JPS61295226A - Hydrophobic zeolite composition and its production - Google Patents

Abstract

PURPOSE:To obtain hydrophobic zeolite wherein the hygroscopicity of zeolite in itself is suppressed by treating the activated natural or synthetic zeolite with a coating agent or a soln. thereof having the hydrophobic property. CONSTITUTION:Activated natural or synthetic zeolite having >=1.5 molar ratio of SiO2/Al2O3 is prepared. After impregnating and treating it in a coating agent or a soln. thereof having the hydrophobic property at >=50 deg.C, a solid phase and a liquid phase are separated. Then the hydrophobic zeolite composition is obtained by heating the treated zeolite phase at >=50 deg.C and removing the residual solvent from the zeolite phase. As the coating agent, liquid paraffin having 0.8-0.9 specific gravity, a fluorine compd. and a silicon series compd. are used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a hydrophobic zeolite composition and a method for producing the same. More specifically, the present invention provides a hydrophobic zeolite composition in which natural or synthetic zeolite is treated with a hydrophobic coating agent or its solution to suppress the zeolite's inherent hygroscopic ability, and a method for producing the same. .

(Prior art) It is known that by thermally activating various zeolites to remove crystallization water, cavities are formed in the zeolite matrix, and water adsorption and selective adsorption of other gases take place here. Utilizing the true properties of zeolite,
Zeolites are widely used in the fields of drying (dehumidification), gas purification, and concentration. It has been found that finely powdered zeolite is added to various polymers as a filler, and has a remarkable effect in improving the properties and functions of the polymers, and in imparting new properties.

For example, it has been confirmed that zeolite fine powder has a favorable effect when added and dispersed in paper compositions, natural or synthetic rubber compositions, plastic compositions, and pigment compositions (non-settling and matte pigments). has been done. As the polymer, polyethylene, polypropylene,
polystyrene, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, AB8 resin, acrylic resin, fluororesin, thermoplastic synthetic polymer with other than polyurethane, phenolic resin, urethane resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, etc. Examples include thermosetting synthetic polymers such as rayon, cupro, acetate, triacetate, and other recycled or semi-synthetic polymers. However, the above-mentioned polymers and organic polymers for the purpose of fiber formation (for example, nylon 6, nylon 66, polyvinyl chloride, polyethylene terephthalate,
When fine particles of zeolite are added to rubber compositions (polyethylene, etc.), rubber compositions, and pigment compositions and are dispersed uniformly, the water contained in the zeolite interferes with uniform dispersion and causes 717 foaming, which has an adverse effect. give. The above-mentioned organic polymer is formed into a thin film), or when it is adsorbed on zeolite during spinning, a swelling phenomenon occurs due to trace amounts of moisture, which may be due to the non-uniformity of the film or the formation of yarn during the spinning process. Usually, various types of zeolite used for kneading into polymers are added in the form of activated fine powder, but fine zeolite powder in this state is extremely active. The inventor of the present invention has confirmed through a number of tests that moisture in the atmospheric gas is easily adsorbed by the polymer, and as mentioned above, it has an adverse effect on the polymer.

The purpose of the present invention is to establish an economical hydrophobization technique for suppressing the hygroscopic ability of various activated zeolite fine powders used for the addition of the above-mentioned polymers, and to The purpose is to establish a technology to temporarily suppress the moisture absorption ability of zeolite molded bodies. For the above purpose, the present inventor conducted a series of tests on the hydrophobization of zeolite and carefully studied the obtained results, and found that zeolite treatment with a coating agent solution is extremely effective for economically obtaining a hydrophobic zeolite composition. 9. We have discovered that this is the case, and have arrived at the present invention.

(Means for Solving the Problems) That is, the present invention provides a hydrophobic zeolite composition comprising an activated natural or synthetic zeolite and a hydrophobic coating agent coated on the surface thereof.

The present invention also provides a method for producing the above hydrophobic zeolite composition, in which activated natural or synthetic zeolite is impregnated with a hydrophobic coating agent or its solution, and then the solid phase and liquid phase are separated. , and then removing residual solvent from the treated zeolite phase.

