JP2003137536A - Zeolite powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a zeolite powder which reveals high cation exchange rate, and also causes little turbidity when it is dispersed into water, and to provide a method of manufacturing the zeolite powder. SOLUTION: The zeolite powder contains zeolite and a dispersant, where the mean primary grain diameter is <=0.2 μm (coefficient of variation is <=100%) and mean aggregated grain diameter is <=1 μm (coefficient of variation is <=100%). The method of manufacturing the zeolite powder contains a process in which the zeolite powder and the dispersant are mixed in an alcohol solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a zeolite powder containing zeolite and a dispersant.

[0002]

2. Description of the Prior Art Zeolite is a crystalline aluminosilicate, which has an arrangement of SiO ₄ tetrahedrons and AlO ₄ tetrahedrons A,
It can be classified into various crystal structures such as X and Y types. Zeolites are used as adsorbents and catalysts (carriers) because they have a uniform pore size depending on the crystal structure and exhibit the function of a molecular sieve. Further, since zeolite has an ion exchange ability, it is used as a builder for detergents, a wastewater treatment agent, and the like. Further, it is also used as a resin additive.

The performance of zeolite largely depends on its particle size (primary crystal particle size, agglomerated particle size). For example, it is known that the cation exchange rate improves as the primary crystals of zeolite become finer. In addition, dispersibility in water is improved and turbidity in water is suppressed according to the decrease in the aggregate particle size of the zeolite and the sharpening of the particle size distribution. Since the performance of zeolite can be improved by reducing the particle size in this way, attempts have been made to manufacture zeolite with a small particle size.

As one method for producing a zeolite having a small particle size, an attempt has been made to reduce the particle size of the zeolite by mechanically pulverizing it. However, in the method of atomizing zeolite by mechanical pulverization, particularly in the dry pulverization method, there is a problem that the crystallinity of zeolite is greatly reduced and the original performance of the zeolite (for example, cation exchange ability) is not expressed. . Further, in the wet pulverization method, the decrease in crystallinity is relatively small as compared with the dry pulverization method, but when the solvent is removed (dried), the atomized zeolite particles are re-aggregated to form a coarse aggregate. Will end up. As a result, zeolite performance (eg,
There is a problem that the dispersibility in water, the fluidity of the powder, etc.) is greatly reduced.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a zeolite powder which exhibits a high cation exchange rate and has little water turbidity when dispersed in water. Moreover, this invention makes it a subject to provide the manufacturing method of this zeolite powder.

[0006]

That is, the present invention is
[1] Zeolite powder containing zeolite and a dispersant, having an average primary particle size of 0.2 μm or less (variation coefficient of 100% or less) and an average aggregate particle size of 1 μm or less (variation coefficient of 100% or less), and [2] The method for producing a zeolite powder according to the above [1], which comprises a step of mixing a dispersant and zeolite in an alcohol solvent.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The zeolite powder of the present invention contains zeolite and a dispersant. As described above, the zeolite powder of the present invention is characterized in that the zeolite particles and the dispersant are mixed, and the dispersant is, for example, a slurry state or a powder state, or a reaction, a pulverization, a drying or the like. During the operation, etc., it works to suppress the aggregation between zeolite particles. The existing form of the dispersant in the zeolite powder of the present invention is not particularly limited as long as it can exert the effect of suppressing the aggregation between zeolite particles, and for example, it exists in a form that substantially covers the surface of the zeolite particles. It may be present in the form of being partially attached to the surface of the zeolite particles, or simply present in the spaces between the zeolite particles. Above all, from the viewpoint of effectively suppressing the aggregation of the zeolite particles, it is preferable to allow the dispersant to exist so as to substantially cover the surfaces of the zeolite particles. That is, the zeolite powder of the present invention is preferably composed of zeolite particles obtained by coating the entire surface with a dispersant. Thus, in the zeolite powder of the present invention,
Aggregation of the zeolite particles, which is a constituent component, is suppressed by the dispersant, and since both the average primary particle diameter and the average aggregate particle diameter of the zeolite powder are small, they exhibit a high cation exchange rate and are dispersed in water. If it does, there is less turbidity in water.

The average primary particle diameter of the zeolite powder of the present invention is specifically 0.2 μm or less, preferably 0.1.
It is 1 μm or less, more preferably 0.05 μm or less.
If the average primary particle size of the zeolite powder is in such a range,
An excellent cation exchange rate is exhibited, which is preferable. The coefficient of variation (%) of the average primary particle size is 100% or less, and preferably 80 from the viewpoint of exhibiting an excellent cation exchange rate.
% Or less, more preferably 50% or less, further preferably 3
It is 5% or less.

