JP2001226167A - Zeolite formed bead, production process of the same and adsorption/removal process using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide zeolite formed beads each concurrently having both high physical strength and excellent water adsorption performance, also to provide a production process by which such zeolite formed beads can easily be produced, and further to provide an adsorption/removal process for adsorbing and removing a specific component(s) such as moisture or water in a gas or liquid, by using the zeolite formed beads. SOLUTION: Each of the zeolite formed beads consists of zeolite, kaolin type clay and an inorganic dispersant. The production process of the zeolite formed beads comprises: dispersing powdery zeolite, kaolin type clay and an inorganic dispersant into water to obtain an aqueous dispersion; subjecting the aqueous dispersion to mixing, kneading, forming and drying, to obtain dry beads; and heating and activating the beads. In this adsorption/removal process, the zeolite formed beads are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zeolite bead molding, a method for producing the same, and a method for removing and adsorbing the zeolite beads using the zeolite bead. More specifically, it is widely used industrially for drying and dehydration or for adsorptive separation.For example, chlorofluorocarbon refrigerants, water removal from organic solvents, adsorption and separation of carbon dioxide, which is an environmental problem of global warming, and oxygen or oxygen in the air Pressure swing adsorption and desorption system (Pressur Sur) that selectively concentrates and separates either nitrogen
e Swing Admission System
The present invention relates to a zeolite bead molded article useful in a field such as m), a method for producing the same, and an adsorption removal method using the zeolite bead molded article.

[0002]

2. Description of the Related Art Usually, a zeolite compact is formed by adding a clay-based binder and a thickening agent or a dispersing agent as a molding aid to zeolite powder, and granulating and forming the desired shape such as beads and pellets.

In an adsorbent produced using a zeolite crystal and a non-adsorbing component clay-based binder, it is important to reduce the binder component in order to exhibit excellent adsorption performance. However, depending on the use of the adsorbent, the required physical properties and characteristics may differ depending on the use, and particularly in the case of a desiccant use for the purpose of removing water, it is used under severe conditions such as vibration and heat regeneration. Therefore, there has been a problem that the performance of the agent becomes insufficient in terms of crushing and cracking due to expansion and contraction of the zeolite lattice in the molded product, peeling due to rubbing of the agent, and powdering.

To solve this problem, attempts have been made to increase the amount of binder in order to improve the physical strength of the molded article. However, as the amount of binder increases, the amount of water adsorbed decreases. As a result, the adsorbent becomes insufficient in drying ability, and the binder is non-uniformly dispersed, so that there is a possibility that a molded product having a large variation in both the strength physical properties and the amount of adsorbed moisture may be obtained.

[0005] In general, an agent for dry dehydration is required to have an adsorption capacity rather than an adsorption rate, so that it is not necessary to make the pore volume excessively large. It is only necessary to provide a molded article having a relatively low mechanical strength to impart physical strength.

[0006] The type of zeolite used for the purpose of drying and dehydrating is determined by the molecular diameter of the substance to be dried, and A-type zeolite or faujasite-type zeolite is widely used industrially. Therefore, to adsorb only water molecules having a molecular diameter of 2.8 angstroms, 3A-type zeolite having an effective pore diameter of 3 angstroms is considered to be effective. However, when a higher adsorption capacity is required, 4A zeolite is required.
Zeolite or faujasite-type zeolite is used, and these are selected based on the fact that they do not adsorb the substance to be dried.

A description will be given below of a 3A zeolite as an example.

[0008] The 3A type zeolite compact is manufactured as follows. First, in a potassium chloride aqueous solution, 35% or more of the sodium ions in the zeolite are exchanged with potassium ions for a synthetic sodium A-type zeolite powder to obtain a 3A-type zeolite powder having an effective pore diameter of 3 angstroms. Next, after washing and filtration, a clay-based binder and a thickener or a dispersant as a molding aid are added to the powder, and the powder is formed into a shape according to the purpose by a granulation molding method such as rolling or extrusion. . The problem with the 3A-type zeolite molded body produced by such a method is how to uniformly disperse the clay component as a binder with a small amount of addition, and maintain the strength and the water adsorption performance.