The present invention will be explained in detail below. The present invention is a hydrophobic zeolite composition obtained by treating an activated natural or synthetic zeolite with a hydrophobic coating agent or a solution thereof. In the present invention, in order to make natural or synthetic zeolite hydrophobic, activated zeolite can be added to a coating agent or its solution at room temperature or by heating, for example. Instead of the above coating method, it is also possible to economically obtain a hydrophobic zeolite composition by spraying a hydrophobic coating agent solution onto activated zeolite at room temperature or under heating to be hydrophobized. It is. Furthermore, a hydrophobic zeolite composition can be easily obtained by adding and mixing a coating agent or a solution containing the coating agent to activated zeolite.

As mentioned above, it is preferable to obtain the hydrophobic zeolite composition of the present invention by treatment under heating.

That is, the activated natural T+ is obtained by treating synthetic zeolite in a hydrophobic coating agent or its solution at a temperature of 50°C or higher, separating the solid phase and liquid phase, and then heating the treated zeolite phase at 50°C. A zeolite composition with high hydrophobicity, which is the object of the present invention, can be easily obtained by heat treatment in a temperature range of .degree. C. or higher.

Activated natural and synthetic zeolites are used in the present invention. Activation of these zeolites can be carried out by carrying out a normal heat treatment under normal pressure or reduced pressure to remove the moisture in the zeolite to the required degree.The activation temperature depends on the type of zeolite. Activation is usually carried out at a temperature in the range of 200 to 600°C, although this varies. Most of the natural or synthetic zeolites used in the present invention have a moisture content of 1% or less upon activation in the temperature range of 400 to 550°C.

The activated natural or synthetic zeolite used in the present invention may be in the form of powder, particles, pellets, tablets, beads, plates, cylinders, or special shaped bodies (e.g. honeycomb shaped bodies, filament shaped bodies). ), and the present invention can also be applied to the above-mentioned side-shaped zeolite.

Therefore, an activated zeolite of any shape suitable for the purpose of use may be appropriately selected. Next, the types of zeolite that can be used in the present invention will be described. In the present invention, the silica-aluminum-to molar ratio Si
n, / AA! Activated natural or synthetic zeolites with a gos of at least 1.5 are preferred, and they may contain some impurities. Zeolites are generally aluminosilicates with a three-dimensionally developed skeletal structure. In general, XM V′nO, AltO,, ysio, with AltOs as a reference.
.

It is represented by 2 horses O. M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and s" corresponds to this valence. On the other hand, X and y are metal oxide and silica coefficients, respectively, and 2 is crystal water Many types of zeolite are known with different compositions, pore diameters, specific surface areas, etc., but in the present invention, as described above, the zeolite is preferably 1.5 or more S i O, / AltO,
have a ratio. 1+, those with well-developed pores and a large specific surface area are more preferred. Representative examples of monovalent metals as M in the above general formula include sodium, potassium, silver, etc., and representative examples of divalent metals include magnesium, calcium, strontite, barium, zinc, and cadmium. , mercury (If), copper (It), iron (1)
, bismuth, etc. There is no problem even if the ion-exchangeable M is a monovalent metal, a divalent metal, or a mixture of the two in the zeolite, and the amount of these metal ions retained in the zeolite phase is controlled by adjusting the ion exchange of the zeolite at room temperature to high temperature. It can be arbitrarily prepared by carrying out the following steps. The zeolite prepared to a predetermined composition by ion exchange is washed with water to remove excess metal ions from the zeolite solid phase, then dried at around 100-110°C, and finally, as mentioned above,
Heat activated at ℃. Next, coating may be performed according to the present invention.

As the zeolite material having a molar ratio of 5ft/AA'*Os of 1.5 or more used in the present invention, either natural or synthetic zeolite can be used.

