JP2009166037A - Apparatus and method for desorption of deposit adhered onto particulate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus which desorbs deposits adhered onto particulates effectively by the use of superheated steam. <P>SOLUTION: The apparatus for desorption of deposits adhered onto particulates has a particulate holding container for sealing of particulates having a large number of holes which particulates cannot pass through, a sealed oven sealing the particulate holding container in a nearly sealed state, a rotation supporting section supporting the particulate holding container in a rotatable way, a rotation driving means of rotating the particulate holding container, and a steam introduction means of introducing superheated steam into the closed oven. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method and an apparatus for desorbing deposits adhering to particulate matter such as sand, earth, and particulate adsorbent. In the present application, “attachment” refers to the case where the particles are physically attached to the surface of the particulate matter (including the inner surface of the hole formed in the surface) by van der Waals force, and the case where the particulate matter is chemically attached by a covalent bond or the like. Both of them are attached to the surface and attached. Further, “desorption” does not mean a so-called desorption reaction, but simply means that the deposit is separated from the particulate matter.

Conventionally, after a harmful substance is adsorbed by an adsorbent, the harmful substance is 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 is adsorbed, there is a method in which the organic substance is vaporized and decomposed by exposing it to high-temperature superheated steam for several tens of minutes.

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 is necessary to spend 60 minutes or more. The test results are shown in FIG. FIG. 7 shows the decomposition rate of the organic substance over time when 100 g of activated carbon adsorbed with the organic substance is reacted with superheated steam at 300 ° C. Moreover, when using 500 degreeC superheated water vapor | steam, it is necessary to take time for 30 minutes to 40 minutes. The test results are shown in FIG. FIG. 8 shows the decomposition rate of the organic substance over time when 100 g of activated carbon adsorbed with the organic substance is reacted with 500 ° C. superheated steam. Also, this method requires exposure to high temperatures for long periods of time, so that activated carbon degrades due to oxidation, so it needs to be almost oxygen-free. Wait until the temperature drops to prevent ignition and oxidation of the activated carbon after treatment. Time is also needed.

Both of these are a desorption method mainly using a chemical reaction and a desorption method using superheated steam, but there are advantages and disadvantages. By the way, the method using superheated steam uses the action of high-temperature steam and the agglomeration action of rapid steam to desorb the deposits, which is less harmful and is not limited to activated carbon. This is a desirable method with a wide range of applications that can be used remotely.
On the other hand, there is a problem that it takes time and energy to desorb an organic substance from activated carbon or the like as described above, and the substance adhering to the granular material becomes uneven as the granular material changes with time. Once solidified on the surface or inside the pores, it is not easy to peel the bonded deposits by the effect of the superheated steam.
In view of the above, it is an object of the present invention to provide an apparatus for effectively desorbing deposits adhering to particulates using superheated steam.

In order to solve the above problems, the present invention has the following configuration.
The invention according to claim 1 includes a granular material holding container that encloses the granular material, provided with a large number of holes through which the granular material cannot pass, and a sealed furnace that encloses the granular material holding container in a substantially sealed state. And a rotating support unit for rotatably holding the granular material holding container, a rotation driving means for rotating the granular material holding container, and a steam introducing means for introducing superheated steam into the sealed furnace. It is a kimono detachment apparatus.
According to a second aspect of the present invention, in the particulate matter desorbing device, a liquid spraying means for spraying a liquid to the particulate matter holding container is provided in the sealed furnace.
According to a third aspect of the present invention, in the particulate matter deposit detachment apparatus according to the first aspect, two or more liquid spraying means are provided.
Invention of Claim 4 is a storage tank which is a tank body which stores the liquid sprayed by the said liquid spraying means in the particulate matter deposit | attachment detachment | desorption apparatus of Claim 1 or 2, Comprising: The said particulate matter A storage tank that is positioned so that at least a part of the holding container exists inside the tank body is provided.

The invention according to claim 5 is the particulate matter depositing and detaching device according to the fifth aspect, wherein the particulate matter holding container is a cylindrical body in which an axis whose both openings are closed faces in a horizontal direction, and the rotation support portion is the cylinder The granular material holding container is rotatably held around the rotation axis of the body.
The invention according to claim 6 is the tip of the particulate matter detachment apparatus according to claim 5, wherein the vapor introducing means is provided along the lower side of the particulate matter holding container constituting the cylindrical body. Is a closed tube body, and has a steam ejection pipe in which openings for ejecting a plurality of steams are formed at positions on the side surface facing the granular material holding container.
According to a seventh aspect of the present invention, in the particulate matter adhering / detaching apparatus according to any one of the second to sixth aspects, the particulate matter holding container is a cylindrical body having both openings closed, and the rotation support portion is the cylindrical body. The granular material holding container is rotatably held around the rotation axis of the body, and the liquid spraying means is provided along the upper side of the granular material holding container constituting the cylindrical body, A closed pipe body is provided with a liquid spraying head in which an opening through which a plurality of solutions are ejected is formed at a position facing the granular material holding container on the side surface.

According to an eighth aspect of the present invention, in the particulate matter depositing and desorbing apparatus, one or more stirring blades are provided inside the particulate matter holding container.
According to a ninth aspect of the present invention, in the particulate matter deposit detachment apparatus, a heating means for heating the sealed furnace from the outside is provided.
According to a tenth aspect of the present invention, in the particulate matter deposit detachment apparatus, a gas spraying means for blowing gas to the particulate matter holding container is provided.
According to an eleventh aspect of the present invention, in the particulate matter deposit detachment apparatus, the liquid spraying means includes a liquid pump and an air compressor connected to the liquid layer so that the spray target can be switched to air. In addition to being connected, a switching valve for switching between introduction from the liquid pump and introduction from the air compressor is provided.

The invention according to claim 12 is a method for desorbing a nitrogen compound from a porous granular material mainly composed of alumina using the granular material adhering substance desorbing device, wherein the granular material is treated with an alkaline solution. An immersion step in which the granular material is enclosed in the granular material holding container after the immersion step, and the granular material is applied to superheated steam by the steam introducing means while rotating the rotation driving means. A method for removing particulate matter including a water vapor step. Nitrogen compounds include nitrate ions and nitrogen oxides.
According to a thirteenth aspect of the present invention, in the particulate matter deposit detachment method, the superheated steam step is performed in an almost oxygen-free state.