[0009]

DISCLOSURE OF THE INVENTION The present invention overcomes the conventional problems of such a zeolite molded article, and has, among others, a combination of strong physical strength and excellent moisture adsorption performance required for a dry dehydrating agent. Another object of the present invention is to provide a molded article in which zeolite such as 3A-type zeolite and 4A-type zeolite are molded into beads, and a production method capable of easily obtaining such a zeolite bead molded article. It is a further object of the present invention to provide a method for adsorbing and removing specific components such as gas and water in a liquid by using the zeolite bead molding.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that zeolite and a condensation binder dissolved in a clay binder having a primary particle system of 1 μm or less with water. An inorganic dispersing agent such as a phosphate is added, and the mixture is kneaded and kneaded so that the bulk density becomes 0.8 to 1.0 kg / l. Then, the mixture is formed into beads by a tumbling granulation method, and then sized. It has been found that by activating after drying, a zeolite bead molded body having high physical strength and excellent moisture adsorption performance can be easily obtained. Furthermore, by bringing such a zeolite bead compact into contact with a refrigerant such as 1,1,1,2-tetrafluoroethane, the refrigerant itself is hardly decomposed, and water and the like contained therein are efficiently removed. They found that they could be adsorbed and finally completed the present invention.

Hereinafter, the present invention will be described in detail.

The zeolite used in the zeolite bead compact of the present invention is not particularly limited as long as the performance of the finally obtained zeolite bead compact can achieve the object of the present invention. As described above, A-type zeolite or faujasite-type zeolite is preferably used in terms of the molecular diameter of the substance to be dried.

For example, 3A type zeolite for ethylene plant, 3A type or 4A type zeolite for removing water from organic solvent for drying and dehydration of chlorofluorocarbon refrigerant, and cryogenic separation pretreatment or double glass. Is generally used for faujasite type zeolites. Conventionally, 3A type zeolite has been used as a refrigerant for car air conditioners, such as 1,1,1,2-tetrafluoroethane (hereinafter, referred to as "HFC-134a"), because of concern about adsorption and decomposition of chlorofluorocarbon. However, the molecular size of HFC-134a is as large as 4.7 × 5.1 × 5.6 angstroms, and even 4A-type zeolite having an effective pore size of 4 angstroms is basically not absorbed. Therefore, it is considered that the solid acid property or the impurity metal cation derived from the clay binder used when adjusting the shape of a certain molded product is affected. In general, clay minerals represented by acid clay, bentonite, sepiolite, kaolin and the like have solid acid properties, which is considered to be a cause of CFC decomposition.

Here, the zeolite bead compact of the present invention will be described by taking a 3A-type zeolite bead compact as an example.
5A or more is exchanged with potassium ions, and 3A type zeolite powder having an effective pore diameter of 3 Å is used as a raw material. The zeolite bead compact of the present invention is a compact comprising such a zeolite, a kaolin-type clay binder and an inorganic dispersant, and the compact has an average particle pressure resistance of 8 kgf or more, In addition, the amount of water adsorption is 20% by weight or more.

The shape of the zeolite bead molded article of the present invention may be a bead shape, and is not limited to a spherical shape or an elliptical shape. Rolling granulation method, plate type,
Examples of using a pan-type or a stirring granulator equipped with stirring blades, etc., are mentioned, and a method using a blade stirring granulator is preferred as a method for producing the zeolite bead compact of the present invention. Regarding the bead diameter, any size may be used according to the purpose of use, but in consideration of the fact that the strength of the molded article is proportional to the bead diameter, ease of molding, or operability,
As the agent for drying and dewatering, a molded article having a diameter of about 1.5 to 3.0 mm is preferably used.

The kaolin-type clay used in the zeolite bead compact of the present invention is present as a binder between the zeolite particles in the compact, and in particular, has a high compact density to improve the strength of the compact, and has a high zeolite density. In order to reduce the ratio of voids present in the bead molding, that is, the porosity, those having a primary particle diameter of 1 μm or less are preferable, and examples thereof include georgia akaolin clay.
These may be used alone or in combination of two or more.

Further, as the inorganic dispersant, those having high solubility in water and whose aqueous solution shows alkalinity are preferably used. Examples of such an inorganic dispersant include condensed phosphate and sodium aluminate, among which condensed phosphates are preferable, and further, sodium pyrophosphate, sodium tripolyphosphate, potassium pyrophosphate, and sodium hexametaphosphate. , Potassium hexametaphosphate and the like, particularly preferably sodium pyrophosphate, sodium tripolyphosphate and potassium pyrophosphate are preferably used. These may be used alone or in a mixture of two or more.

