JP2002128550A - Alkali-based curing agent and water resistant and heat resistant solidified body and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to reuse wastes by producing an inorganic solidified body without pollution and consumption of a large quantity of energy. SOLUTION: This alkali-based hardener is constituted by addition of a calcia composition, an alkaline composition, a water composition, and, if necessary, a hardening assisting composition into a silicate-based raw material (including wastes) and, furthermore, if necessary, a deformed admixture constituted by addition of a functionality supplementing composition is molded and processed into a granular body, a specified structure, a deposited material, an unspecified body, a powdery body, a heavy metal fixing body, and a hardened bulk material, each being made into a hardened body under a normal solidifying condition, and a water resistant and heat resistant solidified body essentially composed of a silica polymer including an aluminum silicate is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-based hardener, a water-resistant and heat-resistant solidified product and its use; more specifically, a calcium composition and an alkali which form a solidified product of a silicate-based material. An alkali-based curing agent comprising a composition and an aqueous composition, and if necessary, a curing auxiliary composition; and an alkali-based curing agent for a silicate-based material, and if necessary, a functional addition composition. The homogeneously mixed deformable admixture is secured in the form of granules, specific structures, adhered and cured products, heterogenous granules, unspecified shapes, powders, and aggregates, and then subjected to room temperature solidification. The present invention relates to a technique for providing a solidified body that exhibits water resistance and heat resistance by being transformed into a cured body of various shapes.

[0002]

[Background] At present, "waste problems" are being seriously tackled alongside "energy problems" and "environmental problems" as the issues of the danger of human existence, and there is a strong demand for waste recycling. Therefore, regarding the disposal of waste, the shortage of suitable places for receiving waste, improper disposal such as illegal dumping, and the spread of harmful substances due to improper disposal have a significant impact on the living environment. , Its improvement is a major problem.

[0003] Further, in view of the depletion of resources such as petroleum and the regulation of carbon dioxide emission associated with global warming, the adoption of a melting method or a sintering method using a large amount of heat energy for waste disposal has been difficult.
They are shunned from wasting resources such as oil and increasing the burden on global warming. Naturally, the simple dumping and disposal of waste is regarded as a blasphemy to the global environment, and there is a strong demand for activities to reuse waste as a resource. Therefore, the waste can be safely treated at room temperature without the use of a large amount of thermal energy and without emission of Diokin and diffusion of heavy metals.
There is a demand for reusable products to be provided stably at low cost.

In addition, construction sites, seas, lakes, swamps, rivers,
Dams, construction by-products generated at construction sites,
The treatment and disposal of muddy mud containing water such as sludge, sludge and dredged soil is no exception. In particular, it is important to efficiently reuse a large amount of hydrous muddy mud as construction material. Moreover, it is important to establish a technology for reusing and utilizing these muddy mud and the like at the generation site, and reusing muddy mud and the like as useful soil.

[0005] Further, since Portland cement contains chromium, the Ministry of Construction dated March 24, 2000, stated, "For the time being, use of cement and cement-based solidification material for ground improvement and reuse of improved soil. A letter entitled "Measures for the measures" was issued to the local construction bureau, cautioning that cement be adopted for ground improvement. In addition, cement-processed products used for shore walls and fishing reefs of rivers, lakes, the sea, etc. tend to inhibit the occurrence of algae, etc., and destroy the living forms of living things in the sea, rivers, etc. There is a strong demand for a solidifying agent to replace cement for the restoration of the global environment.

[0006]

2. Description of the Related Art Conventionally, as inorganic solidified products which can exhibit water resistance and heat resistance, so-called so-called sintering / melting methods which require high energy represented by tiles, tiles, sanitary ware, glass and the like are known. Ceramic bodies have been mentioned.
In addition, examples of the inorganic solidified product that can exhibit water resistance at normal temperature construction include a cement / concrete product that is subjected to hydraulic processing using cements produced by high-temperature treatment as a solidifying agent.

In recent years, however, there has been a strong demand for regulation of carbon dioxide emission due to depletion of oil and global warming, and ceramic bodies manufactured through long-time processing at high temperatures and cements requiring high temperatures for manufacturing have been developed. The products used tend to be shunned. Therefore, there is a great deal of research on room temperature processing materials that can exhibit the same performance as ceramic bodies and cement / concrete products without special consumption of energy.

