KR20110090891A - High-strength zeolite bead molding and method for producing the same - Google Patents

Abstract

In the beads molded articles of zeolite and clay binder produced by electroplating, the strength and the wear resistance were low. In the present invention, after molding a composition of 35 parts by weight or more in a bead shape by electric granulation with respect to 100 parts by weight of the total amount of the zeolite and the clay binder, 4 parts by weight based on 100 parts by weight of the molded body weight (excluding moisture) Zeolite beads molded product having an average particle diameter in the range of 1.0 to 3.0 mm with a hydration breakdown strength of 35 N or more (particularly 70 N or more) and an abrasion resistance of 1.5% or less by adding and sintering and carrying out electrostatic sintering after adding negative clay particles. Can be obtained. It is preferable that the zeolite crystals used are 5 µm or less, the clay binder is 10 parts by weight or more and 50 parts by weight or less, and the same kind of clay binder used for molding and sizing is used.

Description

High-strength zeolite bead molded article and manufacturing method thereof {HIGH-STRENGTH ZEOLITE BEAD MOLDING AND METHOD FOR PRODUCING THE SAME}

The present invention relates to a zeolite bead molded article having high strength and particularly high wear resistance and a method for producing the same. For example, the zeolite bead molded body used for a plon desiccant for air conditioners of automobiles is particularly required to have high strength and wear resistance so as not to be powdered by vibration of the engine drive.

Although zeolite bead molded products are widely used as a desiccant, the demand as a desiccant for automobile air conditioners is increasing recently. Automotive air conditioners are exposed to vibrations during use, so if they have low strength and abrasion resistance, they are powdered and cause clogging. Therefore, a high strength, high wear resistant desiccant is desired.

As a method of obtaining a high strength, high abrasion-resistant desiccant, the method of using additives, such as a condensation phosphate, etc. to a binder (patent document 1), the method of using a special acicular crystal binder as a binder (patent document 2), and treating it with an alkaline compound The method (patent document 3, patent document 4) etc. which are made are proposed. However, these were all the methods which require a special raw material and a special processing process, and were causing the cost increase of a desiccant.

In either method, although the obtained molded object particle was stipulated and the surface of a molded object was smoothed and sphericity was raised, sufficient effect was not acquired.

In addition, the method (patent document 5) which removes an angular part by the electric granulation of a high-strength pellet molded object is known. In such a method, a particle having high strength is obtained, but a molded article having a high sphericity cannot be obtained, and thus it cannot be used for a plon desiccant for automobiles.

JP2001-261330 A JPH11-314913 A JPH4-198012 A JPH6-327968 A JPH10-87322 A

 SUMMARY OF THE INVENTION An object of the present invention is to improve the strength (hydration pressure strength) and wear resistance of a zeolite, in particular, a bead molded body consisting of a 3A zeolite (K ion exchange A zeolite) and a clay binder, without using a special raw material or process. To provide.

The present inventors intensively examined the improvement of the hydration pressure strength and the abrasion resistance of the zeolite bead molded body, and as a result, by adding a clay binder in an amount within a specific range during the electrostatic granulation after granulation, It has been found that the wear resistance is remarkably improved and the present invention has been completed.

That is, the summary of this invention exists in following (1)-(10).

(1) 100 weight part of the obtained molded object solid content (except moisture) after shape | molding the composition which is 35 weight part or more of moisture with a bead shape with respect to 100 weight part of total amounts of a zeolite and a clay binder by electric granulation. A method for producing a zeolite bead molded article, which is dried and calcined by adding 4 parts by weight or less of a clay binder and electrostatically granulating.

(2) Preferably, the manufacturing method according to the above item (1), wherein the moisture in the formed body at the time of electrostatic granulation is 35 parts by weight or more based on 100 parts by weight of the total amount of the zeolite and the clay binder.

(3) Preferably, the manufacturing method according to the above (1) or (2), wherein the clay binder is plate crystal.

(4) The production method according to any one of (1) to (3), wherein the zeolite is preferably a K-ion exchange type A zeolite.

(5) Preferably, the manufacturing method according to the above (4), wherein the zeolite crystal diameter is 5 µm or less.

(6) Preferably, the production method according to any one of (1) to (5), wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite beads molded product is 10 parts by weight or more and 50 parts by weight or less.

(7) The production method according to the above (6), wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite is preferably more than 40 parts by weight and 50 parts by weight or less.