In the present invention, the inorganic dispersant is partly due to the viscosity of the dispersant. For example, lignin sulfonate, which is an organic dispersant described in Japanese Patent Publication No. 39-21821, is often formed because of its high viscosity and high molecular weight of 10,000 or more. In the agitated rolling granulation method in which granulation is performed using the own weight of the agent and centrifugal force, a partial mamako state is easily formed, and the granulation and molding becomes difficult. In addition, the formed bead-shaped compacts adhere to each other, resulting in a distorted shape or severe adherence to the molding apparatus, which is not preferable. Furthermore, in the process of finally firing and activating the molded body, sudden heat generated by combustion gives a thermal shock to the zeolite, which not only impairs the adsorption performance, but also reduces the compactness of the molded body by forming pores. This impairs the strength properties. On the other hand, inorganic dispersants have excellent granulation properties because they do not have high viscosity, and also remain dense between the zeolite particles in the compact even after the firing activation treatment. Is also excellent.

The ratio of zeolite to kaolin-type clay and inorganic dispersant in the zeolite bead compact of the present invention is 100 parts by weight of zeolite and 2 parts of kaolin-type clay.
The preferred range is 0 to 30 parts by weight, and 4 to 10 parts by weight of the inorganic dispersant. In the case of a condensed phosphate, 4 to 10 parts by weight of the inorganic dispersant is about 2 to 2 parts by weight based on phosphorus pentoxide (P ₂ O ₅ ).
The amount is equivalent to 5 parts by weight.

Next, a method for producing a zeolite bead molded product of the present invention will be described.

The production method is as follows: 20 to 100 parts by weight of zeolite powder and zeolite powder on an anhydrous basis are used.
To 30 parts by weight of kaolin-type clay, 4 to 10 parts by weight of an inorganic dispersant dissolved and dispersed in water or the like is added to 100 parts by weight of zeolite powder, and the bulk density is 0.8 to 1.0.
After mixing and kneading to obtain kg / liter, the mixture is formed into beads by a tumbling granulation method using blade stirring or the like.

The kaolin-type clay, which is a clay binder added here, is basically different only in the content of Si and Al or in the content of impurities such as alkali metals, alkaline earth metals and transition metals depending on the kind. Si / Al
It is a plate-like aluminosilicate having a molar ratio of 2.0, and the granulation moldability and the physical properties of the compact are the same in any clay, and there is no problem.

The method for producing a zeolite bead compact of the present invention comprises the steps of mixing and kneading zeolite powder, kaolin-type clay, and an inorganic dispersant dissolved in water, forming the kneaded product into beads, It consists of a step of drying the body and activating the firing, which will be described below in order.

<Mixing and Kneading Step> The zeolite powder used in the method for producing a zeolite bead molded product of the present invention is not particularly limited as long as the performance of the finally obtained zeolite bead molded product can achieve the object of the present invention. It is not limited, and A-type zeolite or faujasite-type zeolite is preferably used, and these zeolite species are properly used depending on the application. Small 3A-type and 4A-type A-type zeolites are preferably used.

For example, 3A type zeolite powder can be prepared by a known method, that is, a method in which a sodium A type zeolite powder synthesized from sodium aluminate and sodium silicate is treated in a potassium chloride aqueous solution with 35% or more of sodium ions in the zeolite. By exchanging with potassium ions, a 3A type zeolite powder having an effective pore diameter of 3 Å can be obtained.

The zeolite powder, kaolin-type clay, and the inorganic dispersant dissolved with the water necessary for granulation molding are:
After being placed in a container, the mixture is mixed and kneaded so as to be uniform, and kneaded sufficiently so that the bulk density becomes 0.8 to 1.0 kg / l. The bulk density of the mixed and kneaded mixture is 0.8 kg
If it is less than 1 / liter, the compacting effect is insufficient and bubbles exist between the mixture particles, which may make it difficult to form a dense molded body.

The amount of the kaolin type clay used is as follows:
In order to increase the physical strength of the molded article and maintain a high water-absorption equilibrium adsorption capacity, the amount is preferably in the range of 20 to 30 parts by weight based on 100 parts by weight of the zeolite powder. When the amount exceeds 30 parts by weight, the zeolite content is relatively reduced, and the amount of water adsorbed by the obtained molded body may decrease. When the amount is less than 20 parts by weight, the physical strength decreases, and as a dry dehydration adsorbent, May be unbearable for intended use.

