JP2010247122A - Method and device for removing adhesion substance from porous adsorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To safely, speedily remove an adhesion substance from a porous adsorbent. <P>SOLUTION: A method for removing an adhesion substance from a porous adsorbent includes; a water-adding process in which an granular porous adsorbent 2, to which an adhesion substance adheres, is immersed in a container 1a so as to make water contained in the pores of the adsorbent concerned; a microwave-irradiating process in which the adsorbent 2 is microwave-heated in the atmosphere by microwave-irradiating devices 70a, 70b in a state, in which the adsorbent contains water in the pores, after the water-adding process; and a washing process in which the adsorbent is washed after the microwave-irradiating process. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method and apparatus for desorbing deposits adhering to pores from a porous adsorbent. In the present application, “attachment” includes both the case of physical attachment by van der Waals force and the case of attachment by chemical bonding by a covalent bond or the like. Further, “desorption” does not mean a so-called desorption reaction, but simply means that the adhering material is separated from the adsorbent.

Conventionally, harmful substances are adsorbed by an adsorbent and then desorbed from the adsorbent. For example, when desorbing a heavy metal ion substance from an ion exchange resin that has taken in a heavy metal ion substance, the ion exchange resin is immersed in a large amount of high-concentration acid or alkali solution to chemically remove heavy metal ions. There is a method of separating from.
In addition, when desorbing an organic substance from activated carbon, which is a porous adsorbent on which the organic substance has been adsorbed, there is a method of vaporizing and decomposing the organic substance by exposing it to tens of minutes of high-temperature superheated steam.

When removing a heavy metal ion substance from an ion exchange resin, a large amount of high-concentration alkaline solution is used in large quantities, so a large facility is required and a large amount of waste liquid is generated. Furthermore, there are various disadvantages such as that it takes several hours for the treatment and it is necessary to wash with a large amount of water in order to regenerate the ion exchange resin after desorption.
Further, when an organic substance is desorbed from activated carbon, a large amount of reaction solution is not required, but there is a problem that processing takes energy and time. For example, when decomposing an organic substance using superheated steam at 300 ° C., it takes time of 60 minutes or more, and even when using superheated steam at a higher temperature of 500 ° C., it is necessary to take 30 to 40 minutes. .
As described above, it takes time to desorb the adhering material from the conventional adsorbent, and there is a problem that a dangerous chemical is used or high energy is required. In view of such a problem, the present invention has an object to remove deposits from an adsorbent safely and at high speed.

In order to solve the above problems, the present invention has the following configuration.
The invention according to claim 1 is a moisture addition step of containing moisture in the pores of the granular porous adsorbent to which deposits have adhered, and after the moisture addition step, moisture is contained in the pores. A porous adsorbent adhering material desorption method comprising: a microwave irradiation step of performing microwave heating on the adsorbent in the atmosphere; and a cleaning step of cleaning the adsorbent after the microwave irradiation step.
Invention of Claim 2 is the air irradiation process which blows air with respect to the said adsorbent in the said deposit | attachment detachment | desorption method of the said porous adsorbent material before the said microwave irradiation process after the said water addition process. It is what has.
According to a third aspect of the present invention, in the porous adsorbent adhering material desorbing method, air is blown against the adsorbent during the microwave irradiation step.
According to a fourth aspect of the present invention, in the porous adsorbent adhering material detachment method, the cleaning step immerses the adsorbent at least once with a cleaning liquid.

According to a fifth aspect of the present invention, in the adhering substance detachment method of the porous adsorbent, in the moisture addition step, the adsorbent is immersed in a liquid so that moisture is included in the pores. is there.
According to a sixth aspect of the present invention, in the porous adsorbent adhering substance detachment method, the moisture addition step is performed by passing a liquid through a container containing the adsorbent.
The invention according to claim 7 is the porous adsorbent adhering substance detachment method, wherein the adsorbent is brought into contact with an acidic solution or an alkaline solution before the moisture addition step, and then the moisture addition step. The adsorbent is washed with water.
The invention according to claim 8 is the porous adsorbent adhering substance detachment method, wherein the moisture is an acidic solution or an alkaline solution.
According to a ninth aspect of the present invention, in the method for depositing and desorbing a porous adsorbent, before the microwave irradiation step, the adsorbent is immersed in a liquid and a microbubble is irradiated into the liquid. It has a bubble irradiation process and the ultrasonic irradiation process which irradiates an ultrasonic wave in the said liquid filled with the microbubble after the microbubble irradiation process. In addition, it does not matter before and after the moisture addition process with respect to the microbubble irradiation process and the ultrasonic irradiation process, and since the microbubble irradiation process and the ultrasonic irradiation process immerse the adsorbent in the liquid, these also serve as the moisture addition process. You can also.
The invention described in claim 10 includes a vapor step of applying vapor to the adsorbent before the microwave irradiation step. In addition, before and after the water addition step with respect to the water vapor step, the water vapor step can also serve as a water addition step because water can be provided in the adsorbent pores.

