JP5410108B2 - Method for producing zeolite-containing cured body - Google Patents

Description

  The present invention relates to a method for producing a zeolite-containing cured body. More specifically, the present invention relates to a method for producing a zeolite-containing cured body suitable for use as a substitute for brick and precast concrete or as a building material.

  Various techniques for producing block- and column-shaped zeolite-containing hardened bodies that can be used as substitutes for concrete products have been proposed.

  For example, there has been proposed a method for producing a cured product containing zeolite by subjecting a granular material of an amorphous material containing silica and alumina to dehydration after alkali treatment and hydrothermal treatment after pressure molding (Patent Document). 1). Specifically, as a granular material of amorphous material containing silica and alumina, coal ash, rock wool or slag slag, etc., which is a waste material, is used, and this granular material is immersed in an aqueous alkali hydroxide solution for a certain period of time. (Alkaline treatment), dehydrated press treatment of the alkali-treated powder particles to remove excess alkali hydroxide aqueous solution, press forming and then hydrothermal treatment (steam curing) using an autoclave to form a block A columnar zeolite-containing cured body is produced. In addition, a calcium compound such as calcium hydroxide, calcium oxide, or calcium chloride is added to the aqueous alkali hydroxide solution used as the immersion liquid during the alkali treatment.

  In the above production method, the calcium compound is added to the aqueous alkali hydroxide solution for the following purposes. That is, the viscosity of the immersion liquid increases with an increase in the concentration of the aqueous alkali hydroxide solution used as the immersion liquid and an increase in the immersion time of the granular material in the immersion liquid. Due to this, drainage resistance increases during the dehydrating press process, and the dehydrating press process cannot sufficiently dehydrate. If sufficient dehydration is not performed, excess water remains in the pressure-molded body, the amount of voids in the zeolite-containing cured body increases, and as a result, the strength of the zeolite-containing cured body decreases. Therefore, in the above production method, a calcium compound is added to the aqueous alkali hydroxide solution for the purpose of suppressing the increase in viscosity of the immersion liquid and ensuring the strength of the zeolite-containing cured body.

  In addition, a method for producing a zeolite-containing cured body by subjecting a waste pulverized product to an alkali treatment and then dehydrating and subjecting it to hydrothermal treatment after pressure molding has been proposed (Patent Document 2). Specifically, as a granular material of amorphous material containing silica and alumina, by using a pulverized product of a specific waste material called waste insulator, calcium hydroxide is used as an aqueous solution for immersion in an alkaline treatment. Without adding a compound, the viscosity increase of the immersion liquid can be suppressed, and the strength of the zeolite-containing cured body can be ensured without adding a calcium compound as in the production method described in Patent Document 1. Is.

JP-A-9-124315 JP2001-172015

  However, even if the strength of the zeolite-containing cured product obtained by the production methods described in Patent Document 1 and Patent Document 2 is the best, the compressive strength is 30 to 35 MPa and the bending strength is only about 6 to 7 MPa. Therefore, the method for producing a zeolite-containing cured body described in Patent Document 1 and Patent Document 2 has a problem that it cannot cope with a case where a zeolite-containing cured body having a higher strength than the above is required as an alternative material for a concrete product. .

  Moreover, in the manufacturing method of the zeolite containing hardened | cured material of patent document 1 and 2, since the granular material and waste insulator of the amorphous material containing a silica and an alumina are immersed in aqueous alkali hydroxide solution, an alkali treatment is performed. There is a problem that a large amount of an aqueous alkali hydroxide solution is required and the production cost increases. Furthermore, since the excess alkali hydroxide aqueous solution is removed by the dehydration press treatment, the entire amount of the alkali hydroxide aqueous solution charged at the initial stage of production cannot be used effectively, and there is a problem in that it is wasteful. Moreover, the strength of the molded body itself is sufficient to the extent that the dehydration press and pressure molding are performed on the amorphous material containing silica and alumina and the waste insulators immersed in an alkali hydroxide aqueous solution. However, it was feared that when the hydrothermal treatment was applied, cracks and the like were generated, and the zeolite-containing cured product contained defects.

  Furthermore, in the manufacturing method described in Patent Document 1, it is necessary to add a calcium compound in order to secure the strength of the zeolite-containing cured body, and there is a problem that the manufacturing cost is further increased.

  In addition, the manufacturing method described in Patent Document 2 does not require the addition of a calcium compound, so that the manufacturing cost can be reduced. From the viewpoint of promoting the use of industrial by-products and restricting the disposal site, such as fly ash discharged in large quantities from thermal power plants, it is desirable to actively increase the proportion of effective use. There was a problem that the waste that cannot be used.

  Then, an object of this invention is to provide the method which makes it possible to manufacture a zeolite containing hardened | cured material higher intensity | strength than the zeolite containing hardened | cured material manufactured with the conventional manufacturing method.

  Moreover, an object of this invention is to provide the manufacturing method of the zeolite containing hardening body which makes it possible to hold down manufacturing cost rather than the conventional manufacturing method.

  Furthermore, the present invention provides a zeolite that can use fly ash as a raw material, which is a waste for which it is desired to actively increase the proportion of effective use, while suppressing the production cost as compared with the conventional production method. It aims at providing the manufacturing method of a containing hardening body.

In order to solve such a problem, the inventors of the present application have intensively studied and developed a novel manufacturing method that is completely different from the conventional manufacturing method of zeolite-containing cured bodies. That is, an amorphous material containing silica and alumina, an alkali hydroxide and water are kneaded and integrated as a kneaded material, and a physical restraining pressure of 0.02 MPa to 0.3 MPa is applied to the kneaded material. A new method for producing a zeolite-containing hardened body has been developed, in which steam curing is applied while being applied. Moreover, when a zeolite-containing cured body is produced by this novel production method, the compression strength is 87.0 MPa and the bending strength is 11.2 MPa, compared with the strength of the zeolite-containing cured body produced by the conventional production method. Thus, the inventors have found that a zeolite-containing cured body having a remarkably high strength can be produced, leading to the present invention.

Based on such knowledge, the method for producing a zeolite-containing cured product of the present invention is as follows: 0.02 MPa for a kneaded material obtained by kneading an amorphous material powder containing silica and alumina, an alkali hydroxide, and water. Steam curing is applied while applying a physical restraint pressure of ˜0.3 MPa.

When the amorphous material containing silica and alumina constituting the granular material comes into contact with the alkali hydroxide, the amorphous phase is eroded. When this erosion reaction is caused at a high temperature in the presence of water, elution of ions such as silicon and aluminum from the amorphous phase is promoted, and there is regularity in the process of rearranging the eluted ions. Zeolite minerals are produced. Physical restraint pressure of 0.02 MPa to 0.3 MPa at the same time when steam curing is applied to a kneaded material obtained by kneading an amorphous material granular material containing silica and alumina, alkali hydroxide and water By applying this, the physical restraint pressure acts to reduce the distance between crystals in the process of producing the zeolitic mineral, and the strength of the zeolite-containing hardened body is increased.