Further, when the condensed phosphate is used, the amount of the inorganic dispersant used in the method of the present invention is 2 to 5 parts by weight of water based on phosphorus pentoxide per 100 parts by weight of zeolite powder. It is preferable to dissolve and add. Similarly, when sodium aluminate is used, it is preferable that 2 to 5 parts by weight of aluminum oxide is dissolved in water and added to 100 parts by weight of zeolite powder.

The amount of water added for mixing and kneading the zeolite powder, the kaolin-type clay binder, and the inorganic dispersant varies depending on the properties of the kaolin-type clay binder and the like, or the amount thereof. The amount to be used is 40 to 100 parts by weight of the zeolite powder.
An amount in the range of 60 parts by weight is preferred. Therefore, when the inorganic dispersant exceeds 10 parts by weight, it cannot be dissolved only by the added water, and is mixed in a slurry state. Therefore, the mixed and kneaded material cannot be uniformly dispersed and uniform molded body strength cannot be obtained. is there.

The inorganic dispersant, that is, phosphorus pentoxide in the condensed phosphate is generally used as a drying / dehydrating agent, and has a water adsorption performance. Because it is an adsorbate, 1
If the amount added exceeds 0 parts by weight, the zeolite content will be reduced, and the water equilibrium adsorption amount will decrease, which is not preferable. On the other hand, if it is less than 4 parts by weight, the effect of addition may be insufficient and the physical strength may not be satisfactory. The same applies to sodium aluminate and the like.

<Molding Step> In the above-mentioned mixing and kneading step, the mixture kneaded sufficiently to have a bulk density of 0.8 to 1.0 kg / liter is formed into a bead shape by a tumbling granulation method such as blade stirring. Is done.

Here, as a granulation method used in the method of the present invention, a rolling granulation method is preferably used, and a method using blade stirring is more preferably used. This is because strong shearing force is given by stirring the blades compared to normal rolling granulation, and the clay binder dispersed in the inorganic dispersant is more uniformly dispersed and attached to the zeolite particles, and the zeolite particles This is because it is possible to form a dense molded body by closing the voids.

The shape of the molded product is not particularly limited as long as it has the features of the present invention. The molded product may be a sphere, an ellipse, or the like, for example, beads having a size of 7 to 10 mesh. It can be a molded article. Furthermore, when physical strength, especially wear strength, is required, it is desirable to be a bead molded body having a high sphericity, and the molded spherical article can be obtained by a known method, for example, an arbitrary number of revolutions using a marmellaizer molding machine, It is a common method to smooth the surface of a molded article by sizing under time conditions.

It is easy to change the diameter of the beads to be formed and sized according to the intended use. If necessary, the diameter may be uniformed by classification using a sieve or the like.

<Activation Step> The compact thus formed is dried, fired and activated, and the added kaolin-type clay binder is sintered and water is desorbed. As a method for drying and activation, a known method can be used. For example, a hot air dryer, an electric muffle furnace, a tubular furnace, a rotary furnace, or the like may be used.

The calcination / activation temperature is 600 ° C. or higher, which is the sintering temperature of kaolin-type clay, in order to stably maintain the physical strength of the obtained molded article and completely desorb moisture in the molded article. , And more preferably at a temperature of 650 to 700 ° C.

As a method for adsorbing and removing a substance to be adsorbed such as water in a gas or liquid using the zeolite bead molded article of the present invention, the zeolite bead molded article of the present invention is brought into contact with a target gas or liquid, What is necessary is just to remove by a well-known method,
Conditions such as the amount used and the temperature can be determined as appropriate.
In particular, the zeolite bead molded product of the present invention can be used for a long period of time because of its excellent strength physical properties and moisture adsorption characteristics.

As described above, the zeolite bead molded product obtained by the method of the present invention is widely used for drying and dehydration or for adsorptive separation. For example, HFC-134a which is a chlorofluorocarbon refrigerant for automobiles or a mixed refrigerant containing the same is used. It is useful for applications in the field of adsorptive separation agents, such as removal of water from organic solvents or air, and adsorption of carbon dioxide, which is an environmental problem of global warming.

The reason for the high physical strength of the zeolite bead molded article of the present invention is that the primary particle diameter of the binder is 1 μm.
m or less, and the use of an inorganic dispersing agent such as a condensed phosphate to disperse the aggregated clay binder. The purpose is to apply a shearing force to disperse these clay binders more evenly. That is, it is considered that the clay binder dispersed in the inorganic dispersant more uniformly disperses and adheres to the zeolite particles, exists between the zeolite particles, closes the voids, and forms a dense compact.