The invention according to claim 11 is an apparatus for detaching deposits from a granular porous adsorbent to which deposits have adhered, a container holding the adsorbent inside, and the adsorbent in the container And a microwave irradiation means for performing microwave heating on the adsorbent in the container.
The invention according to claim 12 is the porous adsorbent adhering substance detaching apparatus, wherein the container is capable of immersing the adsorbent held therein, and has an on-off valve for discharging the liquid inside. And the moisture adding means allows the liquid to flow into the container.
According to a thirteenth aspect of the present invention, in the adhering substance desorbing device for the porous adsorbent, the moisture adding means can allow two or more kinds of liquids to flow.
The invention described in claim 14 is the porous adsorbent adhering substance detaching apparatus, further comprising air irradiation means for blowing air onto the adsorbent in the container.

The invention according to claim 15 is a water treatment apparatus for recovering a target substance using a granular porous adsorbent from a target liquid such as waste water / waste liquid in which the target substance is dissolved or mixed. A container held inside, a target liquid inlet for injecting the target liquid into the container, a discharge port having an on-off valve for discharging the liquid in the container, and microwave heating on the adsorbent in the container It is a water treatment apparatus having a microwave irradiation means to perform and a cleaning water inlet for injecting cleaning water into the container.
The invention according to claim 16 is characterized in that, in the water treatment apparatus, two or more of the containers to which the target liquid inlet, the outlet, the microwave irradiation means, and the cleaning water inlet are attached are arranged in parallel. It is arrange | positioned, Comprising: It can switch to which said target liquid injection port the said target liquid is inject | poured with the switching valve from piping which supplies the said target liquid.
The invention according to claim 17 is the water treatment apparatus, further comprising air irradiation means for blowing air onto the adsorbent in the container.
According to an eighteenth aspect of the present invention, the water treatment apparatus further comprises a solution injection means for injecting an acidic solution or an alkaline solution into the container.

According to the first aspect of the present invention, when microwave heating is performed inside the pores of the adsorbent containing moisture, the moisture contained in the pores vibrates and becomes high temperature and changes to water vapor. The vapor pressure of the water vapor generated in the narrow pores rapidly increases, and jets vigorously toward the surface side of the low-pressure granular material 2. In the process in which water vapor is discharged from the inside of the pores to the outside, the water vapor pushes out deposits remaining inside the pores and discharges them to the outside. Finally, the adhering material pushed out is washed away by washing the adsorbent, and the adhering material can be desorbed.
According to the second aspect of the present invention, by blowing air to the adsorbent, moisture on the adsorbent surface other than the inside of the pores can be blown, and heating by microwaves can be concentrated on the moisture inside the pores. Moisture inside the pores can be heated with time.
According to the third aspect of the present invention, air is blown to the adsorbent while irradiating the microwave, so that the discharged deposits are blown away, and the granular adsorbent is vibrated. The adsorbent can be irradiated with microwaves uniformly.
In the invention according to claim 4, by immersing the adsorbent in the cleaning liquid in the cleaning process, the cleaning liquid enters the inside of the pores and is not completely discharged, and the adhered matter in a peeled state can be discharged together with the cleaning liquid. it can.

In the invention according to claim 5, it is possible to spread moisture in the pores with a high probability by immersing the adsorbent.
The invention according to claim 6 irradiates microbubbles in a state where the adsorbent is immersed, and further irradiates with ultrasonic waves, whereby the microbubbles that enter the adsorbent material and enter the pores are destroyed by ultrasonic waves. Since the adsorbate is easily peeled off by the impact of the breaking pressure, the adsorbent desorption efficiency by the microwave irradiation can be increased.
According to the seventh aspect of the present invention, moisture is contained in the pores by passing the liquid through the adsorbent, so that the adsorbent can be contained in a short time.
In the invention according to claim 8, moisture is contained in the pores by applying the vapor to the adsorbent, so that when the vapor touches the inner wall inside the pores, a condensing action occurs in which the vapor rapidly becomes a liquid. Thus, the adhering matter is easily peeled off, and the effect of removing the adsorbent by microwave irradiation thereafter can be enhanced.
The invention according to claim 9 makes it easy to peel off the adsorbent by contacting the adsorbent in advance with an acidic solution or an alkaline solution in which the adhering substance dissolves, and then detaches the adsorbent by microwave irradiation. The effect can be enhanced. Further, by washing the acidic solution or alkaline solution in the pretreatment step, it is possible to prevent the acidic substance or alkaline substance from being mixed in the liquid obtained in the final washing step.
In the invention according to claim 10, the adsorbent is easily peeled off by immersing the adsorbent in an acidic solution or an alkaline solution in which the adhering material dissolves, and the adsorbent removal effect by microwave irradiation thereafter is enhanced. be able to.