  Here, the kneading material is preferably further kneaded with reinforcing fibers. By further kneading the reinforcing fibers, both the compressive strength and the bending strength of the zeolite-containing cured body can be increased, and in particular, the bending strength can be significantly increased.

  Moreover, it is preferable to use fly ash as the granular material of the amorphous material containing silica and alumina. Since the fly ash particles have a particle size distribution of 1 to 200 μm, many adhesion points can be secured between the fly ash particles. Therefore, the strength of the zeolite-containing cured body can be reliably increased.

  According to the method for producing a zeolite-containing cured body according to claim 1, the physical constraining pressure simultaneously applied during steam curing acts so as to reduce the distance between crystals in the process of producing a zeolite-based mineral. As a result, the strength of the zeolite-containing cured body can be increased.

  Moreover, according to the method for producing a zeolite-containing cured product according to claim 1, physical properties of a kneaded material obtained by kneading an amorphous material powder containing silica and alumina, an alkali hydroxide, and water are obtained. Since steam curing is performed while applying a certain restraining pressure, water is used to immerse the amorphous granular material containing silica and alumina as in the conventional method for producing a cured product containing zeolite. There is no need to use a large amount of an alkali oxide aqueous solution, and there is no need to perform a dehydration press treatment. Further, it is not necessary to add a calcium compound in order to suppress an increase in the viscosity of the immersion liquid. Therefore, it is possible to greatly reduce the manufacturing cost as compared with the conventional method for producing a zeolite-containing cured body.

  Further, according to the method for producing a zeolite-containing cured body according to claim 2, since the reinforcing fibers are further kneaded in the kneaded material, it is possible to increase both the compressive strength and the bending strength of the zeolite-containing cured body, In particular, the bending strength can be significantly increased.

  According to the method for producing a zeolite-containing cured body according to claim 3, since fly ash is used as the powder of amorphous material containing silica and alumina, a large amount of particles between fly ash particles is used. An adhesion point can be secured and the strength of the zeolite-containing cured body can be reliably increased. Moreover, since fly ash can be used as a raw material, it becomes possible to promote the use of fly ash discharged in large quantities from a thermal power plant. Therefore, it becomes possible to contribute to the demand for industrial use promotion of fly ash.

It is a figure which shows the apparatus which provides the physical restraint pressure in this embodiment. It is a figure which shows the influence which curing temperature has on the pore size distribution of a zeolite containing hardening body. It is a figure which shows the influence which the kind of alkali hydroxide has on pore diameter distribution. It is a figure which shows the influence which the difference in the compounding quantity of potassium hydroxide has on pore diameter distribution. It is a figure which shows the mineral species identification result by XRD when an alkali is sodium hydroxide. It is a figure which shows the mineral species identification result by XRD at the time of using alkali as potassium hydroxide. FIG. 6 is a diagram in which the horizontal axis of FIG. 5 is expanded to 2θ = 60 °. It is a figure which shows the difference in the XRD analysis result by curing temperature conditions. It is an electron micrograph of the zeolite containing hardening object manufactured using sodium hydroxide. It is an enlarged photograph of the area | region 1 of FIG. It is an enlarged photograph of the area | region 2 of FIG. It is an enlarged photograph of the area | region 3 of FIG. It is an electron micrograph of the zeolite containing hardening body manufactured using potassium hydroxide. It is an enlarged photograph of the area | region 4 of FIG. It is an enlarged photograph of the area | region 5 of FIG. It is the electron micrograph which image | photographed the area | region different from FIG.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings.

  The method for producing a zeolite-containing cured product of the present invention applies a physical restraining pressure to a kneaded material obtained by kneading an amorphous material granular material containing silica and alumina, an alkali hydroxide and water. However, steam curing is applied.

  As the granular material of amorphous material containing silica and alumina used in the present invention (hereinafter also referred to simply as granular material), for example, clinker ash, cinder ash, fly ash generated from a coal-fired power plant Coal ash such as can be used. In addition, rock wool, blast furnace slag generated from steelworks, ore slag such as converter slag, and waste iron or the like processed into powder can be used. However, the granular material of the amorphous material containing silica and alumina used in the present invention is not limited to these, and the granular material of the material containing silica and alumina and being substantially amorphous. Can be used. That is, the inclusion of crystals in a range that does not hinder the production of the zeolite-containing cured product is also allowed.

  Here, it is particularly preferable to use fly ash as the amorphous material containing silica and alumina used in the present invention. Since fly ash has a particle size distribution of 1 to 200 μm, many adhesion points can be secured between the fly ash particles. Therefore, it is easy to increase the strength of the zeolite-containing cured body. In addition, by processing coal ash other than fly ash, rock wool, slag slag, waste slag, etc. into a granular material having a particle size distribution of 1 to 200 μm, it has the same strength as when fly ash is used. It is estimated that a zeolite-containing cured product can be obtained.

  Next, examples of the alkali hydroxide used in the present invention include sodium hydroxide and potassium hydroxide.

  When sodium hydroxide is used as the alkali hydroxide, a zeolite-containing cured product containing calcite (Analcime-C) and gmelinite-Na can be produced. Further, when potassium hydroxide is used as the alkali hydroxide, a zeolite-containing cured product containing perlialite can be produced.

  Here, when it is desired to increase both the zeolite content and the compressive strength of the zeolite-containing cured product, it is preferable to use potassium hydroxide. The effect of enhancing the compressive strength of the hardened material containing zeolite by using potassium hydroxide is that the zeolite mineral contained in the hardened material containing zeolite is Perlialite and the pore size of the hardened material containing zeolite Is estimated to be due to being smaller than the pore diameter of the zeolite-containing cured product obtained using sodium hydroxide.

  In the present invention, the kneaded material is obtained by kneading powder, alkali hydroxide and water. By kneading the powder, alkali hydroxide and water, the alkali hydroxide and water can be uniformly dispersed in the kneaded material. Accordingly, a homogeneous zeolite-containing cured product can be produced by causing a zeolite formation reaction uniformly in the kneaded material. Here, it is preferable that the alkali hydroxide is previously dissolved in water to obtain an alkali hydroxide aqueous solution, and the aqueous alkali hydroxide solution and the powder are kneaded to obtain a kneaded material. When the alkali hydroxide is dissolved in water and then kneaded with the granular material, the alkali hydroxide and water can be easily dispersed uniformly in the kneaded material, and the kneading time can be shortened.