With the above configuration, the present invention has the following effects.
The invention according to claim 1 is to introduce the superheated steam into the sealed path by the steam introduction means while putting the granular material in the granular material holding container having a large number of holes and rotating in the sealed furnace. Superheated steam can be applied uniformly to the granular material stirred in the granular material holding container.
In the invention according to claim 2, since the liquid can be sprayed to the granular material holding container by the liquid spraying means, if a solution that can act on the deposit as a liquid is used, the solution can be applied to the granular material in the solution. Can be contacted evenly.
In the invention according to claim 3, by providing two or more liquid spraying means, for example, an acidic solution is sprayed from one liquid spraying means and water is sprayed from another liquid spraying means, depending on the situation. The liquid to be switched can be switched.
In the invention according to claim 4, when the sprayed liquid accumulates in the storage tank by providing a storage tank positioned so that at least a part of the granular material holding container exists inside the storage tank. Part of the granular material in the granular material holding container is immersed in the liquid in the storage tank, and the frequency with which the liquid is brought into contact with the granular material can be increased.

Since the invention described in claim 5 is a cylindrical body that rotates while being held in the horizontal direction by holding the granular material holding container, a part of the wall of the granular material holding container that moves so as to move upward is generated by the rotation. It is easier to stir by moving the granular material up and down.
According to the sixth aspect of the present invention, steam is ejected from a plurality of holes from a steam jet pipe along a cylindrical granular material holding container toward the granular material holding container. Steam can be sprayed evenly over the length.
According to the seventh aspect of the present invention, liquid is ejected from a plurality of holes toward the granular material holding container from the liquid spraying head along the cylindrical granular material holding container. The liquid can be evenly distributed over the length direction.
In the invention according to claim 8, the stirring of the granular material can be further promoted by providing the stirring blade in the granular material holding container.
According to the ninth aspect of the present invention, the temperature of the superheated steam in the sealed furnace can be suppressed and the inside of the sealed path can be kept at a high temperature by heating the sealed furnace from the outside by the heating means.
The invention according to claim 10 can dry the particulate matter by blowing the gas to the particulate matter in the particulate matter holding container by the gas spraying means for blowing the gas, thereby promoting the coagulation action by the superheated steam. can do.
According to the eleventh aspect of the present invention, an air compressor is connected to the liquid spraying means to switch between the liquid injection and the gas injection, so that it is not necessary to newly provide a gas injection nozzle or the like. In the case where a means for spraying is provided, the configuration can be simplified.

The invention according to claim 12 dissolves the nitrogen compound together with the alumina of the surface layer by immersing a porous granular material mainly composed of alumina, to which the nitrogen compound is adhered, in an alkaline solution by an immersion step. Then, the superheated steam can be applied to the granular material evenly by allowing the superheated steam to touch the superheated steam in the sealed space while stirring in the granular material holding container in the superheated steam step. Nitrogen compounds that are uniformly dissolved from the particulate matter are decomposed and released as a gas of nitrogen oxides by high-temperature steam, and the nitrogen compounds can be desorbed from the particulate matter.
The invention according to claim 13 suppresses the oxidation of the particulate matter during the treatment when the superheated steam step is performed in an oxygen-free state and the particulate matter to be treated has a problem that the function is deteriorated due to the oxidation. be able to.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Embodiment 1)
The figure which represents typically the structure of the granular material deposit | attachment detachment | desorption apparatus X which concerns on FIG. 1 at embodiment is shown. The particulate matter detachment apparatus X includes a particulate matter holding container 10 that performs a detachment process, a sealed furnace 20 that seals the particulate matter holding container 10, a steam introduction unit 30 that introduces superheated steam into the sealed furnace 20, A liquid / gas spraying unit 40 that sprays liquid onto the granular material holding container 10 in the closed furnace 20 and jets air, and similarly, a liquid spraying unit 50 that sprays liquid onto the granular material holding container 10, and a liquid / gas spraying unit. 40 and a storage tank 60 for storing the solution sprayed from the liquid spraying section 50, a waste liquid recovery section 70 for recovering the liquid stored in the storage tank 60, and a heater section 80. 2 is a partially broken enlarged perspective view showing the inside of the heater section 80, and FIG. 3 is a cross-sectional view taken along line AA of FIG.
The container main body 11 constituting the granular material holding container 10 is formed of a casing in which a net is formed in a cylindrical shape and an opening is sealed with a disk. The size of the mesh is set to a size that the granular material to be processed cannot pass. One of the disks is provided with a lid 11a for taking in and out the particulate matter. Further, four stirring blades 11b formed from a plate body having a cross-sectional shape as shown in FIG. Further, a rotating shaft 12 passing through a cylindrical central axis is fixed at the center of each disk. And the axial support bodies 13a and 13b which consist of the plate body in which the semicircular notch was formed in the both ends of the storage tank 60 mentioned later on which the rotating shaft 12 of the granular material holding | maintenance container 10 was rotatably supported was formed. Is fixed. The rear end side of the rotating shaft 12 is fixed to the rotating shaft of the motor 14 provided outside the sealed furnace 20 via the coupler 14 a, and the granular material holding container 10 is rotated around the rotating shaft 12 by the motor 14. It is like that.

The closed furnace 20 is a cylindrical body with one opening closed, and is closed so that the front is closed by a sealing lid 80a, which will be described later, so that it is in a sealed state except for ventilation from the tubular body leading to the outside. .
The steam introduction unit 30 includes a superheated steam generator 32, a steam ejection pipe 31, a steam outflow pipe 33, and a steam recovery pipe 34. The superheated steam generator 32 has a tank for storing water, and this water flows out from the steam outlet pipe 33 to the outside as superheated steam using high frequency. Two steam ejection pipes 31 are provided above both sides of a storage tank 60 to be described later, and the opening extending along the granular material holding container 10 is sealed, and an opening for ejecting a plurality of steams is provided on the side. It consists of a pipe body, and superheated steam introduced from the steam outflow pipe 33 connected to the rear end is jetted into the sealed furnace 20 from the opening. The steam outlet pipe 33 is a tubular body having a bifurcated tip so that it can be connected to the two steam jet pipes 32. The steam recovery pipe 34 has a through-cylinder 34 a provided in the upper part of the closed furnace 20, and recovers steam from here to the superheated steam generator 32. The recovered steam is heated again by the superheated steam generator 32 to become superheated steam. In addition, when superheated steam is filled in the closed furnace 20, the oxygen ratio in the air that was originally reduced is reduced, and oxygen discharged from the steam recovery pipe 34 is dissolved in water in a high-pressure state. It becomes almost oxygen-free.