Further, the point that the water equilibrium adsorption performance can be maintained is that molding is performed with a relatively small amount of clay binder.
It is also considered that phosphorus pentoxide in the inorganic dispersant has a water adsorption ability.

Further, a chlorofluorocarbon refrigerant HFC-
The superior use of 134a in drying is considered to be due to the solid acid properties of the clay binder, which is considered to decompose CFCs, or the effect of the inorganic dispersant added with the influence of impurity metal cations.

However, such a presumption does not restrict the present invention at all.

[0043]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, each evaluation was implemented by the method shown below.

(1) Bulk Density According to the method using an apparent density measuring device according to JIS-K-3362, the mixture after kneading and kneading was received in a polyethylene cup (W1) having a volume of Vml, and when it was piled up, After rubbing off with a linear spatula, the weight (W2) of the cup containing the mixture was read to the 1 g unit, and the bulk density was calculated by the following equation.

Bulk density (kg / liter) = (W2−W1) / V (2) Pressure resistance After cooling the fired and activated bead compact, 1.7 to 2.
An 8 mm three-stage sieve is quickly sieved so as not to adsorb moisture, and 25 of those having an average size (2.0 to 2.4 mm) are hardness meter (Fujiwara Seisakusho, Model: KHT-2)
0) was measured one by one. The measurement is based on a method in which a weight is applied to the compact at a constant speed by an indenter having a diameter of 5 mm.
f), and the average value of the obtained values was regarded as the pressure resistance of each example and comparative example.

(3) Moisture Equilibrium Adsorption Amount After the calcined and activated bead compact is cooled,
Complete hydration was allowed to take place in a desiccator at 80% relative humidity for 16 hours or more. Then, 900 ° C. in a muffle furnace,
After calcination for 1 hour, the moisture equilibrium adsorption amount adsorbed on the molded body was measured.

(4) Fluorocarbon Decomposition Test The decomposition rate of chlorofluorocarbon was evaluated by an accelerated test method called a shield tube test according to the test method of the American Refrigeration Association (ASRE method). The shield tube test is about 2 g of HFC-134a in a pressure-resistant sealed glass container with an inner volume of about 40 ml,
After about 1 g of the desiccant was sealed and heated to 175 ° C. and left for 30 days or more, the amount of fluorine ions adsorbed on the agent was measured to evaluate the decomposition of the refrigerant.

Example 1 Synthetic sodium A-type zeolite powder (manufactured by Tosoh Corporation, SiO ₂ / Al ₂ O ₃ = 2.0) was brought into contact with an aqueous solution of potassium chloride to exchange 40% of sodium ions for potassium ions and to exchange 3A A type zeolite powder was prepared. This 3
The A-type zeolite powder 100 parts by weight, 30 parts by weight of Georgia kaolin clay, 50 P ₂ O dissolved in water parts ₅ standards 3 parts by weight of sodium pyrophosphate mix muller kneader (Sintokogio Co. Made, Model: MSG-05
The mixture was kneaded and kneaded in S) and kneaded sufficiently. As a result of measuring the bulk density of the obtained kneaded product by the above method, 0.92 k
g / liter.

The kneaded product was stirred and granulated into a bead having a diameter of 1.7 mm to 2.8 mm using a blade stirring type granulator Henschel mixer (manufactured by Mitsui Mining Co., Ltd., model: FM-75), and formed into a marmerizer. Container (made by Fuji Paudal Company, model:
Q-1000), and dried.

Next, a muffle furnace (Advantech,
Model No .: KM-600) and 65
The clay was fired in a 0 ° C. atmosphere for 5 hours to sinter and activate the clay.

The compressive strength, moisture equilibrium adsorption amount, and CFC decomposability of the obtained 3A-type zeolite beads were measured by the methods described above. Table 1 shows the results.

[0052]

[Table 1]

In Table 1, the amount of clay indicates parts by weight based on 100 parts by weight of zeolite, and the amount of dispersant indicates parts by weight of P ₂ O ₅ and Al ₂ O _{3 based} on 100 parts by weight of zeolite. Also, in the type of dispersant used,
Na ₄ P ₂ O ₇ is sodium pyrophosphate, Na ₅ P ₃ O ₁₀
Represents sodium tripolyphosphate, K ₄ P ₂ O 7 represents potassium pyrophosphate, and Na ₂ Al ₂ O ₄ represents sodium aluminate.

