion exchange resin from a boron-containing solution containing anions such as chloride ions, and reducing the boron concentration in treated water and It is an object of the present invention to provide a method capable of suppressing an increase in boron concentration in a recycled waste liquid.
- the desalting method of the present invention is a desalting method for reducing salts other than boron from a boron-containing solution containing at least one anion of chloride ion, nitrate ion, sulfate ion, nitrite ion and sulfite ion.
- each of the outlets of the cation exchange resin packed tower filled with the H-type strongly acidic cation exchange resin is filled with the free base type weakly basic anion exchange resin, and the liquid from the outlet of the cation exchange resin packed tower is Using an ion exchange apparatus in which a two-stage anion exchange resin packed tower that sequentially passes is arranged, the ion exchange apparatus is equipped with a desalting step for passing a boron-containing solution from the inlet of the cation exchange resin packed tower.
- the anion exchange packed column of the anion exchange resin packed column closer to the cation exchange resin packed column in the flow path of the boron-containing solution. Degrees and monitored, characterized by continuing the desalting step until detecting any break in the anion.
- a boron-containing solution is passed through an H-type strongly acidic cation exchange resin to remove cations such as calcium ions (Ca 2+ ) and sodium ions (Na + ) in the solution, and the solution liquid Makes sex acidic.
- the acidified solution is passed through a free base weakly basic anion exchange resin to remove anions such as chloride ions in the solution.
- the use of the free base type weakly basic anion exchange resin instead of the OH type strong base anion exchange resin means that if the OH type strongly basic anion exchange resin is used, a large amount of boron having low selectivity to the ion exchange resin is used. This is because they are removed.
- the boron-containing solution needs to be in an acid state before the weakly basic anion exchange resin.
- a cation exchange resin packed tower filled with an H-type strongly acidic cation exchange resin is provided in the previous stage.
- this strongly acidic cation exchange resin breaks, the liquidity of the boron-containing solution supplied to the anion exchange resin packed tower may not be kept acidic. It is preferable that the exchange capacity of the entire strong acid cation exchange resin is larger than the exchange capacity of the entire free base weakly basic anion exchange resin in the first-stage anion exchange resin packed column.
- the liquid passing is stopped. It is necessary to perform a regeneration process of the ion exchange resin.
- the flow order of the boron-containing solution may be changed between the two-stage anion exchange resin packed towers, and then the flow for the desalting treatment may be resumed.
- some of the boron that has passed through the first-stage anion exchange resin packed column may be adsorbed by the free base weakly basic anion exchange resin of the second-stage anion exchange resin packed tower.
- boron adsorbed in the second anion exchange resin packed tower before the replacement of the flow order is also passed.
- the anion exchange resin packed column is changed to the first stage by changing the liquid order, it is desorbed from the free base form weakly basic anion exchange resin. It will not be adsorbed on the anion exchange resin.
- a conductivity meter can be used for monitoring the anion concentration in the outlet liquid of the first-stage anion exchange resin packed tower.
- Ions having high selectivity with respect to anion exchange resins such as chloride ions, nitrate ions, sulfate ions, nitrite ions, and sulfite ions are easily dissociated and greatly contribute to conductivity.
- boron has a low degree of dissociation and a small contribution to conductivity.
- anion exchange can be performed by tracking the change in conductivity with a conductivity meter without directly measuring the ion concentration. It is possible to easily grasp the break state of those ions in the resin packed tower.
- each of the outlets of the cation exchange resin packed tower filled with the H-type strongly acidic cation exchange resin is filled with the free base type weakly basic anion exchange resin, and is discharged from the outlet of the cation exchange resin packed tower.
- the desalting apparatus shown in FIG. 1 implements the desalting method according to one embodiment of the present invention, and a cation packed with an H-type strongly acidic cation exchange resin as a packed tower packed with an ion exchange resin.
- An exchange resin packed tower 5 and two anion exchange resin packed towers 6 and 7 each filled with a free base weakly basic anion exchange resin are provided.