The average agglomerated particle size of the zeolite powder of the present invention is 1 μm or less, preferably 0.6 μm or less,
More preferably 0.5 μm or less, still more preferably 0.4
μm or less. If the average aggregate particle size of the zeolite powder is in such a range, aggregation between the zeolite particles is suppressed,
The dispersibility in water is good, which is preferable. Further, when the average agglomerated particle size of the zeolite powder is particularly 0.4 μm or less, the transparency of water when dispersed in water is remarkably improved, which is preferable. The coefficient of variation (%) of the average aggregate particle size is 100% or less, preferably 50% or less, more preferably 40% or less.
% Or less, more preferably 30% or less. When the coefficient of variation of the average agglomerated particle size is in such a range, the agglomerated particle size distribution has a substantially single peak, the agglomeration between zeolite particles is suppressed, and the dispersibility in water is good, which is preferable.

The average primary particle diameter and the average agglomerated particle diameter can be measured by the methods described in Examples below.

Further, the zeolite powder of the present invention has an excellent cation exchange rate. In the present specification, the cation exchange rate (CER) refers to the amount of Ca ion-exchanged in 1 minute per 1 g of zeolite contained in the zeolite powder (anhydrous basis). On the other hand, although it may be referred to as the cation exchange capacity of the zeolite powder of the present invention, the cation exchange capacity (CEC) in the present specification means ion exchange in 10 minutes per 1 g of zeolite contained in the zeolite powder (anhydrous basis). It refers to the amount of Ca. CER and CEC are
It can be measured according to the method described in Examples below.

As the CER, for example, when the zeolite powder of the present invention is used as a builder in a detergent composition,
From the viewpoint of mass capture the Ca ions of the washing water in the washing early, preferably 190mgCaCO ₃ / g or more, more preferably 200mgCaCO ₃ / g or more, further preferably 210mgCaCO ₃ / g or more. C
As the EC, for example, when the zeolite powder of the present invention is used as a builder in a detergent composition, from the viewpoint of capturing a large amount of Ca ions in the wash water even in the latter stage of washing,
Preferably 190mgCaCO ₃ / g or more, more preferably 200mgCaCO ₃ / g or more, more preferably 2
It is 10 mgCaCO ₃ / g or more. In addition, CER
When evaluated as the ratio of CER to CEC (CER / CEC), the CER / CEC ratio is preferably 0.8 or more, more preferably 0.8 to 2, and particularly preferably 0.9.
˜1.5, more preferably 0.95 to 1.2, and even more preferably 0.97 to 1.1. CER / C
The EC ratio represents how much CER is expressed in the cation exchange capacity of the zeolite powder immediately after the zeolite powder is dispersed in hard water, and the CER of the zeolite powder of the present invention is expressed. Is extremely excellent in that the average primary particle diameter and average aggregate particle diameter of zeolite are small and the particle diameter distribution is sharp.
Therefore, for example, when the zeolite powder of the present invention is used as a builder in a detergent composition, the cleaning performance of the detergent composition can be improved.

As described above, the average agglomerated particle size of the zeolite powder of the present invention is small, and when the zeolite powder is dispersed in water, the degree of turbidity of water is low. In particular, if the average aggregate particle size is 0.4 μm or less (variation coefficient 100% or less),
Water turbidity can be greatly improved. Further, even if the average agglomerated particle size is the same, if the coefficient of variation is small, that is, the width of the particle size distribution is small, the turbidity of water can be further reduced. The degree of turbidity of water due to the zeolite powder of the present invention can be determined as turbidity by the method described in Examples below. The turbidity is preferably 50% or less,
It is more preferably 40% or less, still more preferably 30% or less. If the turbidity is in the range, the transparency is apparently high, which is preferable. Therefore, for example, when the zeolite powder of the present invention is used by blending it with a detergent composition such as a powder detergent for clothes, the turbidity of washing water and initial rinse water is remarkably improved, and it becomes substantially transparent in appearance. Further, the problem that the zeolite remains on the fiber surface and falls off the powder does not occur. When the zeolite powder is used as a resin additive,
The transparency of the resin can be improved.

Loss on ignition of zeolite powder of the present invention (%)
Is preferably 40% or less from the viewpoint of dispersibility of the zeolite powder in water, although it depends on the amount of the dispersant contained therein.
0% or less is more preferable, and 28% or less is further preferable.
From the viewpoint of maintaining the crystallinity of the zeolite, 0% or more is preferable, 10% or more is more preferable, and 15% or more is further preferable. That is, 0 to 40% is preferable, and 10 to
30% is more preferable, and 15 to 28% is further preferable.
The loss on ignition can be determined by the method described in Examples below.