The invention according to claim 11, when performing microwave overheating to the adsorbent to which the deposits held in the container are adhered, the moisture inside the pores is heated by the microwave and ejected as water vapor. The deposits can be pushed together, thereby allowing the deposits to be desorbed from the adsorbent.
According to the twelfth aspect of the present invention, the adhering substance can be immersed in the container by closing the outlet opening / closing valve and allowing the liquid to flow in from the moisture adding means, and the moisture inside the adhering substance has a high probability. After that, by opening the opening / closing valve of the discharge port, moisture can be discharged and the adsorbent can be heated in the air by microwave irradiation means.
In the invention described in claim 13, since the moisture adding means can flow in two or more kinds of liquids, the adsorbent is first contained in the pores by adding an acidic solution or an alkaline solution according to the deposit. It is possible to increase the desorption efficiency by making it easy to desorb, and it is possible to wash away the desorbed deposits by adding water after microwave irradiation by the microwave irradiation means. .
In the invention described in claim 14, the air irradiation means blows air to the adsorbent before irradiating the microwave, and the moisture on the surface of the adsorbent other than the inside of the pores is blown off, thereby reducing the heating by the microwave. The water inside the pores can be heated in a shorter time by concentrating on the water inside the pores.

According to the fifteenth aspect of the present invention, first, the target liquid is injected from the target liquid inlet and discharged from the outlet, whereby the target substance can be adsorbed and recovered by the adsorbent. Then, after the target liquid is completely discharged, the adsorbent is removed from the adsorbent by heating the adsorbent in a state where moisture is contained in the pores by microwave irradiation means. Can be played back and used.
In the invention described in claim 16, by providing two or more containers in parallel, the recovery process of the adsorbent is performed in another container while the target substance is being collected in the one container. Can do.
In the invention according to claim 17, before performing the microwave heating at the time of regeneration of the adsorbent, air is blown onto the adsorbent, so that moisture on the surface of the adsorbent other than the inside of the pores is blown, and heating by the microwave is performed. By concentrating on the moisture inside the pores, the moisture inside the pores can be heated in a shorter time.
The invention according to claim 18 is the method of injecting an acidic solution alkaline solution into the container, so that the adsorbent is converted into an acidic solution or an alkaline solution according to the deposit before microwave heating during regeneration of the adsorbent. By contacting, deposits can be easily peeled off, and desorption by microwave heating can be performed more efficiently.

It is the schematic which shows typically the structure of the water treatment apparatus which concerns on embodiment. It is a graph which shows the detachment | desorption rate at the time of isolate | separating the hexavalent chromium which adsorb | sucked to the activated alumina adsorbent by the method which concerns on this invention. It is a graph which shows the desorption rate at the time of desorbing the phosphate ion adsorbed to the activated alumina adsorbent by the method according to the present invention. It is a graph which shows the difference in the desorption rate in 1 cycle in the case of desorbing by the method concerning the present invention, and 2 cycles. It is the schematic which shows the structure of the adsorbent adhering material desorption apparatus typically. It is a graph which shows the detachment | desorption rate at the time of detach | desorbing impurities from the commercially available activated alumina adsorbent by the method according to the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(1) Configuration of Water Treatment Device FIG. 1 is a schematic view schematically showing the configuration of the water treatment device X according to the embodiment. The water treatment apparatus X has cylindrical containers 1a and 1b containing granular porous adsorbents 2 arranged in parallel, and waste liquid is passed through one of the containers 1a and 1b. During the water treatment to remove harmful substances from the container, the adsorbent regeneration process is performed to regenerate the adsorbent by desorbing the harmful substances adsorbed from the adsorbent in the other of the containers 1a and 1b. It is.

  The containers 1a and 1b are filled with a porous adsorbent (hereinafter referred to as adsorbent 2) which is a spherical or crushed granular material. Here, as the porous adsorbent, a granular adsorbent having an inorganic porous structure containing activated alumina as a main component and silicon dioxide / sodium oxide as other components is used.

  The containers 1a and 1b are made of metal, and the inner surfaces are coated with ferrite magnetic films 73a and 73b. A plurality of microwave irradiators 71a and 71b connected to the microwave generators 70a and 70b by waveguides are provided on the upper surfaces of the containers 1a and 1b. The microwave generators 70a and 70b used here have a wavelength of 2400 MHz or more and an output of 2000 W or more. Since the insides of the containers 1a and 1b are coated with the ferrite magnetic films 73a and 73b, the microwaves irradiated from above by the microwave irradiators 71a and 71b are not transmitted to the outside and the loss is suppressed and reflected to the bottom surface. Propagating while.

