JP4414841B2 - Dehumidifier - Google Patents

Description

  The present invention relates to a dehumidifying device used for dehumidification of air in a manufacturing apparatus room and a conveying apparatus room in the manufacture of semiconductors, liquid crystals, electronics, etc. The honeycomb rotor is rotated, and the dehumidification of the air to be treated containing moisture by the dehumidifying agent and the regeneration of the dehumidifying agent that has absorbed the moisture are simultaneously performed to continuously dehumidify the air to be treated. The present invention relates to a dehumidifying device.

In a manufacturing process of a silicon wafer or the like in a semiconductor manufacturing factory, the generation of an oxide film causes a product defect, but it has recently been found that moisture has a great influence on the generation of the oxide film. For this reason, in order to reduce product defects, it has become necessary to remove moisture in the air in the manufacturing equipment room and the like.

As a method for removing moisture in the air in the production apparatus, there are mainly a method of purging with dry nitrogen gas and a method of dehumidifying. In the method of purging with nitrogen gas, the moisture in the apparatus chamber is expelled to the outside of the apparatus chamber, so that the amount of moisture is very low. However, the running cost (cost of dry nitrogen gas and N ₂ Pressure Swing Adsorption (PAS; nitrogen generator) ) Is expensive, and it is necessary to control the oxygen gas concentration in the equipment room. On the other hand, the dehumidifying method does not require dry nitrogen gas, and it is not necessary to control the oxygen gas concentration, so that the running cost is lower than the method of purging with the dry nitrogen gas.

  Therefore, in recent years, research on a dehumidifier for the purpose of dehumidification in a semiconductor manufacturing apparatus room or the like has been advanced. As the dehumidifying apparatus, for example, Japanese Patent Application Laid-Open No. 2004-000824 of Patent Document 1 discloses that a part of sodium in a hydrophilic zeolite is replaced with one or more elements selected from La, Nd, Ce, and Pr. The adsorbent made of aluminosilicate is carried and has a rotor having rotating means, the rotation area of the rotor is divided into an adsorption zone and a regeneration zone, and a path for supplying a gas to be treated to the adsorption zone, and the adsorption zone A dehumidifying device is disclosed that includes a path for supplying the gas treated in step 1 to the target space and a path for supplying the regeneration gas to the regeneration zone.

  Moreover, a household dehumidifier is used for drying laundry in the room and preventing condensation in the room in winter. In particular, the dehumidifier is required to be able to dehumidify air having a low absolute humidity, such as winter air.

As the dehumidifying device for home use, Japanese Patent Application Laid-Open No. 2004-3844 of Patent Document 2 has a rotor filled with a hygroscopic agent that absorbs moisture, and the rotor is divided into a hygroscopic part and a regeneration part, A moisture absorption path for absorbing moisture from the moisture absorption air, a regeneration path for regenerating the moisture absorbent, a regeneration heater for raising the temperature of the regeneration air, and a condenser for condensing and removing the moisture in the regeneration air are provided. A dehumidifier is disclosed.
Japanese Patent Laid-Open No. 2004-000824 JP 2004-003844 A

  In the above dehumidifying apparatus, in order to continuously dehumidify the air to be treated, dehumidification of the air to be treated containing moisture by the dehumidifying agent and regeneration of the dehumidifying agent that has absorbed moisture are performed simultaneously. Therefore, during the operation of the dehumidifier, the dehumidifier always repeats moisture absorption and dehumidification of moisture in the air to be treated. Then, the moisture absorption performance of the dehumidifying agent gradually decreases due to the repetition, and eventually the moisture absorption performance necessary as the dehumidifying agent may not be recovered even after dehumidification.

  When the dehumidifying agent can no longer recover the hygroscopic performance, the dehumidifying agent must be replaced with a new dehumidifying agent. However, since the dehumidifying agent is normally carried on a honeycomb structure constituting the honeycomb rotor, the dehumidifying agent alone cannot be replaced, and the honeycomb rotor must be replaced. For this reason, in the case of a dehumidifying device for dehumidification such as in a semiconductor manufacturing apparatus room, replacement of the honeycomb rotor is very costly. Therefore, if the replacement frequency is high, the maintenance cost of the dehumidifying device increases. Therefore, a dehumidifying device with a low frequency of replacement is desired.

  In the case of a household dehumidifier, due to the nature of the product of the dehumidifier, the honeycomb rotor is required to be maintenance-free until the product life is reached. Therefore, a dehumidifier that does not require replacement of the honeycomb rotor is desired.

  Therefore, the problem of the present invention is that the dehumidifying agent carried on the honeycomb rotor has a long life, the honeycomb rotor is not frequently replaced, or has excellent dehumidification over a long period of time without replacing the honeycomb rotor. An object of the present invention is to provide a dehumidifying device capable of maintaining performance.

  As a result of intensive studies to solve the above-described problems in the prior art, the present inventors have found that (1) the faujasite-type zeolite having a specific property maintains its hygroscopicity when moisture adsorption / desorption is repeated. Excellent performance, (2) the faujasite type zeolite has the moisture adsorption and desorption properties necessary for the dehumidifier of the dehumidifier, and (3) the faujasite type zeolite. Has been found to maintain excellent dehumidifying performance over a long period of time, and has completed the present invention. In the present invention, the hygroscopic maintenance performance when moisture adsorption / desorption is repeated is referred to as dry / wet repeated durability.

That is, the present invention (1) includes a honeycomb rotor constituted by a porous honeycomb structure in which Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, a rotating means for rotating the honeycomb rotor, A first divided member that divides one aperture surface of the honeycomb rotor into a dehumidification zone and a regeneration zone, a second divided member that divides the other aperture surface of the honeycomb rotor into a dehumidification zone and a regeneration zone, and the dehumidification zone A first supply means for supplying air to be treated, a second supply means for supplying drying air to the regeneration zone, and a heating means for heating the drying air provided in the preceding stage of the regeneration zone A dehumidifying device comprising:
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
The dehumidifying device characterized by the above is provided.

Further, the present invention ( 2 ) includes a honeycomb rotor constituted by a porous honeycomb structure in which a Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, a rotating means for rotating the honeycomb rotor, A first dividing member that divides one aperture surface of the honeycomb rotor into a dehumidification zone, a regeneration zone, and a cooling zone, and a second segment that divides the other aperture surface of the honeycomb rotor into a dehumidification zone, a regeneration zone, and a cooling zone. A bifurcated member, a first supply means for supplying air to be treated to the dehumidifying zone, a second supply means for supplying drying air to the regeneration zone, and for supplying cooling air to the cooling zone A dehumidifier having a heating means for heating the drying air, which is provided in the front stage of the third supply means and the regeneration zone;
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
The dehumidification apparatus characterized by this is provided.

Further, the present invention ( 3 ) includes a honeycomb rotor constituted by a porous honeycomb structure in which a Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, a rotating means for rotating the honeycomb rotor, A first supply means for supplying the air to be treated to the dehumidification zone, a second supply means for supplying the drying air to the regeneration zone, and a heater for heating the drying air provided in the preceding stage of the regeneration zone A dehumidifying device having a heating means,
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
The dehumidification apparatus characterized by this is provided.

  Since the dehumidifying device of the present invention has a long lifetime of the dehumidifying agent carried on the honeycomb rotor, it can maintain an excellent dehumidifying performance over a long period of time, and is therefore used for dehumidifying the inside of a semiconductor manufacturing apparatus room or the like. In this case, the replacement frequency of the honeycomb rotor is low, the running cost can be kept low, and when used as a household dehumidifying device, the honeycomb rotor can be made maintenance-free until the product life is reached.