The liquid / gas spraying unit 40 includes a spraying head 41, a tank 42, a pump 43, a flow pipe 44, an electromagnetic three-way valve 45, and an air compressor 46. The spraying head 41 is composed of a tubular body provided along the upper side of the granular material holding container and having a closed end, and a plurality of solutions and air are ejected to positions on the side surface facing the granular material holding container. An opening is provided. The tank 42 is a general tank that stores the liquid to be sprayed. The air compressor 46 is composed of a general air compressor that sends out high-pressure air. The distribution pipe 44 is a pipe body for sending a liquid or gas from the tank 42 and the air compressor 46 to the spraying head 41, and a pump 43 directly connected to the tank 42 is provided on the way, and further at a position downstream of the pump 42. A three-way solenoid valve 45 is provided. An air compressor 46 is connected to an inlet that is not on the flow path of the flow pipe 44 of the three-way solenoid valve 45.
That is, by controlling the three-way solenoid valve 45, it is possible to switch between spraying liquid and spraying air from the spraying head 41, and controlling the pump 43 to control liquid injection and stopping. By controlling the compressor 46, the injection and stop of air can be controlled.
The liquid spraying unit 50 has the same configuration as the liquid / gas spraying unit 40, and includes a liquid spraying head 51, a tank 52, a pump 53, and a liquid circulation pipe 54. The liquid circulation pipe 54 is connected to a three-way electromagnetic valve. The difference is that the air compressor is not connected. In FIG. 1, the liquid spraying head 41 and the liquid spraying head 51 are depicted as being deviated from each other. However, this is an expedient expression, and actually, they are arranged in parallel as shown in FIG. 3.
The storage tank 60 is a rectangular parallelepiped box that is slightly longer than the container main body 11 of the granular material holding container 10 and slightly wider than the container main body 11 and is open at the top. At both ends of the storage tank 60, shaft supports 13a and 13b are rotatably fixed that rotatably hold the rotating shaft 12 of the granular material holding container 10. A drain pipe 73, which will be described later, communicates with the outside of the closed furnace 20 is provided on the bottom surface of the storage tank 60. In addition, the storage tank 60 is bent downward from the side at a certain height on the side surface of the storage tank 60. To an overflow pipe 71 which will be described later. Note that the lower end of the container body 11 of the granular material holding container 10 is set at a substantially intermediate position between the position of the overflow pipe 71 and the bottom surface in a state where the granular material holding container 10 is held by the shaft supports 13a and 13b. ing.

The waste liquid recovery unit 70 includes an overflow pipe 71, a drain pipe 73, electromagnetic valves 72 and 74, a first waste liquid tank 75, a second waste liquid tank 76, and an electromagnetic three-way valve 77. As described above, the overflow pipe 71 is connected to the side surface of the storage tank 60 having a certain height, and the liquid exceeding the certain height flows from the storage tank 60. The electromagnetic valve 72 is provided in the overflow pipe 71, but is normally open to allow the liquid from the storage tank 60 to pass through the overflow pipe 71. The drain pipe 73 is connected to the bottom of the storage tank 60 as described above, and is used when the liquid stored in the storage tank 60 is extracted. The drain pipe 73 is provided with an electromagnetic valve 74. The electromagnetic valve 74 is normally closed, and the electromagnetic valve 74 is opened when the liquid in the storage tank 60 is extracted. The first waste liquid tank 75 and the second waste liquid tank 76 are general tanks. The electromagnetic three-way valve 77 switches whether the liquid flowing from the overflow pipe 71 and the drain pipe 73 is led to either the first waste liquid tank 75 or the second waste liquid tank 76, and is connected to the first waste liquid tank 75. The connecting pipe 75a and the connecting pipe 76a connected to the second waste liquid tank 76 are connected.
The heater 80 is a band heater having a cylindrical heat insulating portion surrounding the sealed furnace 20 and heats the inside of the sealed furnace 20. Specifically, the heater 80 feeds back the temperature of a thermometer (not shown) in the closed furnace 20 to maintain the temperature inside the closed furnace 20 at a constant high temperature. The front end side of the heater 80 can be closed in a sealed state by a sealing lid 80a. The sealing lid 80a also seals the opening of the front end of the sealing furnace 20 at the same time.
The motor 14 for rotating the granular material holding container 11, the superheated steam generator 32, the pumps 43 and 53 of the liquid / gas spraying units 40 and 50, the electromagnetic valves 72 and 74 of the waste liquid recovery unit 70, the electromagnetic three-way valve 77, the heater 80 is program-controlled by control means (not shown).

  Next, a particulate matter detachment method using the particulate matter detachment apparatus X having the above configuration will be described. Here, a case where nickel is desorbed from a porous inorganic adsorbent particle (hereinafter referred to as “adsorbent particle”) mainly composed of alumina as a granular material is exemplified. Here, since nickel, which is a heavy metal, is desorbed, a dilute acidic solution is placed in the tank 42 of the liquid / gas spraying unit 40, and water is placed in the tank 52 of the other liquid spraying unit 50. When desorbing anions such as fluorine, a dilute alkaline solution is placed in the tank 42 of the liquid / gas spraying unit 40.

