JPH1087322A - High strength and low wear zeolite granule, its production and adsorption separation method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain zeolite granules having a small diameter, a large pore volume and excellent in pressure and wear resistance by kneading a mixture of zeolite powder with a binder and other additives so that the bulk density of the mixture is regulated to a specified value. SOLUTION: A mixture of zeolite powder with 5-15 pts. wt. binder based on 100 pts.wt. (expressed in terms of anhydride) of the zeolite powder, 1-10 pts.wt. thickener and/or water retaining agent and 50-80 pts. wt. water is kneaded so that the bulk density of the mixture is regulated to 0.7-1.5kg/l. The kneaded mixture is granulated by extrusion and the resultant granules are made uniform by rolling, dried, fired, subjected to ion exchange and activated to obtain the objective high strength low wear zeolite granules having >=85wt.% zeolite content, 0.3-0.5cc/g pore volume and 0.5-2mm diameter. The zeolite is preferably A type, X type, Y type or L type zeolite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-strength, low-wear zeolite granule, a method for producing the same, and a method for adsorptive separation using the same. More specifically, it is widely used as an adsorptive separation agent. For example, a pressure swing adsorption method (hereinafter referred to as a PSA method) in which nitrogen is selectively adsorbed from a mixed gas containing nitrogen and oxygen as main components by an adsorption method and oxygen is concentrated. The present invention relates to a crystalline, high-strength, low-wear zeolite granule useful as an adsorbent for (1), a method for producing the same, and an adsorption separation method using the same.

[0002]

2. Description of the Related Art Conventionally, molded articles containing crystalline zeolites X and A as effective adsorbents have been widely used as adsorbents, and particularly recently as adsorbents for concentrating oxygen from air. Are expanding, and a crystalline zeolite adsorbent having excellent performance is demanded.

Heretofore, crystalline zeolite compacts have been granulated and formed by tumbling granulation or extrusion granulation using a zeolite powder and a clay mineral, silica sol or alumina sol as a binder component. For example, Tokuho 5
No. 82327 discloses a method for producing an adsorbent by tumbling granulation using a silica binder as a binder. However, in the rolling granulation using such a method, it is difficult to obtain a granular material having sufficient strength with a small amount of binder, and the strength is remarkably reduced particularly when the particle diameter is small. On the other hand, Japanese Patent Application Laid-Open No. 62-283812 discloses a method in which a clay mineral is used as a binder, and a raw material treated by a kneader is extruded into a pellet shape by using a granulator. However, although the molded body obtained by this method has a pressure resistance, the abrasion resistance is insufficient. Adsorbents with poor abrasion resistance can be filled or adsorbed in adsorption towers,
Powdering occurs due to repetition of desorption, causing troubles in the valve or the valve, or increasing the pressure loss and causing a decrease in the adsorption separation ability.

[0004] Usually, the adsorbent is used after being molded. However, by reducing the binder component in the molded article, the component having adsorbability is increased, and the target adsorbed substance (hereinafter referred to as "adsorbed substance") is efficiently used. The performance can be improved by reducing the size or the diameter in order to adsorb and desorb the gas. This is because as the size of the molded body increases, the adsorption / desorption speed decreases due to the Sakai film resistance and diffusion resistance, and the performance as an adsorbent decreases.

On the other hand, in the adsorption / desorption operation on the surface used as an adsorbent, since vibration or mutual contact is inevitable, it is required to have excellent strength physical properties such as pressure resistance and wear resistance. However, when the amount of the binder component in the molded body is small or the diameter thereof is small, the strength of the molded body is reduced. Therefore, it is extremely difficult to prepare an adsorbent having a small diameter and a small amount of the binder component with high strength. . For example, in a molded article having crystalline zeolite X type or A type as an effective adsorbing component, one having a small size, a small amount of a binder component, a large pore volume, and a high strength can be said to have high performance. However, reducing the size, reducing the amount of the binder component, and increasing the pore volume contradicts increasing the strength of the molded body.Therefore, it has never been possible to obtain a molded body that satisfies all these requirements. It was difficult.