  A dehumidifying device according to a first embodiment of the present invention (hereinafter also referred to as a dehumidifying device according to a first embodiment) will be described with reference to FIGS. 1 and 2. FIG. 1 is a view showing a honeycomb rotor installed in the dehumidifying device of the first embodiment. Moreover, FIG. 2 is a figure which shows the dehumidification apparatus of 1st embodiment. In FIG. 1, the honeycomb rotor 1 includes a rotor shaft 6 and a honeycomb structure 7. The honeycomb structure 7 supports faujasite type zeolite and has a ventilation cavity in the direction of the rotation axis. Therefore, the one open surface 2a and the other open surface 2b of the honeycomb structure 7 serve as an inlet / outlet of air to be ventilated to the honeycomb rotor, and the vent cavity serves as an air flow path. Then, when the air to be ventilated and the faujasite type zeolite come into contact with each other in the ventilation cavity, moisture moves between the air to be ventilated and the faujasite type zeolite. The aperture surface 2a is divided by the first divided members 3a and 3b, and the aperture surface 2b is divided by the second divided member (not shown), whereby the honeycomb rotor 1 allows the moisture in the air to be treated to Dehumidification zone 4 in which the faujasite type zeolite absorbs moisture and the air to be treated is dehumidified, and the faujasite type zeolite that has absorbed the moisture dehumidifies, and regeneration in which the hygroscopic performance of the faujasite type zeolite is regenerated is performed. Divided into zones 5. The first divided members 3a and 3b and the second divided member are fixed to the rotor case 11 of the dehumidifying device 10 in FIG. 2 so that the rotation of the honeycomb rotor 1 is not hindered. Close to rotor 1. The honeycomb rotor 1 is installed on the rotor case 11 of the dehumidifying device 10 through the rotor shaft 6 so as to be rotatable.

  The honeycomb structure 7 includes a porous flat fiber base paper and a corrugated fiber base paper obtained by corrugating the flat fiber base paper using an inorganic adhesive or an organic adhesive. It is manufactured by laminating and stacking at the peak of the mold fiber base paper. At this time, in the flat fiber base paper and the corrugated fiber base paper, a substantially semi-cylindrical cavity formed between them serves as an air flow path. They are stacked so as to be formed in the direction of the rotation axis. As a method of performing the lamination, for example, a pair of the corrugated fiber base paper and the flat fiber base paper, which are formed to have the same length as the thickness 8 of the honeycomb rotor 1, are stacked and wound up into a roll shape. The method of laminating is mentioned.

  The fiber base paper is a woven or non-woven fabric formed from fibers. The fiber is not particularly limited, and glass fiber such as E glass fiber, NCR glass fiber, ARG fiber, ECG fiber, S glass fiber, and A glass fiber, and its chopped strand, ceramic fiber, alumina fiber, mullite fiber, silica Examples thereof include inorganic fibers and organic fibers such as fibers, rock wool fibers, and carbon fibers. As the organic fiber, an aramid fiber, a nylon fiber, a polyethylene terephthalate fiber, or the like can be used. It is preferable to use inorganic fibers as the fibers of the fiber base paper because the strength of the honeycomb rotor can be increased.

  The fiber base paper is a porous body having a large number of voids between the fibers in the fiber base paper. The inter-fiber porosity of the fiber base paper is usually 80 to 95%, and the thickness of the fiber base paper is usually 0.1 to 1 mm. The inter-fiber porosity is a portion obtained by subtracting the volume of fibers in the fiber base paper from the apparent volume of the fiber base paper (hereinafter also referred to as inter-fiber void), and the apparent volume of the fiber base paper. The percentage of the total.

  The faujasite type zeolite supported on the honeycomb structure 7 is alternately moved to the dehumidification zone 4 and the regeneration zone 5 by the rotation of the honeycomb rotor 1 and repeats moisture absorption and dehumidification. Therefore, the faujasite type zeolite is required to be excellent in repeated wet and dry durability.

  The faujasite-type zeolite has a total content of one or more metals selected from transition metals, zinc and tin of 5% or more in terms of oxides, alkali metals, alkaline earth metals and magnesium. The total content of one or more metals selected from the inside is 1 to 10% in terms of oxide, and the reduction rate of the specific surface area by the wet and dry repeated test is 15% or less.

The faujasite type zeolite is a zeolite having a framework structure generally called a faujasite type. The faujasite type zeolite has the general formula (1);
_{aM x O y · bL p O} q · Al 2 O 3 · cSiO 2 (1)
In the general formula (1), M is one or more metals selected from transition metals, zinc and tin, and L is an alkali metal, an alkaline earth metal and One or more metals selected from magnesium. The values of x and y differ depending on the valence of M, and the values of p and q differ from the valence of L. For example, when M is monovalent, the value of x is 2, and the value of y is 1. When M is divalent, the value of x is 1, the value of y is 1, and M is trivalent. In the case of x, the value of x is 2 and the value of y is 3. The same applies to the relationship between L and p and q. The value of ax + bp is approximately 1.4 to 5.0. Moreover, (the value of _{c) SiO 2 / Al 2 O} 3 molar ratio of the zeolite is 3 to 6.

  The fact that the zeolite is of the faujasite type can be confirmed by a diffraction pattern obtained by taking out the zeolite supported on the honeycomb structure and conducting an X-ray diffraction analysis of the zeolite.

  The faujasite type zeolite of the present invention is preferably a zeolite having a framework structure called Y type.

  The transition metal is not particularly limited as long as it is a Group 3-11 metal in the long periodic table, preferably vanadium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, tungsten, lanthanum, cerium, praseodymium and Neodymium, particularly preferably manganese, iron, cobalt, nickel, copper, zirconium, lanthanum and cerium. Further, the transition metal may be one kind or two or more kinds.

  By containing the transition metal, zinc or tin, the faujasite type zeolite improves the balance between the moisture absorption rate and the dehumidification rate of the faujasite type zeolite.

  The total content of one or more metals selected from the transition metals, zinc and tin is 5% or more, preferably 7% or more in terms of oxide. When the total is less than 5%, the dehumidification amount of the faujasite type zeolite is lowered, or the balance between the moisture absorption rate and the dehumidification rate is deteriorated.

  Although it does not restrict | limit especially as this alkali metal or alkaline-earth metal, Preferably, they are lithium, sodium, potassium, magnesium, and calcium.

  The total content of one or more metals selected from the alkali metals, alkaline earth metals and magnesium is 1 to 10%, preferably 2 to 8% in terms of oxide. When the total is less than 1%, the acid sites whose counter ions are hydrogen ions increase, and dehydration or dealumination easily occurs due to repeated adsorption and desorption of moisture, so that the framework structure of the zeolite becomes weak. On the other hand, when the total exceeds 10%, it becomes difficult to dehumidify, and the balance between the moisture absorption rate and the dehumidification rate becomes worse.

  The acid point constituted by silica alumina in the zeolite has a cation as a counter ion. Among them, the acid point in which the counter ion is a hydrogen ion repeats the adsorption and desorption of moisture. It is easy to cause dehydration or dealumination from the steel, and causes shrinkage of the zeolite framework. For this reason, zeolites with many acid sites, the counter ions of which are hydrogen ions, tend to cause a decrease in the specific surface area or pore volume of the zeolite due to skeletal shrinkage, and the dry and wet repeated durability is poor. In other words, a zeolite having a small number of acid sites in which the counter ion is a hydrogen ion has good wet and dry repeated durability.

  The number of hydrogen ions bonded as counter ions to the acid sites composed of silica alumina in the zeolite is difficult to measure directly, but the small amount of hydrogen ions means that the specific surface area decreases due to repeated wet and dry tests. It can be grasped by the low rate.

