JP7272114B2 - Highly wear-resistant zeolite compact and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly wear-resistant zeolite compact and a method for producing the same. The highly wear-resistant zeolite compact of the present invention is useful for applications such as adsorption separation agents and catalysts.

In recent years, regulations on VOC emissions, which are considered to be one of the causative substances of suspended particulate matter and photochemical oxidants, have started, and attention is focused on techniques for reducing VOC emissions. Zeolite is attracting attention as a VOC adsorbent. Since the skeleton is made of silicon dioxide, which is resistant to heat, it is easy to adsorb and desorb VOCs at high temperatures, is highly safe, and has a high specific surface area. On the other hand, stationary phase or fluidized bed adsorption towers are used to adsorb VOCs in factories, etc., but the adsorbents are pulverized during filling and adsorption/desorption, leading to equipment troubles and pressure loss. Because of this, the adsorbent is required to have high wear resistance, but no zeolite molded article having high wear resistance that can be put into practical use has been invented.

Several methods are known as means for increasing the strength of zeolite compacts. For example, Patent Document 1 discloses a method of mixing, kneading, and molding A-type or X-type zeolite as zeolite, kaolin clay or hydrated halloysite as binder, and CMC (carboxymethyl cellulose) as thickener or water retention agent. .

Patent Document 2 discloses a method of using a low silica X-type zeolite as a zeolite and a plurality of types of kaolin-based clay, sepiolite-based clay, attapulgite-based clay, and bentonite-based clay as binders.

Patent Document 3 discloses a method of mixing, kneading, and molding 3A-type zeolite as a zeolite, kaolin clay as a binder, and condensed phosphate as an inorganic dispersant.

None of the patent documents has led to the invention of a practical wear-resistant zeolite compact, and the invention of a zeolite compact with higher wear resistance is desired.

JP-A-10-87322 JP-A-11-314913 Japanese Patent Application Laid-Open No. 2001-226167

The present invention provides a zeolite molded article having better wear resistance than conventional zeolite molded articles, and a method for producing the same. Highly attrition-resistant zeolite compacts can be used in various adsorption separation applications and catalytic reaction applications.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found a production method using two types of binders, fibrous clay and silica sol, when producing zeolite molded bodies, and have completed the present invention. be. That is, the present invention comprises 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, and 4 parts by weight of molding aid. It contains up to 20 parts by _weight , and the abrasion resistance strength is 90% or more. (g/100 g) or less, a highly wear-resistant zeolite molded body characterized by containing one or more zeolites, 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, and 5 to 40 parts by weight of silica sol parts, 0.5 to 10 parts by weight of water-soluble sodium salt, 4 to 20 parts by weight of molding aid, and 120 to 180 parts by weight of water. It is fired at ~700°C, and the zeolite has a Si/ _Al2 ratio of 10 or more and 100000 or less, and a water adsorption amount of 10 (g/100g) or less at 25°C and a relative pressure of 0.5. A method for producing a highly wear-resistant zeolite molded body characterized by containing one or more types of zeolite.

The present invention will be described below.

The highly wear-resistant zeolite compact of the present invention contains 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, and 0.5 to 10 parts by weight of water-soluble sodium salt per 100 parts by weight of zeolite. , containing 4 to 20 parts by weight of a molding aid.

The zeolite contained in the highly wear-resistant zeolite compact has a Si/Al ₂ ratio of 10 or more and 100000 or less, and a water adsorption amount of 10 (g/100 g) or less under the conditions of 25°C and a relative pressure of 0.5. It is zeolite and contains one or more kinds thereof. When Si/Al ₂ is less than 10, the wear strength decreases when the water adsorption amount exceeds 10 (g/100 g) under the conditions of 25° C. and a relative pressure of 0.5. Examples of types of zeolite include beta-type zeolite, Y-type zeolite, L-type zeolite, ferrierite-type zeolite, mordenite-type zeolite, and ZSM-5-type zeolite. is preferred. Si/Al ₂ is preferably 50 or more and 10,000 or less, more preferably 80 or more and 2,000 or less.

