JP2014087748A - Inter-liquid ion transfer method and inter-liquid ion transfer device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inter-liquid ion transfer method and an inter-liquid ion transfer device, excellent in applicability to a treatment process, and also excellent in removal/recovery efficiency of an ion, by enabling continuous treatment, by stabilizing the treatment, when an undiluted solution is an emulsion, a suspension liquid or a high viscosity liquid.SOLUTION: In the inter-liquid ion transfer method and the inter-liquid ion transfer device, when electrically transferring the ion via a diaphragm to an ion receiving liquid circulating in an ion receiving liquid flow passage from the undiluted solution circulating in an undiluted solution flow passage by an electric potential gradient, the undiluted solution is the emulsion and/or the suspension liquid including a particle of a diameter of 100 μm or more or having viscosity of 100 cp or more, and a flow passage width of the undiluted solution flow passage falls within a range of 1.5 mm-20 mm, and linear velocity of the undiluted solution circulating in the undiluted solution flow passage falls within a range of 10 mm/sec or less, or a staying time in the undiluted solution flow passage of the undiluted solution falls within a range of 10 minutes - several days.

Description

  TECHNICAL FIELD The present invention relates to a liquid ion transfer method and a liquid ion transfer device, and more specifically, a liquid ion transfer method and liquid for transferring ions contained in a stock solution that is a slurry or a highly viscous liquid into an ion receiving liquid. The present invention relates to an interion ion transfer device.

  Attempts have been made to reuse waste from the viewpoint of preventing environmental pollution and saving resources.

  Conventionally, fluid waste with a high water content has been considered difficult to process, and in order to reuse it, for example, a process in which separation of charged substances such as reduction of salt concentration is important. May be one of the following.

  Currently, reverse osmosis and electrodialysis methods are commonly used to remove salts from clear fluids with sufficient fluidity. For example, ions used in seawater desalination and semiconductor manufacturing It is used for the production of exchange water or ultrapure water (Patent Document 1).

  In the conventional electrodialysis tank, the width of the flow path in the tank through which the stock solution flows (the width of the flow path in the direction perpendicular to the ion exchange membrane) is set to 2 mm or less, for example (Patent Documents 2 to 4). By making the stock solution turbulent, the mass mobility was improved and at the same time the current efficiency was improved.

JP 09-239245 A JP 58-112006 A JP-A-2-290227 JP 2003-24947 A

  The present inventor makes effective use of unclear liquids including suspensions and emulsions such as garbage and livestock manure, and liquid slurry-like wastes with relatively high viscosity even without solids. Researching what to do, we focused on the fact that salts (cations and / or anions) contained in these stock solutions at high concentrations hindered effective use, and tried to remove them.

  However, the conventional reverse osmosis method and electrodialysis method have a problem that such a stock solution becomes unstable and it is difficult to obtain sufficient ion removal efficiency. Since the exchange membrane is easily damaged, there is a problem of high cost.

  For such stock solutions, it may be possible to remove ions in a batch process by using a filter press type electrodialysis tank, but continuous processing is not possible, and there is a problem inferior in applicability to the processing process. is there.

  In addition, it is conceivable that ions are removed by adsorption with an ion exchange resin, but the cost of regeneration treatment of the resin after adsorption becomes a problem.

  Therefore, the problem of the present invention is that when the stock solution is an emulsion, suspension or high-viscosity liquid, the treatment is stable and the continuous treatment is possible, so that the applicability to the treatment process is excellent, and further, An object of the present invention is to provide a liquid ion transfer method and liquid ion transfer apparatus that are excellent in removal / recovery efficiency.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1.
A stock solution channel through which a stock solution containing ions to be removed flows between a pair of electrodes consisting of an anode and a cathode, and a receiving solution channel through which an ion receiving solution that accepts the ions removed from the stock solution flows Are arranged side by side through a diaphragm through which at least the ions can pass,
Due to the potential gradient provided between the pair of electrodes, the ions are electrically passed through the diaphragm from the stock solution flowing through the stock solution channel to the ion receiving solution flowing through the ion acceptor channel. A method of transferring ions between liquids,
The stock solution is an emulsion and / or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more,
The flow path width of the stock solution channel is in the range of 1.5 mm or more and 20 mm or less, and the linear velocity of the stock solution flowing through the stock solution channel is in the range of 10 mm / second or less, or the stock solution of the stock solution A method for transferring ions between liquids, wherein the residence time in the channel is in the range of 10 minutes to several days.