(8) The zeolite crystal diameter is 5 µm or less, the total amount of the clay binder relative to 100 parts by weight of the zeolite beads molded body is 10 parts by weight or more and 50 parts by weight or less, the hydration pressure resistance strength of the zeolite beads molded body is 35 N or more, and the zeolite beads molded body A zeolite bead molded article having a wear resistance of 1.5% or less and a bead diameter of 1.0 to 3.0 mm.

(9) The zeolite bead molded article according to the above (8), wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite is preferably more than 40 parts by weight and 50 parts by weight or less.

(10) Preferably, the zeolite bead molded article according to the above (8) or (9), wherein the hydration breakdown strength is 70 N or more.

In the production method of the present invention, after molding a mixture of 35 parts by weight or more in a bead shape by electroplating with respect to 100 parts by weight of the total amount of the zeolite and the clay binder, 4 parts by weight or less of the clay binder is added to the molded product weight. After the granulation is carried out by electrostatic granulation, a zeolite desiccant having high strength and wear resistance can be produced by drying and firing. The zeolite bead molded article obtained by the method of the present invention is excellent in strength and wear resistance.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which showed the surface SEM image after the formation of the molded object of Example 1;
2 is a view showing a surface SEM image after sizing of the molded article of Example 2;
3 is a view showing a SEM image of the surface of Comparative Example 1 (non-molded article);
4 is a diagram showing a surface SEM image after sizing of the molded product of Comparative Example 3. FIG.

Hereinafter, the manufacturing method of the zeolite bead compact of this invention is demonstrated.

According to the method for producing a zeolite bead molded article of the present invention, after molding a composition having a moisture content of 35 parts by weight or more based on 100 parts by weight of the total amount of the zeolite and the clay binder into a bead shape by electric granulation, the solid weight of the molded product (excluding water) 4 parts by weight or less of the clay binder is added and electrostatically granulated, followed by drying and firing.

In the method of this invention, when the water content with respect to the zeolite and a clay binder at the time of shaping | molding is too small, a bead shaped body will not be obtained, and when too large, the molded bodies will adhere to each other, and a molded body will grow abnormally. The amount of water to 100 parts by weight of the total amount of the zeolite and the clay binder is adjusted depending on the particle diameter and the surface area of the clay binder to be used, but at least 35 parts by weight or more, and particularly preferably in the range of 35 to 60 parts by weight.

In this invention, after shape | molding the said composition of water content in the shape of a bead, it adds 4 weight part or less clay binders with respect to 100 weight part of weight of a molded solid content (except moisture), and it is electrostatically granulated to improve strength and abrasion resistance. .

Molding and sizing in the present invention are not particularly limited as long as the molded article in the shape of beads can be molded, and any general electric granulator, drum granulator, or rotary tubular granulator can be used.

It is known that the zeolite bead molded article containing the clay binder smoothes the surface of the molded article by standing up, and the wear resistance is improved to some extent. However, the conventional formulation is an effect by the removal of the foreign material adhering to the molded object surface and the smoothing of the surface, and the effect was limited only.

In the present invention, by adding a clay binder in a specific range during rolling, not only cleans the surface of the molded body during rolling, but also compensates for defects and forms a stronger protective layer, and despite the addition of a small amount of binder, Strength is improved.

In the present invention, the amount of clay binder added at the time of electrostatic granulation is 4 parts by weight or less, particularly 0.01 to 3, based on 100 parts by weight of the solid weight of the molded body (excluding the moisture, which is the weight of the solid content of the zeolite and the clay binder at the time of electric granulation). Part by weight, more preferably 0.1 to 3 parts by weight.

When the amount of the clay binder added at the time of electrostatic sizing is added in excess of 4 parts by weight, the pressure resistance strength of the molded body is improved, but there is a problem that wear resistance is lowered.

The amount of water at the time of electrostatic granulation is 35 parts by weight or more, in particular 35 to 45 parts by weight, based on 100 parts by weight of the solid weight of the molded product (excluding water. The total amount of zeolite and clay binder. Range is preferred.

When adding a clay binder at the time of electric granulation, it is preferable to adjust moisture amount by adding water with a clay binder. Moisture added with the clay binder at the time of electrostatic sizing has the effect of making the added clay binder easily form a protective layer on the surface of the molded body.

At the time of electrostatic sizing, if the molded body is dried by the temperature rise by the friction of particle | grains, even if it carries out electrostatic sizing by adding a clay binder, the effect of this invention is not fully acquired.