The amount of fibrous clay contained in the highly wear-resistant zeolite compact is 35 to 70 parts by weight per 100 parts by weight of zeolite (on a dry basis). If the amount is less than 35 parts by weight, the abrasion resistance is lowered, and if the amount is more than 70 parts by weight, no improvement in abrasion resistance is observed. 40 to 60 parts by weight is preferable, and 45 to 55 parts by weight is more preferable, because the abrasion resistance becomes higher. Although the particle size of the clay is not particularly limited, the average particle size is preferably 0.5 to 30 μm. Examples of fibrous clays include sepiolite clay, attapulgite clay, and palygorskite clay.

The amount of silica sol contained in the highly wear-resistant zeolite compact is 5 to 40 parts by weight per 100 parts by weight of zeolite (on a dry basis). If the amount is less than 5 parts by weight, there is no effect on the abrasion resistance, and as the amount of silica sol added increases, the abrasion resistance also improves. 10 to 30 parts by weight is preferable, and 15 to 25 parts by weight is more preferable in order to maintain both abrasion resistance and extrusion moldability at high levels. Although the particle size of the silica sol is not particularly limited, the average particle size is preferably 5 to 30 nm.

The amount of water-soluble sodium salt contained in the highly wear-resistant zeolite compact is 0.5 to 10 parts by weight per 100 parts by weight of zeolite (on a dry basis). If it is less than 0.5 parts by weight, the effect is not sufficient, and if it exceeds 10 parts by weight, the effect does not change. In order not to increase the amount of sodium derived from the water-soluble sodium salt, 0.5 to 8 parts by weight is preferred, and 0.5 to 6 parts by weight is more preferred. Examples of water-soluble sodium salts include sodium salts of inorganic salts and sodium salts of organic salts.

The sodium inorganic acid may be any water-soluble sodium salt, and examples thereof include sodium phosphate, sodium silicate, and sodium aluminate. Of these, sodium phosphate is preferred. Examples of sodium phosphate include primary sodium phosphate, secondary sodium phosphate, tertiary sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. be done.

The sodium salt of the organic acid may be any water-soluble sodium salt, and examples thereof include general organic carboxylic acids, amino carbonates, ether carboxylates, vinyl-type polymer sodium salts, and the like. Examples of general organic carboxylic acids include sodium citrate, sodium gluconate, sodium oxalate, and sodium tartrate, and examples of aminocarbonates include sodium ethylenediaminetetraacetic acid and sodium diethylenetriaminopentaacetic acid. , Examples of ether carboxylates include sodium carboxymethyl tartronate and sodium carboxymethyl oxysuccinate. Examples of vinyl-type polymer sodium salts include sodium polyacrylate, acrylic acid/maleic acid co- Examples include sodium salts of polymers.

The amount of the molding aid contained in the highly wear-resistant zeolite compact is 4 to 20 parts by weight with respect to 100 parts by weight of zeolite (converted to anhydrous content). If the amount is less than 4 parts by weight, wear resistance will be reduced, and if it exceeds 20 parts by weight, moldability will be significantly reduced. It is preferably 8 to 16 parts by weight. Examples of molding aids include cellulose, alcohol, lignin, starch, guar gum and the like. Among these, cellulose and alcohol are preferred. Examples of cellulose include crystalline cellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC) and the like. Examples of alcohol include polyvinyl alcohol and ethylene glycol.

The highly wear-resistant zeolite compact of the present invention has an abrasion resistance strength of 90% or more. If the abrasion resistance strength is less than 90%, the powder tends to be pulverized and may easily cause pressure loss. Here, the abrasion resistance strength is measured according to the activated carbon test method of JIS-K-1474 (see <Abrasion Resistance Test> in Examples). The abrasion resistance strength is preferably 92% or more, more preferably 95% or more, and particularly preferably 96.5% or more.