Further, it has long been known that the dynamic adsorption / desorption performance of an adsorbent is affected by its pores. However, if pores are given to an adsorbent, the adsorbent becomes porous and its strength is reduced. Had issues.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an adsorbent having properties superior to those of a conventional crystalline zeolite molded article, namely, having a small diameter and a large pore volume.
It is still another object of the present invention to provide a high-strength, low-abrasion zeolite granule excellent in pressure resistance and abrasion resistance, a method for producing the same, and an adsorption separation method using the same.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies on a method for granulating and molding a crystalline zeolite molded body. In order to obtain a molded product having a large pore volume with high strength and excellent abrasion resistance, it has been found that kneading and kneading before granulation is extremely important. By paying attention and extruding and granulating the sufficiently mixed and kneaded raw material, a preformed body having sufficient pressure resistance strength and pore volume can be obtained. The present inventors have found that a molded product having both strength and wear resistance, for example, a columnar molded product with sharp corners, has led to the completion of the present invention.

Hereinafter, the present invention will be described in detail.

First, the high-strength low-wear zeolite granules of the present invention will be described.

Here, in this specification, "granular material"
The term “pillar” may also mean a columnar, pellet-like, or spherical shaped body, and “diameter” means the length of the shortest part of a granular material.

The high-strength, low-wear zeolite granules of the present invention have a zeolite content of at least 85% by weight, a pore volume of 0.3 to 0.5 cc / g and a diameter of 0.5 to 2 mm.
It is.

As used herein, the term "high strength" refers to a test piece using a Kiya type hardness tester, referring to the compression strength test method for fine ceramics described in JIS-R-1608, as shown in Examples. When a compressive load is applied by pressing a pressing plate at a constant speed in the diameter direction of the granular material, the maximum load (unit: kgf) that the granular material can withstand is expressed as pressure resistance. The pressure resistance in this case is preferably 2.0 kgf or more. The reason for this is that if the pressure resistance of the granular material is less than 2.0 kgf, the granular material is unfavorably used, for example, when the granular material is packed into a packed tower as an adsorbent, the damage is increased.

As the low wear property, as shown in Examples, the wear rate calculated according to the particle strength measurement method described in JIS-K-1464 is preferably 1% by weight or less. The reason for this is that the particulate matter is used as an adsorbent and is packed in an adsorption tower, or by repeating adsorption and desorption,
This is because, by making the powdering less likely to occur, problems such as a trouble of a valve, a valve, and the like, and an increase in pressure loss and a decrease in adsorption separation ability are avoided.

[0015] The zeolite component has a capability of adsorbing an adsorbed substance in a granular material. The zeolite component is used for increasing the ion exchange capacity and increasing the pore volume to increase the gas adsorption capacity. X-type zeolite, A-type zeolite, Y-type zeolite, L-type zeolite and the like are preferable.
Further, the content of the zeolite component is 8% of the total amount of the granular material.
5% by weight or more. When the amount is less than 85% by weight, the adsorption capacity is insufficient and the required amount of the adsorbent increases, which is not preferable. These zeolites may be composed of two or more zeolites such as X-type and A-type.

The pore volume is 0.3 to 0.5 cc /
g. If the amount is less than 0.3 cc / g, sufficient adsorptivity cannot be obtained, and if it exceeds 0.5 cc / g, the bulk density of the granular material becomes low and the adsorptivity per unit volume decreases, which is not preferable.

The diameter of the granular material is 0.5 to
2 mm. If the diameter is less than 0.5 mm, sufficient strength cannot be obtained, and if it exceeds 2 mm, a sufficient adsorbing / desorbing speed cannot be obtained.

The type of cation in the high-strength, low-wear zeolite granules of the present invention is not particularly limited, and the desired cations can be obtained by exchanging cations such as alkali metals and alkaline earth metals with cations in the granules. This gives a granular product.

Next, the method for producing the high-strength and low-wear zeolite granules of the present invention will be described. The method for producing a high-strength, low-abrasion zeolite granule according to the present invention is characterized in that the binder component is 5 to 15 parts by weight, a thickener and / or a water retention agent, based on zeolite powder and 100 parts by weight of zeolite powder (in terms of anhydride). A mixture consisting of 1 to 10 parts by weight and 50 to 80 parts by weight of water is kneaded and kneaded, and the bulk density is 0.7 to 1.5 k.
g / l, extrusion granulation, rolling and sizing, drying, firing, ion exchange, and activation. If necessary, binderless treatment can be performed after firing. . Hereinafter, each step will be described.

<Kneading and kneading> The type of zeolite powder used in the method of the present invention is not particularly limited.
For example, X-type zeolite, A-type zeolite, Y-type zeolite, L-type zeolite and the like are preferably used due to their high pore volume. Further, as a kind of these zeolite powders, two or more kinds of zeolite type powders can be used in combination.