First, the sealing lid 80a is opened, the granular material holding container 11 is taken out, and adsorbent particles having adsorbed nickel inside are enclosed. Then, the granular material holding container 11 is set inside the closed furnace 20, and the sealed lid 80a is closed. In this state, the motor 14 is driven to rotate the granular material holding container 11, and the superheated steam generator 32 is operated to introduce superheated steam into the closed furnace (superheated steam step). At this time, the superheated steam is blown evenly from the lower sides toward the inside of the granular material holding container 11 by the steam ejection pipe 31.
Moreover, since the inside of the closed furnace 20 is maintained at a predetermined temperature by the heater 80, the temperature of the superheated steam does not decrease. Further, the superheated steam is discharged to the outside from the steam recovery pipe 34, is heated again via the superheated steam generator 32, and returns to the sealed furnace 20.
By introducing superheated steam into the closed furnace in this way, the agglomeration of superheated steam occurs inside the adsorbent particles and inside the pores, and the pores are filled with water and adsorbed nickel is fine. Float above the hole. The superheated steam is filled in the closed furnace 20, and the adsorbent particles are rotated while being stirred by the stirring blade 11b in the rotating granular material holding container 11, so that most of the adsorbent particles have a coagulation action. It reaches. However, in this state, the temperature of the surface of the adsorbent particles immediately exceeds 100 ° C., and the condensing action does not occur. Conversely, the condensed water is again vaporized and the nickel that has floated up again returns to the pores. End up. Therefore, before the adsorbent particles approach 100 degrees, the diluted acidic solution is sprayed from above the granular material holding container 11 by the liquid / gas spraying unit 40 (solution treatment / cooling step). Since the diluted acidic solution is at room temperature, the adsorbent particles can be cooled, and the nickel that has floated in the vicinity of the pores can be washed away by the action of the acidic solution. Can be easily peeled by a dissolving action. The amount of the dilute acidic solution sprayed is the amount cooled while dissolving the entire surface of the adsorbent particles and the inside of the pores, for example, about 1/10 to the same amount as the amount of adsorbent particles charged. In addition, since the adsorbent particles are rotated while being stirred, the diluted acidic solution can be brought into almost uniform contact. And cooling and condensation can be repeated any number of times by spraying this dilute acidic solution regularly. Note that the generation of superheated steam may be stopped when the dilute acidic solution is sprayed.
Further, in order to further enhance the peeling effect due to condensation, a step of drying the pores on the surface of the adsorbent particles after the application of the dilute acidic solution can be added. That is, after spraying the dilute acidic solution for a certain period of time, the electromagnetic three-way valve 45 of the liquid / gas spraying unit 40 is switched so that the air compressor 46 is in communication with the spraying head 41 and the air compressor is operated. A normal temperature / high pressure air flow from 41 is applied to the adsorbent granules for a certain period of time. Thereby, moisture such as a dilute acidic solution in the adsorbent particle surface and pores is blown off, and at the same time, the temperature in the adsorbent particle surface and pores can be cooled. By this step, since the adsorbent particles are in a drier state, it is possible to effectively cause peeling due to the coagulation action.

Further, the sprayed dilute acidic solution is stored in the storage tank 20 after coming into contact with the adsorbent particles and the granular material holding container 11. When a certain amount of the diluted acidic solution stored in the storage tank 20 is stored, the granular material holding container is immersed in the diluted acidic solution in the storage layer 20, whereby a part of the adsorbent particles in the granular material holding container 10 is formed. The dilute acidic solution in the storage tank is passed through, so that the nickel floating due to the coagulation action adhering to the adsorbent particles is washed away, and the nickel that has not been peeled can be easily peeled off. That is, since the dilute acidic solution and the adsorbent particles are in contact with each other by spraying the solution from above and being immersed in the storage tank 20, the amount of the dilute acidic solution to be used can be reduced. . When a large amount of dilute acidic solution is accumulated in the storage tank 20 and reaches the opening of the overflow pipe 71, the dilute acidic solution exceeding this portion passes through the overflow pipe 71 and is guided by the electromagnetic three-way valve 77. 75 and the second waste liquid tank 76.
In this way, the desorption treatment is completed by periodically spraying the diluted acidic solution in the superheated steam atmosphere. Thereafter, the electromagnetic valve 74 is opened, and the waste liquid collected in the storage tank 20 from the drain pipe 73 is collected in either the first waste liquid tank 75 or the second waste liquid tank 76 guided by the electromagnetic three-way valve 77, and the granular material holding container 10 is collected. Is removed from the closed furnace 20 and the treated adsorbent particles are collected to complete the operation.

  The optimum temperature of superheated steam varies depending on the conditions, but generally the amount of condensation of superheated steam from gas to liquid increases with increasing temperature and the volume of superheated steam increases. It is assumed that the amount of condensation will increase when touching an object, so the amount of condensation will increase as a result, and the diluted acidic solution will be further diluted, resulting in a phenomenon that weakens the dissolving action, and the temperature is high. In some cases, it becomes difficult to cool to 100 degrees or less. FIG. 4 shows an experimental result when an experiment is performed in which the superheated steam temperature is changed in 30 g of adsorbent particles in the present embodiment. FIG. 4 shows data representing the temperature of superheated steam and the desorption rate of nickel. From this experimental result, it was found that the superheated steam temperature of 400 ° C. has the highest desorption rate in this embodiment. When the temperature of superheated steam is high at 600 ° C and 800 ° C, it is speculated that the action of weakening the dissolving action of the acidic solution occurred due to the increase in the amount of condensate. Because it is more advantageous, the minimum superheated steam temperature is considered to be optimal at 400 ° C.

In addition, the spray interval of the dilute acidic solution varies depending on the processing amount of the adsorbent particles, the spray amount and temperature of the dilute acidic solution, the temperature of the superheated steam, the superheated steam temperature of 400 degrees, the adsorbent particles of 30 g, the dilute When the temperature of the acidic solution was normal temperature, the application amount per application was 15 ml, and the number of cycles was 4 times, it was found from the experimental results that the 1 minute interval was optimal. FIG. 5 shows a graph representing the experimental results. It can be seen from this graph that the dilute acidic solution should be sprayed at 1 minute intervals. Such a result is obtained when the surface temperature of the adsorbent particles or the pore internal temperature reaches a saturated water vapor temperature of 100 ° C. after 1 minute or more, and when it is within 0.5 minutes, peeling due to condensation is sufficiently caused. It is thought that the cause is not.
As these data show, if the dilute acid shower is repeated 4 times under such conditions, the condensation of superheated steam for 5 times (5 times because it occurs when the first superheated steam irradiation is started) occurs. It was possible to desorb about 65% or more of the heavy metal substance nickel adsorbed inside the pores of the porous adsorbent by combining the dissolving action and cooling action of four times of acid.

This method is gas desorption due to superheated steam, and the dilute acidic solution to be sprayed is very small because it is applied to the surface of the porous body, and moreover, the water is almost evaporated in the furnace and is generated as waste liquid. The amount is extremely small, and the amount of waste liquid is 30 to 50 times less than the method of desorbing heavy metal substances adsorbed on ordinary ion exchange resins.
In addition, the adsorbed nickel, which is a heavy metal substance, is boiled at a high temperature in the reservoir and the water is evaporated, so that it can be recovered in the waste liquid tank as a high-concentration slurry (nickel concentrate). In other words, since it can be recovered as a highly concentrated nickel concentrate with a low water content, the time of the heating process can be shortened and the cost can be reduced by applying a filter press process that can significantly reduce the time of the water evaporation process. Thus, nickel sludge can be easily produced, and effective use for nickel resource recovery can be realized, and a closed type desorption process can be achieved with low cost and almost no waste.