  The reduction rate of the specific surface area of the faujasite-type zeolite by the dry and wet repeated test is 15% or less. If the reduction rate of the specific surface area exceeds 15%, the hygroscopicity is lowered when moisture adsorption / desorption is repeated. The wet and dry repeated test means that the faujasite type zeolite is heated at 800 ° C. for 10 minutes, then cooled to 25 ° C. in a desiccator containing a desiccant, and then in a desiccator at 25 ° C. and 50% RH. In this test, the operation of leaving for 10 minutes is repeated 100 times. Then, the specific surface area of the faujasite type zeolite before and after the wet and dry repetition test is measured, and the reduction rate is obtained. And, since the faujasite type zeolite has a low specific surface area reduction rate of 15% or less by repeated wet and dry tests, the hydrogen ions bonded to the acid sites composed of silica alumina in the faujasite type zeolite are I understand that there are few.

  Thus, in the faujasite-type zeolite, the counter ion bonded to the acid sites composed of silica alumina is mostly one or more selected from the transition metal, zinc and tin. It is a metal ion, or an ion of one or more metals selected from the alkali metal, alkaline earth metal and magnesium, and has very few hydrogen ions. Therefore, the faujasite type zeolite according to the present invention is excellent in dry and wet repeated durability.

  The faujasite-type zeolite of the present invention is a faujasite-type zeolite in which all or part of the counter ions bonded to the acid sites composed of silica alumina are hydrogen ions, the presence of transition metal ions, zinc ions or tin ions. A first ion exchange step of obtaining a faujasite-type zeolite that is ion-exchanged with a transition metal ion, zinc ion or tin ion by immersing in an aqueous solution or slurry, and the transition metal ion, zinc ion or tin ion The faujasite-type zeolite ion-exchanged in 1 is immersed in an aqueous solution or slurry containing alkali metal ions, alkaline earth metal ions, or magnesium ions, and an ion exchange reaction is performed. Metal ion, alkaline earth metal ion or mug The second ion exchange step to obtain a faujasite-type zeolite ion exchanged can be manufactured performed in Shiumuion.

  In the first ion exchange step, the faujasite type zeolite to be ion-exchanged is a faujasite type zeolite in which all or part of the counter ions bonded to the acid sites composed of silica alumina are hydrogen ions (hereinafter, It is described as H-faujasite type zeolite.). Usually, the faujasite type zeolite is synthesized as a sodium faujasite type zeolite (hereinafter referred to as Na-faujasite type zeolite) in which the counter ion at the acid point is a sodium ion. Then, the Na-faujasite type zeolite is immersed in, for example, an ammonium chloride aqueous solution, and after performing ion exchange between sodium ions and ammonium ions, drying and further firing are performed to obtain H-faujasite type zeolite. Can do.

When the H-faujasite type zeolite is produced from Na-faujasite type zeolite, the sodium content is 0 to 5% in terms of oxide, and the SiO ₂ / Al ₂ O ₃ molar ratio is 3 to 6 It is. In addition, when the H-faujasite type zeolite is produced from a faujasite type zeolite in which the counter ion bonded to the acid site composed of silica alumina is a metal other than sodium, the inclusion of a metal other than the sodium The amount is 0 to 10% in terms of oxide, and the SiO ₂ / Al ₂ O ₃ molar ratio is 3 to 6. Moreover, this H-faujasite type zeolite may contain a sulfur atom other than a metal. In this case, the sulfur atom content is 1% or less in terms of SO ₃ .

  In the first ion exchange step, the metal ion to be ion-exchanged may be one or more of transition metal ions, zinc ions, or tin ions. The transition metal ion is an ion of the same metal as the transition metal contained in the faujasite zeolite of the present invention.

  In the first ion exchange step, the ion exchange reaction is carried out by transition metal salt, zinc compound salt or tin compound salt, such as hydroxide salt, chloride salt, sulfate salt, hydrogen sulfate salt, carbonate salt, bicarbonate salt, Nitrate or the like is added to water to prepare an aqueous solution or slurry containing the metal ions, and the H-faujasite type zeolite is immersed in the aqueous solution or slurry. The transition metal salt, zinc compound salt or tin compound salt may be one kind or two or more kinds, and in the case of two or more kinds, even if they are salts of the same kind of metal, different kinds of metals Or a salt thereof. The concentration of the aqueous solution or slurry is not particularly limited, but 0.01 to 10 mol / L is preferable in that the ion exchange reaction occurs rapidly. The pH in the ion exchange reaction is not particularly limited, but is preferably 3 or more weakly acidic or alkaline. When the pH is less than 3, the crystal structure is easily broken by an acid. The reaction temperature is room temperature to 100 ° C. If it is less than room temperature, the reaction rate of the ion exchange reaction is slow, and if it exceeds 100 ° C., the boiling point of water is exceeded, so a pressure vessel or the like must be used and the reaction becomes complicated. The reaction time varies depending on the reaction temperature, but is generally from 10 minutes to 24 hours. In addition, after ion exchange, washing, drying, and firing can be performed as necessary. The temperature for performing the drying is usually 90 to 200 ° C, and the temperature for performing the firing is usually 400 to 600 ° C. Further, the first ion exchange step can be repeated a plurality of times, and each time the ion exchange may be performed with the same metal ion or the different metal ions may be exchanged.

  By performing the first ion exchange step, a faujasite type zeolite ion-exchanged with transition metal ions, zinc ions or tin ions (hereinafter referred to as a first ion exchange faujasite type zeolite) can be obtained.

  In the second ion exchange step, the first ion exchange faujasite type zeolite is used instead of the H-faujasite type zeolite, and the metal ions to be ion exchanged are replaced with transition metal ions, zinc ions or tin ions, and alkali metal ions are used. Since it is the same as the first ion exchange step except that the alkaline earth metal ion or magnesium ion is used, the description of the same part as the first ion exchange step is omitted, and only the different part will be described. Further, the alkali metal ion, alkaline earth metal ion, or magnesium ion may be one kind or two or more kinds.

  In the second ion exchange step, the metal ion to be ion-exchanged is not particularly limited as long as it is an alkali metal ion, an alkaline earth metal ion or a magnesium ion, but lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion. However, since the radius is small, it is easy to enter an acid site where hydrogen ions remaining without being ion-exchanged with transition metal ions, zinc ions or tin ions (hereinafter referred to as residual hydrogen ions) are present. It is preferable in terms of easy ion exchange with ions.

  In the second ion exchange step, the alkali metal salt, alkaline earth metal salt or magnesium compound salt used in the ion exchange reaction is, for example, a hydroxide salt, a chloride salt, a sulfate salt, a hydrogen sulfate salt, a carbonate salt, a carbonate salt. Hydrogen salt, nitrate, etc. Specifically, sodium hydroxide, sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium nitrate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium chloride, potassium sulfate, potassium hydrogen sulfate , Potassium nitrate, potassium carbonate, potassium hydrogen carbonate, magnesium sulfate, magnesium hydrogen sulfate, magnesium nitrate, magnesium carbonate, magnesium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium nitrate, lithium carbonate, lithium hydrogen carbonate, calcium sulfate, calcium hydrogen sulfate Calcium nitrate , Calcium carbonate, calcium hydrogen carbonate, strontium sulfate, bisulfate strontium, strontium nitrate, strontium carbonate, and the like bicarbonate strontium.

  By performing the second ion exchange step, the remaining hydrogen ions present in the first ion exchange faujasite type zeolite are all or partly replaced with alkali metal ions, alkaline earth metal ions or magnesium ions. Site type zeolite (hereinafter referred to as second ion exchange faujasite type zeolite) can be obtained.