  Here, the mixing amount of water with respect to the granular material may be set so that the kneaded material can be made into one lump and the kneaded material has a viscosity with no fluidity. For example, it is preferable to set it as 200g-300g with respect to 1000g of granular materials, and it is more preferable to set it as about 250g. If the amount of water mixed is too small, it will not be possible to knead the powder particles into one lump. On the other hand, when the amount is too large, the amount of voids generated in the zeolite-containing cured body increases, and the strength of the zeolite-containing cured body cannot be secured.

In the present specification, “ensuring the strength of the zeolite-containing hardened body” means securing the strength required as an alternative material for the zeolite-containing hardened concrete member or as a building material. For example, according to the present invention, a zeolite-containing cured body having a compressive strength of 15 MPa (15 N / mm ² ) or more and a bending strength of 4 MPa (4 N / mm ² ) or more can be obtained.

  The amount of alkali hydroxide mixed with the granular material is preferably as much as possible in order to increase the amount of zeolite mineral produced. For example, when sodium hydroxide is used as the alkali hydroxide, it is preferable to mix 110 g or more with respect to 1000 g of the powder, more preferably 125 g or more, and mix with the powder. Most preferably, a limiting amount of sodium hydroxide that is soluble in the water is mixed. In this case, it is easy to increase the amount of zeolitic mineral produced. Further, when potassium hydroxide is used as the alkali hydroxide, it is preferably 88 g or more, more preferably 176 g or more with respect to 1000 g of the granular material, and it is mixed with the kneaded material. More preferably, a limiting amount of potassium hydroxide that dissolves in water is mixed. In this case, it is easy to achieve both an increase in the amount of zeolitic mineral produced and a sufficient strength of the zeolite-containing cured body.

  The granular material is kneaded with an alkali hydroxide and water to obtain a kneaded material. Here, in the case of mixing 200 to 300 g of water with respect to the above-mentioned preferable range of the amount of water mixed with the granular material, that is, 1000 g of the granular material, the amount of water with respect to the granular material is small. In kneading, it is preferable to knead using a forced kneading mixer with strong stirring power. For example, the MT series manufactured by AICOH can be used, but is not limited thereto. By this kneading step, a so-called kneaded slurry kneaded material is obtained.

  Here, the kneading material is preferably further kneaded with reinforcing fibers. In this case, both the compressive strength and bending strength of the zeolite-containing cured body can be increased, and in particular, there is an effect of remarkably improving the bending strength. As the reinforcing fiber, steel fiber, polypropylene fiber, or the like can be used, but is not limited thereto. Further, the amount of the reinforcing fiber mixed with the granular material is not particularly limited as long as it does not impede the production of the zeolite-containing cured body. For example, if 30 g of the reinforcing fiber is mixed with 1000 g of the granular material, The effect of increasing the strength of the cured body is sufficiently exhibited.

  Next, steam curing is performed while applying a physical restraining pressure to the kneaded material.

  The physical restraint pressure in the present invention refers to a pressure derived from saturated steam pressure when performing steam curing at a curing temperature of 100 ° C. or higher, or from steam introduced when performing steam curing at a curing temperature of less than 100 ° C. In addition to the above pressure, it means the pressure applied to the kneaded material.

  The physical restraint pressure in the present invention can be applied by, for example, the restraint pressure applying device 1 shown in FIG. This apparatus is roughly divided into a mold 2 that contains the kneaded material 6, an upper lid 5 that covers the opening of the mold 2, and an inner lid 3 that is accommodated between the kneaded material 6 and the upper lid 5. Composed. The kneaded material 6 is defoamed and compacted after it is accommodated in the mold 2 and the inner lid 3 is closed.

  The material of the mold 2, the inner lid 3 and the upper lid 5 is, for example, stainless steel. However, the material is not limited to this as long as the material has heat resistance, alkali resistance, and high thermal conductivity. Absent.

  The physical restraint pressure is controlled as follows, for example. That is, the inner lid 3 is provided with a spring 4, and the unloaded position of the spring 4 (position in a state where no force is applied to the spring 4) is set higher than the height of the inner lid 3. . Then, when the upper lid 5 is fixed to the mold 2, the spring 4 can be contracted by the upper lid 5. By configuring in this manner, the spring constant of the spring 4 itself, the bottom area of the inner lid 3 (the area of the kneaded material and the grounding surface of the inner lid 3), and the deviation of the spring 4 from the unloaded position, The physical restraining pressure applied to the kneaded material 6 can be controlled.

  Further, the deviation of the spring 4 from the unloaded position can be controlled by a method other than the above method, and is not limited to applying a physical restraining pressure by the above method. For example, in this embodiment, the spring 4 is fixed to the bottom surface of the inner lid 3, and the upper surface of the inner lid 3 is used as an opening surface, and the spring 4 is projected from the opening surface. The spring 4 may be fixed to the upper surface instead of the surface. In this case, since the spring 4 can be contracted compared to the case of the present embodiment, the displacement of the spring 4 from the unloaded position can be made larger than in the case of the present embodiment, and the stronger physical A constraining pressure can be applied. That is, when springs having the same spring constant are used, the physical restraint pressure can be increased by increasing the displacement of the spring 4 from the unloaded position, and conversely, when the spring 4 is unloaded. By reducing the deviation from the position, the physical restraining pressure can be reduced.

  Moreover, it is not limited to the application method of the physical restraint pressure using the above springs. For example, the kneading material may be accommodated in a container, and a physical restraining pressure may be applied by fixing the kneading material to the container in a state where the kneading material is pressed with the lid. The method of fixing the upper lid 5 to the mold 2 is, for example, screw tightening. However, the method is not limited to this method, and the upper lid 5 is fixed to the mold 2 using a band-type fixture. It may be.

  Further, the shape of the mold 2 is not limited to the shape of the rectangular parallelepiped shown in FIG. 1, and any shape that can uniformly apply a physical restraining pressure to the kneaded material may be used. For example, it may be a cylindrical shape.

For values of physical restraint pressure , 0 . The pressure is preferably set to 02 to 0.3 MPa. If the physical restraint pressure is too small, the action of reducing the distance between crystals in the process of producing the zeolite mineral becomes too small, and the strength of the zeolite-containing hardened body may not be ensured .

  Steam curing in the present invention can impart a heat quantity that can promote the production of zeolitic minerals to the kneaded material, and water contained in the kneaded material when the restraint pressure applying device 1 shown in FIG. 1 is heated. It is carried out under conditions that prevent release to the outside of the apparatus 1, maintain moisture in the kneaded material, and promote the formation reaction of the zeolitic mineral, with a curing temperature of 100 ° C. or higher in a steam autoclave apparatus This includes both curing treatment performed at a saturated vapor pressure of less than or equal to the saturated vapor pressure and curing treatment performed while introducing steam at a temperature of less than 100 ° C. in a steam curing tank. For example, it is preferable that the curing temperature is 160 ° C. to 220 ° C. and the curing time is 6 to 24 hours under saturated steam at a pressure of about 0.6 to 2.3 MPa in a steam autoclave apparatus. Alternatively, by using a steam curing tank and steam curing for 12 days at 50 ° C. or for 3 days at 80 ° C., the amount of zeolite-based mineral produced is reduced, but the strength of the zeolite-containing hardened body can be secured. Therefore, steam curing may be performed under such conditions that a heat amount equivalent to steam curing for 12 days at 50 ° C. or 3 days at 80 ° C. can be applied to the kneaded material.

