JP4793863B2 - Method for producing interlayer cross-linked clay porous body - Google Patents

Description

  The present invention relates to an interlayer crosslinked clay porous body, and more particularly to a method for producing an interlayer crosslinked clay porous body capable of obtaining a mesoporous interlayer crosslinked clay porous body having a pore size between microporous and macroporous.

Porous materials are roughly classified into microporous porous materials having a pore size of nanometer or less, mesoporous porous materials having a pore size of about 2 to 50 nm, and macroporous porous materials having a pore size of 50 nm or more.
Of these porous bodies, mesoporous porous bodies have the ability to adsorb polymer substances, and are being developed for utilization purposes such as gas condensation adsorption and removal of impurities in solutions.
The field of application is not limited to the material field, but covers a wide range of fields such as environmental engineering, food industry, and agriculture.

Specific applications include, for example, the following applications: (a) A brewing agent for brewing products
(B) Humidity control material, anti-condensation material, dehumidifying material
(C) Enzyme carrier for wastewater purification material
(D) Sustained release materials such as fertilizers, insect repellents, and agricultural chemicals
It is expected as a suitable material for applications requiring pores of about 2 to 15 nm.

Here, the suspending agent removes turbidity of brewed products such as soy sauce and liquor by protein adsorption. To be released.
The enzyme carrier for waste water purification material is a material that decomposes dirt in waste water by enzyme, and the sustained release material contains fertilizer or agrochemical in advance and gradually releases it.

Conventionally, zeolite, activated carbon or silica gel has been widely used as the porous body, but these belong to the microporous porous body, and the pore size is too small to adsorb the polymer substance. It is not suitable for use.
However, a mesoporous porous material is also known for silica gel. However, silica gel has no water resistance, and even if it is mesoporous, it cannot be used for the above applications.

On the other hand, a porous layered interlaminar clay (pillared clay) is a chemically stable inorganic substance that has water resistance and chemical resistance, and can be regenerated by heating or chemical treatment, and is a material suitable for the above applications.
However, the conventional inter-layer crosslinked clay porous body is a microporous porous body and cannot be used as a material for the above applications.
Therefore, research is being conducted to increase the pore size in the inter-layer crosslinked clay porous body.
For example, by adding a water-soluble polymer such as PVA (polyvinyl alcohol) as a crosslinking aid to a swellable clay mineral dispersed in a solvent and interposing it between layers of clay mineral, the layer spacing is kept wide, and A production method has been developed in which an interlayer-crosslinked clay mineral is cross-linked with an inorganic material to obtain a porous intercalated clay (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5). ).

Japanese Patent No. 2507903 Japanese Examined Patent Publication No. 62-46490 JP-A-4-254410 Japanese Examined Patent Publication No. 7-106953 Japanese Patent Publication No. 2-28543

However, these production methods have a problem that it is difficult to separate and recover the product by filtration and washing after synthesis, and the product must be dried for a long time without performing centrifugation or separation.
In the case of collecting the target product by the former centrifugation, there is a problem that the recovery of the target product itself by centrifugation is very troublesome. Since it is forcibly removed, the layers are shrunk when it is subsequently fired, resulting in a decrease in layer spacing and a decrease in the pore size of the resulting porous body.

  On the other hand, in the case of the latter method in which the target product is recovered by long-time drying, surplus components such as NaCl remain, resulting in a decrease in physical properties of the resulting interlayer crosslinked clay porous body or generation of secondary products. Inevitable. Furthermore, the pore diameter of the interlayer crosslinked clay porous body obtained by this method is also small, which is still insufficient for a mesoporous material.

  In the background of the above circumstances, the present invention is capable of separating and recovering the target product by general filtration and washing, and the pore size of the resulting porous body is larger than that of the conventional interlayer-crosslinked clay porous body, It aims at providing the manufacturing method of the interlayer bridge | crosslinking clay porous body which can obtain the interlayer bridge | crosslinking clay porous body which can be used conveniently for the illustrated use.

  Thus, the present invention provides a pillar of a reaction product of a carboxylate having a hydrocarbon chain having 11 to 17 carbon atoms as a hydrophobic group or a carboxylate having a benzene or benzene derivative as a hydrophobic group and polyaluminum chloride. The material is characterized in that it is inserted between layers of a swellable clay mineral dispersed in a water-soluble polymer solution, and then the clay mineral layer is cross-linked with the pillar material.

  According to a second aspect of the present invention, in the first aspect, the water-soluble polymer is one or more of PVA, PEO, and PEG.