2.
A stock solution channel through which a stock solution containing ions to be removed flows between a pair of electrodes consisting of an anode and a cathode, and a receiving solution channel through which an ion receiving solution that accepts the ions removed from the stock solution flows Are arranged side by side through a diaphragm through which at least the ions can pass,
Due to the potential gradient provided between the pair of electrodes, the ions are electrically passed through the diaphragm from the stock solution flowing through the stock solution channel to the ion receiving solution flowing through the ion acceptor channel. A liquid ion transfer device configured to transfer,
The stock solution is an emulsion and / or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more,
The flow path width of the stock solution channel is in the range of 1.5 mm or more and 20 mm or less, and the linear velocity of the stock solution flowing through the stock solution channel is in the range of 10 mm / second or less, or the stock solution of the stock solution A liquid ion transfer device characterized in that the residence time in the flow channel is in the range of 10 minutes to several days.

  According to the present invention, when the stock solution is an emulsion, suspension or high-viscosity liquid, the treatment is stable and the continuous treatment is possible, so that it is excellent in applicability to the treatment process, and further the ion removal / It is possible to provide a liquid ion transfer method and liquid ion transfer apparatus that are excellent in recovery efficiency.

Sectional drawing of the principal part which shows an example of the liquid ion transfer apparatus which concerns on this invention Sectional drawing which shows the other example of the liquid ion transfer apparatus which concerns on this invention. Sectional drawing which shows the other example of the liquid ion transfer apparatus which concerns on this invention. Diagram explaining properties of shochu concentrate

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view of an essential part showing an example of a liquid ion transfer apparatus according to the present invention.

  In FIG. 1, reference numeral 1 denotes a liquid ion transfer device. In a liquid ion transfer device main body 10, a stock solution channel 11 through which a stock solution flows between a pair of electrodes C and A composed of an anode C and a cathode A. And a cation receiving liquid channel 12C through which the cation receiving liquid flows, and an anion receiving liquid channel 12A through which the anion receiving liquid flows.

  In the present invention, the stock solution is an emulsion or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more. Here, as ions to be removed, cations and anions Is included.

  The cation receiving liquid is a liquid for receiving a cation removed from the stock solution, and the anion receiving liquid is a liquid for receiving an anion removed from the stock solution.

  111 is an inflow port through which the stock solution flows into the stock solution channel 11, and 112 is an outflow port through which the stock solution flows out from the stock solution channel 11.

  The stock solution stored in the stock solution tank 21 is introduced into the stock solution channel 11 from the inlet 111 at a predetermined flow rate by the metering pump 31, flows through the stock solution channel 11, flows out from the outlet 112, and is processed. It is transferred to the processing liquid tank 23 as a stock solution (processing liquid).

  Further, 121C is an inflow port for flowing the cation accepting liquid into the cation accepting liquid channel 12C, and 122C is an outflow port for flowing out the cation accepting liquid from the cation receiving solution channel 12C.

  The cation receiving liquid is introduced from the circulation tank 22C to the cation receiving liquid channel 12C from the inlet 121C at a predetermined flow rate by the metering pump 32C, and after flowing through the cation receiving liquid channel 12C, from the outlet 122C. It flows out and is returned to the circulation tank 22C again.

  On the other hand, 121A is an inflow port through which the anion receptor liquid flows into the anion receptor liquid channel 12A, and 122A is an outflow port through which the anion receptor liquid flows out of the anion receptor liquid channel 12A.