  When using a steam curing tank and steam curing for 12 days at 50 ° C or 3 days at 80 ° C, the zeolite-containing hardened body should contain Merlinoite and Philipsite. Is possible.

  Here, when the containment of the kneaded material 6 in a completely sealed state can be achieved by the restraining pressure applying device 1 shown in FIG. 1, that is, the water contained in the kneading material 6 accommodated in the restraining pressure applying device 1 is In the case where the apparatus 1 does not leak outside during the heating of the apparatus 1, it has been confirmed by experiments by the present inventors that a zeolite-containing cured body can be obtained simply by heating the apparatus 1 without introducing water vapor. . Therefore, for example, a zeolite-containing cured body can be obtained simply by heating in a drying furnace or the like. However, since the zeolite-containing cured body is often required to have a certain size, it is often necessary to increase the size of the restraint pressure applying device 1 in order to meet this need. Moreover, when mass-producing a zeolite containing hardened | cured material industrially, it is necessary to use the same restraint pressure provision apparatus 1 many times from a viewpoint of suppressing the cost concerning a formwork. Under such circumstances, requesting a completely sealed state as the restraining pressure applying device 1 not only increases the dimensional accuracy required for the restraining pressure applying device 1 and increases the cost of the mold, There is a risk that the manufactured cured product may be defective. That is, when it becomes impossible to maintain the completely sealed state of the apparatus 1 during the heating of the kneaded material, water contained in the kneaded material is discharged outside the apparatus 1 and the hydrothermal reaction in the kneaded material is inhibited. As a result, the zeolite-containing cured product may not be produced. However, when steam curing is performed as in the present invention, even if the apparatus 1 is in a substantially sealed state having a slight gap, steam enters the gap and water contained in the kneaded material (kneaded into the kneaded material). The release of water) can be suppressed. Moreover, the effect of supplying steam into the kneaded material can also be expected when steam enters the gap. Therefore, even if it is substantially sealed, when steam curing is performed, the promotion of the zeolite formation reaction in the kneaded material is not hindered, and a zeolite-containing cured body having excellent strength characteristics can be produced. Is possible. Moreover, since the kneaded material immediately after kneading the powder, alkali hydroxide and water is fragile to excess moisture, even if it is directly subjected to steam curing, its shape is It cannot be maintained. However, if the kneaded material is accommodated in the restraint pressure applying device 1 in a substantially hermetically sealed state, the shape is not destroyed by excessive moisture in steam curing. Therefore, storing the kneaded material in the restraint pressure applying device 1 in a substantially sealed state or a completely sealed state and applying the physical restraint pressure is immediately after being obtained by kneading the powder, alkali hydroxide and water. This kneaded material can be subjected to steam curing, and an additional advantage that a zeolite-containing cured body can be produced in a short period of time is also produced. Here, the gap in the substantially sealed state is a gap where excessive moisture is supplied to the kneaded material and the shape thereof is not destroyed, specifically, the container containing the kneaded material and the periphery of the lid of the container Or a gap of several millimeters between the container containing the kneaded material and the corners of the lid of the container (for example, the four corners of the lid when the container is a rectangular parallelepiped). .

  Here, the steam curing conditions when sodium hydroxide is used as the alkali hydroxide are preferably 24 hours for the curing time. However, for example, when the curing temperature is 220 ° C., the amount of zeolite produced does not change even when the curing time is 6 hours or more. Therefore, when the curing temperature is high, the curing time may be long. Zeolite production may be saturated. On the other hand, when the curing temperature is low, the curing time may be longer than 24 hours in order to obtain a sufficient amount of zeolite. The curing temperature is preferably 160 ° C to 220 ° C. When the curing temperature is 160 ° C. to 200 ° C., it is easy to achieve both the production of zeolitic mineral and the improvement of the strength of the zeolite-containing cured body. In particular, when the curing temperature is 180 ° C., the effect of increasing the compressive strength is the highest, and when the curing temperature is 160 ° C., the effect of increasing the bending strength is the highest. Moreover, when the curing temperature is 200 ° C. to 220 ° C., it is possible to increase the amount of zeolitic mineral produced while ensuring the minimum strength required for the zeolite-containing cured body. However, the steam curing conditions are not limited to the above range, and may be set as appropriate according to the amount of zeolite produced, the zeolite mineral species, and the strength required for the zeolite-containing cured product.

  Further, the steam curing conditions when potassium hydroxide is used as the alkali hydroxide are preferably a curing temperature of 220 ° C. and a curing time of 24 hours. In this case, it is easy to achieve both an increase in the zeolite-based mineral content of the zeolite-containing cured body and an improvement in the strength (compressive strength) of the zeolite-containing cured body. However, the steam curing conditions are not limited to the above range, and may be set as appropriate according to the amount of zeolite produced, the zeolite mineral species, and the strength required for the zeolite-containing cured product.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention.

  Examples of the method for producing a zeolite-containing cured body of the present invention will be described below, but the present invention is not limited to these examples.

(1) Blending conditions of powder material, alkali hydroxide, and mixed water Fly ash corresponding to type II in JIS A 6201 was used as a powder particle. The loss on ignition of this fly ash was 2.9% by weight. The SiO ₂ content was 53.9% by weight, and the CaO content was 7.2% by weight. Sodium hydroxide (Wako Pure Chemical) or potassium hydroxide (Wako Pure Chemical) was used as the alkali hydroxide. Tap water was used as mixing water. The alkali hydroxide was dissolved in water and used as an alkali hydroxide solution.

  In the present Example, the compounding 1-4 shown in Table 1 was set as the compounding conditions of a zeolite containing hardening body manufacturing raw material. All units in Table 1 are “g”.

(2) Manufacturing conditions for zeolite-containing cured body According to the formulation shown in Table 1, each material was weighed with 5000 g of fly ash, an aqueous alkali hydroxide solution was added to fly ash, and a forced kneading mixer (AICOH) (MT series) and kneaded uniformly to obtain a kneaded material. This mixer has two stirrers that move in a planetary motion, and by mixing for about 5 minutes, a homogeneous kneaded material could be obtained.