As the zeolite contained in the zeolite powder of the present invention, from the viewpoint of exhibiting excellent cation exchange ability, the composition of the anhydride is represented by the general formula (I): xM ₂ O.ySiO ₂ .Al ₂ O ₃ ZMeO (I) (where M is an alkali metal and Me is an alkaline earth metal)
Is preferably represented by the formula, and x = 0.2 to
4 is preferable, x = 0.5 to 2 is more preferable, and x =
0.9 to 1.5 is more preferable. y = 0.5-6 is preferable, y = 1-3 is more preferable, y = 1.5-2.5
Is more preferable. z = 0 to 0.2 is preferable, and z = 0.
001-0.1 are more preferable, z = 0.01-0.0
8 is more preferable. Further, in the formula, the alkali metal is an element belonging to Group IA of the periodic table and may be a single kind or a mixture of two or more kinds, and is not particularly limited, but the cost and the high cation exchange ability of the zeolite powder are expressed. From this point of view, sodium is preferable. The alkaline earth metal is an element belonging to Group IIA of the periodic table, and may be a single kind or a mixture of two or more kinds, and is not particularly limited, but in view of cost and expression of high cation exchange ability of the zeolite powder. From calcium and /
Alternatively, magnesium is preferred. Note that, for example, when Me is calcium and magnesium, in the formula, zM
eO represents z ₁ CaO + z ₂ MgO (z = z ₁ + z ₂ ). The same applies to xM ₂ O. Further, an element other than the elements included in the above general formula may be contained as long as the cation exchange ability, that is, CER and CEC are not reduced.

The crystal form of the zeolite is a known crystal system.
Classified into A type, P type, X type, Y type, etc.
Is exemplified. Such crystal forms are not particularly limited
However, from the viewpoint of exhibiting excellent cation exchange ability, A
Type, P type, and X type are preferable, and A type is more preferable. Well
Also, for example, in the case of type A, the X-ray diffraction pattern is known.
Type A zeolite (Joint Committee on Powder Diffra
ction Standards No.38-241)
Well attributed to other crystalline material peaks or amorphous materials
It does not matter if the halo peak is included. Well
Also, a commercially available A-type Zeora having an average primary particle size of 1 μm or more
Ito (for example, 4A type Zeoli manufactured by Zeo Builder Co., Ltd. in Korea)
X-ray with d = 0.3 nm attributed to the (410) plane of g)
Peak intensity (I ₄₁₀) Included in the zeolite powder
Zeolite I₄₁₀The ratio of the
From the viewpoint of expression, preferably 0.1 or more, more preferably
Is 0.2 or more, more preferably 0.3 or more. Na
The crystal phase may be a single phase or a mixed phase.
In addition, the zeolite powder of the present invention contains a binder other than zeolite.
A crystalline substance or an amorphous substance may be contained, but
The content of the substance is 30 from the viewpoint of the expression of cation exchange ability.
% Or less, preferably 10% or less, more preferably 2% or less
Lower is more preferable.

The content of zeolite in the zeolite powder of the present invention (calculated as anhydrous) is preferably 60 to 99.9% by weight in the case of A-type zeolite from the viewpoint of exhibiting the desired effect of the present invention. More preferably 70-9
It is 0% by weight, more preferably 70 to 85% by weight. A
In the case of zeolites other than type zeolite, preferably 70
˜99.9% by weight, more preferably 80-95% by weight,
More preferably, it is 85 to 95% by weight.

The dispersant is not particularly limited as long as it is a compound capable of exhibiting a desired effect in the zeolite powder of the present invention, and may be an inorganic compound (inorganic dispersant) or an organic compound (organic dispersant). Further, it may be a mixture of two or more kinds, but for example, when the zeolite is dispersed or dissolved in an arbitrary solvent during preparation of the zeolite powder of the present invention, it has a functional group that easily interacts with the zeolite surface in the solvent. Compounds are preferred. Although not particularly limited, an organic dispersant is preferable from the viewpoint of dispersibility of the obtained zeolite powder. It is presumed that the effect of the dispersant to suppress the aggregation between the zeolite particles is exhibited by the interaction between the zeolite and the dispersant on the surface of the zeolite particles.

The inorganic dispersant is not particularly limited, but carbonates, sulfates, silicates, aluminates, phosphates, or nitrates are preferable from the viewpoint of dispersibility of the obtained zeolite powder. More preferred are carbonates, sulfates, silicates, aluminates, or phosphates, such as sodium carbonate, sodium sulfate, sodium silicate,
Examples thereof include sodium aluminate and potassium pyrophosphate.

A silane compound such as a silane coupling agent or a silylating agent may be used as the dispersant. The silane compound is not particularly limited, but from the viewpoint of dispersibility of the obtained zeolite powder in water, a silane compound containing a hydrophilic group is preferable, and for example, 3-glycidoxypropyltriethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloxypropyltriexisilane and the like.