For example, natural zeolite is analcin (Anal
cime: 5iOt/A40m-5,6~5.6)
0habazite: Sin, /A
A',○,=5.2~6.0 and 6°4~7.6),
Clinoptilolite (01ino-ptilO'1it
e: SiO, /Al, O, ~8.5~10.5)
, Elionite (Kr 1onite: 5i02
/A4os ~5, 8~7, 4), 7Ojasite (Faujasite: 81017'A1103
= 4.2~4.6), mordenite (morcLe
nite: 5iO1/ml, O, = 8.5-10.0
), Ph1llipsite:
5i04/A40s = 2.6~4,4)
'lk etc. are mentioned. Activated products of these typical natural zeolites are suitable for the present invention. On the other hand, typical synthetic zeolides include A-type zeolite (5i)
Ot/AltOs=1.4~2.4), ~9~10)
, high silica zeolite (1310t AA!tOs
) 20), these activated synthetic zeolites are suitable as zeolite materials for the coating of the present invention. Particularly preferred are Mononoke, synthetic Mu-type zeolite, X-type zeolide, Y-type zeolite. Zeolides, high silica zeolites and synthetic or natural mordenites.

Next, the coating agent and coating method will be explained in detail. As the coating agent of the present invention, five types of coating agents, including liquid paraffin type, fluorine type and silicone type, are suitable for obtaining the hydrophobic zeolite composition of the present invention.

These coating agents are used as solutions in suitable solvents.

As a coating agent based on liquid paraffin, the specific gravity is 0.
Liquid paraffins in the range 8 to 0.9 are suitable for smooth coating of the activated zeolite to suppress its hygroscopic capacity or to make it almost negligible. Typically, the liquid paraffin suitable for use in the present invention is preferably one that is thermally stable at at least 100°C, such as Japanese Industrial Standard X-9003 liquid paraffin (specific gravity) 0,855; boiling point approximately 500°C.
above), sumoyl type P-70 (specific gravity 0.84; flash point 184°C), P-200 (specific gravity 0.86; flash point 21
8°C). The liquid paraffin exemplified above is hydrophobic and almost insoluble in water. In the present invention, when it is necessary to keep the water absorption of activated zeolite to an extremely low level, these fluids and paraffin are used in an undiluted state, while when a slight water absorption is acceptable or preferable from the viewpoint of the purpose of use. is diluted with a suitable solvent and used as a solution.

The degree to which the liquid paraffin-based coating agent is diluted with a solvent varies depending on the type and shape of the target activated zeolite, as well as the required degree of hydrophobicity. As a solvent, a flame retardant solvent such as carbon tetrachloride (C
C14), trichlorethylene (OHC1,0HC1,
) is preferred. The advantage of diluting liquid paraffin with a solvent is that it reduces the original viscosity of liquid paraffin, making operations such as stirring and two-phase separation easier to obtain hydrophobic zeolite. The amount of liquid paraffin described above in the diluted solvent solution is normally required to be at least 30% (volume percent) in order to obtain a zeolite composition with favorable hydrophobicity. Below the above value, the amount of liquid paraffin decreases and the coating of activated zeolite tends to become incomplete. The coating agent or its solution is preferably one that is thermally stable, and preferably one that does not undergo thermal decomposition or denaturation at at least 100°C, and also does not adversely affect the properties of the zeolite itself. In the present invention, it is preferable to carry out coating with activated zeolite under heating.By carrying out coating under heating, excessive adsorption of liquid paraffin and solvent to the zeolite phase can be prevented. There is.

In the present invention, treatment under heating at 50°C or higher is effective.@Also, when separating the two phases of Zeon-1) phase and coating liquid by suction or centrifugation, it is necessary to heat them at 50°C or higher. If the coating is carried out under heating, the excess coating liquid can be more easily separated from the solid phase. The activated zeolite coated to the required extent is then subjected to heat treatment at a temperature of at least 50°C or higher, usually in the range of 50 to 250°C, under normal pressure or reduced pressure. The liquid paraffin and solvent used to carry out the process should be thermally stable at at least 100°C, and the solvent used should preferably be flame-retardant for rounding to avoid ignition. Silicone-based coating agents (silicone oils) are also effective for preparing zeolite compositions. For example, the product name KF- manufactured by Shin-Etsu Chemical Co., Ltd.
Dimethylsiloxane coating agent such as 96, K
Methylhydrodiene polysiloxane coating agents such as P-99, methyltrichlorosilane coating agents such as KO-88, and silane coupling agents such as IBM-41030 are chemically stable, non-corrosive, and non-flammable. It is preferred because it has a high score, excellent durability, and high heat resistance.