Further, on the upper surfaces of the containers 1a and 1b, air introducing pipes 36a and 36b for introducing vertically extending high-pressure air that communicates the inside and the outside, and a plurality of vertically extending pipes that are connected to each other by a reinforcing member that is connected thereto. Air introducing pipes 36a and 36b made of a body are provided. The upper ends of the pipes constituting the air pipes 54a and 54b are branched from the lower ends of the air introduction pipes 36a and 36b and communicate with the air introduction pipes 36a and 36b. A large number of through holes are arranged in a zigzag manner at regular intervals on the side surfaces of each of the air pipes 54a and 54b, and a wire mesh is wound around the through holes so that no adsorbent enters. The pipes constituting the air pipes 54a and 54b are internally threaded, and the amount of air to be ejected is adjusted by adjusting the amount of engagement and disengagement of the male screw engaged therewith. Be able to.
An air pipe 37 having motor-operated valves 12a and 12b is connected to the upper end side connected to the outside of the air introduction pipes 36a and 36b. The air pipe 37 is connected to an air compressor 16 that generates high-pressure air via a pressure regulator 18. ing.

In addition, a shower head is provided in the upper part of the containers 1a and 1b to uniformly spray waste liquid and washing water on the upper surface, and an opening and closing for discharging the liquid in the containers 1a and 1b. Drain ports that are opened and closed by the valves 22a and 22b are provided.
Further, the containers 1a and 1b include a raw water tank 5 for storing waste liquid to be processed, an acidic solution tank 26 for storing dilute sulfuric acid, a water washing tank 27 for storing water, a hot water tank 28 for storing hot water, A treated water tank 52 for collecting treated water, a recovered liquid storage tank 31 for collecting liquid recovered from a regeneration liquid, and a pump and an electric valve are connected. The pump, the motor-operated valve, the microwave generator, the air compressor, and the pressure regulator are operated according to operations programmed in the control microcomputer 33. The control microcomputer 33 is electrically connected to each component / equipment, but the electrical connection is omitted because the diagram becomes very complicated when the connection is illustrated.

  The raw water tank 5 has a conductivity meter 7 that measures the conductivity of the raw water 6, a raw water pump 8 that passes the raw water 6 to the containers 1a and 1b, and a flow meter 9 that indicates the amount of water flow. Control is performed so that the water flow is switched from the line pipe 34 connected to 8 to either the line pipe 35a connected to the shower head of the container 1a or the line pipe 35b connected to the shower head of the container 1b by the three-way motor operated valve 10. ing.

  The treated water tank 52 is connected to a discharge line pipe 45 extending from a drain port provided on the bottom surface of each of the containers 1a and 1b. The treated water tank 52 is provided with an on-off valve 50 for controlling the inflow. The discharge line pipe 45 is provided with a conductivity meter 47 for detecting the concentration of ionic components of the treated water, a discharge valve 49 connected to sewage and the like, an on-off valve 55 for returning to the raw water tank 5, a pump 32 is connected to the return line piping 46.

  The recovered liquid storage tank 31 is branched and connected to the discharge line pipe 45 from the three-way motor operated valve 30. The recovered liquid storage tank 31 is provided with a rod-like sheathed heater inside, and an IH stove for IH heating is provided on the floor surface so that double heating from inside and outside can be performed.

The acidic solution tank 26 is connected via a pump 23 to a line pipe 44 having an on-off valve 21a connected to the shower head of the container 1a and a line pipe 42 having an on-off valve 21b connected to the shower head of the container 1b.
The water washing tank 27 and the hot water washing tank 28 are connected to the pump 24 via the three-way motor-operated valve 10, and the pump 24 has a line pipe 43 having an opening / closing valve 20a connected to the shower head of the container 1a, and the shower head of the container 1b. Is connected to a line pipe 41 having an on-off valve 20b connected to the line.

(2) Water Treatment Next, the operation of the water treatment apparatus X having the above configuration will be described. Here, although the operation | movement which processes the waste liquid containing a phosphate ion as a waste liquid to process is demonstrated, the process can be performed also with the water containing what kind of substance if it can adsorb | suck to a porous adsorbent.

  First, the raw water 6 enters the container 1a through the line piping 34a on the container 1a side by the three-way solenoid valve 10 through the line piping 34. The raw water 6 is sprinkled from the shower head at the top of the container 1a and contacts the adsorbent 2 filled in the container 1a in the process of moving downward in the container. By spraying the raw water 6 in a shower-like manner, the adsorbent 2 and the raw water 6 can be uniformly contacted, and the raw water 2 is filtered by contacting the lower adsorbent 2 one after another over time. The water is passed while falling toward the bottom of the container 1a.