In addition, since the method for desorbing a heavy metal material according to the present embodiment can be desorbed using a few repeated treatments in units of several minutes of about 1 minute, the desorption time is 5 minutes to 10 minutes. Therefore, one small particulate matter depositing apparatus X can be desorbed 6 times in 1 hour operation, and 24 × 6 = 144 times in 24 hours. For example, 3kg x 144 times = 432Kg can be desorbed even if the granular material is only 3kg in one batch, and heavy metal substances can be desorbed from a large amount of granular material even with a small device. It will be cheaper.
As described above, the particulate matter detachment apparatus X has a short processing time even in a small furnace, so that a large amount of particulate matter and porous material can be detached by increasing the number of cycles. Therefore, since the closed furnace 20 can be made small, it is possible to increase the temperature to a high temperature with a small amount of energy, and the volume of superheated steam can be reduced, so that the amount of energy used is extremely low and the energy efficiency is increased. That is, once the temperature rises, the amount of energy for maintaining the temperature is small because the furnace has a small volume, and the temperature is maintained even when superheated steam is injected, so that less energy is required.
Furthermore, since the particulate matter deposit detachment apparatus X can be reduced in size as a whole, the installation area is small and compact. Further, by dividing a plurality of superheated steam from one superheated steam generation source apparatus, the plurality of sealed furnaces 20 are superheated. Since it is also possible to supply water vapor at the same time, the processing for the plurality of granular material holding containers 10 can be performed by one superheated steam generator 32, and even when the processing amount is increased, the manufacturing cost can be suppressed, and the superheated steam generator By using only one 32, it is possible to reduce the amount of increase in the energy cost of running with respect to the increase in the processing amount of granular materials.

  In this example, a porous adsorbent mainly composed of alumina adsorbed with nickel was used as an example, but almost the same treatment is applied to adsorbents and heavy particulates such as sand adhering heavy metal ion substances and anion substances. By performing the above, the deposit can be detached. It should be noted that the solution to be sprayed is either whether the main component of the material constituting the granular material to be processed or the main component of the adhering heavy metal substance or anionic substance is dissolved in acid or alkali, or both acid and alkali. It will be selected after determining whether it dissolves. When the dissolution properties of amphoteric, for example, in the case of aluminum or lead may be selected either to dissolve in the alkali in acid.

  Also, when reducing the number of repetitions of the dilute acidic solution or dilute alkaline solution to be sprayed, or in the case of a solidified state where the binding force of the adhered substance is strong, before subjecting the treated granular material to superheated steam, It is preferable to immerse in an acidic or alkaline solution having a pH value approximate to the solution to be spread for several minutes (immersion step). Actually, by adsorbing the adsorbent with solidified heavy metal in a dilute acidic solution such as HCI with a concentration of several percent of hydrochloric acid for several minutes or more, combined with an acid shower of dilute hydrochloric acid solution in a superheated steam atmosphere. It was possible to desorb. This is because the heavy metal substance is changed from the bonded state to the adhering state after the heavy metal substance is changed from the bonded state to the adhering state by cutting off the binding force of the acid due to the dissolving action of the acid in advance. This is considered to be because the heavy metal substance having a weak binding force can be peeled off by the coagulation action. In addition, when the bond strength of the deposit is not so strong, the bond strength is further weakened, so that the amount of deposit that can be detached can be maintained even if the number of times of dilute acidic solution or dilute alkaline solution is reduced. Time can be shortened.

  By the way, when the granular material is dissolved by the diluted acidic solution or the diluted alkaline solution to be sprayed, particularly when the granular material is the adsorbent and is regenerated, the pores of the adsorbent may be damaged. However, since the coagulation action of superheated steam is a liquefaction action of water vapor, it also has the function of diluting the progress of the melting effect due to the acid or alkali adhering to the particulate matter, and thus the above-mentioned damage is alleviated. Furthermore, in order to alleviate this damage, water can be applied to the application cycle of the dilute acidic solution or dilute alkaline solution (water washing step). By spraying water in this manner, the acidic or alkaline solution is diluted, and damage to the adsorbent that is a granular material due to dissolution can be suppressed. The water may be sprayed from the liquid spraying unit 50. Further, after spraying water, the surface of the adsorbent may be dried by ejecting high-pressure air at room temperature from the liquid / gas spraying unit 40. As a result, the solution is dried while keeping the temperature of the adsorbent surface and pores at a low level, thereby enhancing the setting effect and suppressing the damage caused by the acid or alkaline solution. The setting effect is proportional to the number of spray cycles. Can be obtained.

(Embodiment 2)
Next, the particulate matter detachment method according to the second embodiment will be described. The present embodiment is a desorption process in the case where an organic material having heat resistance and a general organic material having no heat resistance coexist as an adhering substance. Also in the present embodiment, the particulate matter deposit detachment apparatus X used in the first embodiment is used. Here, activated carbon particles are used as the granular material. It is assumed that water is put into the tank 42 of the liquid / gas spraying unit 40.

  First, saturated activated carbon particles in which heat-resistant and non-heat-resistant organic substances are mixed and bonded to the whole pores in a saturated state are immersed in a dilute acidic solution for a certain period of time (immersion step). Thereby, the joint part of an organic substance and activated carbon is dissolved beforehand. In addition, since activated carbon does not melt | dissolve in an acid, the inside of a pore is not melt | dissolved and states, such as the adsorption capacity of a activated carbon, a specific surface area, do not deteriorate. Note that an alkaline solution can be used as the solution to be immersed depending on the dissolution characteristics of the organic substance bonded thereto.