The binder component is not particularly limited. Clay minerals such as kaolinite, hydrohaloysite, bentonite, and attapulgite, which are clay minerals,
Alternatively, inorganic binders such as silica sol and alumina sol are preferably used. The reasons for this are the economics of the price of the material, the operational aspects of sintering at low temperatures,
The physical properties such as the strength of the obtained granular material can be increased and the adsorption capacity can be increased.

Here, the amount of the binder component used is preferably in the range of 5 to 15 parts by weight, more preferably in the range of 5 to 10 parts by weight, based on 100 parts by weight of zeolite powder (in terms of anhydride). Is more preferred. The reason for this is that the content of the zeolite component decreases due to an increase in the amount of the binder component, and a decrease in the adsorption capacity of the obtained granules is suppressed, and the shape of the obtained granules is maintained. Further, the obtained granules may have no binder component, that is, all components may be zeolites. In order to convert all the components into zeolites, it is possible to adopt a known method of converting the binder components into zeolites, that is, a known binderless method.

The amount of the thickener and / or water retention agent used is 100 parts by weight of zeolite powder (in terms of anhydride) in order to avoid a decrease in the operation surface such as ease of granulation and the strength of the obtained granules. On the other hand, it is preferably in the range of 1 to 10 parts by weight, more preferably in the range of 3 to 8 parts by weight. The type is not particularly limited as long as it can be generally used, and examples thereof include carboxymethylcellulose (hereinafter abbreviated as CMC), sodium polyacrylate and the like.

The amount of water used is 50 to 80 parts by weight with respect to 100 parts by weight of zeolite powder (in terms of anhydrous) in order to avoid a decrease in the operation surface such as ease of kneading and kneading and the strength of the obtained granules. The range of parts by weight is preferred, more preferably 60 to 75 parts by weight. Water or warm water can be used as the water.

It is preferable that these raw materials are sufficiently kneaded, and the bulk density of the kneaded mixture is in the range of 0.7 to 1.5 kg / liter, and 0.8 to 1.0 kg / l.
A range of liters is more preferred. The reason for this is that if the bulk density of the mixture is within this range, molding can be easily performed and the obtained granular material can have high strength.

The conditions such as temperature and time for kneading may be the same as those usually used, and the type used for kneading is not particularly limited. Examples thereof include a crusher, a continuous kneader and a mix muller. In particular, a mix muller type is preferably used in order to increase the bulk density of the obtained mixture.

<Extrusion Granulation> Next, the kneaded mixture is extruded and granulated to form a preform. There are various types of extrusion granulators used here, but if classified by the extrusion mechanism that extrudes raw materials from a die screen, it can be used for screw type, roll type, blade type, self-forming type, ram type, etc. They are divided into formats and can be used. There is no particular limitation on the type of the extruder or the thickness of the die screen attached to the extruder, but in order to increase the strength of the preform, preferably a screw-type pelletizer, a roll type It is preferable that the thickness of the die screen is 0.5 to 40 mm using a pellet mill or the like. Further, it is preferable to use a roll-type pellet mill and to set the thickness of the die screen to 0.5 to 15 mm. The size of the preform can be changed depending on the application, and if necessary, the obtained preform may be classified by sieving to make the size uniform.

<Rolling and sizing> Rolling and sizing is performed to impart roundness to the preformed body thus formed. Here, as the model of the rolling sizing machine, there is no particular limitation on the model and conditions as long as it can impart roundness to the compact, and for example, it can be carried out using a marmelizer or the like. Can be illustrated.

<Drying / Firing> As a method for drying and firing, known methods can be used. Here, it is preferable to perform the drying at a temperature of 120 ° C. or less in order to suppress a decrease in the strength physical properties. The type used for drying is not particularly limited, and examples thereof include a vibrating fluidized dryer. The firing temperature is 350 to 65 to maintain the shape of the obtained granular material stably.
It is preferable to carry out at 0 ° C. Examples of a model used for such firing include a shaft kiln and a rotary kiln.

<Binderless treatment> The thus obtained granules can be immersed in an alkali aqueous solution or the like to perform binderless treatment, if necessary. good. By performing this binderless treatment, the adsorption capacity of the obtained particulate matter can be further increased, and an excellent adsorbent can be obtained.

<Ion exchange> The cations in the granules can be exchanged with desired cations by bringing the granules obtained by the above steps into contact with an aqueous solution containing an alkali metal or an alkaline earth metal. As a condition, a known method may be used. As an ion exchange method, a batch contact method, a column flow method, and the like are usually used. The temperature at which the ion exchange is performed is determined in consideration of the speed at which the ion exchange equilibrium is reached, but usually about 50 ° C. is sufficient.