The molecular weight of the organic dispersant is not particularly limited, but is preferably 400 or more, more preferably 1
000 or more, more preferably 10,000 or more. When the molecular weight of the dispersant is in such a range, aggregation between zeolite particles is effectively suppressed, which is preferable. The molecular weight of the dispersant is preferably 1,000,000 or less, more preferably 500000 or less, and further preferably 100000.
It is the following. If the molecular weight of the dispersant is in such a range, it is possible to effectively suppress agglomeration due to crosslinking between zeolite particles,
Further, it is preferable to use a mixed solution in which a dispersant is dissolved (or dispersed) in the preparation of the zeolite powder of the present invention, because the viscosity is appropriate and the mixing property with the zeolite particles is good. That is, the molecular weight of the dispersant is preferably 400 to 1,000,000, more preferably 1,000 to 500,000, and further preferably 10,000.
˜100,000. When the dispersant is a polymer compound (molecular weight of 10,000 or more), the molecular weight is a weight average molecular weight and can be measured by GPC (gel permeation chromatography) according to known conditions.

The functional group is not particularly limited, but is preferably an OR group, a COOR group, a SO ₃ R group,
Examples thereof include PO ₄ R group, CO group, CONH group, NR ₃ group and NR ₄ group. Among them, OR group and COOR group are more preferable, and COOR is still more preferable. In addition,
One or two of these functional groups can be added to the compound that is the dispersant.
There may be more than one species. Further, in the above, R is at least 1 selected from the group consisting of a saturated or unsaturated organic group having 1 to 22 carbon atoms, a hydrogen atom and an alkali metal atom.
It is a seed. Examples of the saturated or unsaturated organic group having 1 to 22 carbon atoms include an ethyl group, a phenyl group, a hexyl group and a dodecyl group, and examples of the alkali metal atom include sodium and potassium. In addition, these functional groups may constitute a main chain of a compound used as a dispersant, or may constitute a side chain.

As the organic dispersant used in the present invention, compounds having the above-mentioned properties are suitable, and specific examples thereof include vinyl polymers, polyesters, polyethers, polyamides, polyalkyleneimines and the like, and particularly vinyl polymers. preferable. Examples of the vinyl polymer include (meth) acrylic acid and salts thereof, styrenecarboxylic acid and salts thereof, maleic acid and salts thereof, itaconic acid and salts thereof, styrenesulfonic acid and salts thereof, and (meth) allylsulfone as vinyl monomers. Acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, vinylsulfonic acid and its salts, vinyl alcohol, (meth) acrylic acid 2-
Hydroxyethyl, 2-hydroxyethyl (meth) acrylamide, 4-hydroxymethylstyrene, mono-2-[(meth) -acryloyloxy] ethyl phosphate, 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride, vinyl chloride Benzyltrimethylammonium, ethyl sulfate 2-[(meth) acryloyloxy] ethyldimethylethylammonium chloride 3-
Examples thereof include [(meth) acrylamide] propyltrimethylammonium, diallyldimethylammonium chloride, N-vinylpyrrolidone, and vinylpyridine.
Specific examples of the vinyl polymer include polyethylene glycol monomethacrylic acid ester / methacrylic acid copolymer described in Production Example 2 described below, which uses (meth) acrylic acid and salts thereof as vinyl monomers. Polyesters such as those obtained by polycondensing terephthalic acid or succinic acid with divalent carboxylic acids and polyethylene glycol, polyethers such as polyethylene glycol, polyoxyethylene, polyoxyethyleneoxypropylene, etc. Polyoxyethylene having an amino group and polycondensation of a divalent carboxylic acid such as terephthalic acid or succinic acid. Examples of polyalkyleneimine include polyethyleneimine and poly (N-acetylethyleneimine).

The content of the dispersant in the zeolite powder of the present invention is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, from the viewpoint of manifesting the desired effects of the present invention. More preferably, it is 5 to 15% by weight.

Further, the zeolite powder of the present invention may contain other components as long as the desired effects of the present invention are not impaired. As the component, for example,
Examples include mixed solvents and monomers. The content of the component in the zeolite powder of the present invention may be appropriately selected within the range in which the desired effect of the component is obtained.

Next, the method for producing the zeolite powder of the present invention will be described. The zeolite powder of the present invention may be such that the zeolite particles and the dispersant are contained together in such a manner that the aggregation of the zeolite particles can be suppressed, and the existence form of the zeolite particles and the dispersant in the zeolite powder is particularly Although not limited, it is preferable to use zeolite particles having the entire surface substantially covered with a dispersant. The method for producing zeolite powder of the present invention described below is effective for producing such suitable zeolite powder.