  The total content of transition metals, zinc and tin in the second ion exchange faujasite type zeolite is 5% or more in terms of oxides, and the total content of alkali metals, alkaline earth metals and magnesium is oxidized. 1 to 10% in terms of physical properties. Further, the reduction rate of the specific surface area of the faujasite-type zeolite by the repeated wet and dry test is 15% or less.

  In the second ion exchange step, residual hydrogen ions that have not been exchanged for transition metal ions, zinc ions, or tin ions in the first ion exchange step are ion-exchanged with alkali metal ions, alkaline earth metal ions, or magnesium ions. Therefore, the acid sites where the counter ion is hydrogen can be extremely reduced. Therefore, the faujasite-type zeolite produced by performing the first ion exchange step and the second ion exchange step has little skeletal shrinkage due to dehydration or dealumination, even after repeated moisture adsorption and desorption, and has a specific surface area or pore volume. Is less likely to drop and has excellent durability against repeated drying and wetting.

  The method for supporting the faujasite type zeolite on the honeycomb structure 7 is not particularly limited, and can be performed by a conventional method. For example, a suspension is prepared by suspending the faujasite type zeolite in water together with an inorganic binder such as silica sol, alumina sol, or titania sol, and the honeycomb structure 7 is immersed in the suspension, or the By applying the suspension to the honeycomb structure 7, the faujasite-type zeolite is sufficiently absorbed by the honeycomb structure 7, and after removing the excess suspension, drying and fixing, The faujasite type zeolite is supported on the honeycomb structure 7. At this time, the amount of the inorganic binder to be used is the minimum necessary for fixing to the surface of the honeycomb structure 7, and the cured product of the inorganic binder covers the surface of the faujasite type zeolite. This is preferable in that the decrease in the hygroscopic performance of the faujasite type zeolite can be reduced.

  Further, the fauxite-type zeolite is supported on the unmolded fiber base paper to obtain a fiber base paper carrying the faujasite-type zeolite, and then the fiber base paper carrying the zeolite is molded. A honeycomb structure 7 on which the faujasite type zeolite is supported can also be obtained.

  Further, the Na-faujasite type zeolite is supported on the honeycomb structure 7, and then the obtained honeycomb structure 7 on which the Na-faujasite type zeolite is supported is made of an ammonium salt such as ammonium chloride. Immersion in an aqueous solution, ion exchange of sodium ions to ammonium ions, washing with water, drying, and firing to remove ammonia to obtain a honeycomb structure 7 carrying H-faujasite type zeolite, The honeycomb structure 7 carrying the faujasite type zeolite can also be obtained by performing the first ion exchange step and the second ion exchange step.

  The ratio of the dehumidifying zone 4 and the regeneration zone 5 is not particularly limited, but is generally 7: 1 to 1: 1, preferably 5: 1 to 2: 1 in terms of the area ratio of the aperture surface 2a or 2b. . Further, the shape of the regeneration zone 5 in the aperture surface 2a or 2b is usually a sector shape, and the central angle of the sector shape is approximately 45 to 180 degrees, preferably 60 to 120 degrees.

  The form of the first divided member and the second divided member is not particularly limited as long as the honeycomb rotor can be divided into a dehumidification zone and a regeneration zone. For example, the circumference from the rotation center of the honeycomb rotor And partition plates (first divided members 3a and 3b in FIG. 1) that are provided radially toward and fixed to the rotor case.

  Further, the honeycomb rotor can be divided into the dehumidification zone and the dehumidification zone by extending the pipe connected to the rotor case to the inside of the rotor case and bringing the outlet of the pipe close to the honeycomb rotor. In this case, a portion of the piping located inside the rotor case is a divided member.

  In FIG. 2, the dehumidifier 10 includes a rotor case 11 in which the honeycomb rotor 1 shown in FIG. 1 is rotatably installed, first divided members 3 a and 3 b, a second divided member (not shown), and a first feeder 15. , The second feeder 16, the heating device 17, and a motor for rotating the honeycomb rotor 1 (not shown). In addition, a to-be-processed air supply pipe 18 connecting the first supply machine 15 and the rotor case 11, a dehumidified air exhaust pipe 19 for exhausting dehumidified air from the dehumidification zone 4, the second supply machine 16 and the heating device 17. A first drying air supply pipe 20 that connects the heating device 17 and the rotor case 11, and a drying air exhaust pipe 22 that exhausts the hygroscopic air from the regeneration zone 5.

  The first supply means or the second supply means according to the dehumidifying device of the first aspect of the present invention is not particularly limited, and an apparatus generally used for supplying gas can be used. Examples include blowers and compressors.

  Further, the installation position of the first supply means or the second supply means is the front stage of the honeycomb rotor 1 in the dehumidifying apparatus 10, but in the dehumidifying apparatus of the first aspect of the present invention, the installation position is after the honeycomb rotor 1. There may be. In this case, the first supply means or the second supply means is a device that supplies the air to be treated A or the drying air C into the honeycomb rotor 1 by suction from the opposite side of the honeycomb rotor 1, for example, An example is a suction fan.

  The heating means according to the dehumidifying device of the first aspect of the present invention is not particularly limited, and examples thereof include an electric heater, and a device generally used for heating a gas can be used as appropriate.

  The operation of the dehumidifier 10 is performed as follows. First, air to be treated A in a clean room or the like containing moisture is supplied to the dehumidifying zone 4 of the honeycomb rotor 1 using the first supply unit 15. When the air to be treated A contacts the faujasite type zeolite when passing through the honeycomb rotor 1, moisture in the air to be treated A moves to the faujasite type zeolite. The processing air A is dehumidified. The dehumidified air B from which moisture has been removed is discharged from the dehumidifying zone 4 of the honeycomb rotor 1 through the dehumidified air exhaust pipe 19 and returned to a clean room or the like.

  Next, the faujasite type zeolite that has absorbed moisture in the dehumidifying zone 4 moves to the regeneration zone 5 as the honeycomb rotor 1 rotates. Then, the drying air C is supplied to the heating device 17 using the second supply device 16, heated by the heating device 17, and then supplied to the regeneration zone 4 of the honeycomb rotor 1. When the drying air C comes into contact with the faujasite type zeolite, moisture in the faujasite type zeolite moves to the drying air C, so that the faujasite type zeolite is dehumidified. The moisture absorption air D that has absorbed moisture is discharged from the regeneration zone 5 of the honeycomb rotor 1 to the outside through the drying air exhaust pipe 22. Further, the drying air C is not particularly limited, and examples thereof include outside air, air in a clean room, etc., or the dehumidified air A. It is preferable to use the dehumidified air A as the drying air C in terms of increasing the regeneration efficiency of the faujasite type zeolite.

  Next, the faujasite type zeolite dehumidified in the regeneration zone 5 moves to the dehumidifying zone 4 as the honeycomb rotor 1 rotates, and is used again for dehumidifying the air to be treated A.

  The air to be treated A and the drying air C are supplied to the honeycomb rotor 1, and the honeycomb rotor 1 rotates to continuously dehumidify the air to be treated A.

  The rotation of the honeycomb rotor 1 may be continuous or intermittent. When the honeycomb rotor 1 rotates continuously, the rotation speed is not particularly limited, but is approximately 1 to 30 rotations / hour, preferably 5 to 20 rotations / hour. Further, when the honeycomb rotor 1 rotates intermittently, the rotation amount of the honeycomb rotor 1 per rotation is 1/12 to 1/3 rotation, and the rotation interval may be either regular or irregular. . By rotating the honeycomb rotor 1 continuously, a certain amount of regenerated faujasite-type zeolite is always supplied to the dehumidification zone 4, so that the dehumidification efficiency is high and the dehumidification performance is stable. preferable.