  According to a third aspect of the present invention, in any one of the first and second aspects, the swellable clay mineral is a smectite or a swellable mica mineral.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the clay mineral in which the pillar material is inserted between layers is separated and recovered by filtration from a solvent, and then heat-treated at 450 to 950 ° C. .

Effects and effects of the invention

  As described above, the present invention uses a carboxylate having a hydrocarbon chain having 11 to 17 carbon atoms as a hydrophobic group or a reaction product of a carboxylate having a benzene or benzene derivative as a hydrophobic group and polyaluminum chloride as a pillar material. , Interspersed between layers of swellable clay minerals dispersed in a water-soluble polymer solution, and then a cross-linking reaction between the layers of the clay minerals with this pillar material to obtain an interlayer crosslinked clay porous body It is.

FIG. 1 schematically shows a typical example of the production method of the present invention.
In the figure, 10 represents a swellable clay mineral. One unit is composed of a layer composed of tetrahedral SiO ₄ and an octahedral layer composed of Al, Mg, O, and OH. Layers 12 and 12 are stacked.
Each layer 12 has a negative charge due to Al → Mg substitution or lattice defects, and exchangeable cations 14 such as Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ (hereinafter represented by Na ⁺ ) are present between the layers 12. It is surrounded by water molecules.

In the present invention, as shown in (IV), a carboxylate (a carboxylate having a hydrocarbon chain having 11 to 17 carbon atoms as a brine group or a carboxylate having benzene or a benzene derivative as a brine group) 16 and A reaction product 20 with polyaluminum chloride 18 which is a polycationic inorganic substance is inserted between layers 12 of swellable clay mineral 10 in which a pillar material is dispersed in a solution of a water-soluble polymer such as PVA (polyvinyl alcohol). It will be in the state.
In FIG. 1, 22 represents the water-soluble polymer.

The water-soluble polymer 22 is taken in between the layers 12 and 12 in the same manner as water, and acts as a support rod with respect to them and keeps the distance between the layers 12 and 12 wide.
The reactant 20 described above is taken in between the layers 12 and 12 that are kept wide in this manner, and inserted between the layers 12.

It is considered that the reactant 20 is formed by the reaction of the polyaluminum chloride and the carboxylate in a form in which the chloride anion of the polyaluminum chloride is replaced with the carboxylate anion of the carboxylate. Therefore, it is considered that the reactant 20 is formed in a form in which a plurality of carboxylate anions having a large molecular weight are added to polyaluminum chloride. The reactant 20 is bulky as a whole, and the layers 12 and 12 It is considered that the bulky reactant 20 is taken in between the layers 12 and 12 so that the layers 12 and 12 are more effectively spread or maintained.
Moreover, the reaction product 20 is imparted with hydrophobicity as a whole by addition of a carboxylate anion.

In (IV), the following method can be suitably employed as a method for inserting the reactant 20 between the layers 12 and 12.
That is, first, the swellable clay mineral 10 is mixed and dispersed in a water-soluble polymer solution in which the water-soluble polymer 22 is dissolved in an aqueous solvent.
(II) shows the state at this time, and the water-soluble polymer 22 such as PVA is taken in between the layers 12 and 12 on the same principle that water is taken in between the layers 12 and 12. . Then, the polymer 22 taken in between the layers 12 and 12 functions as a support rod, widens the space between the layers 12 and 12 and holds it at a wide interval.

Next, by adding polyaluminum chloride as a polycation, the exchangeable cation 14, typically Na ⁺ ion, incorporated between layers 12 and 12 is ion-exchanged with polyaluminum chloride. The cations of the polyaluminum chloride 18 are inserted between the layers 12 and 12 (intercalation). (III) represents the state at this time.
Thereafter, a carboxylate is added to the solution to react the carboxylate with polyaluminum chloride.
In this way, as shown in (IV), the reactant 20 can be inserted between the layers 12 and 12, that is, inserted between the layers.

In the present invention, hydrophobicity can be imparted to the swellable clay mineral 10 itself as described above by this step (IV). Therefore, the swellable clay mineral 10 obtained in the step (IV) is water as a solvent. Separation from is very easy.
Therefore, the swellable clay mineral 10 in the step (IV) can be easily recovered by centrifugation or other separation methods, but in the present invention, the swellable clay mineral 10 in the step (IV) is preferably separated by filtration. Recover this by

  In other words, since the swellable clay mineral 10 in the step (III) has high hydrophilicity in the water-soluble polymer 22 and the polyaluminum chloride 18 itself, the swellable clay mineral 10 itself is also extremely hydrophilic and has water. It is very difficult to separate the swellable clay mineral 10, and the swellable clay mineral 10 is in a mixed state in the water solvent in an integrated state, and as a whole, it is in a muddy state.