- the cation exchange resin packed tower 5 is an H-type strongly acidic cation exchanger, and the anion exchange resin packed towers 6 and 7 are free base type weakly basic anion exchangers.
- the anion exchange resin packed towers 6 and 7 are connected in series to the outlet of the cation exchange resin packed tower 5.
- a boron-containing solution containing anions such as chloride ions is used as raw water, and salts other than boron are reduced by ion exchange treatment.
- the anions constituting the salts other than boron include nitrate ions, sulfate ions, nitrite ions and sulfite ions in addition to chloride ions.
- the first stage refers to the anion exchange resin packed tower closer to the cation exchange resin packed tower 5 in the flow path of the raw water, and the second stage is the farther from the cation exchange resin packed tower 5. It refers to an anion exchange resin packed tower.
- the desalination apparatus further regenerates the raw water tank 1 that stores the raw water, the supply pump 8 that supplies the raw water in the raw water tank 1 to the inlet of the cation exchange resin packed tower 5 through the valve 21, and the ion exchange resin.
- a clarified water tank 2 for storing the clarified water used for the regeneration process a supply pump 9 for supplying the clarified water in the clarified water tank 2 to the clarified water pipe 51, a hydrochloric acid storage tank 3 for storing the hydrochloric acid used for the regeneration process, and a valve 39
- the supply pump 10 supplies the hydrochloric acid in the hydrochloric acid storage tank 3 to the inlet of the cation exchange resin packed tower 5, the sodium hydroxide solution storage tank 4 that stores the sodium hydroxide solution used for the regeneration treatment, and the water through the valve 41.
- a supply pump 11 for supplying the sodium hydroxide solution in the sodium oxide solution storage tank 4 to the intermediate pipe 52.
- the intermediate pipe 52 is for supplying the liquid from the outlet of the cation exchange resin packed tower 5 to the anion exchange resin packed towers 6 and 7 and is connected to the outlet of the cation exchange resin packed tower 5 through the valve 22. At the same time, they are connected to the inlets of the anion exchange resin packed towers 6 and 7 through valves 23 and 26, respectively.
- a pipe 53 connecting the outlet of the first anion exchange resin packed tower 6 and the inlet of the second anion exchange resin packed tower 7 is provided, and a valve 24 and a conductivity meter 12 are provided in the middle of the pipe 53. Yes.
- a pipe 54 connecting the outlet of the second anion exchange resin packed tower 7 and the inlet of the first anion exchange resin packed tower 6 is provided, and a valve 27 and the conductivity meter 13 are provided in the middle of the pipe 54. Is provided.
- the treated water pipe 55 is for supplying treated water treated by the desalting apparatus to the outside.
- the treated water pipe 55 is connected to the outlet of the anion exchange resin packed tower 6 through the valve 28 and connected to the anion through the valve 25. It is connected to the outlet of the exchange resin packed tower 7.
- any one of the anion exchange resin packed towers 6 and 7 is arbitrarily set to the first stage by opening and closing the valves 23 to 28, and the other is set to 2 It can be a step.
- the clarified water pipe 51 is connected to the outlet of the cation exchange resin packed tower 5 through the valve 36, is connected to the outlet of the anion exchange resin packed tower 6 through the valve 37, and is connected to the treated water pipe 55 through the valve 38. They are connected, connected to the inlet of the cation exchange resin packed tower 5 through the valve 40, and connected to the intermediate pipe 52 through the valve 42.
- the discharge ports provided at the bottoms of the packed towers 5 to 7 are connected to the pipe 56 via valves 32 to 34, respectively, and the recycled waste liquid is discharged from the pipe 56 via the valve 43.
- the liquid in the pipe 56 is returned to the raw water tank 1 through the valve 35.
- valves 29 to 31 for communicating the inside of the packed tower with the atmosphere are provided at the upper part of the packed towers 5 to 7, respectively.
- this desalination apparatus is to connect the anion exchange resin packed towers 6 and 7 in series to the outlet of the cation exchange resin packed tower 5 to reduce salts other than boron in the raw water by ion exchange treatment.