These are thermally stable even in a temperature range of 100°C or higher, and have sufficient hydrophobicity and water repellency, and are suitable for obtaining the hydrophobic zeolite composition targeted by the present invention. It is. In the present invention, these silicone-based coating agents are applied to commercially available anti-inflammatory agents in an undiluted state.
Maku is used by diluting it to the required concentration with a solvent that is thermally stable at at least 100°C, and forms a silicone film on activated zeolite, which has the function of keeping it hydrophobic or water repellent. have. In general, hydrocarbon solvents, aromatic solvents, and many other solvents can be used to dilute silicone-based commercially available coating agents, but if heat treatment is also performed in the present invention, flame retardant A solvent that is stable at 100°C is preferred. Examples of solvents having such characteristics include carbon tetrachloride and trichloroethylene.

Silicone occupied in the diluent containing the above-mentioned silicone
The amount of zeolite is determined depending on the type and shape of the activated zeolite in question, as well as the degree of water repellency (hydrophobicity) required. In the present invention, in order to obtain a hydrophobic zeolite composition with satisfactory properties, the lower limit of the silicone coating agent in the diluent is 0.1% (volume percent). Below the above lower limit, the hydrophobic ability of the resulting zeolite decreases significantly as the silicone content decreases. The silicone coating agent or its diluted solution can be sprayed onto the activated zeolite or mixed with the zeolite as in the case of the liquid paraffin described above; The required amount of coating liquid may be added and blending may be carried out using a mixer or the like, or the activated zeolite may be mixed into the coating liquid and coating may be carried out. Next, the treated zeolite phase obtained by carrying out the silicone coating treatment pot is preferably finally subjected to a heat treatment at a temperature range of 50 to 500°C under normal pressure or reduced pressure to remove excess zeolite phase. The solvent and the like are removed, and a uniform silicone film is formed and the zeolite phase is uniformly wetted with the silicone coating agent to achieve a desirable coating, and the activated zeolite obtained is hydrophobic or water repellent. become.

Similar to the liquid paraffin-based and silicone-based coating agents mentioned above, fluorine-based coating agents also form a coating film on activated zeolite and are effective for making it hydrophobic or water repellent.For example, Sumitomo 3M Co., Ltd. Fluorine-based coating agent such as product name JX-900,
The PC-721 corner remains chemically stable and has high heat resistance even in a temperature range of 100°C or higher, and forms a film on activated zeolite to make the zeolite hydrophobic.

The above-mentioned fluorine-based coating agent is commercially available, and is used undiluted or diluted with a chlorine-based solvent as a diluted solution for the treatment of activated zeolite. The content of fluorine-based coating agent in the diluent is 0.5% (by volume)
-%) or more is preferred. The solvent in this case is preferably a flame-retardant solvent. The method for diluting the fluorine-based coating agent and the heat treatment method for the treated zeolite may be similar to those for the liquid paraffin and silicone coatings described above.

When using a fluorine-based coating agent manufactured by Sumitomo 3M Co., Ltd., such as ffX-900, the boiling point is 74°C.
1.1- Trichloroethane is preferred as the solvent, while if FC-721 is used, FC-77 with a boiling point of 97°C is preferred as the solvent. Both of the above two types of coating agents have high heat resistance, with the former having a maximum of 150
It is stable up to around 205°C, and the latter is stable up to around 205°C. Formation of a fluorine-based coating using the above-mentioned coating agent or its diluted solution for hydrophobization is carried out at room temperature. ? When using 0-721, heat treatment is 50-1
A temperature range of 50°C is a preferred range.