The method for producing a highly wear-resistant zeolite molded product of the present invention (hereinafter also referred to as the “production method of the present invention”) comprises 100 parts by weight of zeolite, 15 to 50 parts by weight of fibrous clay, and 5 parts by weight of silica sol. ~40 parts by weight, 0.5 to 10 parts by weight of a water-soluble sodium salt, 4 to 20 parts by weight of a molding aid, and 120 to 180 parts by weight of water. It is characterized by firing the body at 400-700°C.

The zeolite contained in the mixture used in the production method of the present invention has a water adsorption amount of 10 (g / 100 g) under the conditions of Si / Al ₂ of 10 or more and 100000 or less, 25 ° C. and a relative pressure of 0.5. It must contain one or more of the following zeolites. When Si/Al ₂ is less than 10, when the moisture adsorption amount exceeds 10 (g/100 g) under the conditions of 25°C and a relative pressure of 0.5, moisture in the atmosphere is likely to be adsorbed, resulting in reduced wear strength. decreases. Examples of types of zeolite include beta-type zeolite, Y-type zeolite, L-type zeolite, ferrierite-type zeolite, mordenite-type zeolite, and ZSM-5-type zeolite. is preferred. Si/Al ₂ is preferably 50 or more and 10,000 or less, more preferably 80 or more and 2,000 or less.

Included in the mixture used in the manufacturing method of the present invention is a fibrous clay. There are various types of clay, but fibrous clay does not clog the pores present in zeolite crystals, so there is no deterioration in performance. Plate-like crystal clay such as kaolin clay is not preferable because it may clog the pores of the zeolite crystal. Examples of fibrous clays include sepiolite clay, attapulgite clay, and palygorskite clay. The amount of fibrous clay is 35 to 70 parts by weight with respect to 100 parts by weight of zeolite (on an anhydrous basis). If the amount is less than 35 parts by weight, the abrasion resistance is lowered, and if the amount is more than 70 parts by weight, no improvement in abrasion resistance is observed. 40 to 60 parts by weight is preferable, and 45 to 55 parts by weight is more preferable, because the abrasion resistance becomes higher. Although the particle size of the clay is not particularly limited, the average particle size is preferably 0.5 to 30 μm.

A silica sol is included in the mixture used in the production method of the present invention. The amount of silica sol is 5 to 40 parts by weight per 100 parts by weight of zeolite (on an anhydrous basis). If the amount is less than 5 parts by weight, there is no effect on the abrasion resistance, and as the amount of silica sol added increases, the abrasion resistance also improves. 10 to 30 parts by weight is preferable, and 15 to 25 parts by weight is more preferable in order to maintain both abrasion resistance and extrusion moldability at high levels. Although the particle size of the silica sol is not particularly limited, the average particle size is preferably 5 to 30 nm. Although the pH is not particularly limited, it is preferably 7.0 to 10.0.

Included in the mixture used in the manufacturing method of the present invention is a water-soluble sodium salt. Examples of water-soluble sodium salts include sodium salts of inorganic salts and sodium salts of organic salts. The water-soluble sodium salt preferably contains at least one of inorganic sodium salts and organic sodium salts. For unknown reasons, the use of water-soluble sodium salts significantly increases wear resistance. The amount of water-soluble sodium salt is 0.5 to 10 parts by weight with respect to 100 parts by weight of zeolite (on an anhydrous basis). If it is less than 0.5 parts by weight, the effect is not sufficient, and if it exceeds 10 parts by weight, the effect does not change. In order not to increase the amount of sodium derived from the water-soluble sodium salt, 0.5 to 8 parts by weight is preferred, and 0.5 to 6 parts by weight is more preferred.

The sodium inorganic acid may be any water-soluble sodium salt, and examples thereof include sodium phosphate, sodium silicate, and sodium aluminate. Among these, sodium phosphate can be preferably used because it is easy to handle. Examples of sodium phosphate include primary sodium phosphate, secondary sodium phosphate, tertiary sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. can.