- a clarified water containing no boron is put in from the lower part of the packed tower, and the H-type strongly acidic cation exchange resin in the cation exchange resin packed tower 5 and the first stage
- the first stage of the anion exchange resin packed towers 6 and 7 refers to the anion exchange resin packed tower located immediately after the cation exchange resin packed tower 5.
- the order of connection between the anion exchange resin packed towers 6 and 7 with respect to the outlet of the cation exchange resin packed tower 5 can be changed.
- the first and second stages are interchanged.
- the liquid removal process and the pasting process are associated with the regeneration process as a preparation stage for the regeneration process.
- the anion exchange resin packed tower 6 if the anion exchange resin packed tower 6 is in the first stage, the raw water passes through the anion exchange resin packed tower 6 from the cation exchange resin packed tower 5 and passes through the anion exchange resin packed tower 7 and is subjected to desalting treatment.
- the treated water is supplied from the treated water pipe 55 to the outside. If the anion exchange resin packed tower 7 is in the first stage, the raw water flows from the cation exchange resin packed tower 5 to the anion exchange resin packed tower 6 through the anion exchange resin packed tower 7.
- the desalting step is a conductivity meter provided between the first-stage anion exchange resin packed tower and the second-stage anion exchange resin packed tower, that is, if the anion exchange resin packed tower 6 is the first stage, the conductivity If a total of 12 and the anion exchange resin packed tower 7 is the 1st stage, it will continue until the electrical conductivity measured by the electrical conductivity meter 13 shows an upward tendency.
- the conductivity of the liquid flowing therethrough is increasing, which means that ions having a large contribution to the conductivity, such as chloride ions, are present in the first-stage anion.
- the valves 29, 32 and 35 are opened. Further, if the anion exchange resin packed tower 6 is in the first stage, the valves 30 and 33 are opened, and the anion exchange resin packed tower 7 is in the first stage. For example, the valves 31 and 34 are opened, and the liquid in the cation exchange resin packed tower 5 and the liquid in the first anion exchange resin packed tower are drained. The extracted liquid is returned to the raw water tank 1 through the pipe 56.
- the sodium hydroxide solution in the sodium hydroxide solution storage tank 4 is supplied to the first-stage anion exchange resin packed tower, and the free base form weakly basic anion exchange in the anion exchange resin packed tower Regenerate the resin.
- the recycled waste liquid is discharged to the outside through the pipe 56 and the valve 43.
- the supply pumps 10 and 11 are stopped and the valves 39 and 41 are closed. After that, by operating the supply pump 9 and opening the valves 40 and 42, the clarified water in the clarified water tank 2 is sent to the packed tower that has been regenerated, and the chemical solution remaining in those packed towers. Extrusion of The waste liquid at this time is also discharged to the outside through the pipe 56 and the valve 43.
- the regeneration process is completed, so that the desalting process of the next cycle can be performed by stopping the supply pump 9 and closing all the valves.
- valves 23 to 25 are opened at the start of the desalination process.
- the first-stage anion exchange resin packed tower is replaced with the second-stage anion exchange resin packed tower. That is, the anion exchange resin packed tower that was the first stage in the previous cycle is the second stage in the next cycle, and the anion exchange resin packed tower that was the second stage in the previous cycle is the first stage in the next cycle.
- regeneration of the anion exchange resin is always performed only for the first-stage anion exchange resin packed tower, and efficient operation can be achieved when the entire apparatus for carrying out the desalting method is considered. It will be able to plan.
- Example 1 An apparatus similar to that shown in FIG. 1 was manufactured as a test apparatus, and each step was advanced as described in the embodiment of the present invention.
- the adopted conditions are as follows.