  The anion accepting liquid is introduced from the circulation tank 22A to the cation accepting liquid flow path 12A from the inlet 121A at a predetermined flow rate by the metering pump 32A, and after flowing through the cation receiving liquid flow path 12A, from the outlet 122A. It flows out and is returned to the circulation tank 22A again.

  The undiluted solution channel 11, the cation receiving solution channel 12C, and the anion receiving solution channel 12A are arranged in parallel via at least diaphragms 13A and 13C through which ions to be removed can pass.

  That is, an anion receiving liquid channel 12A is arranged in parallel on the anode C side of the stock solution channel 11 via a diaphragm 13A through which at least anions can pass, while at least on the cathode A side of the stock solution channel 11 A cation receiving liquid channel 12C is arranged in parallel through a diaphragm 13C through which the cation C can pass.

  Thus, in the present invention, the diaphragms 13A and 13C are not particularly limited as long as at least ions (anions or cations) to be removed can pass therethrough. For example, a membrane having ion selective permeability such as an ion exchange membrane or a dialysis membrane may be used, but a microporous membrane can be more preferably used. In the present invention, it is also preferable to use the same membrane for the diaphragm 13A and the diaphragm 13C.

  In the present invention, as the microporous membrane, a membrane having no ion selective permeability such as an MF membrane, a UF membrane, or an NF membrane can be preferably used.

  In the present invention, the flow path width W of the stock solution flow path 11 is 1.5 mm or more, preferably 2.1 mm or more. The channel width W is the width of the stock solution channel 11 in the direction perpendicular to the membrane surfaces of the diaphragms 13A and 13C.

  In the ion removing apparatus 1 configured as described above, the stock solution formed in the stock solution channel 11 in a state where the metering pumps 31, 32C, 32A are driven and a potential gradient is provided between the pair of electrodes C, A. The liquid flow is caused to contact in parallel with the liquid flow caused by the ion receiving liquid formed in the receiving liquid flow paths 12A and 12C through the diaphragms 13A and 13C.

  At this time, in the present invention, the linear velocity of the stock solution flowing through the stock solution channel 11 is in the range of 10 mm / second or less, or the residence time of the stock solution in the stock solution channel 11 is in the range of 10 minutes to several days. To be adjusted. This adjustment can be performed by setting the metering pump 31.

  Ions in the undiluted solution flowing through the undiluted solution channel 11 move from the undiluted solution to the ion receiving solution via the diaphragm 13 by electrophoretic migration under a potential gradient. Specifically, the cation in the stock solution moves into the cation acceptor flowing through the cation acceptor flow channel 12C provided on the cathode A side, while the anion in the stock solution is on the anode C side. It moves into the anion receptor liquid flowing through the anion receptor liquid channel 12A.

  In this way, it is possible to remove ions from the stock solution and collect ions with the ion acceptor solution.

  In the prior art, the width of the flow path in the tank through which the stock solution circulates is set to 2 mm or less, for example, thereby increasing the material mobility by making the stock solution turbulent and at the same time improving the current efficiency. Was described above.

  On the other hand, in the present invention, when the stock solution contains particles having a diameter of 100 μm or more, or is an emulsion or suspension having a viscosity of 100 cp or more, the stock solution flow path is reversed. 11 is set in a range of 1.5 mm or more and 200 mm or less, and the linear velocity of the stock solution flowing through the stock solution channel 11 is in a range of 10 mm / second or less, or in the stock solution channel 11 of the stock solution By adjusting the residence time to a low speed (slow flow) in the range of 10 minutes or more and several days or less, the treatment is more stable than the conventional method, and continuous treatment is possible. It has been found that an effect of excellent ion removal efficiency can be obtained.

  In the present invention, the residence time of the undiluted solution in the undiluted solution channel 11 during the ion transfer treatment is preferably several days as described above, but is adjusted to a range of 20 minutes to 10 hours, for example. It is more preferable. As a result, even if the voltage applied between the electrodes is reduced, an effect of maintaining the ion removal efficiency can be obtained.