The sodium salt of the organic acid may be any water-soluble sodium salt, and examples thereof include general organic carboxylic acids, amino carbonates, ether carboxylates, vinyl-type polymer sodium salts, and the like. Examples of general organic carboxylic acids include sodium citrate, sodium gluconate, sodium oxalate, and sodium tartrate. Examples of aminocarbonates include sodium ethylenediaminetetraacetic acid and sodium diethylenetriaminopentaacetic acid. As the ether carboxylate, for example, sodium carboxymethyl tartronate, sodium carboxymethyl oxysuccinate, etc. can be used, and as the vinyl type polymer sodium salt, for example, sodium polyacrylate, acrylic acid / maleic acid Sodium salts of polymers and the like can be used.

Included in the mixture used in the manufacturing method of the present invention is a molding aid. Molding aids improve moldability, and examples thereof include cellulose, alcohol, lignin, starch, guar gum, and the like. Among these, cellulose and alcohol are preferred because they are easy to handle. Examples of cellulose include crystalline cellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC) and the like. Examples of alcohol include polyvinyl alcohol and ethylene glycol. The amount of the molding aid is 4 to 20 parts by weight, preferably 8 to 16 parts by weight, per 100 parts by weight of zeolite (on an anhydrous basis). If the amount is less than 4 parts by weight, wear resistance will be reduced, and if it exceeds 20 parts by weight, moldability will be significantly reduced.

The amount of water contained in the mixture used in the production method of the present invention is 120 to 180 parts by weight, preferably 140 to 160 parts by weight, with respect to 100 parts by weight of zeolite (on an anhydrous basis). When the amount is less than 120 parts by weight or when the amount is more than 180 parts by weight, molding may become difficult.

The mixture used in the production method of the present invention contains 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, and 0.5 to 10 parts by weight of water-soluble sodium salt with respect to 100 parts by weight of zeolite. , 4 to 20 parts by weight of a molding aid and 120 to 180 parts by weight of water are mixed and kneaded. The method of mixing and kneading is not particularly limited, and for example, a roll-type kneader mix muller, a blade stirring type Henschel mixer, a batch-type or continuous-type kneader, and the like can be used.

The production method of the present invention comprises 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, and a molding aid. A mixture containing 4 to 20 parts by weight and 120 to 180 parts by weight of water is molded. The molding method is not particularly limited, and may be, for example, rolling granulation, stirring granulation, extrusion molding, spray granulation, or a combination of two or more of these methods. The shape of the molded body is not particularly limited, but spherical, cylindrical, elliptical, bale-shaped, trefoil, ring-shaped, and the like are preferable, and spherical and cylindrical are more preferable. The size of the compact is not particularly limited, but the average particle size is preferably 0.1 to 3 mm. The aspect ratio (ratio of major axis to minor axis) of the molded product is not particularly limited, but is preferably 3 or less.

The shaped zeolite shaped bodies are dried. The drying method is not particularly limited, and for example, a box-type dryer, a continuous dryer, or the like can be used. The drying temperature can be 50-200°C. The drying atmosphere can be air or nitrogen atmosphere under atmospheric pressure. The dried zeolite shaped bodies are classified into desired sizes. Classification can also be performed before drying.

The dried zeolite compact is calcined. The firing method is not particularly limited, and for example, it can be carried out in an apparatus such as a box-type muffle furnace, rotary kiln, shaft kiln, or the like. The sintering temperature may be any temperature at which the fibrous clay can be sintered to exhibit strength, and is preferably 400 to 700°C. The firing atmosphere can be air or nitrogen atmosphere under atmospheric pressure.

The highly wear-resistant zeolite compact of the present invention has high wear resistance. In particular, it can be usefully used in adsorption separation applications including thermal regeneration processes and catalytic reaction applications.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.

<Measurement of water adsorption amount>
The water adsorption amount was measured at a temperature of 25° C. using a spring balance adsorption device.