  Next, this kneaded material was accommodated in the mold 2 (inner dimensions: 20 cm × 20 cm cross section, height 35 cm) of the restraint pressure applying apparatus 1 shown in FIG. A PEEK release plate (not shown) was installed on the inner surface of the mold 2 in order to facilitate removal of the zeolite-containing cured body after completion of steam curing. Moreover, the height of the kneaded material accommodated was 15 cm.

  After the kneaded material is stored in the mold 2, the mold 2 on which the inner lid 3 is placed is placed on a vibration table (TV series manufactured by EXEN), and vibrations with a frequency of 2500 Hz and an amplitude of 1.5 mm are kneaded. The material was defoamed and compacted for 4 minutes.

  Next, the upper lid 5 was fixed to the frame mold 2 by screwing. Then, the displacement of the spring 4 accommodated in the inner lid 3 from the equilibrium position (the difference in length of the spring 4 before and after the upper lid 5 is screwed), the spring constant of the spring 4 itself, and the bottom area of the inner lid 3 From this, the magnitude of the physical restraining pressure applied to the kneaded material was calculated to be 0.13 MPa. And the restraint pressure provision apparatus 1 was put into the water vapor autoclave apparatus in the state which gave restraint pressure to the kneading | mixing material, and the steam curing was given on various conditions.

  The material of the mold 2, the inner lid 3 and the upper lid 5 was stainless steel.

(3) Characteristic evaluation items of zeolite-containing hardened body The zeolite-containing hardened body produced as described above has compression strength measurement, bending strength measurement, pH measurement, synthetic mineral phase identification, pore volume ratio measurement, pore size distribution measurement and elution. It used for the test and evaluated the characteristic.

  The compressive strength measurement was performed according to JIS R 5201 using a test body obtained by cutting the produced zeolite-containing cured body into a cylindrical shape having a diameter of 35 mm and a height of 70 mm.

  The bending strength measurement was performed according to JIS R 5201 using a test body obtained by cutting the produced zeolite-containing cured body into a 40 mm × 40 mm × 160 mm rectangular parallelepiped.

  The pH measurement was performed by adjusting the produced zeolite-containing cured product to a powder form, adding the powder to ion-exchanged water, stirring the mixture at 20 ° C. for 6 hours, and then measuring the pH of the ion-exchanged water. In addition, the addition amount with respect to ion-exchange water of a zeolite containing hardening body powder was made into the weight of 1/10 of the weight of ion-exchange water.

  The identification of the synthetic mineral phase was performed by powder X-ray diffraction (XRD), and the main mineral species constituting the zeolite-containing hardened body were identified based on the identification result.

  The total pore volume ratio was measured with a mercury intrusion pore size distribution measuring device. The pore size distribution was measured with a mercury intrusion pore size distribution measuring device.

  The dissolution test was conducted according to the Environmental Agency Notification No. 46 method.

(4) Experimental results (4-1) Effect of blending amount of sodium hydroxide In order to clarify the effect of blending amount of sodium hydroxide on the characteristics of the zeolite-containing cured body, blending amount 1 with different blending amounts of sodium hydroxide And the zeolite containing hardening body was manufactured on the conditions of the mixing | blending 2, and the characteristics of these zeolite containing hardening bodies were compared and examined. The results are shown in Table 2. In addition, the steam curing conditions at the time of manufacture of a zeolite containing hardening body were 180 degreeC which is general purpose curing temperature, and the curing time was 24 hours. Steam curing was performed under a saturated steam pressure of 1.0 MPa.

As shown in Table 2, both the conditions of Formulation 1 and Formulation 2 showed very high compressive strength and bending strength, and particularly when Formulation 2 was applied, the compressive strength was 87 N / mm ² and The bending strength was 11.2 N / mm ² , and it was revealed that a zeolite-containing cured body having a very high strength can be produced. In addition, the condition of Formulation 2 in which the amount of sodium hydroxide close to the limit value of the solubility of sodium hydroxide in water was slightly increased in compressive strength and bending strength compared to the condition of Formulation 1, but the difference Was not significant.

  About pH value, it was confirmed that the conditions of the mixing | blending 2 become higher than the conditions of the mixing | blending 1, and the tendency for pH value to increase was seen, so that the compounding quantity of sodium hydroxide is large.

  A negative correlation was observed between the total pore volume ratio and the compressive strength. That is, the higher the compressive strength, the lower the total pore volume ratio. From this, it became clear that by increasing the amount of sodium hydroxide, the fly ash dissolution reaction easily proceeds and the gaps between the particles are easily filled.

  The results of XRD analysis of the main constituent minerals contained in the zeolite-containing hardened body are shown in FIGS. 5 and 7 show the same measurement result, and FIG. 7 is an enlarged view of the range of the horizontal axis (2θ) than FIG. Further, the solid line spectrum in FIG. 7 is the result of XRD analysis of fly ash. Formation of gmelinite-Na, a zeolitic mineral, was confirmed from both zeolite-containing hardened bodies produced under the conditions of Formulation 1 and Formulation 2. In addition, in Formulation 1, formation of zeolite KI was confirmed in addition to gmelinite-Na. It was also confirmed that a relatively large amount of mullite, quartz, magnetite and hematite contained in fly ash remained. However, the mountain-like peak generated at 2θ = 15 to 35 ° indicating the amorphous phase contained in fly ash almost disappears, and a new peak is obtained at 2θ = 25 to 40 ° indicating another amorphous phase. It was confirmed that a mountain-shaped peak was generated. From this, it was considered that the zeolitic mineral was formed by the amorphous phase of fly ash mainly reacting with sodium hydroxide.

(4-2) Influence of curing temperature In order to clarify the influence of curing temperature on the properties of the zeolite-containing cured body, the curing temperature is 160 ° C, 180 ° C, 200 ° C or 220 ° C. The body was manufactured and the various characteristics were compared and examined. The results are shown in Table 3. In addition, the curing time of the steam curing at the time of manufacturing the zeolite-containing cured body was 24 hours. Moreover, steam curing was implemented under the saturated vapor pressure of 0.62, 1.0, 1.6, and 2.3 MPa.

  As shown in Table 3, the compressive strength was maximum at a curing temperature of 180 ° C, and the bending strength was maximum at a curing temperature of 160 ° C. In addition, although the compressive strength and bending strength of the zeolite-containing hardened body obtained at 220 ° C. with the highest curing temperature were lower than those cured at other curing temperatures, it was an alternative material for concrete members and construction. It became clear that the strength which can be used as a material was secured.

  The pH value was 11.2 for the zeolite-containing cured product obtained at a curing temperature of 220 ° C, and when the curing temperature was 180 ° C or higher, a tendency to decrease with an increase in the curing temperature was observed. From this, it became clear that the dissolution reaction of fly ash is likely to proceed as the curing temperature increases.