  The adsorbent 2 mainly composed of activated alumina is a porous body, and has a structure having van der Waals force on the surface or inside the pores. Therefore, in the process in which the raw water 6 is passed through the container 1a, phosphate ions contained in the raw water 6 are adsorbed on the surface and inside the pores by van der Waals force working on the surface of the adsorbent 2 or inside the pores.・ Attached and captured. On the other hand, the raw water 6 is discharged as treated water 51 from which phosphoric acid ions contained therein are removed and hardly contain phosphoric acid. Since the container 1a (1b) has a cylindrical shape that is long in the height direction with respect to the inner diameter, the filtration resistance of the adsorbent 2 that is filled increases, and thereby phosphate ions contained in the raw water 6 are absorbed into the adsorbent 2. Therefore, the concentration of the phosphoric acid component contained in the discharged treated water 51 can be made extremely small.

  The treated water 51 from which the phosphate ions have been removed by the adsorption / adhesion action of the adsorbent 2 moves from the drain to the discharge line piping 45 and is stored in the treated water tank 52. Since this treated water is treated water 51 from which the phosphoric acid component has been removed, it can be reused as washing water. The treated water 51 may be discharged by opening the discharge electromagnetic valve 49 without accumulating the treated water 51.

  In the discharge line piping 45, the conductivity is measured by the conductivity meter 47 and compared with a reference value set in advance by the control microcomputer 33. The treated water 51 in which phosphate ions have been appropriately adsorbed has almost no ionic components because phosphate ions have been removed, and the conductivity is small. On the other hand, if the conductivity value is equal to or higher than the reference value, the treated water 51 is regarded as being insufficiently treated, the on-off valve 50 is closed, the on-off valve 55 is opened, and the raw water tank 5 is returned via the regression line piping 46. It comes to return. The returned treated water 51 will be treated again.

  Further, when the conductivity continuously exceeds a reference value for a certain period of time, it is determined that the adsorption saturation of the adsorbent 2 has occurred, and the control microcomputer 33 changes the three-way motor operated valve 10 from the line pipe 35a to the line pipe 35b. By switching to the side, the flow direction of the raw water 6 is switched to the container 1b side. The on-off valve 22a connected to the drain of the container 1a is opened until the raw water in the container 1a runs out, and then closed. Hereinafter, in the container 1b, the same raw water 6 adsorption treatment as that in the container 1a is performed. On the other hand, in the container 1a, a process of desorbing phosphate ions and regenerating the adsorbent 2 (adsorbent regeneration process) is performed.

(3) Adsorbent regeneration process In the regeneration process, first, in the container 1a, the on-off valve 21a is opened and the dilute sulfuric acid stored in the acidic solution tank 26 is sprinkled from the shower head of the container 1a into the container 1a. At this time, the on-off valve 22a at the drain port of the container 1a is closed. The sprinkled dilute sulfuric acid is contacted and filtered over the area where the adsorbent 2 is laminated while taking time, but since the drain electric valve 22a is closed, the dilute sulfuric acid accumulates in the cylindrical container 1a and is adsorbed. The material 2 is immersed. The dilute sulfuric acid has a function of stripping phosphate ions adsorbed or adhering to the entire surface of the adsorbent 2 and the inside of the pores by a weak dissolving action. This dissolving action is a dissolving power of a degree that breaks the bond between the adsorbing material 2 and the adsorbed phosphate ions, and does not have an action of greatly dissolving the adsorbing material 2. It is a small dissolving power that peels off the skin.

  After the adsorbent 2 is immersed in dilute sulfuric acid for a certain period of time, the drain electric valve 22a is opened to dilute the dilute sulfuric acid. The dilute sulfuric acid and the cleaning liquid discharged are stored in the recovered liquid storage tank 31 by switching the three-way electric valve 30a. Thereafter, water or hot water is sent from the water washing tank 27 or the hot water washing tank 28 to the container 1a, and the adsorbent 2 is washed by the water washing shower or the hot water washing shower.

Next, the air compressor 16 is operated and high-pressure air is irradiated from the air pipe 54a. This high-pressure air is controlled to an appropriate pressure by the pressure regulator 18 to reduce or reduce the amount of moisture contained in the adsorbent 2 wetted by the above-mentioned immersion, and the action of stirring or vibrating the adsorbent 2 filled in the container 1a. Has a dehydrating effect. Due to this dehydration effect, the amount of water contained in the adsorbent 2 can be reduced, so that the microwave irradiation time described later can be shortened.

After completing the air irradiation process with high-pressure air for a certain period of time, with the high-pressure air being continuously irradiated, the microwave generator 70a is activated and microwaves are irradiated from the microwave irradiator 71a for a certain period of time. Microwave heating is performed on the adsorbent 2. Although the amount of water contained in the adsorbent 2 in the air irradiation process is reduced, the pores contain some moisture. When microwave heating is performed on the adsorbent in this state, the microwave vibrates the moisture contained in the pores of the adsorbent 2, and the temperature becomes high, and the moisture inside the pores changes to water vapor.
Thus, since water vapor | steam generate | occur | produces inside a pore, the vapor | steam pressure inside a pore increases, and the produced | generated water vapor tends to come out to the surface side of the adsorbent 2 with a low pressure. In the process in which water vapor is discharged from the inside of the pores to the outside, the water vapor pushes out the phosphate ions remaining inside the pores and discharges them together with the water vapor to the outside.