The zeolite used as a raw material in the present invention is not particularly limited, and a commercially available zeolite may be used, or a zeolite obtained by a known method may be used. Preferably, a zeolite whose anhydrous composition can be represented by the above general formula (I) is used. Also,
From the viewpoint of suppressing the crystallinity deterioration of the zeolite due to the mixing and pulverization performed in the manufacturing process of the zeolite powder, a zeolite having a small average primary particle size is preferable, specifically, 2 μm or less, more preferably 1 μm or less, particularly It is preferably 0.1 μm or less, more preferably 0.05 μm or less. The coefficient of variation of the average primary particle size is preferably 100% or less, more preferably 70% or less, particularly preferably 50% or less, and further preferably 35% or less, from the viewpoint of suppressing the crystallinity deterioration of zeolite due to pulverization. Is preferred. If the average primary particle size and its coefficient of variation are in such a range, the decrease in crystallinity of the zeolite due to the mixing and pulverization performed in the manufacturing process of the zeolite powder is suppressed, and the obtained zeolite powder may exhibit an excellent cation exchange ability. . The level of decrease in crystallinity of the zeolite is represented by the crystallinity residual rate (%), preferably 60 to 100%, more preferably 70%.
~ 100%. The crystallinity residual rate can be determined by the method described in Examples described later.

The zeolite powder of the present invention is obtained by mixing zeolite and a dispersant. The mixing method of the zeolite and the dispersant is not particularly limited,
For example, if desired, the atomized (crushed) zeolite and the dispersant may be simply mixed, or may be mixed by allowing the dispersant to coexist in the zeolite crushing step. From the viewpoint of simplifying the production process and improving the dispersibility of the obtained zeolite powder, it is preferable to mix them by coexisting with a dispersant in the pulverizing process of zeolite. The other components may be appropriately added and mixed in the step of mixing the zeolite and the dispersant.

The zeolite and the dispersant may be mixed by dry mixing or wet mixing using a solvent.
From the viewpoint of adsorption efficiency of the dispersant on the zeolite surface, wet mixing is preferably performed. The solvent used for wet mixing may be an aqueous solvent or a non-aqueous solvent, and depends on the type of the dispersant, but from the viewpoint of adsorption efficiency of the dispersant on the zeolite surface, a solvent capable of uniformly dissolving the dispersant to be used. Is preferred. Further, from the viewpoint of efficiently adsorbing the dispersant to the surface of the zeolite, which is hydrophilic, a hydrophilic solvent is preferable and is not particularly limited. For example, water, alcohol solvent, acetone, etc., alone or in combination of two or more. It is preferable to mix and use. Particularly, from the viewpoint of improving the dispersibility of the zeolite powder of the present invention, methanol, ethanol, alcohol solvents such as isopropanol are preferable,
Ethanol is more preferred. That is, as a method for producing the zeolite powder of the present invention, a method including a step of mixing a dispersant and zeolite in an alcohol solvent, especially ethanol is suitable, and the method is included in the present invention.

The method of pulverizing the zeolite in the case where the dispersant is mixed by coexisting in the pulverizing step of the zeolite is not particularly limited and may be wet pulverization or dry pulverization, but the dispersibility of the zeolite powder is improved. From the viewpoint of, wet pulverization is preferable. In the pulverization, for example, the Chemical Engineering Handbook (Maruzen, 1
(988) Fifth edition 826 to 838 can also be used the crusher.

As the dispersion medium used for wet pulverization, in addition to water, the above alcohol solvents such as ethanol can be used alone or in admixture of two or more. From the viewpoint of improving the dispersibility of the zeolite powder, alcohol solvents such as methanol, ethanol and isopropanol are preferable, and ethanol is more preferable. When wet milling, the zeolite concentration in the slurry is 5% by weight from the viewpoint of productivity.
The above is preferable, 10% by weight or more is more preferable, and 15
More preferably, it is at least wt%. Further, the zeolite concentration in the slurry is 60 from the viewpoint of handleability of the slurry during wet pulverization and the viewpoint of preventing reaggregation of the zeolite particles after pulverization.
It is preferably not more than 50% by weight, more preferably not more than 55% by weight, still more preferably not more than 50% by weight. That is, the concentration of zeolite in the slurry during wet grinding is preferably 5 to 60% by weight, more preferably 10 to 55% by weight,
It is more preferably 15 to 50% by weight.

The mixing ratio of the zeolite and the dispersant is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and further preferably 8 parts by weight or more with respect to 100 parts by weight of the zeolite. Within this range,
It is preferable because zeolite powder having high dispersibility can be obtained.
From the viewpoint of cost and productivity, the mixing ratio of the zeolite and the dispersant is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 100 parts by weight of the zeolite. It is 15 parts by weight or less. That is, as the mixing ratio of the zeolite and the dispersant, the dispersant is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and further preferably 8 to 15 parts by weight with respect to 100 parts by weight of the zeolite. is there.