Next, the characteristics of the hydrophobic zeolite composition obtained by the present invention will be described. The hygroscopic capacity (water absorption capacity) of the hydrophobic zeolite obtained in the present invention is extremely low compared to that of uncoated active zeolite, and as is clear from the water absorption test data described in the Examples below, the hygroscopic capacity is It is also possible to reduce it to almost zero. The hygroscopic ability of the targeted activated zeolite can be adjusted by using the three types of liquid paraffin mentioned above,
The coating is carried out by selecting silicone or fluorine-based material depending on the purpose of use, and adjusting the content of the coating agent in the coating solution, coating method, heat treatment conditions, etc. When any of the coating methods of the present invention is applied to activated zeolite, the resulting hydrophobic zeolite composition has the advantage of being structurally stable and highly heat resistant.

Furthermore, as mentioned above, the hygroscopicity of the zeolite composition of the present invention can be extremely reduced, and the individual crystalline particles constituting the composition have little agglomeration, and it has been confirmed that the zeolite composition has favorable properties as a filler. Just in case. It has been found that when the zeolite composition of the present invention is used as a filler for a polymer, the zeolite fine particles are uniformly dispersed in the polymer. This method can be applied not only to zeolite powder but also to hydrophobizing granular products, as shown in the examples below.

Next, the hydrophobic zeolite composition of the present invention can be heated to exhibit its original zeolite function.

Although the optimum regeneration temperature varies depending on the type of hydrophobic zeolite composition, heating activation is usually carried out in a temperature range of 300 to 600°C, but the present invention is limited to this example without exceeding its gist. It's not something you can do.

Examples 1 and 2 In this example, liquid paraffin (LP; first grade reagent; specific gravity)
0,855; boiling point > 300°C) or liquid paraffin/
This paper relates to a hydrophobization test of A-type synthetic zeolide powder (NaZ) using a mixed solution of carbon tetrachloride.

(Moo type synthetic zeolite powder sodium type zeolite (NaZ) used; pore size.

4 μm; average particle diameter Dav = 3.8 μm A-type zeolide powder having the above characteristics is 500-5 μm
(1) Hydrophobization method The 8-type zeolide (Na
Z) 80 ml of liquid paraffin (LP) solution or LP-001 solution was added to about 509 and kept at room temperature for 20 minutes under stirring to hydrophobize the zeolite. Next, after centrifuging the two phases to remove excess LP and solvent from the solid phase, the hydrophobized zeolite phase was separated at 100 to 110°C for 30 to
A heat treatment step of heating for 40 minutes was carried out. After the above heat treatment, 4 to 8 g of the hydrophobized zeolite phase was accurately weighed, and a moisture absorption test was carried out on it under certain conditions. That is, heat-treated hydrophobic zeolite was used under certain conditions (temperature 18@±2°C; relative humidity RH=66±2.
5%) The composition of the coating liquid used in this test is listed in Table 1, and the moisture absorption test results are listed in Table 2. In Table 2, in comparative test 1,
The above (1) K-activated zeolite was added to the above (1).
Table 1 Composition of coating liquid Table 2 Moisture absorption test Moisture absorption ability of the hydrophobic zeolite obtained in Example 1 as shown in Table 2 was found to have a favorable hydrophobic capacity. Furthermore, the hygroscopic capacity of the hydrophobic zeolite obtained in Example 2 using a diluted solution of LPloo as the coating liquid was extremely low, and after 24 hours, it was about 173 times the hygroscopic capacity of activated zeolite (NaZ).

From a comparison of Comparative Test 1 and the water absorption capacity of the hydrophobic zeolite of the present invention, it is clear that the hydrophobization method of the present invention is extremely effective and significantly suppresses the inherent hygroscopicity of the activated zeolite.

Example 3.4 This example uses Mu-type synthetic zeolite powder (Waz) using a mixed solution of liquid paraffin/trichlorethylene (LA70HO1,04FiO1t) as a coating liquid.
This is related to the hydrophobization test of Y-type synthetic zeolide powder (NaY).Liquid paraffin (LP) is a first-class reagent (specific gravity) 0,855; boiling point>300°C
)It was used. Now, in this example, unlike Examples 1 and 2, the coating of activated zeolite was heated at approximately 70°C, and the heat treatment of coated zeolite was performed at 12°C.
It was carried out for 30 minutes at 0°C. Furthermore, in this example, in place of carbon tetrachloride as a flame retardant solvent, as mentioned above,
Trichlorethylene was used - (1) Synthetic zeolite powder used Mu-type zeolite-sodium zeolite (11aZ
); Pore diameter, 4 μm; Dav = 5.95 μm Y-type zeolide-sodium type zeolite (NaY)
; Pore diameter, 8 μm; Dav = 4.0 μm Both of the two types of zeolite powders, NaZ and NaY, having the above characteristics were heated in an electric furnace at 550 to 560°C for 2.5 hours to remove the water content. especially) activated.