Next, the activated carbon particles subjected to the immersion treatment are put in the granular material holding container 11 in the same manner as in the first embodiment, set in the closed furnace 20, and in this state, the motor 14 is driven to rotate the granular material holding container 11. . Thereafter, the superheated steam generator 32 is operated to introduce superheated steam into the closed furnace 20 (superheated steam step). The inside of the closed furnace 20 is maintained at a constant high temperature by the heater 80, and the superheated steam circulates through the inside of the closed furnace 20. Here, as described later, the temperature of the superheated steam is set to 300 ° C.
By introducing superheated steam into the closed furnace in this way, the agglomerated action of superheated steam occurs on the surface of the activated carbon particles and inside the pores, and the organic substance whose bonding strength has been weakened by the immersion treatment is caused by the condensation action. Part of the organic compound that peels off and has no heat resistance is vaporized and decomposed by high-temperature superheated steam. On the other hand, the organic compound having heat resistance rises to the upper part of the pores due to the coagulation action. As in the first embodiment, superheated steam is filled in the closed furnace 20, and the activated carbon particles are rotated while being stirred by the stirring blade 11b in the rotating granular material holding container 11, so that most of the activated carbon particles. Condensation effect is exerted on. In such an overheated steam atmosphere, water is further sprayed through the liquid / gas spraying section 40 to wash away the organic compound floating above the pores. Moreover, activated carbon is cooled by spraying water. Thereafter, when watering is stopped, a coagulation action occurs on the cooled activated carbon, and vaporization decomposition of the organic compound having no heat resistance and increase in peeling of the organic compound having heat resistance occur. Then, by repeating watering intermittently, the action of superheated steam, water washing and cooling are performed alternately. At this time, in the last step, the watering is stopped for a certain time or more to raise the temperature of the activated carbon particles to about 200 ° C., thereby vaporizing and decomposing all organic compounds having no heat resistance. Note that generation of superheated steam may be stopped when water is sprayed.
Further, after the water is sprayed, the electromagnetic three-way valve 45 of the liquid / gas spraying unit 40 is switched so that the air compressor 46 and the spraying head 41 communicate with each other. You may make it hit for a fixed time. Thereby, the water | moisture content in the activated carbon particle surface and pore is blown off, and the temperature of adsorption | suction can be cooled simultaneously. This step allows the activated carbon particles to be in a drier state while maintaining a state close to room temperature, so that peeling due to the setting action can be more effectively caused.
Finally, the activated carbon particles are cooled by spraying water through the liquid / gas spraying unit 40 (water washing step), and the desorption process is completed. When the desorption process is completed, the electromagnetic valve 74 is opened, and the waste liquid collected in the storage tank 20 from the drain pipe 73 is collected in either the first waste liquid tank 75 or the second waste liquid tank 76 guided by the electromagnetic three-way valve 77, The particulate holding container 10 is taken out of the closed furnace 20 and the treated adsorbent particles are collected to complete the operation.
In this way, an organic compound having no heat resistance is vaporized and decomposed by superheated steam, and the organic compound having heat resistance is peeled off by the coagulation action of the superheated steam, and desorbed by washing with water. Even if organic compounds having heat resistance are mixed, both can be desorbed. When this is performed only with superheated steam, for example, when a heat-resistant organic substance that is difficult to thermally decompose even at a temperature of 200 ° C. or higher, such as a bisarylfluorene compound or polyphenylene sulfide, is included, for vaporization decomposition Requires a high temperature of 300 ° C. or higher, ideally 400 ° C. or higher, and high temperature superheated steam of 400 ° C. to 500 ° C. or higher is required to bring the temperature inside the activated carbon to 300 ° C. to 400 ° C. This consumes extra electrical energy and is wasteful. On the other hand, for such heat-resistant organic compounds, if the water-washing treatment is not performed, in which water is sprinkled after peeling by a relatively low-temperature superheated steam condensing action that does not vaporize and decompose, the condensed water will be vaporized immediately and peel off. The heat-resistant organic compound thus returned returns to the pores and cannot be desorbed.

In addition, the temperature of superheated steam can be adjusted with a superheated steam generator, and here the temperature of superheated steam is about 300 degreeC. The optimum processing time in this case is shown by the experimental data in FIG. This figure is a graph showing the relationship between the treatment time and the decomposition rate of an organic compound having no heat resistance when the amount of activated carbon is 100 g and the superheated steam temperature is 300 ° C. From this experimental result, it can be seen that when the superheated steam is 300 ° C., 80% or more of the organic substance can be desorbed in a treatment time of 5 minutes or more. This is an effect equivalent to or higher than the conventional vaporization decomposition rate of organic substances only by superheated steam shown in FIG. 7, and as described above, the conventional method takes 60 minutes or more of processing time with superheated steam at 300 ° C. A significant time reduction was achieved. In addition, by spraying water after vaporization and decomposition of the organic substance, the activated carbon particles having reached about 200 ° C. or higher are instantaneously cooled to below 100 ° C. in an oxygen-free furnace, and then exposed to the atmosphere. No burning phenomenon occurs, and the activated carbon particles can be taken out in a short time without damaging them. Since the cooling with water is short, the cooling time required for the extraction is less than about 1 minute, and the total processing time is as short as about 10 minutes per time.
In addition, in the watering repeatedly performed before the last cooling process, it may replace with spraying water and may spray the acid or alkali solution at the time of immersion.

(Embodiment 3)
The particulate matter depositing method according to the third embodiment is also a desorption treatment in the case where the deposit is an organic substance, but unlike the second embodiment, the first immersion treatment with a dilute acidic solution is not performed. Also in the present embodiment, the particulate matter deposit detachment apparatus X used in the first embodiment is used. Here, activated carbon particles on which organic substances are adsorbed are also used as the granular materials. It is assumed that a dilute acidic solution is placed in the tank 42 of the liquid / gas spraying unit 40 and water is placed in the tank 52 of the liquid spraying unit 50.

First, saturated activated carbon particles in which organic substances are saturatedly bonded to the entire inside of the pores are placed in the granular material holding container 11 in the same manner as in the first embodiment, set in the closed furnace 20, and in this state, the motor 14 is turned on. Driven to rotate the granular material holding container 11. Thereafter, the superheated steam generator 32 is operated to introduce superheated steam into the closed furnace 20 (superheated steam step). The inside of the closed furnace 20 is maintained at a constant high temperature by the heater 80, and the superheated steam circulates through the inside of the closed furnace 20.
By introducing superheated steam into the closed furnace in this way, the agglomeration of superheated steam occurs on the surface of the activated carbon particles and inside the pores, and part of the organic substance is peeled off due to the condensation action, Vaporizes and decomposes with superheated steam. However, in this state, the temperature on the surface of the granular material immediately exceeds 100 ° C. and no condensing action occurs. Therefore, before the granular material approaches 100 degrees, the liquid / gas spraying unit 40 sprays the diluted acidic solution from the granular material holding container 11 (solution treatment / cooling step). Since the dilute acidic solution is at room temperature, the particulate matter can be cooled, and the action of the acidic solution makes it easy to vaporize and decompose organic substances that have not been vaporized and decomposed by a single coagulation action. In addition, since the granular material is rotating while being stirred, the diluted acidic solution can be brought into almost uniform contact. And cooling and condensation can be repeated any number of times by spraying this dilute acidic solution regularly. Note that an alkaline solution may be used as the solution to be dispersed depending on the solubility characteristics of the organic substance to be desorbed. Moreover, you may stop generation | occurrence | production of superheated steam at the time of dispersion | distribution of a solution.
Furthermore, just like the first embodiment, immediately after the solution is sprayed, the activated carbon particles may be dried by spraying air from the liquid / gas spraying unit 40.