It is preferable to mix an appropriate amount of zeolite and a dispersant to eliminate excess and deficiency of the dispersant, but when it is necessary to remove the excess dispersant, it is not particularly limited, but it is filtered and washed. May be removed by thermal decomposition,
You may remove by methods, such as deaeration.

The mixing temperature is not particularly limited, but from the viewpoint of the fluidity of the reaction liquid (slurry), it is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. From the viewpoint of energy load, 100 ° C or lower is preferable, and 80 ° C
The following is more preferable. The mixing time is not particularly limited, but from the viewpoint of dispersibility of the obtained zeolite powder, it is preferably 1 minute or longer, more preferably 3 minutes or longer, still more preferably 5 minutes or longer. From the viewpoint of productivity, it is preferably 24 hours or less, more preferably 2 hours or less, still more preferably 1 hour or less.

By wet mixing the zeolite and the dispersant,
Alternatively, when mixed by wet pulverization, the zeolite powder of the present invention can be obtained by removing the solvent and excess dispersant. Removal of the solvent may be carried out by using a known drying method, and although not particularly limited, it is preferable to use an electric dryer, a spray dryer, a freeze dryer, a vacuum dryer, etc., and reduced pressure drying is preferable. . The drying temperature is not particularly limited, but is 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 50 ° C. or lower, from the viewpoint of maintaining the crystallinity of the zeolite.

The zeolite powder of the present invention is used for detergent builders, water treatment agents, papermaking fillers, resin fillers, oxygen / nitrogen separators, adsorbents, catalyst carriers, horticultural soil conditioners, abrasives and the like. It is preferably used as a builder for detergents.

[0037]

[Examples] The methods for measuring physical properties in Examples and Comparative Examples are summarized below.

(1) Average agglomerated particle size Using a laser scattering particle size distribution meter (LA-920 manufactured by Horiba, Ltd.), the sample powder had a refractive index of 1.2, an ultrasonic wave intensity of 7, an ultrasonic wave irradiation time of 1 minute, and a stirring speed of 4 Under the conditions described above, water was used as the dispersion medium, and the average agglomerated particle size (μm) and the coefficient of variation (%) were determined on the volume basis. The coefficient of variation was calculated by the following formula. Coefficient of variation (%) = 100 × standard deviation (μm) / average aggregate particle size (μm)

(2) Average primary particle size Electron emission type high resolution scanning electron microscope (FE-SEM, Hitachi S-4000) scanning electron microscope (SEM) photograph of sample powder (magnification: 1000 to 10000 times) ) Is further enlarged (magnification: 40000 to 400000 times), the primary particle size (100 or more particles) is measured using a digitizer (Graphtec made, Digitizer KW3300), and all the obtained measured values are population. The number average value [average primary particle size (μ
m)] and the coefficient of variation (%) were determined. When the shape of the zeolite primary crystal was not spherical, the average value of the major axis length and the minor axis length was taken as the primary particle size. The coefficient of variation was calculated by the following formula. Coefficient of variation (%) = 100 × standard deviation (μm) / average primary particle size (μm)

(3) X-ray peak intensity, crystal morphology and crystalline residual ratio Powder X-ray diffractometer (RINT2500VPC manufactured by Rigaku Denki, light source Cu K
α, tube voltage 40 kV, tube current 120 mA), 2θ = 5
In the range of 40 °, the scanning interval is 0.01 °, the scanning speed is 10 ° /
min. The sample powder was measured at room temperature (20 ° C.) under conditions of a divergence vertical restriction slit of 10 mm, a divergence slit of 1 °, a light receiving slit of 0.3 mm, and a scattering slit of automatic. Crystallinity was evaluated from the strongest X-ray peak intensity of zeolite.
In the case of the A-type zeolite, the X-ray peak intensity (I ₄₁₀ ) with the interplanar spacing d = 0.3 nm attributed to the (410) plane was used for the evaluation of crystallinity. The crystallinity residual rate (%) after crushing with respect to before crushing was calculated by the following formula. Crystallinity residual rate (%) = [Amount of dispersant added (parts by weight) + 10
0] of the zeolite powder after × milling I ₄₁₀ (cps) / milled before zeolite powder I ₄₁₀ (cps)

The crystal form of zeolite is A type zeolite (Joint Committee on Powder) whose X-ray diffraction pattern is known.
Diffraction Standards No.38-241), and if it is substantially the same, it was set to A type.

(4) Ignition loss The sample powder was put into a magnetic crucible that had reached a constant weight, which was prebaked in an electric furnace at 800 ° C. for 1 hour and allowed to cool in a desiccator.
It was precisely weighed. Then, this was ignited in an electric furnace at 800 ° C. for 1 hour and then allowed to cool in a desiccator, and the weight (g) that reached a constant weight was precisely weighed to determine the ignition loss (%).