<Abrasion resistance test>
The abrasion resistance strength in the abrasion resistance test was measured according to JIS-K-1474. Briefly, the sample was filled to the 100 mL mark in a 200 mL graduated cylinder by tapping. A sample weighed with a graduated cylinder was placed in an abrasion resistance test dish together with 15 steel balls each having a diameter of 12.7 mm and 9.5 mm. Attached to a sieve shaker and shaken for 30 minutes. Using a sieve with half the size of the sieve with the most sample remaining and a saucer, the entire sample except the steel balls was put in and attached to a sieve shaker. After shaking for 3 minutes, the mass of the sample remaining on the sieve and on the pan was weighed to the order of 0.1 g. The abrasion resistance strength was calculated by the following formula 1.

H=W/S×100 (Formula 1)
Here, H: abrasion resistance strength (mass fraction %), W: mass (g) of the sample remaining on the sieve, and S: total mass (g) of the sample remaining on the sieve and the tray.

Example 1
Y-type zeolite powder (HSZ (registered trademark)-385HUA: manufactured by Tosoh (Si/Al ₂ : 100, water adsorption amount: 2 g/100 g)) 80 parts by weight (1627 g; water content 2%), MFI-type zeolite powder (HSZ (registered trademark)-891HOA: manufactured by Tosoh (Si/Al ₂ : 1500, water adsorption amount: 4 g/100 g)) 20 parts by weight (413 g; water content 3%), attapulgite clay (mini gel MB: active Minerals) 50 parts by weight (1253 g; moisture content 22%), 6 parts by weight (120 g) of carboxymethylcellulose sodium, 6 parts by weight of crystalline cellulose (Seolus (registered trademark) RC-591; Asahi Kasei Chemicals) (120 g) was weighed and mixed for 5 minutes with a mix muller (manufactured by Shinto Kogyo Co., Ltd.). 1639 g of silica sol (Snowtex C-30: manufactured by Nissan Chemical Industries) was added and mixed for 5 minutes. A solution of 1.5 parts by weight (30 g) of sodium dihydrogen phosphate (NaH ₂ PO ₄ manufactured by Rin Kagaku Kogyo Co., Ltd.) was added to 1000 g of water and mixed for 5 minutes. After that, 960 g of water was further added and stirred and kneaded for 10 minutes to obtain a mixture. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour, and the result was 109 parts by weight per 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 900 rpm to transform the cylindrical compact into a spherical shape. It was dried at 100° C. for 12 hours or more and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 1.2.

The abrasion resistance strength after the abrasion resistance test was 96.7%.

Example 2
Example 1 except that 4 parts by weight (80 g) of sodium carboxymethylcellulose, 4 parts by weight (80 g) of crystalline cellulose (Seolus (registered trademark) RC-591: manufactured by Asahi Kasei Chemicals), and 1350 g of silica sol were added. A mixture was obtained by performing the same operation. The ignition loss of the obtained mixture was measured at 650° C. for 1 hour, and the result was 106 parts by weight per 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 900 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 1.2.

The abrasion resistance strength after the abrasion resistance test was 96.4%.

Example 3
A mixture was obtained in the same manner as in Example 1, except that the mix marler was changed to a Henschel mixer and the amount of water to be added was changed to 1088 g. The ignition loss of the obtained mixture was measured at 650° C. for 1 hour, and the result was 106 parts by weight per 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 900 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 1.2.

The abrasion resistance strength after the abrasion resistance test was 96.7%.

Example 4
A mixture was obtained in the same manner as in Example 1 except that the amount of silica sol was changed to 25 parts by weight. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour and found to be 101 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 900 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 1.2.

The abrasion resistance strength after the abrasion resistance test was 96.8%.

Example 5
A mixture was obtained in the same manner as in Example 1, except that 10 parts by weight (653 g) of silica sol and 1350 g of water to be added were used. The ignition loss of the obtained mixture was measured at 650° C. for 1 hour, and the result was 95 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 900 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 1.2.