Examples 2 to 13 A 3A-type zeolite bead molding was prepared in the same manner as in Example 1 except for the amount of the Georgia kaolin clay shown in Table 1 and the type or amount of the inorganic dispersant. SiO ₂ / Al ₂ O _{3 of} 3A type zeolite powder used
The molar ratio was 2.0, the potassium ion exchange rate was 40%, and the bulk density of the obtained kneaded product was measured by the method described above, and was found to be in the range of 0.88 to 0.99. After the granulation molding, the pressure resistance, moisture equilibrium adsorption amount, and CFC decomposability of the obtained 3A-type zeolite beads were measured by the above-described methods. Table 1 shows the results.

Example 14 100 parts by weight of synthetic sodium A-type zeolite powder (manufactured by Tosoh Corporation, SiO ₂ / Al ₂ O ₃ = 2.0), 30 parts by weight of Georgiakaolin clay and 50 parts by weight of water 4 parts by weight of sodium tripolyphosphate based on the dissolved P ₂ O ₅ was mixed and kneaded with a mix muller kneader (manufactured by Shinto Kogyo Co., Ltd., model: MSG-05S) and kneaded sufficiently. As a result of measuring the bulk density of the obtained kneaded product by the above method, it was 0.94 kg / liter.

The kneaded product was stirred and granulated into a bead having a diameter of 1.7 mm to 2.8 mm using a blade stirring type granulator Henschel mixer (manufactured by Mitsui Mining Co., Ltd., model: FM-75), and formed into a marmellaizer. Container (made by Fuji Paudal Company, model:
Q-1000), and dried.

Next, a muffle furnace (Advantech,
Model No .: KM-600) and 65
The clay was fired in a 0 ° C. atmosphere for 5 hours to sinter and activate the clay.

The pressure-resistant strength, water equilibrium adsorption amount, and CFC decomposability of the obtained 4A-type zeolite beads were measured by the above-mentioned methods. Table 2 shows the results.

[0059]

[Table 2]

In Table 2, the amount of clay means zeolite 1
The amount of aluminum hydroxide refers to parts by weight of Al ₂ O ₃ relative to 100 parts by weight of zeolite, and the amount of dispersant refers to parts by weight of P ₂ O ₅ relative to 100 parts by weight of zeolite. Show. Further, in the type of dispersant, Na ₅ P ₃ O ₁₀ is sodium tripolyphosphate,
Na ₄ P ₂ O ₇ represents sodium pyrophosphate.

Examples 15 to 18 A 4A-type zeolite bead molding was prepared in the same manner as in Example 14 except for the addition amount of the Georgia kaolin clay and the type and amount of the inorganic dispersant shown in Table 2. SiO ₂ / Al ₂ O _{3 of} 4A type zeolite powder used
The molar ratio was 2.0, and as a result of measuring the bulk density of the obtained kneaded product by the above method, it was in the range of 0.90 to 0.99. After the granulation molding, the pressure resistance, moisture equilibrium adsorption amount, and CFC decomposability of the obtained 4A-type zeolite bead molding were measured by the methods described above. Table 2 shows the results.

Comparative Examples 1 to 5 A 3A-type zeolite bead molding was prepared in the same manner as in Example 1 except that the amount of addition of the Georgiakaolin clay shown in Table 3 and the use of the inorganic dispersant were not used. The SiO ₂ / Al ₂ O ₃ molar ratio of the 3A type zeolite powder used was 2.0, the potassium ion exchange rate was 40%, and the bulk density of the obtained kneaded product was measured by the method described above.
It was in the range of 0.83 to 0.95. After the granulation molding, the compression strength, the moisture equilibrium adsorption amount, and the CFC decomposability of the obtained 3A-type zeolite bead molding were measured by the methods described above. Table 3 shows the results.

[0063]

[Table 3]

In Table 3, the amount of clay means zeolite 1
Parts by weight relative to 00 parts by weight are shown.