(1) Hydrophobization method Mubase zeolite (Na
Z) or Y-type zeolide (NaY) LP/(!) for about sag! IJ, 0HOJ! Diluted liquid 80m
The resulting mixture was heated to about 70'C4C.
The zeolite was hydrophobized by keeping it under stirring for 25 minutes. The two phases were then separated by suction. Subsequently, a heat treatment was carried out in which the zeolite phase was heated to approximately 120°C and held under VC for 50 minutes.Next, after the heat treatment was completed, 4 to 8 g of hydrophobic zeolite was accurately weighed, and a moisture absorption test was performed on it under the certain conditions described below. The preparation method of the coating liquid used in this test is listed in Table 3, and the related moisture absorption test results are listed in Table 4. Table 3 Composition of coating liquid Table 4 Moisture absorption ability test As shown in Table 3, in Example 3, the coating liquid was LPloHCl, CTIC/, diluted liquid (LP 70
ηO) was used, while in Example 4 a diluent of the same type (
LP=60x10) was used. Using hydrophobic zeolite that has been heat treated, it is kept at constant temperature and humidity (23°±2°C;
The hygroscopic capacity test was carried out under RH=757±2).

Hydrophobic zeolite composition (NaZ) obtained in Example 3
Even after 24 hours, its water absorption capacity is still zero.

In Comparative Test 2, the same activated Mu-type zeolite (NaZ) (without hydrophobic treatment) used in Example 3 was used to evaluate the water absorption rate under the same conditions as the moisture absorption test in Example 3. From the comparison between the two, it is clear that complete hydrophobization can be achieved with the present invention. Next, the hygroscopic capacity of the hydrophobic Y-type zeolide composition (NaY) obtained in Example 4 decreased and increased compared to that of the untreated activated Y-type zeolide (NaY) (Comparative Test 3). ), and after 24 hours, the former is about 1/1 of the latter.
It has dropped to 3.

Example 5 This example shows activated X-type zeolide powder (Nap
) As in Examples 3 and 4, a liquid paraffin/triclene mixed solution was used as the coating liquid. As liquid paraffin (LP), a first grade reagent (specific gravity: 0.855; boiling point > 300°C) was used, and LP = 5O
r/Ic dilution scene.

(I) Synthetic zeolite powder used: X type zeolite - sodium type zeolite (NaX);
Pore diameter, 10 μm; Dav = 4.2 μm NaX zeolite powder with the above characteristics has a temperature of 1.5 at 550-560°C
X-type zeolide (Na
X) To about 55 g, 80 ml of I, P10HOlψ aHc4 diluted solution (I, P = 50) was added, and the resulting mixture was heated to about 75° C. and stirred for 50 minutes. After separating the zeolite phase hydrophobized by this method, heat treatment was performed at 130°C for 30 minutes.Next, the hydrophobic X-type zeolide composition after the heat treatment was
Weigh 8g accurately and conduct a moisture absorption test on it at 23°±1°C.
Table 5: Preparation of coating liquid Table 6: Test of hygroscopic ability Used for coating the fine powder of activated X-type zeolide in this example. The preparation method of the LPloHCl, CHC1t diluted solution is shown in Table 5, and the test results regarding the moisture absorption capacity of this example are shown in Table 6. Comparative Test 4 in Table 6 is a hydrophobic X-type zeolide composition obtained in Example 5 using the same activated X-type zeolite (NaX) powder (without hydrophobization treatment) as in this example. The moisture absorption capacity was measured under the same conditions as . The hydrophobic X-type zeolide composition obtained in this example absorbed moisture very gradually, and even after 24 hours, the moisture absorption was only 6.72, which corresponds to about 30% of the water absorption capacity of activated NaX. Roar.