  Next, a dehumidifying device according to a second embodiment of the present invention (hereinafter also referred to as a dehumidifying device according to the second embodiment) will be described with reference to FIGS. FIG. 3 is a view showing a honeycomb rotor installed in the dehumidifying apparatus according to the second embodiment. FIG. 4 is a diagram showing a dehumidifying device according to the second embodiment. The dehumidifying device of the second embodiment will be described only with respect to the main differences from the dehumidifying device of the first embodiment, and the description of the same points as the dehumidifying device of the first embodiment will be omitted. That is, the point that the dehumidifying device of the second embodiment is different from the dehumidifying device of the first embodiment is that the honeycomb rotor is divided into a dehumidifying zone, a regeneration zone, and a cooling zone. In FIG. 3, the honeycomb rotor 31 includes a rotor shaft 37 and a honeycomb structure 38 on which the faujasite type zeolite is supported. One honeycomb surface 38a and the other porous surface 32b of the honeycomb structure 38 are divided by the first divided members 33a, 33b and 33c and a second divided member (not shown), thereby the honeycomb rotor 31. Is divided into a dehumidifying zone 34, a regeneration zone 35 and a cooling zone 36. The honeycomb rotor 31 is installed in the rotor case 41 of the dehumidifier 40 in FIG. 4 via the rotor shaft 37.

  The ratio of the dehumidifying zone 34 and the regeneration zone 35 is not particularly limited, but is generally 6: 1 to 1: 1, preferably 4: 1 to 0.8: 1, in terms of the area ratio of the aperture surface 32a or 32b. The ratio of the dehumidifying zone 34 and the cooling zone 36 is not particularly limited, but is generally 6: 1 to 1: 1, preferably 4: 1 to 1.1, as the area ratio of the aperture surface 32a or 32b. 6: 1. In addition, the shape of the regeneration zone 35 in the aperture surface 32a or 32b is generally a sector shape, and the central angle of the sector shape is approximately 45 to 120 degrees, preferably 60 to 100 degrees. The shape of is also the same, and the central angle is about 45 to 120 degrees, preferably 60 to 100 degrees.

  In FIG. 4, the dehumidifying device 40 includes a rotor case 41 in which the honeycomb rotor 31 shown in FIG. 3 is rotatably installed, first divided members 33a, 33b and 33c, a second divided member (not shown), and a first supply. The machine 46, the 2nd supply machine 47, the 3rd supply machine 48, the heating apparatus 49, and the motor for rotating this honeycomb rotor 1 which is not shown in figure are comprised. In addition, a to-be-processed air supply pipe 50 connecting the first supply machine 46 and the rotor case 41, a dehumidified air exhaust pipe 51 for exhausting dehumidified air from the dehumidification zone 42, the second supply machine 47 and the heating device 49. A first drying air supply pipe 52 that connects the heating device 49 and the rotor case 41, a drying air exhaust pipe 54 that exhausts hygroscopic air from the regeneration zone 43, and the third A cooling air supply pipe 55 that connects the feeder 48 and the rotor case 41 and a cooling air exhaust pipe 56 for exhausting the endothermic air from the cooling zone 44 are provided.

  Further, the installation position of the first supply means, the second supply means or the third supply means is the front stage of the honeycomb rotor 31 in the dehumidifying device 40, but in the dehumidifying device of the second aspect of the present invention, The latter stage of the rotor 31 may be sufficient. In this case, the first supply means, the second supply means, or the third supply means is configured to suck the air to be treated E, the drying air G, or the cooling air I from the opposite side of the honeycomb rotor 31 to the honeycomb rotor 31. For example, a suction fan may be used.

  The operation of the dehumidifier 40 is performed as follows. First, the air to be treated E in a clean room or the like containing moisture is supplied to the dehumidifying zone 34 of the honeycomb rotor 31 using the first supply unit 46. Then, when the air to be treated E comes into contact with the faujasite type zeolite when passing through the honeycomb rotor 31, moisture in the air to be treated E moves to the faujasite type zeolite. The air to be treated E is dehumidified. The dehumidified air F from which moisture has been removed is discharged from the dehumidifying zone 34 of the honeycomb rotor 31 through the dehumidified air exhaust pipe 51 and returned to a clean room or the like.

  Next, the faujasite type zeolite that has absorbed moisture in the dehumidifying zone 34 moves to the regeneration zone 35 as the honeycomb rotor 31 rotates. Then, the drying air G is supplied to the heating device 49 using the second supply device 47, heated by the heating device 49, and then supplied to the regeneration zone 35 of the honeycomb rotor 31. Then, when the drying air G comes into contact with the faujasite type zeolite, moisture in the faujasite type zeolite moves to the drying air G, so that the faujasite type zeolite is dehumidified. The moisture absorption air H that has absorbed moisture is discharged from the regeneration zone 35 of the honeycomb rotor 31 to the outside through the drying air exhaust pipe 54.

  Further, the faujasite type zeolite dehumidified in the regeneration zone 35 moves to the cooling zone 36 as the honeycomb rotor 31 rotates. Then, the cooling air I is supplied to the cooling zone 36 of the honeycomb rotor 31 using the third supply device 48. When the cooling air I comes into contact with the dehumidified faujasite zeolite, the heat of the faujasite zeolite is transferred to the cooling air I, so that the faujasite zeolite is cooled. The endothermic air J that has absorbed the heat of the faujasite type zeolite is discharged from the cooling zone 36 of the honeycomb rotor 31 to the outside through the cooling air exhaust pipe 56.

  Further, the drying air G or the cooling air I is not particularly limited, and examples include the outside air, the air in a clean room, the dehumidified air F, and the like. It is preferable to use the dehumidified air F as the drying air G or the cooling air I in terms of increasing the regeneration efficiency of the faujasite type zeolite.

  Next, the faujasite type zeolite cooled in the cooling zone 36 moves to the dehumidifying zone 34 when the honeycomb rotor 31 rotates, and is used again for dehumidifying the air E to be treated.

  Then, the air to be treated E, the drying air G and the cooling air I are supplied to the honeycomb rotor 31 and the honeycomb rotor 31 rotates continuously or intermittently, whereby the air to be treated E Is dehumidified continuously.

  In the dehumidifying device of the second form, endothermic air can be used as the drying air. An example of using the endothermic air as the drying air is a dehumidifying device 60 shown in FIG. In FIG. 5, the dehumidifying device 60 is not provided with the second supply unit 47 in FIG. 4. Instead, a connecting pipe 61 that connects the cooling air exhaust pipe 56 and the first dry air supply apparatus 52 is provided. Except for being provided, it is the same as the dehumidifying device 40 in FIG. That is, in the dehumidifier 60 shown in FIG. 5, the connecting pipe 61 is the second supply means. It is preferable to use endothermic air as the drying air because the heat absorbed by the endothermic air in the cooling zone can be used and the burden on the heating device can be reduced.

  Next, a dehumidifying device according to a third embodiment of the present invention (hereinafter also referred to as a dehumidifying device according to a third embodiment) will be described with reference to FIGS. FIG. 6 is a diagram showing a configuration of members in the rotor case of the dehumidifying device according to the third embodiment, and FIG. 7 is a diagram showing members in the rotor case of the dehumidifying device according to the third embodiment. 8 is a perspective view of the dehumidifying device according to the third embodiment. FIG. 9 is a perspective view of the dehumidifying device according to the third embodiment of the honeycomb rotor. It is the figure seen from the opening surface 78b side.