  In the present invention, for example, from the viewpoint of increasing the throughput, as shown in FIG. 2, a plurality of pairs of electrodes C and A are provided, and between each pair of electrodes C and A, as in FIG. It is also preferable to arrange the stock solution channel 11, the anion receptor fluid channel 12A, and the cation receptor fluid channel 12C in parallel through the diaphragms 13A and 13C.

  At this time, the anode C and the cathode A adjacent to each other are preferably formed by the plate surfaces of the bipolar partition plate B as shown in FIG.

  Moreover, in the liquid ion transfer apparatus according to the present invention, as shown in FIG. 3, the stock solution channel 11 and the receiving solution channel 12 are alternately arranged between the pair of electrodes C and A via the diaphragms 13A and 13C. It is also preferable to stack a plurality of layers.

  As shown in FIG. 3, in the inter-liquid ion transfer device 1, the receiving liquid flowing through one receiving liquid channel 12 is a cation and an anion from the raw solution flowing through the raw liquid channels 11, 11 arranged on both sides. In order to receive each, it serves as both an anion receptor liquid and a cation receptor liquid.

  In the embodiment of FIG. 3, the membrane 13A on the anode C side of the stock solution channel 11 is an anion exchange membrane, and the membrane 13C on the cathode A side is a cation exchange membrane, so that the adjoining from the stock solution channel 11 is received. It is possible to prevent ions removed to the liquid flow path 12 from moving to other stock solution flow paths 11 (ion movement indicated by broken line arrows in the figure) by the ion selective permeability of the diaphragms 13A and 13C.

  However, even if an ion exchange membrane is not used in this way, in the present invention, the stock solution is the above-described emulsion or suspension, and the flow passage width W of the stock solution passage 11 is 1.5 mm or more and 200 mm or less. And the linear velocity of the stock solution flowing through the stock solution channel 11 is in the range of 10 mm / second or less, or the residence time of the stock solution in the stock solution channel 11 is adjusted in the range of 10 minutes to several days. As a result, the effect of suitably preventing the ion movement indicated by the broken-line arrow in the figure can be obtained.

  Therefore, also in the embodiment of FIG. 3, as the diaphragms 13A and 13C, a film having no ion selective permeability such as an MF film, a UF film, and an NF film can be suitably used. Also, the diaphragms 13A and 13C can be used. The same film can be preferably used.

  In the above description, the case where the receiving liquid channel 12 (12A, 12C) is provided between the pair of electrodes C, A on both sides of the stock solution channel 11 via the diaphragm 13 (13A, 13C) has been described. However, the present invention is not limited to this, and between the pair of electrodes C and A, the receiving liquid is passed through the diaphragm 13 only on either the anode C side or the cathode A side of the stock solution flow path 11. The flow paths 12 may be provided side by side. When the receiving liquid channel 12 is provided only on the anode C side via the diaphragm 13, the anion removed from the stock solution channel 11 can be received by the receiving liquid channel 12, and only on the cathode A side. When the receiving liquid channel 12 is provided via the diaphragm 13, the cation removed from the stock solution channel 11 can be received by the receiving liquid channel 12. When the ions to be removed in the stock solution are either anions or cations, they can be suitably removed by the method as described above.

  As described above, the stock solution used in the present invention is an emulsion or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more, and is positive as ions to be removed. There is no particular limitation as long as it contains ions and / or anions.

  Specifically, a slurry containing a biomass-derived component can be preferably exemplified as the stock solution.

  For example, as a slurry containing a biomass-derived component, slurryed food waste (food waste paste), livestock manure, etc. can be preferably exemplified.

  Moreover, the digestive liquid after carrying out the methane fermentation of the slurry containing a biomass origin component can also be preferably used as a stock solution.

  Furthermore, the present invention can be preferably applied as a pretreatment before subjecting a slurry containing biomass-derived components to methane fermentation.