This example uses activated Mu-type zeolite powder (NaZ
) liquid paraffin-based SMOIL (8mail) P-70 (trademark, specific gravity 0.84;
This article relates to the method for producing the hydrophobic zeolite composition of the present invention using P-200 (specific gravity 0.86: flash point 218°C) and its performance test. Mu-type synthetic zeolite powder The same A-type zeolite (NaZ) used in Example 1.2 was used. The activation method is also exactly the same as in the previous example.

(If) Hydrophobization heat-activated human-type zeolite) (NaZ) approx. 50
Smoil for 9? -70'i Taij P -20
807 of 0 was added. The above mixture was kept under stirring at room temperature for 20 minutes to perform hydrophobization of the zeolite. Next, the zeolite phase was centrifuged to remove excess coating solution, and then the zeolite phase was heated at 120°C for 30 minutes. Accurately weigh 4 to 8 g of the hydrophobic A-type zeolide obtained by the above method, and perform a moisture absorption test on it at 23°±
The test was carried out at a constant temperature of 1° C. and R, H = 70±1%.

The preparation method of the coating liquid used in this test is shown in Table 7, and the moisture absorption test results are shown in Table 8.Table 7 = - Preparation of coating liquid Table 8 Moisture absorption ability test Comparative test 5 is activated Mu-type zeolite (NaZ)
It is related to the hygroscopic ability of. From this, it can be seen that the activated MaZ powder has extremely high hygroscopicity, but if the hydrophobization method of the present invention is applied to it, it is possible to completely suppress the hygroscopicity peculiar to zeolite. . In other words, liquid paraffin-based SMOIL P-70 and P-200
It is clear from this example that when the hydrophobization according to the present invention is carried out using a zeolite composition, the moisture absorption capacity of the resulting hydrophobic zeolite composition can be suppressed to almost zero over a long period of time. ◎ Examples 8 to 10 The examples relate to the production of a hydrophobic zeolite composition of the present invention using a silicone-based and fluorine-based coating agent as a coating liquid for activated zeolite, and its performance test #1.

(1) Used synthetic zeolite powder (Example 9) Mu-type zeolite fine powder: The same NaX zeolite used in Example 1 (Example 10) The above Mu,! The method for activating the Y-type zeolite fine powder is also the same as in the previous example.

(1 Coating liquid used Example 8: KF-96 (500CPEl) 10H
IJ, CHC! /.

(KF→6-4 K/O) Example 9: Same as Example 8※※ Example 10: JX-900/1, 1.1) ”)
apyxfin (JX-q OO=40 r7o)
Silicone-based coating agent (dimethylsiloxane-based) manufactured by Hata Shin-Etsu Chemical Co., Ltd. Fluorine-based coating agent (II) manufactured by Sumitomo 3M Co., Ltd. Hydrophobization method For about 50 g of the above heat-activated zeolite fine powder 80 ml of the above coating solution was added, and the zeolite was made hydrophobic by keeping it at room temperature for 15 minutes under stirring to separate the 90 zeolite phase, and heat treatment was performed as follows. Heat treatment temperature and time Example 8.9: 100°C, 30 minutes Example 10:1
The hydrophobic zeolite prepared through the above heat treatment at 00°C for 10 minutes was subjected to a moisture absorption test according to the above example, and the results shown in Table 9 were obtained. However, the moisture absorption tests in Examples 8 to 10 were carried out at a temperature of 21°±2.
℃, humidity RFI = 69 ± 2% Table 9 Moisture absorption test Comparative tests 6 and 7 in Table 9 were carried out under constant temperature and humidity conditions of RFI = 69 ± 2%.
This relates to a hygroscopic test of NaY and NaY (without hydrophobization treatment). Comparison of Example 8 and Comparative Test 6,
A comparison between Example 9 and Comparative Test 7 shows that the hygroscopic ability of the hydrophobic zeolite composition obtained according to the present invention is extremely reduced, and a favorable effect is obtained.

The water absorption rate of the hydrophobic mu-type zeolite obtained in Example 10 at a constant temperature and humidity of 21° ± 2°C and humidity RFl = 69 ± 2% after 24 hours was lower than that of activated NaZ. It was found that the amount decreased to 1/4.