  Further, since the microwave is irradiated while irradiating the high-pressure air, the adsorbent 2 is stirred and vibrated and is in contact with the microwave. Moreover, the effect which blows away the phosphate ion discharged | emitted on the surface of the adsorbent 2 and promotes the fall to the bottom face side direction is also acquired. The microwave irradiation time does not irradiate until the inside of the pores of the adsorbent 2 is completely dried, but vapor pressure is generated inside the pores, which are minute spaces, and the surface of the adsorbent 2 It is sufficient to irradiate the inside of the hole for a short time enough to maintain a slightly wet state.

When irradiation with high-pressure air and microwave is completed for a certain time, the air compressor 16 and the microwave generator 70a are stopped, water or hot water is sent from the water washing tank 27 or the water washing tank 28 to the container 1a, and the adsorbent 2 is washed with water. Wash with a shower or hot water shower. As a result, the phosphate ions pushed out onto the surface of the adsorbent 2 can be washed away and desorbed from the granular material 2, and the wash water containing phosphate ions flows to the bottom side and flows from the drain to the recovered liquid storage tank 31. And discharged.
As a method of washing away phosphate ions by washing with water, the drain electric valve 22a is closed, immersion in water or hot water is performed for a certain period of time, and then the drain electric valve 22a is opened to remove the immersed liquid. Cleaning can be performed using two types: an immersion cleaning method and a shower cleaning method in which water or hot water is washed while showering with the drain electric valve 22a open.
In addition, whether water or hot water is selected for cleaning depends on the nature of the substance to be washed out and the concentration of the substance to be washed, and the one having a higher cleaning effect is selected. Since the phosphate ions can be desorbed by 60% or more by the treatment as described above, the water treatment with the adsorbent 2 can be performed again.

Here, activated alumina is used as the adsorbent, and phosphate ions are used as the substance adhering to the adsorbent. However, since desorption by microwave heating is due to physical force, activated carbon, zeolite, etc. Any porous adsorbent can be used, and deposits can also be applied to various things. Furthermore, although the immersion treatment with dilute sulfuric acid is performed here, it is needless to say that an immersion treatment with an alkaline solution such as a sodium hydroxide solution may be performed as long as a solution suitable for peeling off the deposits is used.

The regeneration treatment of the adsorbent according to the present embodiment is performed immediately after immersion in an acidic solution or an alkaline solution, and the amount of the adsorbent itself dissolved by an acid or the like can be reduced. Can be made smaller.
In addition, since it is difficult to wash the inside of the pores with water by shower, a dilute acidic or alkaline solution that has entered the inside of the pores by immersion treatment with an acidic solution or an alkaline solution remains inside the pores. . The diluted acidic solution or alkaline solution remaining inside the pores due to microwave irradiation is concentrated with the evaporation of moisture and the concentration increases, so that the effect of peeling off the deposits inside the pores is enhanced, and the vapor pressure is applied. Combined with the action of pushing out the kimono to the outside, the deposit can be effectively desorbed from the inside of the pores to the outside.

  Furthermore, even if some deposits remain inside the pores, immediately after the cleaning treatment by immersion, the washing water is contained in the pores, and the deposits peeled off inside the pores are washed. The remaining adhering component can be discharged from the inside of the pores by removing the wash water that has been immersed in water and drained from the drain. By repeating such a washing operation a plurality of times, the deposits can be efficiently desorbed from the pores of the adsorbate 2.

本試験は、リン酸イオンを吸着して飽和した活性アルミナからなる多孔質吸着材からリン酸を脱離し、脱離率を求めたものである。なお、リン酸イオンはトータルリン濃度で評
価確認できるためトータルリンで分析評価した。 (4) Test Table 1 and FIG. 2 show the results of a test conducted to investigate the desorption effect by microwave heating.

In this test, phosphoric acid was desorbed from a porous adsorbent made of activated alumina saturated by adsorbing phosphate ions, and the desorption rate was determined. Since phosphate ions can be evaluated and confirmed with the total phosphorus concentration, they were analyzed and evaluated with total phosphorus.