(5) Cation exchange capacity CaCl ₂ aqueous solution (100 ppm in terms of CaCO ₃ ) 1
0.04 g of the sample powder was added to 00 mL, and the mixture was stirred at 20 ° C. for 1 or 10 minutes. Then, it filtered with a 0.2-micrometer disposable filter, and Ca concentration in the obtained filtrate 10mL was measured with the hardness titrator (made by Kyoto Electronics Manufacturing). The cation-exchanged Ca weight (calculated as CaCO ₃ ) per 1 g of zeolite (calculated as anhydrous) was defined as the cation-exchange capacity (mgCaCO ₃ / g). Cation exchange time 1
Cation exchange capacity (CER),
The cation exchange capacity (CEC) was defined as the cation exchange capacity for 10 minutes of cation exchange time. In addition, the ratio (CER / C
EC) was calculated.

(6) Turbidity The sample powder was added to water, and the mixture was mixed with water (hardness:
The turbidity (%) of the sample solution (zeolite anhydrous concentration: 0.01% by weight) obtained by stirring in 4 ° for 10 minutes was measured by a turbidimeter (Murakami Color Research Laboratory, reflection transmission meter HR-100). ) Was used at room temperature (20 ° C.).

(7) Zeolite content When it is judged from the X-ray diffraction pattern of the sample powder that the crystalline substance or the amorphous substance is not substantially contained, the content is from 100% to the ignition loss ( %) Was calculated as a value calculated by subtracting (%) (the unit of the content is% by weight).

Production Example 1 Synthesis of Zeolite Sodium aluminate aqueous solution (Na ₂ O; 21.01% by weight, Al ₂ O ₃ ; 28.18% by weight) 8 k in a 20 L stainless steel container
g, stainless steel propeller type stirring blade (80 mm long,
2.74 kg of polyethylene glycol (PEG600, molecular weight 600, Wako Pure Chemical Industries, Ltd.) at room temperature (20 ° C) with stirring (Motor RINGCONE NRXM-60, Matsushita Electric Works) with stirring (Bayer max)
Was added and heated to 50 ° C. (20 minutes). In this solution, 50
No. 3 water glass heated to ℃ (Na ₂ O; 9.68 wt%, SiO 2
₂ ; 29.83 wt%, made by Osaka Silica Co., Ltd., 8.96 kg was dripped over 5 minutes using a roller pump (MASTERFLEX 7018-20, made by COLE-PERMER). After completion of dropping, the mixture was further stirred for 10 minutes, heated to 80 ° C. over 20 minutes, and then aged for 60 minutes. The obtained zeolite aqueous solution was filtered (filter paper No.
2), wash with water (until the pH of the filtrate exceeds 12), then 1
It was dried at 00 ° C. for 13 hours and crushed with a cooking cutter for 1 minute. From the powder X-ray diffraction measurement of the obtained zeolite,
It was confirmed that the A-type zeolite was generated, and substantially no crystalline substance or amorphous substance was contained.

In the following, commercially available zeolite was also used. As the zeolite, 4A type zeolite manufactured by Korea Zeobuilder Co., Ltd. was used.

Production Example 2 Synthetic Dispersant 20 g of polyethylene glycol (EO addition mole number: 23) monomethacrylic acid ester (NK ester M230G, Shin Nakamura Chemical Co., Ltd.) and 80 g of methacrylic acid were dissolved in 200 g of ethanol, and the mixture was placed under a nitrogen atmosphere. Stir for 10 minutes. To this, 2, 2 '
-Azobis- (2,4-dimethylvaleronitrile) (V-
65, Wako Pure Chemical Industries, Ltd.) 11 g and heated under a nitrogen atmosphere,
The stirring was continued for 6 hours while maintaining the temperature at 75-80 ° C. Thereafter, the temperature was returned to room temperature, reprecipitation purification was performed with hexane, and drying was performed to obtain a dispersant (polyethylene glycol monomethacrylic acid ester / methacrylic acid copolymer). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 38,000 (calculated as polyethylene glycol). The GPC measurement conditions were: column: 2 TSK GMPWXL (manufactured by Tosoh), eluent: 0.
2 mol / L phosphate buffer / acetonitrile = 9/1, detector:
Differential refractometer, temperature: 40 ° C.