As a clay binder used by this invention, it is preferable that the clay binder used for shaping | molding and the clay binder added at the time of granulation are a clay binder of the same kind. By using the same clay binder, a molded article having particularly high wear resistance is obtained by addition of a small amount of clay binder.

Although the clay binder used for this invention is not specifically limited, Kaolin type, bentonite type, talc type, pyrophyllite type, molybite type, vermiculite type, montmorillonite type, montmorillonite type, claw Clay, such as a chlorite system and a halloysite system, can be illustrated, Especially kaolin clay which is plate-shaped crystal | crystallization is preferable. The amount of the clay binder added to the zeolite is preferably 10 parts by weight or more and 50 parts by weight or less, particularly 40 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight (excluding water) of the zeolite in the finally obtained molded article. If the amount of the binder is too small, the strength is insufficient. If the amount of the binder is too large, the performance as a drying agent per unit weight is reduced.

The clay binder added at the time of electric granulation is 4% by weight or less of the weight of the molded body (excluding water) at the time of granulation, and the clay binder in the finally obtained molded body has 40 parts by weight or more and 44 parts by weight or less with respect to 100 parts by weight of zeolite. desirable.

The zeolite used in the present invention is not particularly limited, but when used as a desiccant for automobile air conditioners, it is preferable that the zeolite is a K-ion exchange type A zeolite (3A type zeolite) that selectively adsorbs only moisture without adsorbing the flon.

The 3A type zeolite powder is a known method, that is, a sodium A zeolite powder synthesized from sodium aluminate and sodium silicate is exchanged in a potassium chloride aqueous solution for 35% or more of the sodium ions in the zeolite with potassium ions, thereby increasing the effective pore diameter. It is possible to set it as 3A type zeolite powder which is 3 kPa.

It is preferable that the particle diameter of the zeolite crystal used by this invention is 5 micrometers or less, especially 3-4 micrometers. When the particle diameter of a zeolite crystal is too large, abrasion resistance will fall easily.

Although the setting time in this invention is not limited, since sufficient effect is not acquired in a short time, it is preferable to process at least 10 minutes or more, especially 60 minutes or more.

In this invention, in addition to a clay binder, you may contain a dispersing agent and shaping | molding adjuvant (preparatives, such as CMC), as long as it does not adversely affect the performance of a zeolite drying agent.

The drying and firing conditions in the production method of the present invention are not particularly limited, but the zeolite is hydrothermally deteriorated in firing in a dry state having a high moisture content or firing at a high temperature, and the performance as a drying agent is poor. Degrades. The moisture content during drying is 10 to 32%, especially 10 to 25% in terms of ig-loss, and the firing temperature may be exemplified by baking for several hours to 10 hours in the range of 600 to 800 ° C, especially 600 to 700 ° C. have.

As a drying and activation method, it can carry out using a well-known method, For example, a hot air dryer, an electric muffle furnace, a tube furnace, a rotary furnace, etc. may be used.

In the method of this invention, zeolite crystal diameter is 5 micrometers or less, a clay binder is 10 weight part or more and 50 weight part or less, especially 40 weight part or more and 50 weight part or less, and the hydration breakdown strength of a zeolite bead molded body is 35 N (= 3.57 kgf) ), In particular 70N (= 7.14 kgf) or more, a zeolite bead molded article having a wear resistance of the zeolite bead molded article of 1.5% or less and an average bead diameter of 1.0 to 3.0 mm can be obtained.

It is preferable that a zeolite crystal diameter is 5 micrometers or less, especially 3-5 micrometers. Zeolite crystal diameter can be confirmed by SEM observation. When the zeolite crystal diameter is larger than 5 µm, wear resistance tends to be lowered.

The clay binder in the zeolite bead molded product finally obtained is 10 weight part or more and 50 weight part or less with respect to 100 weight part of zeolites (except moisture), It is preferable that it is especially more than 40 weight part and 50 weight part or less. In addition, the clay binder to be used is a plate-shaped crystal, preferably of the same size as the zeolite particles or of a crystal size smaller than that. If the binder is less than 10 parts by weight, the strength and abrasion resistance are insufficient. If the binder is more than 50 parts by weight, the performance as a desiccant (adsorbent) is lowered.