  A negative correlation was observed between the total pore volume ratio and the compressive strength. That is, there was a tendency for the total pore volume ratio to increase as the compressive strength was lower. From this, it was considered that when the curing temperature is increased, the dissolution reaction of fly ash is likely to proceed, while the increase in the total pore volume ratio is likely to occur and the compressive strength is decreased.

  Next, the result of having measured the pore size distribution of the manufactured zeolite containing hardening body is shown in FIG. In FIG. 2, □ indicates the measurement result of the zeolite-containing hardened body manufactured at a curing temperature of 160 ° C., ☆ indicates the measurement result of the zeolite-containing hardened body manufactured at a curing temperature of 180 ° C., and ▽ indicates the curing temperature of 200 The measurement result of the zeolite containing hardened | cured material manufactured as ℃ is shown, ■ shows the measurement result of the zeolite containing hardened | cured material manufactured as the curing temperature is 220 degreeC.

  As shown in FIG. 2, the zeolite-containing cured product produced at a curing temperature of 180 ° C. has many voids with a pore diameter of less than 0.02 μm, but has almost no voids of 0.02 μm or more, It was estimated that this was a factor that increased the compressive strength. On the other hand, the zeolite-containing cured product produced at a curing temperature of 220 ° C. has many voids having a pore diameter of 0.1 to 2 μm, and this is presumed to have caused a decrease in compressive strength. .

  Next, as a result of analyzing the main constituent mineral contained in the zeolite-containing hardened body by XRD, it was confirmed that the main constituent mineral changes with the change in curing temperature. That is, when the curing temperature was set to 160 ° C., zeolite KI, zeolites not assigned a name, and hematite were detected. When the curing temperature was 180 ° C., zeolite KI and zeolites to which no name was assigned decreased, and gmelinite-Na, which is a mineral belonging to zeolite, was detected. When the curing temperature was 200 ° C., zeolitic (Analcime-C), which is a mineral belonging to zeolite, and zeolite P1 were detected in addition to gmelinite-Na. When the curing temperature was 220 ° C., gmelinite-Na and calcite (Analcime-C) were detected.

  Moreover, the difference of the XRD analysis result by curing temperature conditions is shown in FIG. From this result, it became clear that the production amount of the zeolitic mineral increases as the curing temperature increases.

  From the above results, as the curing temperature increases, the amount of zeolitic mineral produced increases and the type of zeolitic mineral also changes, but the compressive strength and bending strength decrease, so as the curing temperature increases. It was thought that many pores were easily formed between crystals.

  Therefore, when the purpose is to increase the content of the zeolitic mineral in the zeolite-containing cured body, it is appropriate to increase the curing temperature to 220 ° C, but by setting the curing temperature to 160 ° C to 200 ° C. , It becomes easy to increase the strength of the cured body while containing the zeolite-based mineral in the zeolite-containing cured body. Particularly, the compression strength can be remarkably increased by setting the temperature to 180 ° C., and the bending strength is remarkably increased by setting the temperature to 160 ° C. It has become clear that it is possible to increase it. That is, it was clarified from this result that the strength of the zeolite-containing hardened body, the type of zeolitic mineral, and the amount of zeolitic mineral produced can be controlled by controlling the curing temperature.

(4-3) Effect of curing time In order to clarify the effect of curing time on the properties of the zeolite-containing cured body, a cured zeolite-containing body is produced under the conditions of Formulation 2, with the curing time being 6 hours, 18 hours, and 24 hours. The characteristics were compared. The results are shown in Table 4. In addition, the curing temperature at the time of manufacture of a zeolite containing hardening body was 220 degreeC. Moreover, the steam curing was carried out under a saturated steam pressure of 2.3 MPa.

  As shown in Table 4, when the curing time is 24 hours, the compressive strength and bending strength are the lowest values, but the change width of the compressive strength and bending strength is that the curing time is 6 to 24 hours. Within the range, it was confirmed that there was relatively little. And it became clear that the intensity | strength of the grade which can be used as a substitute material of a concrete member was ensured under any conditions. Further, the total pore volume ratio was 30% by volume at any curing time, and was almost unchanged.

  About pH, the tendency which falls with the increase in curing time was seen. This is considered to be due to the fact that the fly ash dissolution reaction has progressed with the increase in curing time.

  Next, as a result of XRD analysis of main constituent minerals contained in the zeolite-containing hardened body, zeolitic (Analcime-C), gmelinite-Na, other zeolites, In addition, it was confirmed that mullite and quartz, which are residual mineral phases contained in fly ash, are the main constituent minerals. In addition, no significant difference was observed in the peak height in the XRD spectrum at any curing temperature.

  From the above results, it was clarified that when the curing temperature is 220 ° C. and the curing time is 6 hours, the amount of zeolite-based mineral produced can be made sufficient.

(4-4) Influence of blended alkali species In order to clarify the influence of blended alkali species on the properties of the zeolite-containing cured body, a zeolite-containing cured body was produced under the conditions of blend 2 and blend 4 with different alkali species. The properties of these zeolite-containing cured bodies were compared and examined. The results are shown in Table 5. In addition, the curing temperature and curing time of the steam curing at the time of manufacturing the zeolite-containing cured body were set to 220 ° C. and 24 hours. Moreover, the steam curing was carried out under a saturated steam pressure of 2.3 MPa. In addition, the compounding quantity of sodium hydroxide shown to the compounding 2 and the compounding quantity of the potassium hydroxide shown to the compounding 4 were made into the equivalent in molar conversion.

  As shown in Table 5, with respect to compressive strength, bending strength, and pH, the condition of Formula 4 showed a larger value than the condition of Formula 2. The total pore volume ratio was about 30% by volume for both conditions of Formulation 2 and Formulation 4, and no difference was observed.

  Here, potassium hydroxide is blended in blend 4 and sodium hydroxide is blended in blend 2. Therefore, the compressive strength and bending strength are increased by using potassium hydroxide as the alkali species to be blended. In particular, it has become clear that the compression strength can be significantly increased.

  Next, the result of having measured the pore diameter distribution of the manufactured hardening body is shown in FIG. In FIG. 3, ■ indicates the measurement result of the cured product (mixed with sodium hydroxide) manufactured under the conditions of Formulation 2, and ○ indicates the measurement result of the cured product (mixed with potassium hydroxide) manufactured under the conditions of Formulation 4. Show.

  From this result, in the zeolite-containing cured body blended with sodium hydroxide, the pore diameter is mainly distributed in the range of 0.1 to 2 μm, whereas in the zeolite-containing cured body blended with potassium hydroxide, It was confirmed that the pore diameter was distributed in the range of 0.01 to 0.1 μm. Therefore, the compressive strength of the zeolite-containing cured body containing potassium hydroxide was higher than that of the zeolite-containing cured body containing sodium hydroxide in terms of the diameter of the pores forming the voids of the zeolite-containing cured body. It was thought that one factor was that it was fine.