Therefore, in the conventional manufacturing method, as shown in (IV) ′, centrifugation is performed to forcibly separate and recover the clay mineral 10 of (III).
However, this centrifugation requires many operations and is a very troublesome operation, and it is actually a difficult method to adopt when attempting to mass-produce the final interlayer crosslinked clay porous body. That is, this method is not suitable for mass production.
In addition, when such centrifugation is performed, most or a part of the water-soluble polymer 22 existing between the layers 12 and 12 and maintaining a large distance between the layers is removed from between the layers 12 together with water. Therefore, the space between the layers 12 and 12 is reduced to narrow the gap between the layers (see (V) ′), and the pores (pore diameter) of the interlayer crosslinked clay porous body 15 obtained by subsequent firing are also reduced.

In contrast, in the present invention, since the hydrophobicity is imparted to the swellable clay mineral 10 of (IV) by the reactant 20, it can be easily performed by ordinary filtration and washing without difficult and forced centrifugation. The swellable clay mineral 10 can be separated and recovered.
At this time, a part of the water-soluble polymer 22 existing between the layers is also removed between the layers 12 and 12 together with the water between the layers, but the bulky reactant 20 is present between the layers 12 and 12. Since it is still present, the gap between the layers 12 and 12 is still maintained at a large distance.
Therefore, according to the present invention, the mesoporous interlayer cross-linked clay porous body 15 having a larger pore diameter than that of the prior art can be obtained by subsequent firing.
In the firing, polyaluminum chloride serves as an alumina column to crosslink layers 12 and 12 to form a porous intercalated clay.

According to the present invention as described above, a mesoporous interlayer-crosslinked clay porous body (pore diameter can be about 13 nm at a peak diameter) can be produced at low cost by a simple operation.
In addition, since the excess components can be removed when the target clay mineral is recovered in the production process, the properties of the inter-layer cross-linked clay porous body are good, and an inter-layer cross-linked clay porous body of excellent quality can be obtained.
In the present invention, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, and sodium oleate can be suitably used as a carboxylate having a hydrocarbon chain having 11 to 17 carbon atoms as a hydrophobic group.
On the other hand, sodium benzoate and sodium salicylate can be suitably used as a carboxylate having benzene or a benzene derivative as a hydrophobic group.
In the present invention, one or more of PVA, PEO (polyethylene oxide) and PEG (polyethylene glycol) can be suitably used as the water-soluble polymer (Claim 2), and the swellable clay mineral can be used. Smectite or a swellable mica mineral can be suitably used (Claim 3).

  Moreover, the said baking can be performed at the temperature of 450-950 degreeC (Claim 4).

<Example 1>
(Raw material adjustment)
Synthetic hectorite (Topy Industries, Ltd., NHT-70B, CEC: 0.7 meq / g), which is a swelling clay mineral, was dispersed in distilled water to obtain a 6.6 mass% clay suspension. Polyvinyl alcohol (Wako Pure Chemical Industries, complete saponification type, average polymerization degree: 900 to 1100), which is a water-soluble polymer, was dissolved by heating in distilled water to obtain a 10 mass% PVA solution. A 6.6 mass% clay suspension and a 10 mass% PVA solution were mixed at a weight ratio of 3: 1 to obtain a clay 5.0 mass% -PVA 2.5 mass% solution (hereinafter, clay solution H).
Polyaluminum chloride solution (Taki Chemical Co., Ltd., Takibaine # 1500), a chlorine-containing polycation, is diluted so that Al becomes 0.1 mol with respect to 100 g of solution, and Al 0.1 mol / 100 g solution (hereinafter referred to as Al solution) It was.
(Intercalation)
Add 210g of Al solution (weight ratio 1 in terms of Al ₂ O ₃ to clay content in clay solution) to 200g of clay solution, stir for 1 hour, and hold for 36 hours in a constant temperature bath at 80 ° C. Calated.
(Give hydrophobicity)
Fatty acid salt solution (21.79 g of sodium laurate dissolved in 200 g of distilled water) was added to the solution after the intercalation, stirred for 1 hour, and then kept in a constant temperature bath at 80 ° C for 24 hours to make it hydrophobic Gender was added.
(Solid-liquid separation / firing)
The solution imparted with hydrophobicity was washed by filtration, dried at room temperature, and then subjected to a heat baking treatment at 320 ° C. for 4 hours and at 600 ° C. for 4 hours to obtain an interlayer crosslinked clay porous body.

<Example 2>
The same as Example 1 except that the aromatic carboxylate solution (15.69 g of sodium salicylate dissolved in 200 g of distilled water) was used in place of the fatty acid salt solution in Example 1 (Granting hydrophobicity). In the step, an interlayer crosslinked clay porous body was obtained.