Here, the desorption rate is (initial value) where the total phosphorus content adsorbed on the granular material is (initial value) and the total phosphorus content in the desorbed granular material is (residual amount). )-(Residual amount), which is derived from the following equation.
Desorption rate (%) = desorption amount / initial value × 100
The blank sample relating to the alkaline solution is immersed in an alkaline solution of about 1% for 3 minutes, and phosphate ions are desorbed only by about 10%. On the other hand, after immersing in an alkaline solution for 3 minutes, microwave irradiation is performed while jetting high-pressure air, followed by washing with water. When the microwave irradiation time is 20 seconds, 60%, 40 seconds 70%, 1 minute 40 A desorption rate of 65% was obtained in seconds. Moreover, the blank sample regarding an acidic solution is what was immersed in the thin acidic solution for 3 minutes, and has only about 6% detachment | desorption rate. On the other hand, when immersed in an alkaline solution for 3 minutes and then irradiated with microwaves while jetting high-pressure air and then washed with water, a 50% detachment rate was obtained with a microwave irradiation time of 40 seconds. Thus, it can be seen that a sufficient desorption effect can be obtained by microwave irradiation for 1 minute or less.

Furthermore, the test was performed in the same manner as described above for the elimination of hexavalent chromium which is a cation. The results are shown in Table 2 and FIG.

  The blank sample relating to the alkaline solution is immersed in an alkaline solution of about 1% for 3 minutes, and phosphate ions are desorbed only by about 14%. On the other hand, when immersed in an alkaline solution for 3 minutes and then irradiated with microwaves while jetting high-pressure air and then washed with water, a desorption rate of 65% was obtained with a microwave irradiation time of 40 seconds. Moreover, the blank sample regarding an acidic solution is what was immersed in the thin acidic solution for 3 minutes, and has only about 9% detachment | desorption rate. On the other hand, when immersed in a thin acidic solution for 3 minutes and then irradiated with microwaves while jetting high-pressure air and then washed with water, a 50% detachment rate was obtained with a microwave irradiation time of 40 seconds. Thus, it can be understood that effective desorption can be performed with a similar short microwave irradiation time in addition to phosphoric acid.

  In order to further improve the desorption rate, it is effective to perform a plurality of cycles. FIG. 4 shows the test results. This is a process of immersing in a thin sodium hydroxide solution for 5 minutes, washing, irradiating with microwaves for 1 minute or more, then immersing twice in hot water, and then washing with water as one cycle. Comparison of desorption rates. As can be seen from the figure, the desorption rate is clearly improved by performing a plurality of cycles. In addition, since the time for one cycle is extremely short compared with the conventional desorption method, there is little time burden even if it is repeated a plurality of cycles.

(5) Others In the above-described embodiment, microwave heating is used for the regeneration treatment of the adsorbent in the water treatment apparatus, but it is not necessary to integrate it into the water treatment apparatus, and the dedicated adsorbent desorption process is performed. Microwave heating may be used in the apparatus. As an apparatus configuration example in this case, the waste water treatment line may be omitted from one container constituting the water treatment apparatus X. An example is shown in FIG. Since the desorption process method is the same as the adsorbent regeneration process described above, a description thereof will be omitted.
The test data by the desorption processing apparatus is shown below. In the test, a treatment for removing impurities adhering to the granular porous adsorbent made of activated alumina was performed. In many cases, porous adsorbents made of activated alumina contain impurities such as sodium and aluminum inside, and when adsorbing valuable metals etc. from waste liquid and recovering it, it contains impurities. Since it is desirable to use a non-adsorbing material, the process of desorbing impurities from the adsorbing material is useful as a pretreatment of the adsorbing material.

  In the test, a commercially available activated alumina adsorbent was immersed in a dilute sulfuric acid solution for a certain period of time and then washed with water, and irradiated with microwaves for 2 minutes or more for several minutes. This was immersed in a chromic acid solution and the concentrations of sodium and aluminum eluted were measured. The results are shown in FIG. In addition, BL is a blank sample which is a comparison object, and is a case where desorption processing is not performed. As can be seen from the figure, in the case of sodium, the Na elution concentration is about 50 ppm in the blank sample, whereas in the case of desorption treatment, the Na elution concentration is about 2 ppm, which is an elution concentration of about 1/25 or less. Became. In the case of aluminum, the Al elution concentration in the blank sample was about 640 ppm, while the Al elution concentration in the case of desorption treatment was about 50 ppm or less, which was about 1/13 or less. As described above, it can be seen that impurities contained in the adsorbent can be greatly reduced by the method of the present invention.

  In desorption using microwave heating, the inside of the pores of the adsorbent after the generation of water vapor by microwaves becomes high temperature, causing oxidation, and the aluminum component inside the pores is aluminum oxide (active It is thought that the effect of changing to the (alumina) film also occurs. As a result, the inside of the pore is resistant to erosion due to the dissolving action of acid, alkali or the like, and even if the pore is immersed in acid or alkali, further elution of impurities from the inside of the pore is difficult to occur. For this reason, when removing impurities from the activated alumina adsorbent, it is desirable to perform microwave heating until there is no moisture in the pores.