  Next, as a result of XRD analysis of the main constituent minerals contained in the zeolite-containing hardened body, the zeolite-containing hardened body blended with sodium hydroxide (blending 2) and the zeolite-containing hardened body blended with potassium hydroxide (blending 4) It was revealed that the main constituent minerals were different. That is, it was confirmed that the zeolite-containing cured product (compound 4) containing potassium hydroxide contains a lot of perlite, which is a zeolitic mineral containing a lot of potassium. On the other hand, it was confirmed that the zeolite-containing hardened body containing sodium hydroxide (formulation 2) contained a large amount of calcite (Analcime-C) and gmelinite-Na. It was thought that the difference in these major constituent minerals led to a large difference in compressive strength.

  From the above results, it is preferable to use sodium hydroxide for the purpose of producing a large amount of zeolitic (Analcime-C), producing a large amount of Perlialite and increasing the compressive strength. For this purpose, it has become clear that it is preferable to use potassium hydroxide.

In addition, when the density was measured about the zeolite containing hardening body manufactured on the conditions of the mixing | blending 4, it was 1.6 g / cm < ³ >. From this, it became clear that the zeolite-containing cured product obtained by the present invention is very light while having high strength.

  Moreover, when the water absorption rate was measured about the zeolite containing hardening body manufactured on the conditions of the mixing | blending 4, it became clear that a water absorption rate is 20%. From this, it became clear that the zeolite-containing cured product of the present invention can be used as a solid adsorbent utilizing the adsorption capacity of zeolite.

(4-5) Effect of Compounding Amount of Potassium Hydroxide In order to clarify the effect of the compounding amount of potassium hydroxide on the properties of the zeolite-containing cured body, the conditions of Formulation 3 and Formulation 4 with different compounding amounts of potassium hydroxide Zeolite-containing hardened bodies were produced by the above, and the characteristics of these zeolite-containing hardened bodies were compared and examined. The results are shown in Table 6. In addition, the curing temperature and curing time of the steam curing at the time of manufacturing the zeolite-containing cured body were set to 220 ° C. and 24 hours. Moreover, the steam curing was carried out under a saturated steam pressure of 2.3 MPa.

  As shown in Table 6, with respect to compressive strength and pH, the condition of Formulation 4 showed a larger value than the condition of Formulation 3. On the other hand, regarding the bending strength and the total pore volume ratio, the condition of the composition 4 showed a smaller value than the condition of the composition 3.

  Here, since the compounding amount of potassium hydroxide is more in the condition of compounding 4 than in the condition of compounding 3, the compressive strength and pH can be increased by increasing the compounding amount of potassium hydroxide, It was revealed that the total pore volume ratio can be lowered. On the other hand, regarding bending strength, it became clear that the one where the compounding quantity of potassium hydroxide was decreased increased.

  Next, the result of having measured the pore diameter distribution of the manufactured hardening body is shown in FIG. In FIG. 4, ● represents the measurement result of the cured product (potassium hydroxide blending amount 88.1 g) manufactured under the condition of blending 3, and ○ represents the cured product (potassium hydroxide blending amount 176. The measurement result of 2g) is shown.

  From this result, it was confirmed that the diameter of the pores was smaller in the cured product produced under the condition of Formulation 4 in which the amount of potassium hydroxide was large. Therefore, it was considered that the difference in pore diameter had an effect on the compressive strength.

  Next, the result of having analyzed by XRD about the main component mineral contained in a zeolite containing hardening body is shown in FIG. In Formulation 3, Zoisite, which is a zeolitic mineral, was slightly produced, but no significant decrease was observed in mullite, quartz, etc., which are the main constituents of fly ash. From this, it was considered that the compressive strength expressed in Formulation 3 was brought about by adhesion between fly ash particles. From this result, when the blending amount of potassium hydroxide is 88.1 g or less with respect to 1000 g of fly ash, there is no practical problem in terms of strength, but the amount of zeolitic mineral produced may be reduced. It became clear. And from this result, it became clear by reducing the compounding quantity of potassium hydroxide, the production amount of a zeolitic mineral decreases, compressive strength becomes small, and bending strength can be raised. On the contrary, by increasing the blending amount of potassium hydroxide, it was revealed that the amount of zeolite mineral produced can be increased and the compressive strength can be increased, while the bending strength is decreased.

(4-6) Dissolution test results Under the conditions of Formulations 2, 3, and 4, the cured zeolite-containing product produced at a curing temperature of 220 ° C and the curing time of 24 hours; Table 7 shows the results of analysis of trace elements eluted from the zeolite-containing cured product produced with a curing time of 24 hours. In Table 7, the unit of numerical values is “mg / L”. For comparison, a dissolution test was also conducted with fly ash alone.

  In any of the zeolite-containing cured bodies, it was confirmed that the total chromium elution amount was reduced by about 80 to 90% as compared with the case of fly ash alone. From this, it became clear that the total chromium elution amount can be suppressed by the zeolite-containing cured product of the present invention regardless of the amount of zeolite-based mineral produced.

  Moreover, when the alkali to mix | blend was potassium hydroxide, the elution amount of boron decreased 10 to 30% compared with the case of a fly ash plain. From this, it became clear that the effect which suppresses the elution amount of a boron is acquired in addition to the effect which suppresses the total chromium elution amount by making the alkali seed | species mix | blended into potassium hydroxide.

  As for arsenic and selenium, the elution amount of any zeolite-containing cured product was higher than that of fly ash, but by using potassium hydroxide as the alkali to be mixed, the elution of arsenic is somewhat suppressed. Was confirmed.

  From the above results, it became clear that it is better to use potassium hydroxide in order to suppress elution of chromium and boron and to suppress the elution of arsenic as much as possible compared to the fly ash.

(5) Effect of reinforcing fiber addition 3% of the fly ash mass (steel fiber 30g with respect to 1000g of fly ash) is mixed with the condition of compound 4 and steam curing is performed at a curing temperature of 220 ° C and a curing time of 24 hours ( 2.3 MPa) to produce a zeolite-containing cured body, and the performance was compared with the zeolite-containing cured body produced without adding steel fibers. The results are shown in Table 8. The added steel fibers were BeKaert OL fibers (diameter 0.2 mm, length 13 mm).

  As shown in Table 8, it was revealed that mixing steel fibers has an effect of increasing the compressive strength and bending strength of the zeolite-containing cured body, and is particularly excellent in the effect of increasing the bending strength.