  For example, since pigs sometimes add zinc to their feed during feeding, if livestock manure contains swine manure, they contain a relatively large amount of zinc, which causes environmental problems when reusing such as agricultural land returns. Although it is large, according to the present invention, such heavy metal ions can also be suitably removed.

  Moreover, this invention can be preferably used also for removal of the salt from food processing residues, such as a plum fermentation residual liquid, and the potassium salt removal from food processing residues, such as a shochu concentrate, for example. Of course, it can be suitably used not only for food processing residues but also for reducing salt from foods.

  For example, as the shochu concentrate, a shochu obtained after removing contaminants by a screw press or the like can be preferably exemplified by concentrating it with a multi-effect evaporator or the like. A shochu concentrate, a rice shochu concentrate, a brown sugar shochu concentrate or the like is in a sol form, and a shochu shochu concentrate or the like is in a gel form.

  The stock solution (treatment solution) from which ions have been removed according to the present invention can be suitably used as, for example, a nutrient solution for house cultivation or a livestock feed. In particular, when used as a nutrient solution for house cultivation, it is excellent in the effect of preventing accumulated salt damage due to the soil in the house not being exposed to rain. The effect that potassium which becomes becomes suitable can be acquired.

  In addition, according to the present invention, valuable materials such as polyphenols, citric acid, organic acids, and potassium ions contained in the stock solution can be suitably recovered as ions in the receiving solution, and the reuse of valuable materials is efficient. Can be

  Furthermore, in the present invention, a contaminated soil slurry can be preferably treated as a stock solution. For example, the contaminated soil is dispersed in water to form a slurry, which is treated as a stock solution with the liquid ion transfer apparatus of the present invention. Ionized contaminants are removed in the receiving solution, and the soil components (solid content) decontaminated from the treated stock solution (treatment solution) can be easily recovered.

  In particular, when the pollutant is cesium, it was confirmed that the present invention can be suitably removed in the receiving solution. This is presumed to be due to the relatively fast movement speed of cesium ions under a potential gradient.

  In the present invention, the ion to be removed contained in the stock solution is not particularly limited as long as it is a cation and / or an anion. The valence of the ion may be either monovalent or divalent or higher, and may be any form such as a monoatomic ion, polyatomic ion, complex ion, or cluster ion.

  Examples of the present invention will be described below, but the present invention is not limited to such examples.

1. Properties of Stock Solution In the following examples, raw methane fermentation digestive juice, raw paste, brown sugar shochu concentrate, plum fermentation residue, porcine manure or saline was used as the stock solution.

  The brown sugar shochu concentrate used as the stock solution is obtained by collecting the liquid side after solid-liquid separation of the brown sugar shochu using a centrifuge and concentrating it with a multi-effect evaporator.

  Table 1 shows the results of evaluating the properties of each stock solution (excluding saline) with the following items.

<Property evaluation items>
-Solid content concentration (wt%): by dry weighing method at 107 ° C-Viscosity (PaS): by vibration plate viscometer method at 20 ° C-Particle size (diameter, µm): by sieving magnifying glass pH: According to JIS K0102.12.1. Conductivity (S / cm): According to JIS K0102.13. Sodium ion concentration (mg / L): Acid decomposition. By atomic absorption method. Potassium ion concentration (mg / L):・ Acid decomposition ・ Atomic absorption method ・ Zinc ion concentration (mg / L): Acid decomposition ・ ICP method ・ Chloride ion concentration (mg / L): Ion chromatographic method

2. Liquid ion transfer test (Example 1)
A test was performed under the following test conditions using a garbage mixed paste as an undiluted solution using a small liquid ion transfer device for testing having the same configuration as that shown in FIG.

  Table 2 shows the linear velocity of the stock solution in the stock solution channel 11, the residence time (RT) of the stock solution channel 11, the change in ion concentration before and after the test, the applied voltage / current, and the current efficiency.