  As shown in FIG. 6, in the rotor case of the dehumidifier of the third embodiment, a honeycomb rotor 71 composed of a rotor shaft 72 and a honeycomb structure 73 carrying the faujasite type zeolite, the first It is comprised by the supply machine 77, the 2nd supply machine 74, the heating apparatus 75, and the moisture absorption air exhaust duct 76, and the arrangement position in the rotor case of each structural member is as showing in FIG.

  8 and 9, the dehumidifying device 80 includes a rotor case 82 in which the aperture surfaces 78a and 78b of the honeycomb rotor 71 are formed of radial ribs 84, and the honeycomb rotor installed in the rotor case 82. 71, the first supply unit 77, the second supply unit 74, the heating device 75 and the hygroscopic air exhaust duct 76, the dry air intake duct 81, and the drain pipe 86 are attached, and cooling fins are installed therein. It comprises a condenser 85 and a motor for rotating the honeycomb rotor 71 (not shown). The second feeder 74 and the heating device 75 are installed in the dry air suction duct 81.

  The honeycomb rotor 71 is the same as the honeycomb rotor 1 shown in FIG.

  The hygroscopic air exhaust duct 76 is an exhaust duct for exhausting the hygroscopic air L to the outside of the rotor case 82 and is supplied into the honeycomb rotor 82 by the first feeder 77 as shown in FIG. It is also a blocking wall for preventing the air to be treated M from flowing into the regeneration zone in the honeycomb rotor 71.

  The first supply means and the second supply means related to the dehumidifying device of the third embodiment are air supply fans in the dehumidifying device 80, but are not limited thereto, and may be compressors or the like.

  Further, in the dehumidifying apparatus 80, the first supply means is of a size that can supply the air to be treated M to almost the entire aperture surface 78b of the honeycomb rotor 71. The size is not limited, and may be a size capable of supplying the air to be treated M to a part of the aperture surface 78b. Among these, it is preferable that the air supply fan has such a size that the air to be treated M can be supplied to almost the entire opening surface 78b of the honeycomb rotor 71 in view of high dehumidification efficiency.

  Further, the installation position of the second supply means is the front stage of the honeycomb rotor 71 in the dehumidifier 80, but may be the rear stage of the honeycomb rotor 71 in the dehumidifier of the third aspect of the present invention. . In this case, the second supply means is a device that supplies the drying air K into the honeycomb rotor 71 by suction from the opposite side of the honeycomb rotor 71, and examples thereof include a suction fan.

  The heating device 75 in FIG. 6 is a heating device in which a nichrome wire is installed in a spiral shape, but the heating means according to the dehumidifying device of the third embodiment is not particularly limited, and an electric heater or the like is generally used. An apparatus used for heating the gas can be appropriately used. Among them, an electric heater is preferable in that the dehumidifying device can be reduced.

  Since the dehumidifying device 80 is not provided with a dividing member, the dehumidifying zone and the regeneration zone are formed in the honeycomb rotor 71 by the flow of air supplied from the first supply unit 77 and the second supply unit 74. Is formed. That is, a portion where the air to be treated M flows in the honeycomb rotor 71 is a dehumidification zone, and a portion where the drying air K is flowing is a regeneration zone. The surface of the aperture surface 78a that is supplied with the drying air K by the second supply device 74 is a regeneration zone, and the moisture absorbing air exhaust duct 76 in the aperture surface 78b is covered with the honeycomb rotor 71. The area other than the surface where the supply of the processing air M is blocked is the dehumidification zone.

  The area of the regeneration zone occupying the open surface 78a is 7.6 to 25%, preferably 9.1 to 20%.

  The condenser 85 is not necessary when a pipe or the like for discharging the hygroscopic air L to the outside of the dehumidifying target space is installed, but when the pipe or the like is not installed, the hygroscopic air exhaust duct 76 is not provided. Moisture in the hygroscopic air L is removed by cooling fins installed at the subsequent stage and installed inside the condenser 85. And the air P from which the water | moisture content was removed is discharge | released to the periphery. Further, the water removed at this time can be extracted from the drain pipe 86.

  The operation of the dehumidifier 80 is performed as follows. The dehumidifying device 80 is installed in a semiconductor manufacturing apparatus room or the like where the air to be processed M exists. Then, the to-be-processed air M present in the periphery is supplied into the honeycomb rotor 71 by the first supply unit 77, and the faujasite type zeolite is passed when the to-be-processed air M passes through the inside of the honeycomb rotor 71. Since the moisture in the to-be-treated air M moves to the faujasite type zeolite by contacting with the to-be-treated air M, the to-be-treated air M is dehumidified. The dehumidified air N from which moisture has been removed is discharged from the aperture surface 78a of the honeycomb rotor 71 to the periphery.

  Next, the faujasite-type zeolite that has absorbed moisture in the dehumidifying zone moves to the regeneration zone as the honeycomb rotor 71 rotates. Then, using the second supply device 74, the drying air K that has been heated and passed through the heating device 75 is supplied to the honeycomb rotor 71. When the drying air K comes into contact with the faujasite type zeolite, moisture in the faujasite type zeolite moves to the drying air K, so that the faujasite type zeolite is dehumidified. The moisture-absorbing air L that has absorbed moisture is discharged from the moisture-absorbing air exhaust duct 76 to the outside of the honeycomb rotor 71, and the moisture-absorbing air L comes into contact with the cooling fins in the condenser 85, so that moisture is removed from the moisture-absorbing air L. The air P that has been removed by condensation and from which moisture has been removed is discharged to the periphery.

  Next, the faujasite type zeolite dehumidified in the regeneration zone moves to the dehumidification zone when the honeycomb rotor 71 rotates, and is used again for dehumidification of the air M to be treated.

  The rotation of the honeycomb rotor 71 may be continuous or intermittent. When the honeycomb rotor 71 rotates continuously, the rotation speed is not particularly limited, but is approximately 10 to 120 rotations / hour, preferably 20 to 80 rotations / hour. Further, when the honeycomb rotor 71 rotates intermittently, the rotation amount of the honeycomb rotor 71 per rotation is 1/12 to 1/3 rotation, and the rotation interval may be either regular or irregular. . It is preferable that the honeycomb rotor 71 is continuously rotated because a constant amount of regenerated faujasite type zeolite is always supplied to the dehumidifying zone, so that the dehumidifying efficiency is high and the dehumidifying performance is stable.

  The dehumidifying device of the third form is a dehumidifying device used mainly in a room where air to be treated exists, and is often used as a dehumidifying device for home use. Therefore, the to-be-processed air M and the drying air K are supplied from the same space, and the dehumidified air N and the air P from which the moisture has been removed are discharged to the same space.

  The dehumidifying apparatus according to the present invention uses the faujasite type zeolite, which is excellent in repeated wet and dry durability, as the dehumidifying agent, so that the frequency of replacing the honeycomb rotor or the honeycomb structure can be extremely reduced. Therefore, the dehumidifying device can reduce the maintenance cost extremely.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

Example 1
1. Production of faujasite-type zeolite (preparation of faujasite-type zeolite ion-exchanged with hydrogen ions)
Synthetic Y-type zeolite (hereinafter referred to as the cation at the acid point of the Y-type zeolite is sodium ion, the SiO ₂ content is 63%, the Al ₂ O ₃ content is 24%, and the Na ₂ O content is 13%) And Na-Y type zeolite A) was immersed in a 10% aqueous ammonium chloride solution at room temperature for 2 hours. The Y-type zeolite was filtered off, dried at 110 ° C. for 1 hour, and calcined at 500 ° C. for 1 hour. The steps from immersion in the aqueous ammonium chloride solution to calcination at 500 ° C. were further performed twice to obtain hydrogen-exchanged Y-type zeolite (hereinafter referred to as H-Y type zeolite B).