- H-type strongly acidic cation exchange resin The product name “Amberlite IR120BH” (manufactured by Dow Chemical Co., Ltd., total exchange capacity 1.9 eq / LR (resin)) volume 300 mL is used as the H-type strongly acidic cation exchange resin, and this cation exchange resin is used as a resin column. To form a cation exchange resin packed tower. The resin column had a cylindrical shape and had an inner diameter of 25.4 mm and a length of 1000 mm.
- Free base weakly basic anion exchange resin The product name “Amberlite IRA96SB” (manufactured by Dow Chemical Co., Ltd., total exchange capacity 1.3 eq / LR (resin)) volume 300 mL is used as a free base weakly basic anion exchange resin.
- An anion exchange resin-packed tower was constructed by packing the column. The resin column had a cylindrical shape with an inner diameter of 25.4 mm and a length of 1000 mm. Two such anion exchange resin packed towers were produced.
- the liquid quality of the boron-containing solution used as raw water is as follows: boron concentration is 2000 mg / L, chloride ion concentration is 3000 mg / L, sulfate ion concentration is 200 mg / L, pH is 7.5, and conductivity is 18000 ⁇ S / cm. there were.
- the clarified water had a boron concentration of less than 0.1 mg / L, a chloride ion concentration of 10 mg / L, a sulfate ion concentration of 10 mg / L, a pH of 7.0, and a conductivity of 100 ⁇ S / cm.
- Desalination process end point The desalting step was performed until the electrical conductivity at the outlet liquid of the first-stage anion exchange resin packed tower reached 2000 ⁇ S / cm. This time was taken as the end point of the desalting step. As a result, the flow rate was 3.6L.
- Amount of water put into each packed tower The amount of clarified water applied to each packed tower in the application step was 200 mL.
- Regeneration conditions cation exchange resin: In the regeneration of the H-form strongly acidic cation exchange resin, 5% hydrochloric acid (HCl) was used as a regenerant. The regeneration level was set to 60 g HCl / LR (resin), the flow rate of the regenerant and the flow rate of extrusion with clarified water were 4 BV / hour, and the extrusion time was 45 minutes.
- HCl hydrochloric acid
- Regeneration conditions anion exchange resin
- NaOH sodium hydroxide
- the regeneration level was 60 g NaOH / LR (resin)
- the flow rate of the regenerant and the flow rate of extrusion with clarified water were 4 BV / hour, and the extrusion time was 45 minutes.
- Example 1 the end point of the desalting step was set to the 2.4 L passing point before the conductivity at the outlet liquid of the first-stage anion exchange resin packed tower showed an increasing tendency. Other conditions are the same as those in Example 1.
- Example 2 In Example 1, as the anion exchange resin packed in the anion exchange resin packed tower, instead of the free base type weak base anion exchange resin, an OH type strong basic anion exchange resin (trade name “Amberlite IRA-402BL (OH ) ", Manufactured by Dow Chemical Co., Ltd.) A volume of 300 mL was used. The size of the resin column and other conditions were the same as in Example 1. In Comparative Example 2, the conductivity at the outlet liquid of the first-stage anion exchange resin packed tower reached 2000 ⁇ S / cm when the liquid flow rate reached 3.0 L. This time was taken as the end point of the desalting step.
- an OH type strong basic anion exchange resin trade name “Amberlite IRA-402BL (OH ) ", Manufactured by Dow Chemical Co., Ltd.
- Example 1 and Comparative Examples 1 and 2 the boron concentration in the outlet liquid of the first-stage anion exchange resin packed tower and the boron concentration in the recycled waste liquid were measured. The results are shown in Table 1.
- the boron concentration in the regenerated waste liquid was measured by collecting the waste liquid when supplying the regenerant and the waste liquid during extrusion. Since the regeneration treatment was performed separately for the cation exchange resin and the anion exchange resin, those relating to the regeneration treatment for the cation exchange resin are described in the column of “cation” in the table, and related to the anion exchange resin. Is described in the column of “anion” in the table, and the total regenerated waste liquid obtained is described in the column of “total”.
- Example 1 compared with each comparative example, the boron concentration in the exit liquid of the first-stage anion exchange resin packed tower was high, and the boron concentration in the regeneration waste liquid was low.