(6) Examination of lowering of curing temperature Various characteristics in the case of producing a zeolite-containing cured body at a lower curing temperature were examined under the conditions of Formulation 2. The results are shown in Table 9. Curing conditions were the following two conditions. Note that the conditions for introducing steam were 95% or higher relative humidity.
Curing temperature: 50 ° C, curing time: 12 days (hereinafter referred to as 50 ° C-12 days curing)
Curing temperature: 80 ° C, curing time: 3 days (hereinafter referred to as 80 ° C-3 days curing)

  As a result of XRD analysis of the main constituent mineral species of the zeolite-containing hardened body, it was found that in the curing at 50 ° C. for 12 days, a large amount of constituent minerals contained in fly ash remained and only a small amount of zeolite was produced. confirmed. In addition, it was confirmed that a relatively large amount of fly ash constituent mineral remained even after curing at 80 ° C. for 3 days, but compared with the case of curing at 50 ° C. for 12 days, Merlinoite and Ash Cross It was confirmed that a lot of zeolitic minerals such as Philite were produced.

In curing at 50 ° C for 12 days when the amount of zeolitic mineral was small, the compressive strength was 39.1 N / mm ² and the bending strength was 4.7 N / mm ² , and steam curing was performed at 220 ° C for 24 hours with the same composition. The cured zeolite-containing cured product showed higher strength than the compressive strength (15.4 N / mm ² ) and bending strength (4.0 N / mm ² ). This is because the effect of increasing the strength by adhesion of the amorphous phase of fly ash is higher in the case of curing at 50 ° C. for 12 days than in the case of steam curing at 220 ° C. for 24 hours. Inferred.

When the steam curing temperature is low, the reaction does not proceed sufficiently even when blended with a large amount of zeolitic minerals during hydrothermal synthesis, so the amorphous reaction phase is the main component. Is about 40 N / mm ² , and a relatively high strength can be secured. From this, it was clarified that steam curing conditions of 50 ° C. for 12 days or 80 ° C. for 3 days may be sufficient unless the purpose is to produce a large amount of zeolitic minerals. From this result, it is possible to obtain the same effect as described above by applying steam curing under conditions capable of imparting to the kneaded material energy equivalent to steam curing for 12 days at 50 ° C. or 3 days at 80 ° C. Inferred.

  In addition, since it became clear that zeolitic minerals such as merlinolite (Merlinoite) and asbestos (Phillipsite) can be generated by lowering the curing temperature in this way, by changing the curing temperature Thus, it has been clarified that the type of zeolitic mineral as a constituent component of the zeolite-containing cured body can be changed.

(7) Electron Microscope Observation The zeolite-containing cured product produced under the conditions of Formulation 2 and Formulation 4 with a curing temperature of 220 ° C. and a curing time of 24 hours was observed with an electron microscope to examine the crystal shape and the like.

  FIGS. 9 to 12 show electron micrographs of the zeolite-containing cured product obtained under the condition of Formulation 2, which is a condition in which the alkali hydroxide is sodium hydroxide. 10 is an enlarged image of region 1 in FIG. 9, FIG. 11 is an enlarged image of region 2 in FIG. 9, and FIG. 12 is an enlarged image of region 3 in FIG. As shown in FIGS. 9, 10 and 12, it was confirmed that a relatively large number of columnar and fibrous crystals were formed. Further, it was confirmed that a large number of coarse and dense crystals having a particle size of about 10 μm as shown in FIG. 11 were produced. A void having an opening width of about 0.1 μm was formed around the dense crystal, and this opening was considered to correspond to a void having a pore size distribution of 0.1 to 2 μm.

  Next, FIGS. 13 to 16 show electron micrographs of the zeolite-containing cured body obtained under the condition of Formulation 4, which is a condition in which the alkali hydroxide is potassium hydroxide. 14 is an enlarged image of region 4 in FIG. 13, and FIG. 15 is an enlarged image of region 5 in FIG. FIG. 16 is an electron micrograph obtained by photographing a region different from FIG. As shown in FIG. 13 to FIG. 16, many micro columnar crystals and stacked columnar crystals are generated. In FIG. 14, the presence of strip-like crystals is confirmed, and in FIG. 16, the presence of microfibrous crystals is confirmed. . In addition, there are solid stacked products surrounding the microcolumnar crystals and the stacked columnar crystals (see FIGS. 13 and 15), and the form thereof is calcium silicate hydrate (C -SH) form. From this observation result, it is considered that the similarity to the form of calcium silicate hydrate (C—S—H) in cement hydrate is one of the factors of strength development of the zeolite-containing hardened body. It was.

(8) Summary As described above, according to the method for producing a zeolite-containing cured body of the present invention, a high-strength block-like zeolite containing a compressive strength of 15 to 87 N / mm ² and a bending strength of 4.0 to 13 N / mm ² is contained. It has become clear that a cured product can be produced. Therefore, according to the method for producing a zeolite-containing cured body of the present invention, it is possible to produce a high-strength zeolite-containing cured body as compared with a conventional method for producing a zeolite-containing cured body. It is possible to cope with the case where a high-strength zeolite-containing cured body is required as a building material.

Further, steam curing (curing temperature: 220 ° C.) while applying physical restraint pressure to the kneaded material prepared by mixing 176.1 g of potassium hydroxide and 248.4 g of water with respect to the condition of Formulation 4, that is, 1000 g of fly ash. , The cured zeolite-containing body produced as a curing time of 24 hours) has a very light density of 1.6 g / cm ^3, and according to the method for producing a cured zeolite-containing body of the present invention, the strength is high. It has been found that a very light zeolite-containing cured product can be produced. Further, since the water absorption of the zeolite-containing cured product was 20%, it can be used as a solid adsorbent. In addition, when a zeolite-containing hardened body having a water absorption of 5% or less is obtained by the production method of the present invention, it can be used as a fine aggregate for high-strength concrete by pulverizing it. It is.

  The zeolite-containing cured product obtained by the production method of the present invention can be used as a substitute material for a concrete member that is desired to be used stably for a very long period of time, and as a block material such as brick. Moreover, since zeolite has a deodorizing, moisture absorption, humidity control, and moisture releasing function, it can also be used as a building material having these functions. As a specific example, it can be used as a building material having a function of adsorbing organic molecules that cause sick house syndrome. Further, it can be used as a solid adsorbent, an ion exchange material, a catalyst, and the like. It can also be used as an adsorbent for carbon dioxide, which is a greenhouse gas.

Claims (3)

Steam curing while applying a physical restraint pressure of 0.02 MPa to 0.3 MPa to a kneaded material obtained by kneading an amorphous material powder containing silica and alumina, an alkali hydroxide and water. A method for producing a zeolite-containing cured body, characterized by being applied.   The method for producing a zeolite-containing cured body according to claim 1, wherein reinforcing fibers are further kneaded in the kneaded material.   The manufacturing method of the zeolite containing hardening body of Claim 1 which uses a fly ash as the granular material of the amorphous material containing the said silica and an alumina.