<Activation> By further activating the granules thus obtained, an adsorptive separating agent having high adsorption performance can be obtained. The condition for the activation is to desorb water in the molded body for the purpose, and any condition can be used as long as the granular material is activated and the adsorption performance is improved. For example, in the case of X-type zeolite, 6
This can be achieved by performing the process at 00 ° C. for about one hour.
Further, as a model of the device used for activation, a shaft kiln or the like can be exemplified.

As described above, there is no problem if the production conditions and the like are appropriately selected so long as the molded product having the characteristics of the high-strength and low-abrasive zeolite granules of the present invention can be obtained.

The high-strength and low-wear zeolite granules of the present invention have a small diameter, a large pore volume, and excellent pressure resistance and abrasion resistance. Therefore, they can be used as adsorbents in various fields. Can be. For example, it can be used for gas adsorption separation by pressure swing adsorption method and the like. Specifically, it is possible to adsorb nitrogen in the air and obtain a high oxygen concentration gas with an increased oxygen concentration in the remaining components. It can be used in the production of steel, steel, glass and the like, and can also be applied to the medical field.

Even when the high-strength, low-abrasive zeolite granules of the present invention have a reduced diameter, the static nitrogen adsorption capacity can be increased without impairing the pressure resistance and abrasion resistance essential for the adsorptive separation agent. The reason is that the amount of the binder is reduced, and the raw materials are sufficiently kneaded and kneaded by a kneading machine having a high kneading and kneading effect to increase the bulk density.

However, such presumption does not restrict the present invention.

[0037]

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.

-Pore Volume- The activated round pellet compact is placed in a pore sizer 9
310 (manufactured by Micromeritics) and 1 to 30
It was measured in a pressure range of 000 psia.

-Bulk density of mixture-According to the method using an apparent density measuring device according to JIS-K-3362, the kneaded mixture is received in a Vml acrylic cup, and when it reaches the peak, it is straightened with a spatula. After dropping, weigh the cup containing the mixture to 0.1 g. The bulk density of the mixture was calculated by the following equation (1).

E = (W2−W1) / V (1) where E is the bulk density of the mixture (unit: g / ml), W2
Is the weight of the cup containing the compact (unit is g), W1 is the weight of the empty cup (unit is g), V is the capacity of the cup (unit is ml), and the unit of the bulk density is arbitrarily converted. . In this specification, the measured apparent density is described as the bulk density of the mixture.

Compressive Strength In the measurement of compressive strength, a Kiya type hardness tester is used in a normal temperature and normal pressure atmosphere using a Kiya hardness tester with reference to the compressive strength test method for fine ceramics described in JIS-R-1608. When a compressive load was applied by pressing a pressure plate at a constant speed in the diameter direction of a granular material as a piece, the maximum load (unit: kgf) that the granular material could withstand was measured.

Specifically, the compressive strength was measured by a Kiya type digital hardness tester (type KHT-20). That is,
The ion-exchanged and dried zeolite granules were classified by sieving, excluding 1 mm under and 2 mm over for 1 mm diameter pellets, and 1.5 mm under and 3 mm over for 1.5 mm diameter pellets. As described above, the particles were classified using a sieve having a diameter twice as large as the diameter of the pellet and used for measurement. However, for the granules of Comparative Example 3, those excluding 2 mm under and 3 mm over were used. The classified granules were activated, the granules for compressive strength measurement were taken out, and the compressive strength in the diameter direction was measured by a Kiya hardness tester equipped with a cylindrical pressure plate having a diameter of 5 mm. The pressure plate used was made of stainless steel, and the crosshead speed was 0.8 mm / sec. In this way, the compressive strength of 30 granular materials was measured, and the average of the results was taken as the compressive strength.

-Abrasion Rate-The abrasion rate was calculated according to the particle strength measurement method described in JIS-K-1464 (1962 version). That is, a molded body as a sample was previously subjected to a temperature of 25 ° C. and a relative humidity of 80%.
In the desiccator for more than 16 hours. Then, about 70 g of the sample was sieved for 3 minutes using a sieve (manufactured by Tokyo Screen Co., Ltd., model: JIS Z-8801) having 850 μm, 355 μm, and a saucer, and then the sieve from which adhering substances were removed was filtered.
Sieved for minutes. The remaining 50 g of sample is accurately weighed, and at the same time, five 10-yen coins are set and shaken for 15 minutes. The wear rate was calculated by the following equation (2) using the sample dropped on the tray as Xg.