The particle diameter of the zeolite bead molded article is in the range of 1.0 to 3.0 mm, particularly preferably in the range of 1.4 to 2.5 mm.

Since the zeolite bead molded article obtained by the method of the present invention does not add (impregnated) to a conventional vitrification agent such as soda silicate, it is excellent in toughness and adsorptive because there is no closure of the molded body pores by the vitrification agent. The performance is excellent. Whether it is a molded object which added vitrification agents, such as a soda silicate, can confirm a structure | tissue by an electron microscope.

The hydration breakdown strength of the zeolite bead molded article of the present invention is 35 N (= 3.57 kgf) or more, in particular 70 N (= 7.14 kgf) or more, and wear resistance is 1.5% or less. Abrasion resistance is particularly preferably 1% or less. The pressure resistance and abrasion resistance of the present invention are all in the state of hydration (80% upper body humidity). Higher pressure resistance and wear resistance are exhibited in the dry (non-hydrated) state, but hydration is in a state where strength and wear are problematic in practical use. In the present invention, it is significant that the pressure resistance and the wear resistance are high in a hydrated state.

Hydration pressure strength in this invention is the value which measured the sample hydrated by 80% of the relative humidity based on the crush strength test method of the granules described in the granule-strength test method described in JIS-Z-8841, and abrasion resistance Is measured by weight loss ratio by shaking for 1 hour with a general-purpose paint conditioner using 100 ml of a hydrated sample and 55 ml of an organic solvent (trichloroethylene) as a test.

Example

Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples.

(Measurement method of strength (hydration breakdown strength))

The zeolite beads molded body hydrated at a relative humidity of 80% is measured based on the crush strength test method of the granules described in the granule-strength test method described in JIS-Z-8841. Using a hardness meter, the maximum load that a zeolite bead molded body can endure is measured when the pressure plate is pressed by pressing the pressure plate at a constant speed in the radial direction of the granular material as a test piece in an atmosphere of normal temperature and normal pressure.

In the present invention, a cylindrical pressure of 5 mm in diameter is obtained by using a zeolite bead molded body having a diameter of 1.4 mm to 2.4 mm using a wood type digital hardness meter (KHT-20 type). It measured by the pressure plate of the. The pressure plate was made of stainless steel, and the pressure resistance strength of 25 pieces was measured.

(Measurement of wear rate)

100 ml of zeolite beads molded at 80% relative humidity and 55 ml of trichloroethylene were loaded into a bottle (130 ml) with a thread formed at the inlet, and a paint shaker (manufactured by Toyo Seiki Seisakusho) was added. The reduced weight ratio after shaking for 1 hour was used. After shaking, the wear powder was separated with a 1 mm sieve and the weight change was measured.

Example  One

40 parts by weight of kaolin clay is mixed with 100 parts by weight of zeolite (K ion exchange A-type zeolite), and then 50 parts by weight of water is mixed with respect to 100 parts by weight of the total amount of zeolite and kaolin clay, followed by shaping by electric granulation. By separation, a preform of 1.7 mmφ was obtained. The moisture content (equivalent to ig-loss at the time of 900 degreeC baking) of the preform after shaping | molding was 36 weight part. 3 parts by weight of kaolin clay having a different origin than the one used for molding was added to the molded product, based on 100 parts by weight of the solid content of the preform, the water content of the molded product was adjusted to 37 parts by weight by a sprayer, and then electrostatically granulated for 70 minutes. Then, it dried and baked at 680 degreeC for 5 hours.

The characteristic of the obtained beads molded object is shown in Table 1, and the molded object cross section (surface) after sizing is shown in FIG. Formation of a protective layer was confirmed on the molded body surface.

Example  2

The same treatment as in Example 1 was carried out except that kaolin clay of the same region was used for molding and rolling, and 0.1 parts by weight of the binder added during rolling was set.

The characteristic of the obtained beads molded object is shown in Table 1, and the cross section (surface) of the molded object after sizing is shown in FIG. Formation of a protective layer was confirmed on the molded body surface.

Example  3

43 parts by weight of kaolin clay is mixed with 100 parts by weight of zeolite (K-ion exchange A-type zeolite), followed by mixing 55 parts by weight of water with respect to 100 parts by weight of the total amount of zeolite and kaolin clay, and shaping by electric granulation. By separation, a preform of 1.7 mmφ was obtained. The moisture content (equivalent to ig-loss at the time of 900 degreeC baking) of the preform after shaping | molding was 38 weight part. 3 parts by weight of kaolin clay of the same production region as the one used for molding was added to 100 parts by weight of the solid content of the preform, and the molded article-containing water was adjusted to 39 parts by weight with a sprayer, followed by electric granulation for 70 minutes. Then, it dried and baked at 680 degreeC for 5 hours.