- the boron concentration in the outlet liquid of the first-stage anion exchange resin packed tower is higher than that in each comparative example. It means that it will be higher than the example. Therefore, when reducing salts other than boron by using an ion exchange resin from a boron-containing solution containing anions such as chloride ions, according to the present invention, it is possible to reduce the boron concentration in treated water and It can be seen that an increase in the boron concentration of can be suppressed.
- Example 1 boron is detected from the recycled waste liquid due to moisture retained inside the ion exchange resin, that is, moisture that cannot be completely removed in the liquid removal step. This is supported by the fact that boron is also detected in the regenerated waste liquid from the cation exchange resin.
- Example 1 the chloride ion concentration and the sulfate ion concentration were measured in the first stage anion exchange resin packed column outlet liquid at the end of each desalting step. The results are shown in Table 2.
- the target of break detection in the outlet liquid of the first-stage anion exchange resin packed tower is It can be seen that it is preferable to use a chloride ion as the anion to be used.
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Abstract
Description
供給ポンプ8を稼働させ、バルブ21,22を開き、さらに、アニオン交換樹脂充填塔6を1段目とするのであればバルブ23~25を開き、アニオン交換樹脂充填塔7を1段目とするのであればバルブ26~28を開け、原水槽1内の原水を各充填塔5~7内へ順次送液する。原水は、各充填塔5~7内のイオン交換樹脂によりイオン交換処理される。このとき、アニオン交換樹脂充填塔6が1段目となっていれば、原水は、カチオン交換樹脂充填塔5からアニオン交換樹脂充填塔6を通りアニオン交換樹脂充填塔7を経て、脱塩処理がなされた処理水として処理水配管55から外部に供給される。アニオン交換樹脂充填塔7が1段目となっていれば、原水は、カチオン交換樹脂充填塔5からアニオン交換樹脂充填塔7を経てアニオン交換樹脂充填塔6に流れる。
脱塩工程の終了後、バルブ29,32、35を開け、さらに、アニオン交換樹脂充填塔6が1段目であればバルブ30,33を開け、アニオン交換樹脂充填塔7が1段目であればバルブ31,34を開け、カチオン交換樹脂充填塔5内の液と1段目のアニオン交換樹脂充填塔内の液を抜く。抜かれた液は配管56を通って原水槽1に戻される。