Abrasion rate (% by weight) = (X / 50) × 100 (2) —Static nitrogen adsorption amount—Static nitrogen adsorption amount was measured by a volumetric method. That is, a granular material having a calcium ion exchange rate of 90% was used as a sample for measurement, activated, and then evacuated at 350 ° C. for 2 hours under vacuum, and the static nitrogen adsorption amount at 25 ° C. and 700 Torr was measured. did. Example 1 X-type zeolite powder (manufactured by Tosoh Corporation, trade name: zeolam) and 10 parts by weight of kaolin-type clay and 3 parts by weight of CMC were mixed with 100 parts by weight (in terms of anhydride) of this powder. 70 parts by weight of water was added, and the mixture was kneaded and kneaded for 60 minutes using a mix marler granulator. The bulk density of the obtained mixture was measured by the method described above, and the results were shown in Table 1.
It was shown to.

Thereafter, the product was extruded as a columnar product having a diameter of 1.5 mm using a screw extrusion granulator having a die thickness of 5 mm, and then tumbled to obtain a columnar product having a sharp corner. After drying this at 110 ° C., it was fired in a muffle furnace (manufactured by Advantech Co., model: KM-600) for 2 hours in an atmosphere of 600 ° C. to sinter the kaolin-type clay,
Cooled in air. After the obtained zeolite compact was subjected to calcium ion exchange, a tubular furnace (manufactured by Advantech)
At 600 ° C. for 1 hour under flowing air. The pore volume, compressive strength, and the abrasion rate of the hydrated product of the obtained activated product were measured by the above-described method. The results are shown in Table 1.

[0046]

[Table 1]

Example 2 10 parts by weight of kaolin clay and 3 parts by weight of CMC were mixed with 100 parts by weight of the X-type zeolite powder and 100 parts by weight of the powder (in terms of anhydride), and 70 parts by weight of water was further added and kneaded. Kneaded. The bulk density of the obtained mixture was measured by the method described above, and the results are shown in Table 1.

Thereafter, the product was extruded as a columnar product having a diameter of 1.5 mm by a roll-type pellet mill type extrusion granulator having a die thickness of 3 mm, and then tumbled and sized with a marmellaizer to obtain an angular columnar product. . Thereafter, after treating in the same manner as in Example 1, the obtained activated product was measured for the pore volume, the pressure resistance, and the wear rate of the hydrated product by the method described above. It was shown to.

Example 3 10 parts by weight of kaolin clay and 8 parts by weight of CMC were mixed with 100 parts by weight of the X-type zeolite powder and 100 parts by weight of the powder (anhydrous equivalent), and 70 parts by weight of water was further added and kneaded. Kneaded. The bulk density of the obtained mixture was measured by the method described above, and the results are shown in Table 1.

Thereafter, the product was extruded as a columnar product having a diameter of 1 mm by a roll-type pellet mill type extrusion granulator having a die thickness of 3 mm, and tumbled and sized with a marmellaizer to obtain a columnar product having a sharp corner. Thereafter, after treating in the same manner as in Example 1, the obtained activated product was measured for the pore volume, the pressure resistance, and the wear rate of the hydrated product by the method described above. It was shown to.

Example 4 A-type zeolite powder, 100 parts by weight of this powder (in terms of anhydride), 10 parts by weight of hydrolyzed halloysite clay, C
3 parts by weight of MC were mixed, and 65 parts by weight of water was further added and kneaded and kneaded. The bulk density of the obtained mixture was measured by the method described above, and the results are shown in Table 1.

Thereafter, the resulting product was extruded as a columnar product having a diameter of 1.5 mm by a roll-type pellet mill type extrusion granulator having a die thickness of 1.5 mm, and tumbled and sized with a marmellaizer to obtain a columnar product having a sharp corner. After that, the treatment was performed in the same manner as in Example 1 except that the activation was performed at 400 ° C., and the pore volume, the compressive strength, and the wear rate of the hydrated product of the activated product were described above. Table 1 shows the measurement results.
It was shown to.

Comparative Example 1 X-type zeolite powder and 10 parts by weight of kaolin clay and 3 parts by weight of CMC were kneaded with a kneader while adding water to 70 parts by weight of water with respect to 100 parts by weight of the powder (in terms of anhydride). Kneaded. The bulk density of the obtained mixture was measured by the method described above, and the results are shown in Table 1.