<Test conditions>
-Membrane 13C: cation exchange membrane (manufactured by Tokuyama, monovalent selective cation exchange membrane)
-Diaphragm 13A: Anion exchange membrane (Asahi Kasei Co., Ltd., anion exchange membrane)
・ Membrane area: width (perpendicular to liquid flow) 10 mm x height (liquid flow direction) 100 mm
-Apparent electrode area: Same as above-Channel width W of the stock solution channel 11 = 2.1 to 3.0 mm
・ Average liquid flow rate: 0.1-1 ml / hr

(Example 2)
In Example 1, the test was performed in the same manner as in Example 1 except that the raw solution was replaced with the garbage-based methane fermentation digestion liquid and the test conditions shown in Table 2 were adopted. The results are shown in Table 2.

(Example 3)
In Example 1, the test was performed in the same manner as in Example 1 except that the stock solution was replaced with the brown sugar shochu concentrate and the test conditions shown in Table 2 were adopted. The results are shown in Table 2.

(Example 4)
In Example 1, the test was performed in the same manner as in Example 1 except that the stock solution was replaced with the ume fermentation residue and the test conditions shown in Table 2 were adopted. The results are shown in Table 2.

(Example 5)
In Example 1, the test was performed in the same manner as in Example 1 except that the stock solution was replaced with pig manure and the test conditions shown in Table 2 were used. The results are shown in Table 2.

(Example 6)
In Example 3, the test was performed in the same manner as in Example 3 except that the test conditions in Table 2 were used. The results are shown in Table 2.

(Example 7)
In Example 6, the tests were performed in the same manner as in Example 6 except that the diaphragms 13C and 13A were replaced with MF membranes (Yumicron manufactured by JS Yuasa Co., Ltd.) and the test conditions shown in Table 2 were adopted. The results are shown in Table 2.

(Example 8)
In Example 7, the test was performed in the same manner as in Example 7 except that the stock solution was changed to saline and the test conditions shown in Table 2 were used. The results are shown in Table 2.

1: Liquid ion transfer device 10: Liquid ion transfer device body 11: Stock solution flow channel 111: Inlet 112: Outlet 12: Receptor flow channel 12C: Cation acceptor flow channel 12A: Anion acceptor flow channel 13, 13C, 13A: Diaphragm C: Anode A: Cathode

Claims (2)

A stock solution channel through which a stock solution containing ions to be removed flows between a pair of electrodes consisting of an anode and a cathode, and a receiving solution channel through which an ion receiving solution that accepts the ions removed from the stock solution flows Are arranged side by side through a diaphragm through which at least the ions can pass,
Due to the potential gradient provided between the pair of electrodes, the ions are electrically passed through the diaphragm from the stock solution flowing through the stock solution channel to the ion receiving solution flowing through the ion acceptor channel. A method of transferring ions between liquids,
The stock solution is an emulsion and / or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more,
The flow path width of the stock solution channel is in the range of 1.5 mm or more and 20 mm or less, and the linear velocity of the stock solution flowing through the stock solution channel is in the range of 10 mm / second or less, or the stock solution of the stock solution A method for transferring ions between liquids, wherein the residence time in the channel is in the range of 10 minutes to several days. A stock solution channel through which a stock solution containing ions to be removed flows between a pair of electrodes consisting of an anode and a cathode, and a receiving solution channel through which an ion receiving solution that accepts the ions removed from the stock solution flows Are arranged side by side through a diaphragm through which at least the ions can pass,
Due to the potential gradient provided between the pair of electrodes, the ions are electrically passed through the diaphragm from the stock solution flowing through the stock solution channel to the ion receiving solution flowing through the ion acceptor channel. A liquid ion transfer device configured to transfer,
The stock solution is an emulsion and / or suspension containing particles having a diameter of 100 μm or more, or having a viscosity of 100 cp or more,
The flow path width of the stock solution channel is in the range of 1.5 mm or more and 20 mm or less, and the linear velocity of the stock solution flowing through the stock solution channel is in the range of 10 mm / second or less, or the stock solution of the stock solution A liquid ion transfer device characterized in that the residence time in the flow channel is in the range of 10 minutes to several days.

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