Example 1 1.6 g of a dispersant (10 parts by weight based on 100 parts by weight of zeolite) was completely dissolved in 62 g of ethanol, and 16 g of the zeolite synthesized in Preparation Example 1 was added to the solution to homogenize it using a spatula. Mixed. The obtained slurry was put into a batch type sand mill (made by AIMEX) with a capacity of 1 L together with 500 g of zirconia beads having a diameter of 0.5 mm, and the disc rotation speed was 15
It was ground at 00 rpm for 40 minutes. The average agglomerated particle size of zeolite in the ground slurry was 0.36 μm (coefficient of variation 25%). This slurry was dried under reduced pressure at room temperature (20 ° C.) for 1 day and then crushed lightly in a mortar to obtain a zeolite powder. Various physical properties were measured using the obtained zeolite powder as a sample powder.

Example 2 1.6 g of a dispersant (10 parts by weight based on 100 parts by weight of zeolite) was completely dissolved in 62 g of ethanol, and 16 g of a commercially available zeolite (4A type manufactured by Zeo Builder Co., Korea) was added to the solution to prepare a spatula. Used to mix uniformly. The obtained slurry was put together with 500 g of zirconia beads having a diameter of 0.5 mm in a batch type sand mill (made by AIMEX) having a volume of 1 L, and pulverized at a disc rotation speed of 1500 rpm for 60 minutes. The average aggregate particle size of the zeolite in the ground slurry is 0.35 μm
(Variation coefficient 29%). This slurry at room temperature,
After being dried under reduced pressure for 1 day, it was lightly crushed into a mortar to obtain zeolite powder. Various physical properties were measured using the obtained zeolite powder as a sample powder.

Comparative Example 1 A slurry prepared by dispersing 16 g of the zeolite synthesized in Preparation Example 1 in 64 g of water was placed in a batch type sand mill (made by AIMEX) having a volume of 1 L together with 500 g of beads made of zirconia having a diameter of 0.5 mm, and a disk rotation speed of 1500. Milled for 25 minutes at rpm. The average aggregate particle size of the zeolite in the ground slurry is 0.37 μm
(Variation coefficient 25%). This slurry at room temperature,
After being dried under reduced pressure for 1 day, it was lightly crushed into a mortar to obtain zeolite powder. Various physical properties were measured using the obtained zeolite powder as a sample powder.

Comparative Example 2 16 g of commercially available zeolite (Korean Zeobuilder, 4A type)
A slurry in which 64 g of water was dispersed was placed in a batch type sand mill (made by AIMEX) with a capacity of 1 L together with 500 g of zirconia beads having a diameter of 0.5 mm, and the disk rotation speed was 1500 rpm.
Grinded for 40 minutes. The average agglomerated particle size of the zeolite in the ground slurry was 0.34 μm (variation coefficient 24%). This slurry was dried under reduced pressure at room temperature for 1 day and then crushed lightly in a mortar to obtain a zeolite powder. Various physical properties were measured using the obtained zeolite powder as a sample powder.

Comparative Example 3 Various physical properties were measured using the zeolite synthesized in Production Example 1 as a sample powder.

Comparative Example 4 Various physical properties were measured by using a commercially available zeolite (4A type manufactured by Zeo Builder Co., Ltd.) as a sample powder.

The zeolites in the zeolite powders obtained in Examples 1 and 2 and Comparative Examples 1 and 2 and the zeolites in Comparative Examples 3 and 4 were type A zeolite as a result of X-ray diffraction measurement, and were substantially It was confirmed that no crystalline substance or amorphous substance was contained. The obtained results are summarized in Table 1.

[0056]

[Table 1]

From the results shown in Table 1, the zeolite powders of Examples 1 and 2 of the present invention were compared with the zeolite powders of Comparative Examples 1 and 2 and the zeolites of Comparative Examples 3 and 4 as an index of dispersibility in water. It can be seen that the average agglomerated particle size is small, the cation exchange rate is excellent, and the turbidity of water is low.

[0058]

EFFECT OF THE INVENTION The present invention provides a zeolite powder which exhibits a high cation exchange rate and has little water turbidity when dispersed in water. The zeolite powder is particularly suitable as a builder for detergents.

Claims (5)

[Claims] 1. A method comprising a zeolite and a dispersant,
The average primary particle size is 0.2 μm or less (variation coefficient 100% or less) and the average aggregate particle size is 1 μm or less (variation coefficient 100%).
The following) zeolite powder. 2. The zeolite powder according to claim 1, wherein the ratio (CER / CEC) of the cation exchange rate (CER) to the cation exchange capacity (CEC) is 0.8 or more. 3. The zeolite powder according to claim 1, which has an average agglomerated particle size of 0.4 μm or less (variation coefficient of 100% or less). 4. The turbidity (20 ° C.) of water when dispersed in water (dispersed so as to have a zeolite anhydrous concentration of 0.01% by weight) is 50% or less. The described zeolite powder. 5. The method for producing a zeolite powder according to claim 1, comprising a step of mixing a dispersant and zeolite in an alcohol solvent.