脱液工程の実施後、バルブ32~35が全て閉じた状態となるようにし、供給ポンプ9を稼働し、バルブ36を開け、さらに、アニオン交換樹脂充填塔6が1段目であればバルブ37を開け、アニオン交換樹脂充填塔7が1段目であればバルブ38を開け、カチオン交換樹脂充填塔5と1段目のアニオン交換樹脂充填塔においてイオン交換樹脂が全て水に浸かる状態になるまで清澄水槽2内の清澄水をこれらの充填塔に送水する。
張り込み工程の実施後、供給ポンプ9を停止し、開いているバルブをすべて閉じる。続いて、供給ポンプ10を稼働させ、バルブ39,42,43を開くことにより、塩酸貯槽3内の塩酸をカチオン交換樹脂充填塔5に供給し、H形強酸性カチオン交換樹脂の再生を行う。同時に、供給ポンプ11を稼働させ、バルブ41を開け、さらに、アニオン交換樹脂充填塔6が1段目であればバルブ23,33を開け、アニオン交換樹脂充填塔7が1段目であればバルブ26,33を開けることにより、水酸化ナトリウム溶液貯槽4内の水酸化ナトリウム溶液を1段目のアニオン交換樹脂充填塔に供給し、そのアニオン交換樹脂充填塔内の遊離塩基形弱塩基性アニオン交換樹脂の再生を行う。再生廃液は、配管56及びバルブ43を介して外部に排出される。
図1に示したものと同様の装置を試験装置として製作し、上記の発明の実施の形態に記載した通りに各工程を進行させた。採用した条件は以下の通りである。
(1)H形強酸性カチオン交換樹脂:
H形強酸性カチオン交換樹脂として商品名「アンバーライトIR120BH」(ダウ・ケミカル社製、総交換容量1.9eq/L-R(樹脂))体積300mLを使用し、このカチオン交換樹脂を樹脂製カラムに充填してカチオン交換樹脂充填塔を構成した。樹脂製カラムは円筒形状のものであり、その内直径は25.4mm、長さは1000mmであった。
遊離塩基形弱塩基性アニオン交換樹脂として商品名「アンバーライトIRA96SB」(ダウ・ケミカル社製、総交換容量1.3eq/L-R(樹脂))体積300mLを使用し、このアニオン交換樹脂を樹脂製カラムに充填してアニオン交換樹脂充填塔を構成した。樹脂製カラムは円筒形上のものであり、その内直径は25.4mm、長さは1000mmであった。このようなアニオン交換樹脂充填塔を2つ製作した。
原水として用いられたホウ素含有溶液の液質は、ホウ素濃度が2000mg/L、塩化物イオン濃度が3000mg/L、硫酸イオン濃度が200mg/L、pHが7.5、導電率が18000μS/cmであった。
清澄水の液質は、ホウ素濃度が0.1mg/L未満、塩化物イオン濃度が10mg/L、硫酸イオン濃度が10mg/L、pHが7.0、導電率が100μS/cmであった。
脱塩工程での各充填塔での流量は、10m/hr(5.1L/hr)であった。
脱塩工程は、1段目のアニオン交換樹脂充填塔の出口液での導電率が2000μS/cmになるまで行った。この時点を脱塩工程の終点とした。結果として、通液量は3.6Lとなった。
脱液工程において、その開始から、カラム下部から液が出てこなくなるまでの時間は、10分であった。
張り込み工程において各充填塔に張り込んだ清澄水の量は200mLであった。
H形強酸性カチオン交換樹脂の再生では、再生剤として5%塩酸(HCl)を使用した。再生レベルを60gHCl/L-R(樹脂)に設定し、再生剤の流量及び清澄水による押出しの流量を4BV/時間とし、押出時間を45分とした。
遊離塩基形弱塩基性アニオン交換樹脂の再生では、再生剤として、4%水酸化ナトリウム(NaOH)を使用した。再生レベルを60gNaOH/L-R(樹脂)とし、再生剤の流量及び清澄水による押出しの流量を4BV/時間とし、押出時間を45分とした。
実施例1において、脱塩工程の終点を1段目のアニオン交換樹脂充填塔の出口液での導電率が上昇傾向を示す前の2.4L通液時点とした。他の条件は実施例1と同じである。
実施例1において、アニオン交換樹脂充填塔に充填されるアニオン交換樹脂として、遊離塩基形弱塩基性アニオン交換樹脂の代わりにOH形強塩基性アニオン交換樹脂(商品名「アンバーライトIRA-402BL(OH)」、ダウ・ケミカル社製)体積300mLを用いた。樹脂製カラムのサイズや他の条件については実施例1と同じにした。比較例2では、通液量が3.0Lとなった時点で1段目のアニオン交換樹脂充填塔の出口液での導電率が2000μS/cmに到達した。この時点を脱塩工程の終点とした。