(First ion exchange process)
The H-Y type zeolite B obtained as described above was immersed in a 0.2 mol / L lanthanum chloride aqueous solution at 80 ° C. for 2 hours. The Y-type zeolite was filtered and washed with water, dried at 110 ° C. for 1 hour, further calcined at 500 ° C. for 1 hour, and ion-exchanged with lanthanum ions (hereinafter referred to as first ion-exchanged Y-type zeolite C). Described).

(Second ion exchange process)
The first ion exchange Y-type zeolite C obtained by the first ion exchange step was immersed in a 0.5 mol / L lithium chloride aqueous solution at 80 ° C. for 12 hours. The Y-type zeolite is filtered and washed with water, dried at 200 ° C. for 2 hours, and ion-exchanged with lanthanum ions and lithium ions (hereinafter referred to as second ion-exchanged Y-type zeolite D). Obtained. The composition of the obtained second ion-exchanged Y-type zeolite D has a SiO ₂ content of 63%, an Al ₂ O ₃ content of 24%, a Na ₂ O content of 3%, and a La ₂ O ₃ content of 8 %, Li ₂ O content was 2%. Therefore, the Si content was 29.5%, the Al content was 12.7%, the Na content was 2.2%, the La content was 6.8%, and the Li content was 0.9%.

(Measurement of specific surface area reduction rate by repeated wet and dry test)
The second ion exchange Y-type zeolite D obtained by the second ion exchange step was heated at 800 ° C. for 10 minutes, then cooled in a desiccator containing a desiccant, and then controlled at 25 ° C. and 50% RH. The operation of leaving in a desiccator for 10 minutes was repeated 100 times, and a dry and wet test was performed. As a result, the specific surface area of the second ion-exchanged Y-type zeolite D was 753 m ² / g before the test and 681 m ² / g after the test. At this time, the reduction rate of the specific surface area was 9.6%.

(Evaluation of repeated wet and dry durability of faujasite type zeolite)
The moisture absorption rate of the second ion-exchanged Y-type zeolite D before and after the dry and wet repeated test was measured. The measurement of the moisture absorption rate is controlled at 25 ° C. and 50% RH for 1 g of the second ion exchange Y-type zeolite D after being heated in a desiccator containing a desiccant after heating at 200 ° C. for 1 hour. Place it on a balance installed indoors. The weight is measured once every 5 seconds, and the weight measurement is performed for 10 minutes. Next, for each weight measurement made at 5-second intervals, calculate the amount of weight increase from the previous weight measurement, and divide by the measurement interval (5 seconds) to change the weight per unit time (mg / second) Is calculated. The weight change is calculated for every weight measurement performed for 10 minutes, and the average value (mg / second) is obtained. Then, the average value is divided by 1 g of the weight of the second ion exchange Y-type zeolite D to obtain a moisture absorption rate per 1 g (mg / sec). The moisture absorption rate of the second ion-exchanged Y-type zeolite D was 0.26 mg / second per gram in air at 25 ° C. and 50% RH before the test, and changed to 0.26 mg / second after the test. There wasn't.

2. Production of honeycomb structure carrying faujasite type zeolite Honeycomb structure made of silica alumina fiber paper (thickness 0.2 mm, porosity 90%) and having cells 3.0 mm wide and 1.6 mm high A carrier (manufactured by NICHIAS Corporation, trade name: Hanicle) was cut into a cylindrical shape having a diameter of 270 mm and a thickness of 17 mm to obtain a carrier.
Next, 90 parts by weight of the second ion exchange Y-type zeolite D obtained as described above, 30 parts by weight of silica sol (“trade name: Snowtex” (solid content: 30% by weight, manufactured by Nissan Chemical Co., Ltd.)), And 130 parts by weight of water were mixed to prepare a slurry. After the honeycomb structure carrier was immersed in the obtained slurry, excess slurry was removed and dried to obtain a honeycomb structure E on which the second ion exchange Y-type zeolite D was supported.

3. Production of Dehumidifier Device A honeycomb rotor F is produced by attaching a rotor shaft to the rotation center of the honeycomb structure E, and the honeycomb rotor F, the first supply device, the second supply device, the heating device, and the moisture absorption air exhaust duct are provided. The dehumidifying device 80 shown in FIG. 8 arranged as shown in FIG. 7 was manufactured.
・ First feeder 77
Air supply fan size: 175 mm in diameter, number of wings: 45, second feeder 74
Size of air supply fan; diameter 60mm, number of feathers; 24 sheets

4). Dehumidification endurance test The dehumidifier 80 was installed in a constant temperature and humidity chamber controlled at 25 ° C. and 50% RH, and dehumidified for 100 hours under the following operating conditions. And the dehumidification amount for 1 hour (between the first hour and the second hour) from 1 hour after the start of the test and the dehumidification amount for 1 hour (from the 99th hour to the 100th hour) after 99 hours are measured, and the dehumidification durability Asked. The results are shown in Table 1. The amount of dehumidification was determined by placing a dehumidifier on an electronic balance, recording the increase in weight every minute, and measuring the total increase in weight for one hour. Also, the dehumidification rate reduction rate is obtained by the following equation (1) where the dehumidification amount between the first hour and the second hour is Gg / hour, and the dehumidification amount between the 99th hour and the 100th hour is Hg / hour. Value.
Reduction rate of dehumidification amount (%) = {(GH) / G} × 100 (1)
(Test conditions)
-Surface temperature of the honeycomb rotor on the heating device side: 800 ° C
-Air temperature after passing through the condenser 85; 80 ° C
・ Rotation speed of honeycomb rotor 1: 0.5 rotation / min

(Comparative Example 1)
1. Production of zeolite SiO ₂ content 63 wt%, Al ₂ O ₃ content 24 wt%, Na ₂ O content 13 wt% (SiO ₂ / Al ₂ O ₃ molar ratio 4.46, Na ₂ O / Al ₂ O ₃ molar ratio of 0.89) sodium Y zeolite was immersed in an aqueous solution of 0.3 mol / L lanthanum chloride (LaCl ₃ ) at 80 ° C. for 12 hours. The Y-type zeolite was filtered and washed with water, and then dried at 200 ° C. for 2 hours to obtain a Y-type zeolite ion-exchanged with lanthanum ions (hereinafter referred to as lanthanum Y-type zeolite J). The composition of the obtained lanthanum Y-type zeolite J has a SiO ₂ content of 60.6% by weight, an Al ₂ O ₃ content of 20.8% by weight, a La ₂ O ₃ content of 14.7% by weight, Na _{The 2} O content was 3.7% by weight (SiO ₂ / Al ₂ O ₃ molar ratio was 5.0, and Na ₂ O / Al ₂ O ₃ molar ratio was 0.3).

2. Production of honeycomb structure supporting faujasite-type zeolite The same method as in Example 1 except that 90 parts by weight of the second ion-exchanged Y-type zeolite D is replaced by 90 parts by weight of the lanthanum Y-type zeolite J The honeycomb structure K carrying the lanthanum Y-type zeolite J was obtained.

3. 3. Production of dehumidifier and Dehumidification endurance test The test was performed in the same manner as in Example 1 except that the honeycomb structure E carrying the lanthanum Y-type zeolite J was used instead of the honeycomb structure E carrying the second ion-exchanged Y-type zeolite D. . The results are shown in Table 1.

  Thus, even if the dehumidification apparatus of Example 1 performed the dehumidification durability test for 100 hours, the dehumidification fall was very low and it was excellent in durability.