In this example, liquid paraffin-based sumoy # (smoil) P-70 or P-200 (
A molded body of Mu-type zeolite (NaZ-1716, whose trademark and physical properties are listed in Examples 6 and 7)
The present invention relates to a method for producing a molded hydrophobic zeolite composition.

(11 Molded A-type zeolite of Mu type synthetic zeolite used) The molded body of (NaZ) used is a 1/16' pellet (average compressive strength ff = 7.7 Icg/pellet). (If hydrophobization method activated A-type zeolite) was activated by calcining at 500'C for 1 hour prior to coating. Example 11) 70 companies of i or P-200 (Example 12) were added. The above mixture was heated to 65°C and then maintained at the same temperature for 25 minutes with stirring to make it hydrophobic.Then, the zeolite phase was centrifuged to remove excess coating liquid, and the zeolite phase was heated to 65°C. The phase was heated at 120°C for 35 minutes. 5 to 5 of the molded product of the hydrophobic A-type zeolide composition obtained by the above method.
7I was accurately weighed and a moisture absorption test was conducted on it at 25°±2°C.
The test was carried out under constant temperature and humidity at RH=69±5%. The results of the moisture absorption test are shown in Table 10.

Comparative Test 8 is a case in which the same 1716' pellets used in this example were activated and tested. Comparison of these moisture absorption tests revealed that this coating method has a favorable effect of suppressing moisture absorption of activated molded bodies.

In this example, the liquid paraffin (T, +I') used in Example 1 and of the same quality as 9 was used to hydrophobize Mu-type zeolite powder (NaZ), but different from Example 1. This was carried out using the mixing method.

Sodium type synthetic zeolite (NaZ; pore size, 4
m; average particle diameter, Da = 3.8 μm] Powder is 500 ~
It was activated by heating at 550° C. for 2 hours and 30 minutes in an electric furnace. Next, 250
- IJP was added.

The obtained mixture was mixed using a mixer for 50 minutes while shutting off the outside air. The mixture obtained by this mixing method was subjected to a heat treatment step of heating at 120° C. for 2 hours.

The moisture absorption test for the hydrophobic zeolite composition produced through the above steps was conducted under the same constant temperature and constant temperature conditions as in Example 1 (temperature 1
(Test method is the same as Example 1). In this case, the water absorption rate was almost zero after 15 hours had elapsed, and it was confirmed that a preferable hydrophobic zeolite composition could be obtained.

The method of hydrophobizing activated zeolite by the mixing method of this example has the advantage that the amount of coating agent used can be reduced.

Claims (1)

[Claims] 1. A hydrophobic zeolite composition comprising an activated natural or synthetic zeolite and a hydrophobic coating agent coated on its surface. 2. Zeolite is at least 1.5 SiO_2/Al_
A hydrophobic zeolite composition according to claim 1 having a molar ratio of 2O_3. 3. The hydrophobic zeolite composition according to claim 1 or 2, wherein the coating agent is liquid paraffin having a specific gravity of 0.8 to 0.9. 4. The hydrophobic zeolite composition according to claim 1 or 2, wherein the coating agent is a fluorine compound. 5. The hydrophobic zeolite composition according to claim 1 or 2, wherein the coating agent is a silicone compound. 6. After impregnating the activated natural or synthetic zeolite with a hydrophobic coating agent or its solution,
A method of making hydrophobic zeolite compositions by separating solid and liquid phases and then removing residual solvent from the treated zeolite phase. 7. The method according to claim 6, wherein the impregnation treatment is performed at a temperature of 50°C or higher, and the solvent removal is performed by heating at 50°C or higher. 8. The method according to claim 6 or 7, wherein the zeolite is a preformed compact. 9. The method according to any one of claims 6 to 8, wherein the coating agent or its solution is thermally stable at at least 100°C or lower. I0, the hydrophobic coating agent is liquid paraffin, a fluorine compound and/or a silicone compound having a specific gravity of 0.8 to 0.9, according to any one of claims 6 to 9. Method.