実施例1及び比較例1,2において、1段目のアニオン交換樹脂充填塔の出口液でのホウ素濃度と再生廃液でのホウ素濃度を測定した。結果を表1に示す。再生廃液でのホウ素濃度は、再生剤を供給しているときの廃液と押出を行っているときの廃液とをまとめて測定した。なお、再生処理は、カチオン交換樹脂に対するものとアニオン交換樹脂に対するものとを別々に実行したので、カチオン交換樹脂に対する再生処理に関するものが表中「カチオン」の欄に記載され、アニオン交換樹脂に関するものが表中「アニオン」の欄に記載され、得られた再生廃液全体に対するものが「全体」の欄に記載されている。
表1より、実施例1では、各比較例と比較して、1段目のアニオン交換樹脂充填塔の出口液でのホウ素濃度は高くなり、再生廃液でのホウ素濃度は低くなった。実施例1において1段目のアニオン交換樹脂充填塔の出口液でのホウ素濃度が各比較例よりも高いということは、2段目のアニオン交換樹脂充填塔の出口液でのホウ素濃度も各比較例より高くなるということを意味する。したがって、塩化物イオン等のアニオンを含むホウ素含有溶液の中からイオン交換樹脂を用いてホウ素以外の塩類を低減する際に、本発明によれば、処理水でのホウ素濃度の減少と再生廃液でのホウ素濃度の増加とを抑制することが可能となることがわかる。なお、実施例1において再生廃液からホウ素が検出されるのは、イオン交換樹脂内部に保持される水分、すなわち脱液工程で除去しきれない水分に起因する。このことは、カチオン交換樹脂からの再生廃液においてもホウ素が検出されることなどからも支持される。
2 清澄水槽
3 塩酸貯槽
4 水酸化ナトリウム溶液貯槽
5 強酸性カチオン交換樹脂充填塔
6,7 弱塩基性アニオン交換樹脂充填塔
8~11 供給ポンプ
12,13 導電率計
21~43 バルブ
51 清澄水配管
52 中間配管
53,54,56 配管
55 処理水配管
Claims (6)
- 塩化物イオン、硝酸イオン、硫酸イオン、亜硝酸イオン及び亜硫酸イオンのいずれか1つ以上のアニオンを含むホウ素含有溶液の中から、ホウ素以外の塩類を低減する脱塩方法において、
H形強酸性カチオン交換樹脂が充填されたカチオン交換樹脂充填塔の出口に対し、いずれも遊離塩基形弱塩基性アニオン交換樹脂が充填されて前記カチオン交換樹脂充填塔の出口からの液が順次通過する2段のアニオン交換樹脂充填塔を配置したイオン交換装置を用い、前記イオン交換装置に対し、前記カチオン交換樹脂充填塔の入口から前記ホウ素含有溶液を通液する脱塩工程を備え、
前記2段のアニオン交換樹脂充填塔のうち前記ホウ素含有溶液の通液経路において前記カチオン交換樹脂充填塔に近い方のアニオン交換樹脂充填塔の出口液中での前記アニオンの濃度を監視して、前記アニオンのいずれかのブレークを検出するまで前記脱塩工程を継続することを特徴とする、脱塩方法。 - 前記脱塩工程の後に少なくとも前記カチオン交換樹脂充填塔内及び前記カチオン交換樹脂充填塔に近い方のアニオン交換樹脂充填塔内のイオン交換樹脂を再生する樹脂再生工程をさらに有し、
前記樹脂再生工程の実施ごとに前記イオン交換装置内において、前記2段のアニオン交換樹脂充填塔の間で前記ホウ素含有溶液の通液順序を入れ換え、前記脱塩工程と前記樹脂再生工程とを繰り返して実行する、請求項1に記載の脱塩方法。 - 前記カチオン交換樹脂充填塔内のH型強酸性カチオン交換樹脂全体の交換容量が、前記カチオン交換樹脂充填塔に近い方のアニオン交換樹脂充填塔内の遊離塩基形弱塩基性アニオン交換樹脂全体の交換容量よりも大きい、請求項1または2に記載の脱塩方法。
- 前記ホウ素含有溶液は塩化物イオンを含み、前記出口液での塩化物イオンの濃度を監視して、前記塩化物イオンのブレークを検出するまで前記脱塩工程を継続する、請求項1乃至3のいずれか1項に記載の脱塩方法。
- 前記ホウ素含有溶液は、さらに、硝酸イオン、硫酸イオン、亜硝酸イオン及び亜硫酸イオンにいずれか1つ以上のアニオンを含む、請求項4に記載の脱塩方法。
- 前記アニオンの濃度を導電率計により監視する、請求項1乃至5のいずれか1項に記載の脱塩方法。
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