(Example 2)
1. Production of faujasite-type zeolite Preparation of faujasite-type zeolite ion-exchanged with hydrogen ions in the same manner as in Example 1, the first ion exchange step, the second ion exchange step, and the second ion exchange Y-type zeolite D was obtained.

2. Manufacture of honeycomb structure carrying faujasite type zeolite (Manufacture of honeycomb structure)
The honeycomb structure carrier used in Example 1 (thickness 0.2 mm, porosity 90%, cell width 3.0 mm, cell height 1.6 mm) was cut into a cylindrical shape having a diameter of 400 mm and a thickness of 420 mm to obtain a honeycomb structure. Body P was obtained.

(Supporting faujasite type zeolite)
90 parts by weight of the second ion-exchanged Y-type zeolite D, 30 parts by weight of silica sol (solid content 30% by weight, manufactured by Nissan Chemical Co., Ltd., trade name Snowtex), and 130 parts by weight of water were mixed to prepare a slurry. After the honeycomb structure P was immersed in the obtained slurry, excess slurry was removed and dried to obtain a honeycomb structure Q on which faujasite-type zeolite was supported.

3. Dehumidifying device A rotor shaft is attached to the rotation center of the honeycomb structure Q to prepare a honeycomb rotor R, the honeycomb rotor R is installed in a rotor case, and a motor is attached to the rotor shaft. 10 was produced.
Dehumidification zone Fan-shaped center angle of dehumidification zone 4 in apertured surface 2a; 270 degrees Regeneration zone Fan-shaped center angle of regeneration zone 5 in apertured surface 2a; 90 degrees

4). Dehumidification durability test Using the dehumidification device 10 manufactured as described above, a dehumidification durability test was performed for 100 hours under the conditions shown in Table 2. The results are shown in Table 2.

(Comparative Example 2)
1. Production of faujasite-type zeolite Lanthanum Y-type zeolite J was obtained in the same manner as in Comparative Example 1.

2. 2. Manufacture of honeycomb structure supporting faujasite type zeolite; 3. Production of dehumidifier Dehumidification endurance test The same procedure as in Example 2 was performed, except that 90 parts by weight of the second ion-exchanged Y-type zeolite D was used and 90 parts by weight of the lanthanum-Y type zeolite J was used. The results are shown in Table 2.

  In the case of the dehumidifying apparatus of Example 2, the dew point of the dehumidifying air did not change to −4.2 ° C. both at the start of the test and after 100 hours had elapsed, and the dehumidifying performance of the honeycomb rotor of the dehumidifying apparatus decreased. Was not seen. On the other hand, in the case of the dehumidifying device of Comparative Example 2, the dew point of the dehumidified air was −4.4 ° C. at the start of the test, while −4.2 ° C. and 0.2 ° C. after 100 hours. It was higher, and a decrease in dehumidification performance was observed in the honeycomb rotor of the dehumidifier.

It is a figure which shows the honeycomb rotor installed in the dehumidification apparatus of 1st embodiment of this invention. It is a figure which shows the dehumidification apparatus of 1st embodiment of this invention. It is a figure which shows the honeycomb rotor installed in the dehumidification apparatus of the 2nd embodiment of this invention. It is a figure which shows the dehumidification apparatus of the 2nd embodiment of this invention. It is a figure which shows the dehumidification apparatus of the 2nd embodiment of this invention which has a connection pipe. It is a figure which shows the structure of the member in the rotor case of the dehumidification apparatus which concerns on the example of 3rd embodiment. It is sectional drawing which shows the arrangement position of the member in the rotor case of the dehumidification apparatus which concerns on the example of 3rd embodiment. It is a perspective view of the dehumidification apparatus which concerns on the example of 3rd embodiment. It is the figure which looked at the dehumidification apparatus which concerns on 3rd embodiment from the aperture surface 78b side of the honeycomb rotor.

Explanation of symbols

1, 31, 71 Honeycomb rotor 2a, 2b, 32a, 32b, 78a, 78b Opening surface 3a, 3b, 33a, 33b, 33c First split member 4, 34 Dehumidification zone 5, 35 Regeneration zone 6, 37, 72 Rotor Shaft 10, 40, 60, 80 Dehumidifier 11, 41, 82 Rotor case 15, 46, 77 First feeder 16, 47, 74 Second feeder 17, 49, 75 Heating device 18, 50 Air supply pipe to be treated 19, 51 Dehumidified air exhaust pipe 20, 52 First drying air supply pipe 21, 53 Second drying air supply pipe 22, 54 Drying air exhaust pipe 36 Cooling zone 48 Third supply 55 Cooling air supply pipe 56 Cooling air exhaust pipe 61 Connecting pipe 76 Hygroscopic air exhaust duct 81 Drying air intake duct 84 Radial rib 85 Condenser 86 Drain pipe A, E, M Cover Sense air B, F, N dehumidified air
C, G, K Drying air D, H, L Hygroscopic air I Cooling air J Endothermic air P Air from which moisture has been removed

Claims (3)

Honeycomb rotor constituted by a porous honeycomb structure on which Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, rotating means for rotating the honeycomb rotor, one aperture surface of the honeycomb rotor Is divided into a dehumidification zone and a regeneration zone, a second divided member that divides the other aperture surface of the honeycomb rotor into a dehumidification zone and a regeneration zone, and a second for supplying air to be treated to the dehumidification zone A dehumidifying device having one supply means, a second supply means for supplying drying air to the regeneration zone, and a heating means provided in a preceding stage of the regeneration zone for heating the drying air,
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
Dehumidifier characterized by. Honeycomb rotor constituted by a porous honeycomb structure on which Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, rotating means for rotating the honeycomb rotor, one aperture surface of the honeycomb rotor Is divided into a dehumidification zone, a regeneration zone and a cooling zone, and a second divided member which divides the other aperture surface of the honeycomb rotor into a dehumidification zone, a regeneration zone and a cooling zone, and the dehumidification zone is covered. First supply means for supplying process air, second supply means for supplying drying air to the regeneration zone, third supply means for supplying cooling air to the cooling zone, A dehumidifying device provided in the preceding stage and having a heating means for heating the drying air,
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
Dehumidifier characterized by. A honeycomb rotor composed of a porous honeycomb structure in which a Y- type zeolite is supported and a ventilation cavity is formed in the rotation axis direction, a rotating means for rotating the honeycomb rotor, and air to be treated is supplied to the dehumidification zone A dehumidifying device having a first supply means for supplying, a second supply means for supplying drying air to the regeneration zone, and a heating means for heating the drying air, which is provided upstream of the regeneration zone. ,
The Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 6 obtained by ion-exchange of synthetic sodium Y-type zeolite with hydrogen ions, and the sodium content is 0 to 5% in terms of oxide. The Y-type zeolite ion-exchanged with a certain hydrogen ion is immersed in an aqueous solution or slurry in which transition metal ions, zinc ions or tin ions are present, and an ion exchange reaction is performed, and ion exchange is performed with transition metal ions, zinc ions or tin ions. A first ion exchange step for obtaining a Y-type zeolite, and immersing the Y-type zeolite ion-exchanged with the transition metal ion, zinc ion or tin ion in an aqueous solution or slurry containing lithium ions to perform an ion exchange reaction Second ion to obtain Y-type zeolite in which all or part of residual hydrogen ions are ion-exchanged with lithium ions A Y-type zeolite manufactured performs conversion step,
The total content of one or more metals selected from transition metals, zinc and tin of the Y-type zeolite is 5% or more in terms of oxide, and the lithium content is 1 to 10 in terms of oxide. % der Ru it,
Dehumidifier characterized by.

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