On the other hand, when treating and disposing of wastes containing an inorganic compound as a main component, in the prior art, incineration ash or molten slag in which the wastes are subjected to calcination means to reduce the volume of the wastes are treated in a specific control area. Has been dumped. However, dumping of incinerated ash and molten slag is in a direction that is not permissible due to environmental destruction, and a method of processing these incinerated ash and molten slag into bricks, building materials, and the like has been used. But,
Products manufactured for the purpose of reuse are also restricted by being waste, and are also subject to costs, trends and preferences,
It has not grown to a product that enables stable production and sales.

[0009] The method of reusing water-containing muddy mud, etc., is summarized in the "Construction Generation Utilization Technical Manual" (published in July 1994) supervised by the Technical Research Office of the Secretary-General of the Ministry of Construction. Guidelines for the reuse of muddy mud etc. are given. In this technical manual, regarding the use of waste soil generated, depending on the properties of the soil and the intended use, "use directly without any modification", "use the properties improved on the generating or using side" However, the technical standards for "utilizing via plants and stockyards" and usage methods for each application such as study procedures are suggested in detail, but are inconclusive.

As typical hardening agents capable of inexpensively solidifying at room temperature, there are generally three types of hydraulic hardening agents shown below. Cementing material by hydration of hydraulic minerals, mainly calcium salts, as seen in plaster and cement. As seen in sulfate bands, alumina sol-based binder material obtained by alkali neutralization of aluminum sulfate. As shown in the acid neutralization reaction of alkali silicate such as water glass, a siloxane-bonded silica-based curing agent material formed by polymerization of silanol groups.

Concrete is generally used as a cementing material containing a calcium salt as a hydraulic hardener as a main component. This concrete is used in the field of construction and civil engineering by adding aggregate and water to cement powder produced by high heat treatment at 1400 ° C. and kneading to form a hydrated product of a calcium-based mineral. It is widely used in the processing field of concrete secondary products, is JIS-compliant and is widely used.

The hardening mechanism of cement is described as being based on the formation of a solid matrix by a hydrated compound such as calcium silicate hydrate or ettringite formed by a hydration reaction. Therefore, concrete is a general term for a solidified body in which a matrix structure is formed of a hydrate mainly composed of a calcium compound.

However, these consolidated solids do not have resistance to acids, and the hydrated minerals are dehydrated under heating conditions to destroy the solidified matrix, and the solidified form is not maintained. It is difficult to expect the solidified body to exhibit so-called acid resistance and exhibit heat resistance.

Further, when various aggregates are solidified using cement, when organic components such as saccharides and phosphoric acid components coexist in the aggregates, these saccharides and phosphoric acid components are used as the cement minerals. Since the calcium salt is digested, it is not possible to expect strong solidified properties of the solidified concrete formed here.

As a method for solidifying muddy mud, sludge, soft soil, and even hydrous mud such as volcanic ash clay, various cements or improved cements are used to form hydrated minerals and ettringite. Techniques for modifying soil such as highly watery muddy mud into a solidified body have been disclosed and used.

However, when the soil composed of fine particles such as clayey soil, silt, and clay is to be solidified with cement, the particle size of the soil of the clayey soil, silt, clay, and the like to be solidified is reduced by the cement grain. Since the diameter is smaller than the diameter, fine soil particles surround the cement particles, hindering the hydration mechanism of the cement, and good and efficient formation of a solidified body cannot be expected.

More recently, rivers, bay shores, dams and other barriers constructed from concrete structures and fishing reefs set on the sea floor are different from natural rock barriers and fishing reefs. It has been found that there is a tendency to suppress the breeding of concrete, and the construction of concrete structures in rivers, bays, dams, etc. is being eliminated. In addition, when cement or the like is adopted for ground improvement, etc., chromium contained in the cent is eluted into the surrounding soil, and the adoption of cement is restricted due to environmental pollution problems.

As the alumina sol-based binder material,
A binder effect of alumina sol generated by neutralizing an acidic compound such as aluminum sulfate with an alkaline compound is expected. However, since the neutralization reaction at this time proceeds very quickly, it is difficult to control this neutralization reaction in accordance with the working time, and it is difficult to secure a so-called working pot life, and practical application is not possible. far cry.

As the silica-based curing agent, an alkali silicate containing a silanol group represented by water glass is generally used. The application as a binder utilizes the formation of a silica polymer composed of a polysiloxane bond composed of silicic acid formed by adding an acidic curing agent to a water-soluble alkali silicate and then neutralizing the acid.

Liquid alkali silicate represented by water glass is inexpensive and has a siloxane bond (-Si-
O-) is mainly used in the fields of construction and civil engineering, as well as binders, coatings, adhesives, raw materials for the production of silica gel, structural solids requiring acid resistance and heat resistance, and applications for secondary processed products. Has been used since ancient times.