The abrasion resistance strength after the abrasion resistance test was 96.5%.

Example 6
A mixture was obtained by performing the same operation as in Example 4. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour and found to be 101 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 600 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 2.3.

The abrasion resistance strength after the abrasion resistance test was 95.0%.

Example 7
A mixture was obtained by performing the same operation as in Example 4. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour and found to be 101 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 450 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 2.5.

The abrasion resistance strength after the abrasion resistance test was 93.2%.

Example 8
A mixture was obtained by performing the same operation as in Example 4. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour and found to be 101 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, rolling sizing was performed with a Marumerizer (QJ-400, manufactured by Dalton) at a rotation speed of 300 rpm to transform the cylindrical compact into a spherical shape. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact. The aspect ratio of the zeolite compact was 3.

The abrasion resistance strength after the abrasion resistance test was 90.9%.

Comparative example 1
Without adding silica sol, 4 parts by weight (80 g) of sodium carboxymethyl cellulose, 4 parts by weight (80 g) of crystalline cellulose (Seolus (registered trademark) RC-591: manufactured by Asahi Kasei Chemicals), and 1740 g of water to be added. performed the same operation as in Example 1 to obtain a mixture. The ignition loss of the obtained mixture was measured at 650° C. for 1 hour, and the result was 95 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact.

The abrasion resistance strength after the abrasion resistance test was 84.9%.

Comparative example 2
The same operation as in Example 1 was performed except that attapulgite clay (minigel MB: manufactured by Active Minerals) was changed to kaolin clay (plate-like clay), silica sol was not added, and 1400 g of water was added. A mixture was obtained. The loss on ignition of the obtained mixture was measured at 650° C. for 1 hour, and the result was 83 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact.

The abrasion resistance strength after the abrasion resistance test was 45.3%.

Comparative example 3
A mixture was obtained in the same manner as in Example 1 except that 25 parts by weight of silica sol, 30 parts by weight of attapulgite-type clay, and 1530 g of water were added. The ignition loss of the obtained mixture was measured at 650° C. for 1 hour, and the result was 95 parts by weight with respect to 100 parts by weight of zeolite. The resulting mixture was molded into a cylindrical shape with a diameter of 0.6 mm. After that, it was dried at 100° C. for 12 hours or longer and calcined at 650° C. for 3 hours to obtain a zeolite compact.

The abrasion resistance strength after the abrasion resistance test was 89.6%.

Since the highly abrasion-resistant zeolite molded article of the present invention is excellent in abrasion resistance, it can be used in applications such as adsorption separation agents and catalysts without causing equipment troubles, pressure loss, and the like.

Claims (3)

With respect to 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, 4 to 20 parts by weight of molding aid, In addition, the abrasion resistance strength is 90% or more, and the zeolite has a water adsorption amount of 10 (g / 100 g) or less under the conditions of Si / Al ₂ of 10 or more and 100000 or less, 25 ° C., and a relative pressure of 0.5. A highly wear-resistant zeolite molded body characterized by containing at least one type of zeolite. 100 parts by weight of zeolite, 35 to 70 parts by weight of fibrous clay, 5 to 40 parts by weight of silica sol, 0.5 to 10 parts by weight of water-soluble sodium salt, 4 to 20 parts by weight of molding aid, water _After molding a mixture containing 120 to 180 parts by weight of the 2. The method for producing a highly wear-resistant zeolite compact according to claim 1, characterized in that it contains at least one type of zeolite having a water adsorption amount of 10 (g/100 g) or less under the conditions of 0.5 ° C. and a relative pressure of 0.5. . High wear resistance according to claim 2, wherein the zeolite contains at least one of beta-type zeolite, Y-type zeolite, L-type zeolite, ferrierite-type zeolite, mordenite-type zeolite, and ZSM-5-type zeolite. A method for producing a zeolite compact.