  Moreover, in the said embodiment, although the container on a cylinder was used, the form of a container can employ | adopt various forms, such as a rectangular parallelepiped shape. In the above-described embodiment, the adsorbent is immersed in an acidic solution or an alkaline solution before microwave heating in order to facilitate the desorption of the deposits, but various methods can be considered as a pretreatment for desorption. For example, by irradiating the immersed adsorbent with microbubbles and irradiating with ultrasonic waves, the microbubbles that enter the pores of the adsorbent are destroyed with ultrasonic waves, and the adsorbent is easily detached by this impact. Etc. may be adopted. Furthermore, a method of facilitating desorption of the adsorbent by the action of the water vapor entering the adsorbent pores rapidly condensing by applying water vapor to the adsorbent in the dry state can be employed. When water vapor is used, it is possible to have a role of containing moisture inside the pores of the adsorbent.

1a, 1b Container 2 Adsorbent 5 Raw water tank 10 Three-way solenoid valve 16 Air compressor 22a, 22b Drain open / close valve 26 Acid solution tank 27 Flush tank 28 Hot water wash tank 36a, 36b Air introduction pipe 54a, 54b Air pipe 70a, 70b Microwave Generator 71a, 71b Microwave irradiator

Claims (18)

A moisture addition step for containing moisture in the pores of the granular porous adsorbent to which the deposit has adhered,
After the moisture addition step, a microwave irradiation step of performing microwave heating on the adsorbent in the atmosphere with moisture contained in the pores;
A porous adsorbent adhering material desorbing method comprising a washing step of washing the adsorbent after a microwave irradiation step. After the moisture addition step and before the microwave irradiation step,
The porous adsorbent deposit desorption method according to claim 1, further comprising an air irradiation step of blowing air to the adsorbent.   The porous adsorbent adhering material desorption method according to claim 1 or 2, wherein air is blown against the adsorbent during the microwave irradiation step.   The porous adsorbent adhering material desorption method according to any one of claims 1 to 3, wherein the cleaning step includes immersing the adsorbent in a cleaning liquid at least once.   The porous adsorbent adhering material detachment according to any one of claims 1 to 4, wherein, in the moisture addition step, the adsorbent is immersed in a liquid so that moisture is contained in the pores. Method.   5. The porous adsorbent adhering material desorption method according to claim 1, wherein the moisture adding step is performed by passing a liquid through a container containing the adsorbent.   The adsorbent according to any one of claims 1 to 6, wherein an acid solution or an alkaline solution is brought into contact with the adsorbent before the water addition step, and then the adsorbent is washed with water as the water addition step. Attachment removal method.   The method according to any one of claims 1 to 7, wherein the moisture is an acidic solution or an alkaline solution. Before the microwave irradiation process,
A microbubble irradiation step of immersing the adsorbent in a liquid and irradiating microbubbles in the liquid;
The porous adsorbent adhering material removal according to any one of claims 1 to 8, further comprising: an ultrasonic irradiation step of irradiating ultrasonic waves into the liquid filled with microbubbles after the microbubble irradiation step. Separation method. Before the microwave irradiation process,
The porous adsorbent adhering material desorption method according to any one of claims 1 to 9, further comprising a vapor step of applying vapor to the adsorbent. An apparatus for desorbing deposits from a granular porous adsorbent with deposits,
A container for holding the adsorbent inside;
Moisture adding means for containing moisture in the pores of the adsorbent in the container;
A porous adsorbent adhering substance desorbing device comprising microwave irradiation means for performing microwave heating on the adsorbent in the container. The container is capable of immersing the held adsorbent, has a discharge port having an on-off valve for discharging the liquid inside, and the moisture adding means allows the liquid to flow into the container. 11. The porous adsorbent deposit desorption apparatus according to 11. The porous adsorbent adhering substance desorbing device according to claim 12, wherein the moisture adding means is capable of allowing two or more kinds of liquids to flow therein.   The porous adsorbent adhering substance detachment apparatus according to any one of claims 11 to 13, further comprising air irradiation means for blowing air onto the adsorbent in the container. An apparatus for recovering a target substance from a target liquid such as waste water / waste liquid in which the target substance is dissolved or mixed, using a granular porous adsorbent,
A container for holding the adsorbent inside;
A target liquid inlet for injecting the target liquid into the container;
A discharge port having an on-off valve for discharging the liquid in the container;
Microwave irradiation means for performing microwave heating on the adsorbent in the container;
A water treatment apparatus having a cleaning water inlet for injecting cleaning water into the container.   Two or more of the containers to which the target liquid injection port, the discharge port, the microwave irradiating means, and the washing water injection port are attached are arranged in parallel, and supply the target liquid. The water treatment device according to claim 15, wherein the target liquid injection port can be switched to which target liquid injection port by a switching valve.   The water treatment apparatus according to claim 15 or 16, further comprising air irradiation means for blowing air onto the adsorbent in the container.   The water treatment apparatus according to any one of claims 15 to 17, further comprising solution injection means for injecting an acidic solution or an alkaline solution into the container.

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