Further, the sprayed diluted acidic solution is stored in the storage tank 20 after contacting the granular material or the granular material holding container 11. When a certain amount of the diluted acidic solution stored in the storage tank 20 is stored, the granular material holding container is immersed in the diluted acidic solution in the storage layer 20, whereby a part of the granular material in the granular material holding container 10 is stored. The dilute acidic solution in the tank is passed through, so that it is possible to easily vaporize and decompose organic substances that have not been peeled off. In this way, since the solution is sprayed from above and immersed in the storage tank 20, the diluted acidic solution and the granular material are in contact with each other, so that the amount of the diluted acidic solution to be used can be reduced. .
As described above, most of the organic substances can be vaporized and decomposed when the agglomeration action occurs multiple times in the activated carbon particles while repeating cooling and dissolution with a dilute acidic solution. When the desorption of the organic substance is completed, the activated carbon particles are finally cooled by spraying water through the liquid spraying unit 50 for cooling (water washing step), and the particulate matter holding container 10 is taken out from the sealed furnace 20, The treated adsorbent particles are collected, the electromagnetic valve 74 is opened, and the waste liquid accumulated in the storage tank 20 from the drain pipe 73 is guided to either the first waste liquid tank 75 or the second waste liquid tank 76 guided by the electromagnetic three-way valve 77. The work is completed after collection. In this embodiment, the superheated steam temperature is set to 300 ° C., a dilute acidic solution is sprayed twice at intervals of 5 minutes, and water is sprayed after 5 minutes, thereby realizing one desorption process in about 12 minutes. We were able to.

  This method is effective for decomposing organic substances having strong binding strength and organic substances that are completely bonded and solidified to activated carbon or the like after a long time because of the cyclic treatment of the same process. Further, since the immersion treatment with a dilute acidic solution in advance is not performed, it is effective when it is desired to greatly reduce the amount of waste liquid.

(Embodiment 4)
In the present embodiment, a nitrogen compound is desorbed from a granular material of a porous adsorbent mainly composed of alumina. Also in the present embodiment, the particulate matter deposit detachment apparatus X used in the first embodiment is used. Furthermore, granules with adsorbent particles containing alumina as a main component as in the first embodiment, illustrating a case where nitrate nitrogen (NO ₃ -N) is attached as a deposit. The adsorbent grains contain 90% or more of alumina, and the remaining main components are silicon dioxide and sodium oxide. In addition, it is assumed that water is placed in the tank 42 of the liquid / gas spraying unit 40.

First, the adsorbent particles having adsorbed nitrate nitrogen are immersed in an alkaline solution having a pH of 10 or more for about 20 minutes (immersion step). Here, a sodium hydroxide solution having a pH of 10 or more is used as the alkaline solution. At this time, with the elution of activated alumina, the nitrate nitrogen adsorbed inside the pores of the adsorbent particles is also dissolved and eluted as nitrate ions NO ₃ ⁻ .

Next, the adsorbent particles subjected to the immersion treatment are put in the granular material holding container 11 in the same manner as in the first embodiment, set in the sealed furnace 20, and in this state, the motor 14 is driven to rotate the granular material holding container 11. Let Thereafter, the superheated steam generator 32 is operated to introduce superheated steam into the closed furnace 20 (superheated steam step). The inside of the closed furnace 20 is maintained at a constant high temperature by the heater 80, and the superheated steam circulates through the inside of the closed furnace 20. Here, the temperature of the superheated steam is set to 400 ° C.
Thus, when superheated steam is introduced into the closed furnace and 15 minutes or more elapses, nitrate ions are decomposed by the action of superheated steam and gasified as nitrogen oxides. The gasified nitrogen oxide can be finally released into the atmosphere as nitrogen gas by using a denitrification catalyst by a general ammonia catalytic reduction method.
The following equation shows the final reaction.
4NOx + 4NH ₃ + O ₂ → 4N ₂ ↑ + 6H ₂ O
The nitrogen oxides thus desorbed are decomposed into nitrogen N ₂ and water H ₂ O. That is, nitrogen oxides can be returned to the atmosphere as nitrogen.
Finally, the adsorbent particles are cooled by spraying water through the liquid / gas spraying unit 40 (water washing step), and the desorption process is completed. Thereafter, the electromagnetic valve 74 is opened, and the waste liquid collected in the storage tank 20 from the drain pipe 73 is collected in either the first waste liquid tank 75 or the second waste liquid tank 76 guided by the electromagnetic three-way valve 77 to hold the particulate matter. The container 10 is taken out of the closed furnace 20 and the treated adsorbent particles are collected to complete the operation.

As the time of immersion in the alkaline solution is longer, the nitrogen compound is eluted, but the adsorbent particles are also dissolved. Therefore, it is preferable that the temperature is reduced as long as the temperature decomposition by superheated steam is sufficient. From this point of view, a nitrate nitrogen desorption decomposition experiment was conducted by the method described below.
First, 120 g of adsorbent particles are immersed in 1 L of liquid containing 1% or more of nitrate nitrogen concentration for 1 hour or more to adsorb nitrate nitrogen. Separate the adsorbent particles adsorbing nitrate nitrogen into 20g portions, leaving one for the blank, and the rest is how much nitrate nitrogen is desorbed and decomposed by changing the immersion treatment time and the reaction time of superheated steam, respectively. Compared. The results are shown in Table 1 below.
Here, the adsorbent particles taken out by reaction with superheated steam are completely melted with an acid to obtain the concentration of nitrate nitrogen (X) remaining in the adsorbent particles, and the concentration of nitrate nitrogen in the alkaline solution after immersion treatment is ( A).