<Example 3>
In Example 1 (intercalation), the same procedure as in Example 1 was repeated except that the Al solution was 105 g (weight ratio 0.5 in terms of Al ₂ O _{3 with} respect to the clay content in the clay solution). A crosslinked clay porous body was obtained.

<Example 4>
(Raw material adjustment)
Montmorillonite (Kunimine Kogyo Co., Ltd., Kunipia F, CEC: 1.15 meq / g), a swellable clay mineral, was dispersed in distilled water to obtain a 2.2 mass% clay suspension. The clay suspension and the 10 mass% PVA solution described in Example 1 were mixed at a weight ratio of 9: 1 to obtain a clay 2.0 mass% -PVA 1.0 mass% solution (hereinafter, clay solution M).
The polyaluminum chloride solution described in Example 1 was used as the stock solution to obtain an Al 0.46 mol / 100 g solution (hereinafter referred to as Al stock solution).
(Intercalation)
After adding 45 g of Al raw solution (500 wt% in terms of Al ₂ O _{3 with} respect to the clay content in the clay solution) to 500 g of clay solution, stirring for 1 hour, and holding in a constant temperature bath at 80 ° C. for 36 hours Intercalation was performed.
Both (hydrophobicity imparting) and (solid-liquid separation / firing) were obtained by the same steps as in Example 1 to obtain an interlayer crosslinked clay porous body.

<Example 5>
In Example 4 (intercalation), the same procedure as in Example 4 was repeated except that the Al raw solution was 23 g (weight ratio 0.5 in terms of Al ₂ O _{3 with} respect to the clay content in the clay solution). A crosslinked clay porous body was obtained.

<Comparative Example 1>
In Example 1 (giving hydrophobicity), only 200 g of distilled water was added without adding sodium laurate, and the mixture was stirred for 1 hour and then kept in a thermostat at 80 ° C. for 24 hours as Comparative Example 1. A filterability comparison with Example 1 was performed.
When 100 ml of each solution was collected and subjected to suction filtration, the solution of Example 1 was completely filtered in 4 and a half minutes, whereas in Comparative Example 1, only 6 ml could be separated even after 30 minutes. It was. (Filtration condition: φ90mm No.5B filter paper, water aspirator used)
Therefore, the solution of Comparative Example 1 was separated into solid and liquid by centrifugal separation, and calcination was performed in the same manner as in Example 1 to obtain an interlayer crosslinked clay porous body.

<Result>
Table 1 and FIG. 2 show the specific surface area and the peak value of the pore diameter distribution of the interlayer crosslinked clay porous bodies obtained in these Examples and Comparative Examples. Here, the specific surface area and pore size distribution were measured by nitrogen adsorption.

As is apparent from Table 1 and FIG. 2, in the comparative examples, only small pore diameters were obtained, whereas in each example, an interlayer-crosslinked clay porous body having large pores having a pore diameter of 5 nm or more was obtained. did it.
Further, in Comparative Example 1, the target clay mineral could not be separated and collected by suction filtration, whereas in each example, the target clay mineral was easily obtained by suction filtration. It was possible to separate and recover.

It is the figure which represented typically a typical example of the manufacturing method of this invention. It is the figure showing the pore size distribution of the interlayer bridge | crosslinking clay porous body obtained in the Example and the comparative example.

Explanation of symbols

10 Swelling Clay Mineral 12 Layer 16 Carboxylate 18 Polyaluminum Chloride 20 Reactant 15 Interlayer Crosslinked Clay Porous Body

Claims (4)

  Disperse in a water-soluble polymer solution using as a pillar material a reaction product of a carboxylate containing a hydrocarbon chain having 11 to 17 carbon atoms as a hydrophobic group or a carboxylate containing benzene or a benzene derivative as a hydrophobic group and polyaluminum chloride. A method for producing an inter-layered crosslinked clay porous body, characterized in that the clay mineral layer is inserted between layers of the swellable clay mineral, and then the layer of the clay mineral is crosslinked with the pillar material.   The method for producing a porous interlayer crosslinked clay according to claim 1, wherein the water-soluble polymer is one or more of PVA, PEO, and PEG.   The method for producing a porous interlayer crosslinked clay according to any one of claims 1 and 2, wherein the swellable clay mineral is smectite or a swellable mica mineral.   4. The production of an inter-layer crosslinked clay porous body according to any one of claims 1 to 3, wherein the clay mineral in which the pillar material is inserted between layers is separated and recovered from a solvent by filtration and then heat-treated at 450 to 950 ° C. Method.

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