Comparative Examples 6 to 8 Except for the type and amount of the dispersant shown in Table 4, the same operation as in Example 1 was carried out to prepare 3A-type zeolite beads. SiO ₂ / Al ₂ O of 3A type zeolite powder used
_{The 3} molar ratio was 2.0, the potassium ion exchange rate was 40%, and 30 parts by weight of Georgiakaolin clay was added and mixed and kneaded. As a result of measuring the bulk density of the obtained kneaded product by the above-mentioned method, it was in the range of 0.80 to 0.84 kg / liter. After the granulation molding, the compression strength and the water balance of the obtained 3A-type zeolite bead molding were measured by the above-described methods. Table 4 shows the results.

[0066]

[Table 4]

In Example 4, the amount of the dispersant indicates the parts by weight of the dispersant with respect to 100 parts by weight of the zeolite.
The sun extract therein represents sodium lignin sulfonate.

Comparing the above example with the comparative example, it can be seen that the obtained 3A-type or 4A-type zeolite bead molded product has a remarkably strong pressure resistance and a high water equilibrium adsorption amount. In particular, when the same amount of clay binder is used for the zeolite powder, the effect of adding an inorganic dispersant such as a condensed phosphate is apparent. The effect was clear when compared with the case where no inorganic dispersant was added or the case where sodium lignin sulfonate which was an organic dispersant was added.

Further, in the results of a CFC decomposition test performed using the zeolite beads obtained in the examples, the decomposition rate of CFC was extremely small as compared with the result of the comparative example, and CFC was hardly decomposed. You can see that.

[0070]

According to the present invention, the following effects can be obtained.

(1) The zeolite bead molded article of the present invention is a molded article having both high pressure resistance and high moisture equilibrium adsorption amount and excellent physical properties of the adsorbent.

(2) According to the production method of the present invention, a molded zeolite bead having excellent performance can be easily obtained.

(3) The adsorption and removal method of the present invention can adsorb water and the like contained therein without decomposing gas and liquid.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D017 AA03 BA01 CA01 CA17 CB01 DA01 DB03 4D052 HA00 HA03 HA09 HA24 HB02 4G030 AA01 AA37 BA32 CA07 GA09 GA13 GA16 GA17 HA05 PA06 4G066 AA13D AA20D AA50D AA61DA21 DA01 FAA FA21 FA26 FA28 FA37 GA01

Claims (12)

[Claims] 1. A zeolite bead compact comprising zeolite, kaolin-type clay and an inorganic dispersant. 2. A zeolite and 20 to 30 parts by weight of a kaolin type clay per 100 parts by weight of the zeolite,
The zeolite bead molded product according to claim 1, comprising 10 parts by weight of an inorganic dispersant. 3. A molded zeolite bead according to claim 1, wherein the zeolite is an A-type zeolite and / or a faujasite-type zeolite. 4. The molded zeolite bead according to claim 3, wherein the zeolite is 3A zeolite and / or 4A zeolite. 5. The molded zeolite beads according to claim 1, wherein the inorganic dispersant has high solubility in water and the aqueous solution is an alkaline condensed phosphate. 6. The condensed phosphate is sodium pyrophosphate,
The zeolite bead molded product according to claim 5, characterized in that it is at least one member selected from the group consisting of sodium tripolyphosphate and potassium pyrophosphate. 7. An inorganic dispersant dispersed in water is added to zeolite powder and kaolin-type clay, kneaded and kneaded, then formed into beads by a tumbling granulation method, dried, and then fired and activated. The method for producing a zeolite bead molded product according to any one of claims 1 to 6, wherein 8. A zeolite powder and the zeolite powder 1
20 to 30 parts by weight of kaolin type clay per 100 parts by weight, and 4 to 10 parts by weight of 100 parts by weight of the zeolite powder.
A part by weight of an inorganic dispersant is dispersed in water, added, kneaded and kneaded so as to have a bulk density of 0.8 to 1.0 kg / liter, and then formed into beads by a tumbling granulation method and dried. The method for producing a molded zeolite bead according to claim 7, wherein firing is then performed. 9. The method for producing a molded zeolite bead according to claim 7, wherein kneading is performed so that the primary particle diameter of the kaolin-type clay is 1 μm or less. 10. A method for adsorbing and removing a substance to be adsorbed in a gas or a liquid by bringing the molded zeolite bead according to claim 1 into contact with a gas or a liquid. 11. The method according to claim 10, wherein the substance to be adsorbed is water. 12. The method according to claim 10, wherein water is adsorbed and removed from a refrigerant containing 1,1,1,2-tetrafluoroethane (HFC-134a).