Thereafter, the mixture was extruded as a columnar product having a diameter of 1.5 mm with a screw extrusion granulator, and then tumbled and sized with a marmerizer to obtain a columnar product having a sharp corner. Thereafter, after treating in the same manner as in Example 1, the obtained activated product was measured for the pore volume, the pressure resistance, and the wear rate of the hydrated product by the method described above. It was shown to.

From these results, it was found that when the bulk density of the mixture was low, only an insufficient one having a low pressure resistance and a high wear rate was obtained.

Comparative Example 2 A-type zeolite powder and 2 parts by weight of pregelatinized starch, 10 parts by weight of kaolin clay, 10 parts by weight of montmorillonite clay, fiber length of 10 to 100 μm based on 123 parts by weight of this powder
After mixing 10 parts by weight of the amorphous pulp short fibers, 42 parts by weight of water was added and kneaded and kneaded with a kneader for 20 minutes. The bulk density of the obtained mixture was measured by the method described above, and the results are shown in Table 1.

Then, using a screw extrusion granulator,
A die having a diameter of 1.5 mm was set and extruded to obtain a cylindrical molded product. After drying the obtained molded article at 110 ° C. for 2 hours,
It was calcined at 600 ° C. for 2 hours to obtain zeolite pellets having a diameter of 1.5 mm. The pore volume, compressive strength, and the wear rate of the hydrated pellet were measured by the above-mentioned method. The results are shown in Table 1. Here, the calcium ion exchange rate was 74%.

From these results, it was found that when the bulk density of the mixture was low, only a material having a low wear rate was obtained even if the number of parts by weight of the binder was increased.

Comparative Example 3 To 30 kg of type A sodium zeolite having a water content (loss on ignition) of 10% by weight was added 15 liters of 30% by weight silica sol having a BET value of about 300 m ² / g. And processed in a high intensity mixer as particles with a particle size of about 0.1 to 0.8 mm. The bulk density of the obtained workpiece was measured by the method described above, and the results are shown in Table 1.

Next, after putting the coarse particles into a granulating pan, the finely pulverized A-type zeolite is continuously introduced into a rotating pan, and simultaneously on the particles moving from other parts of the pan. Was sprayed with 30% by weight of silica sol. Thereafter, water glass was poured into the silica sol through an injector, and the ratio of sol to water glass was adjusted to 10: 1 to obtain a spherical granular material having a diameter of 2 to 3 mm. After that, the treatment was performed in the same manner as in Example 1 except that the activation was performed at a temperature of 400 ° C., and the pore volume, the pressure resistance, and the wear rate of the hydrated product of the obtained activated product were obtained. Was measured by the method described above, and the results are shown in Table 1.

From these results, it was found that when the bulk density of the mixture was low, only an insufficient one having a low pressure resistance and a high wear rate was obtained.

[0062]

As is clear from the above description, the high-strength, low-abrasive zeolite granules of the present invention have a high nitrogen adsorption capacity, and are excellent in pressure resistance and abrasion resistance. Further, according to the production method of the present invention, it is possible to easily obtain a high-strength, low-abrasion zeolite granular material having excellent pressure resistance and abrasion resistance without impairing the nitrogen adsorption ability. Further, by using the high-strength and low-wear zeolite granules of the present invention, nitrogen can be selectively adsorbed from a mixed gas by an adsorption method, and is useful as an adsorbent.

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Claims (4)

[Claims] 1. A high-strength low-wear zeolite granule having a zeolite component content of 85% by weight or more, a pore volume of 0.3 to 0.5 cc / g, and a diameter of 0.5 to 2 mm.
A high-strength, low-wear zeolite granule characterized by the following: 2. The high-strength, low-wear zeolite granule according to claim 1, wherein the zeolite is a zeolite selected from the group consisting of A-type, X-type, Y-type and L-type zeolites. Zeolite granules with low strength and low wear. 3. The method for producing a high-strength low-wear zeolite granule according to claim 1 or 2, wherein the binder component 5 is added to the zeolite powder and 100 parts by weight of zeolite powder (in terms of anhydride). １５15 parts by weight, 1-10 parts by weight of a thickener and / or water retention agent, and 50-80 moisture
The mixture consisting of parts by weight is kneaded and kneaded to have a bulk density of 0.7.
A method for producing a high-strength, low-wear zeolite granule, comprising extruding, granulating, rolling and sizing, drying, calcining, ion-exchanging, and activating after adjusting to 1.5 kg / liter. 4. An adsorption separation method comprising using the high-strength and low-wear zeolite granules according to claim 1 or 2 to concentrate oxygen from air by a pressure swing adsorption method.