Table 1 shows the characteristics of the obtained bead molded article.

Comparative example  One

The same treatment as in Example 1 was performed without electroforming the preform of Example 1.

The characteristic of the obtained beads molded object is shown in Table 1, and the molded object cross section (surface) is shown in FIG. The molded body had many irregularities on the surface, and had insufficient hydration pressure strength and wear resistance.

Comparative example  2

The same treatment as in Example 1 was performed except that the clay binder added at the time of electrostatic granulation was 7 parts by weight.

Table 1 shows the characteristics of the obtained bead molded article. Since many clay binders were added during the sizing, the strength was improved, but the molded article was large in wear rate. Although the formation of the protective layer formed at the time of sizing was confirmed on the surface of a molded object, since it is a thick layer of binder alone, the difference of the structure with the inside of a molded object was remarkable.

Comparative example  3

The same treatment as in Example 1 was carried out except that the clay binder added at the time of electrostatic granulation was 5 parts by weight.

Table 1 shows the characteristics of the obtained bead molded article, and a cross section (surface) of the molded article is shown in FIG. 4. The wear rate was improved compared to Comparative Example 2, but was not sufficient.

Amount of binder added during formulation
(Part by weight) ^{Note 1} Amount of binder during assembly
(Part by weight) ^{Note 2} Hydration Pressure Resistance
(N) ^{Note 3} Wear resistance
(%) Example 1 3.0 40 73 1.2 Example 2 0.1 40 74 1.0 Example 3 3.0 43 49 0.8 Comparative Example 1 - 40 58 3.6 Comparative Example 2 7.0 40 67 3.5 Comparative Example 3 5.0 40 60 2.9 Note 1: For parts by weight (100 parts by weight of the total amount of zeolite and clay during assembly)
Note 2: for 100 parts by weight of zeolite
Note 3: 1 N = 0.102 kgf

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on Japanese Patent Application No. 2008-279410 of October 30, 2008 and Japanese Patent Application No. 2009-199873 of August 31, 2009, the contents of which are incorporated herein by reference.

TECHNICAL FIELD The present invention relates to a zeolite bead molded article having high strength and particularly high wear resistance and a method for producing the same. For example, it can be used for the flon desiccant for air conditioners of automobiles where high strength and abrasion resistance are required. Therefore, the industrial value of this invention is remarkable.

Claims (10)

Molding a composition having a moisture content of 35 parts by weight or more based on 100 parts by weight of the zeolite and the clay binder into a bead shape by rolling granulation; And
A method for producing a zeolite bead molded article, comprising the steps of adding 4 parts by weight or less of a clay binder to electroforming, and drying and firing the resulting molded article solid content (excluding water). The method for producing a zeolite bead molded article according to claim 1, wherein the water in the molded article at the time of electrostatic granulation is 35 parts by weight or more with respect to 100 parts by weight of the total amount of the zeolite and the clay binder. The method of claim 1, wherein the clay binder is a plate crystal. The method of claim 1, wherein the zeolite is a K ion exchange type A zeolite. The method for producing a zeolite bead molded article according to claim 4, wherein a crystal diameter of the zeolite is 5 µm or less. The method for producing a zeolite bead molded article according to claim 1, wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite bead molded article is 10 parts by weight or more and 50 parts by weight or less. The method for producing a zeolite bead molded article according to claim 6, wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite is more than 40 parts by weight and 50 parts by weight or less. Zeolite crystal diameter is 5 micrometers or less, the total amount of a clay binder with respect to 100 weight part of zeolite beads of a zeolite beads molded article is 10 weight part or more and 50 weight part or less, the hydration pressure resistance strength of a zeolite beads molded object is 35N or more, and a zeolite beads molded object The wear resistance of the zeolite beads is 1.5% or less, and the bead diameter is 1.0 to 3.0 mm. The zeolite bead molded article according to claim 8, wherein the total amount of the clay binder with respect to 100 parts by weight of the zeolite is more than 40 parts by weight and 50 parts by weight or less. The zeolite bead molded article according to claim 8, wherein the hydration withstand strength is 70 N or more.

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