As shown in the experimental results, the nitrate nitrogen contained in the adsorbent granule is 20 minutes or 60 minutes or more in a furnace in which superheated steam at 400 ° C. or higher is convected in a state where immersion treatment is not performed. It remained at a ratio of 90 or more close to the initial value of 100, that is, the desorption rate was less than 10%. This is because nitrate nitrogen is hardly decomposed into gas, and mere superheated steam cannot be desorbed even if it reacts for a long time of 60 minutes or more with this adsorbent particle bonded with nitrate nitrogen. Recognize.
Next, when this immersion treatment time is compared, when the concentration of sodium hydroxide is 10%, if the immersion time is about 10 minutes, even if superheated steam at 400 ° C. is reacted for 60 minutes, the desorption rate is It is a small value of about 33%. On the other hand, when the immersion time is 20 minutes, there is a desorption rate of about 90% or more even when superheated steam at 400 ° C. is reacted for only 15 minutes, and nitrate nitrogen in the adsorbent grains is 7.2%. It was found that almost no residue. Note that even if the reaction time with the superheated steam is doubled for 30 minutes, no significant improvement in the desorption rate is seen, so considering the efficiency of the treatment process, the reaction time of about 15 minutes is sufficiently practically satisfactory. it is conceivable that.
This is because the adsorbent grains adsorbing nitrate nitrogen in a sodium hydroxide solution having a pH of 10 or more are immersed in a time of about 20 minutes, so that the aluminum component which is the main component constituting the pores of the adsorbent grains. It is thought that the dissolution starts and the inner aluminum film is peeled off inside the pores, and nitrate nitrogen bound to the peeled aluminum film is detached with the peeling of the aluminum film. Inferred. When superheated steam at 400 ° C. or higher is allowed to react for about 15 minutes or more immediately after this state is reached, nitrate nitrogen exfoliated inside the pores becomes a temperature inside the pores due to the action of hydroxyl groups and heating of the high-temperature steam of the superheated steam. It is thought that as temperature rises, it is decomposed by heating to a gas such as nitrogen oxides and water.
Although nitrate nitrogen is exemplified here as the nitrogen compound, other nitrogen compounds can also be desorbed by gas decomposition as nitrogen oxides by the same method.
This nitrogen oxide can be finally decomposed into nitrogen gas and released into the atmosphere by using a catalyst of the ammonia catalytic reduction method.

It is a figure which represents typically the structure of the granular material deposit | attachment detachment apparatus X which concerns on embodiment. It is a partially broken expanded perspective view which shows the inside of the heater part of a granular material deposit | attachment detachment | desorption apparatus. It is AA sectional drawing of FIG. It is a figure which shows the change of the desorption rate at the time of changing superheated steam temperature in Embodiment 1. FIG. In Embodiment 1, it is a figure which shows the change of a desorption rate when changing the spreading | spreading cycle of a dilute solution. In Embodiment 2, it is a figure which shows the reaction time of superheated steam, and the change of a decomposition rate. It is a figure which shows the relationship between the reaction time in the superheated steam temperature of 300 degreeC by the conventional method, and the detachment | desorption rate which detach | desorbs an organic substance from activated carbon. It is a figure which shows the relationship between the reaction time in the superheated steam temperature of 500 degreeC by the conventional method, and the detachment | desorption rate which detach | desorbs an organic substance from activated carbon.

Explanation of symbols

X particulate adhering substance detaching apparatus 10 granular substance holding container 11 container main body 11b stirring blade 12 rotating shafts 13a and 13b shaft support body 14 motor 20 sealed furnace 30 steam introduction part 31 steam ejection pipe 32 superheated steam generator 40 liquid / gas Spraying unit 50 Liquid spraying unit 41, 51 Liquid spraying head 45 Three-way solenoid valve 46 Air compressor 60 Storage tank 70 Waste liquid recovery unit 80 Heater unit

Claims (13)

A granular material holding container that encloses the granular material and provided with a number of holes through which the granular material cannot pass;
A closed furnace for sealing the granular material holding container in a substantially sealed state;
A rotation support unit for rotatably holding the granular material holding container;
A rotation driving means for rotating the particulate holding container;
A particulate matter desorbing device having steam introducing means for introducing superheated steam into the closed furnace.   The particulate matter detachment apparatus according to claim 1, further comprising a liquid spraying means for spraying a liquid to the particulate matter holding container in the sealed furnace.   The particulate matter detachment apparatus according to claim 2, wherein two or more liquid spraying means are provided.   The storage tank which is a tank body which stores the liquid sprayed by the said liquid spraying means, Comprising: The storage tank positioned so that at least one part of the said granular material holding | maintenance container exists in the said tank body was provided. Or the particulate matter desorbing device according to 3. The granular material holding container is a cylindrical body whose axis with both openings closed is oriented in the horizontal direction,
The particulate matter detachment device according to any one of claims 1 to 4, wherein the turning support portion rotatably holds the particulate matter holding container around a rotation axis of the cylindrical body. .   The steam introducing means is a tube body provided along the lower side of the granular material holding container constituting the cylindrical body, the tip of which is closed, and a plurality of steam introduction means are provided at positions facing the granular material holding container on the side surface. The particulate matter detachment apparatus according to claim 5, further comprising a steam ejection pipe in which an opening for ejecting steam is formed. The granular material holding container is a cylindrical body whose both openings are closed,
The rotation support unit is configured to rotatably hold the granular material holding container around a rotation axis of the cylindrical body,
The liquid spraying means is a tube body provided along the upper side of the granular material holding container constituting the cylindrical body and having a closed end, and a plurality of liquid spraying means are disposed at positions facing the granular material holding container on the side surface. The particulate matter detachment apparatus according to any one of claims 2 to 6, further comprising a liquid spraying head in which an opening through which the solution is ejected is formed.   8. The particulate matter desorbing device according to claim 1, wherein one or more stirring blades are provided inside the particulate matter holding container.   The particulate matter detachment apparatus according to any one of claims 1 to 8, further comprising heating means for heating the sealed furnace from the outside.   The particulate matter detachment apparatus according to any one of claims 1 to 9, wherein gas dispersion means for blowing gas to the particulate matter holding container is provided.   The liquid spraying means is connected to a liquid pump and an air compressor connected to the liquid layer so that the object to be sprayed can be switched to air, and introduces from the liquid pump and the air compressor. The particulate matter desorption device according to any one of claims 2 to 9, wherein a switching valve for switching is provided. A method for desorbing a nitrogen compound from a porous granular material mainly composed of alumina using the particulate matter desorbing device according to any one of claims 1 to 11,
An immersion step of immersing the granular material in an alkaline solution;
After the dipping step, the granular material is sealed in the granular material holding container, and the granular material includes a superheated steam step of applying the granular material to superheated steam by the steam introducing means while rotating the rotation driving means. The method for desorbing deposits.   The particulate matter desorption method according to claim 12, wherein the superheated steam step is performed in an almost oxygen-free state.