However, silica-based curing agents have various problems. For example, a silica-based curing agent using an alkali silicate as a raw material is based on a combination of an alkali silicate and an acidic curing agent, and has a poor balance between on-site workability and expression of various physical properties of a solidified product. That is, if the work time is secured with emphasis on the workability, the manifestation of various physical properties of the solidified product is poor. On the other hand, if the manifestation of various physical properties of the solidified product is accelerated, the workability tends to deteriorate.

In the case of these silica-based curing agents made of alkali silicate as a raw material, in a solidified body formed by being subjected to ordinary temperature construction, generally, a water-soluble alkali salt remains as a by-product in the formed solidified body. There is a tendency. Therefore, when water comes into contact with the solidified product, the by-product alkali salt is re-dissolved in water to dissolve the silica component, and the water resistance of the solidified product is prevented, and the basics of the solidified product tend to collapse. is there. Therefore, these solidified bodies are not suitable for use outdoors or the like exposed to rainwater.

Further, the water-soluble alkali salt remaining in the solidified product reacts with moisture or carbon dioxide in the air to generate alkali carbonate, and it is inevitable that a so-called whitening phenomenon occurs on the surface of the solidified product. . These problems have not been solved in practical use with silica-based curing agents using alkali silicate as a raw material, and product troubles caused by this are constantly occurring. Commercialization of applying alkali silicate as a curing agent is still a number of problems. Leaving a point.

An improvement study to solve these problems,
In particular, there is a great deal of improvement research on curing agents and curing conditions to be incorporated into alkali silicates such as water glass, and various improvements and development techniques have been proposed. Some of these research results have been attributed to "inorganic adhesives" Association Journal 12 394 (1976)].

A typical technical disclosure on a self-hardening type alkali silicate is disclosed in US Pat. No. 2,662,022.
(1953). Further, the technical disclosure of a cured composition comprising a combination of a modified water glass solution and an inorganic phosphate is disclosed in JP-B-53-24212 and JP-B-53-1095.
No. 58, JP-B-56-6387, JP-B-57-425
No. 81 and the like, and Japanese Patent Publication No. 53-24206 describes various silicon phosphates effective for alkali silicate in detail. Furthermore, an example of an acid-resistant mortar obtained by reacting water glass with sodium fluorosilicate as a curing agent has been reported (Kairakyo 69 284 (1961)).

Further, the disclosure of an inorganic binder composition one-packed based on a powdery alkali silicate is disclosed in Japanese Patent Publication No. 58-1983.
No. 58306, No. 1-53230, No. 2-1
791 and Japanese Patent Publication No. 2-56299.
In particular, Japanese Patent Publication No. 1-53230, Japanese Patent Publication No. 2-1791,
In Japanese Patent Publication No. 2-56299, a crystalline or amorphous barium silicate powder specially manufactured under the conditions specified for a powdery one-pack inorganic binder composition (high-temperature heat treatment at 700 ° C. or higher) is used. It is disclosed that the combined use improves the fluidity of the paste slurry. Furthermore, Japanese Patent Publication No. 53-24206 discloses in the above-mentioned patent publications.
In JP-A No. 11-284, there is a technical disclosure of a water glass composition containing a curing agent specified for the sustained release of phosphoric acid.

As an application of forming a heat-resistant and water-resistant solid or granule at room temperature using a silica-based curing agent, an aluminate composition specified without using an acidic curing agent with alkali silicate is used. The present inventors have developed a technique for blending a material and fixing an alkali component liberated from a siloxane bond to be generated as an alkali aluminosilicate zeolite or zeolite precursor to utilize waste as a reusable material. Patent application (Japanese Patent Application Laid-Open
-263661) and has been put to practical use.

Typical methods for consolidating and solidifying soft ground include the following three methods. If necessary, quicklime or light burnt magnesia, etc., with additives added, is piled into the ground to form a pile, and while the quicklime, light burnt magnesia, etc. absorbs water in the process of becoming hydroxide, simultaneously uses volume expansion. Alkaline earth oxide method that strengthens the ground by heating. A hardening agent consisting of a powdery material such as cement slurry or cement is mixed and injected into deep soft clayey or sandy soil, and the ground is formed by the pozzolanic reaction between the cement and the silicic acid of the clayey soil. Deep mixing method to strengthen. Into the ground, cement milk, bentonite, water inject various chemicals such as lath to increase the water stoppage of the ground,
Chemical injection method to increase the strength of the ground.

The alkaline earth oxide method is a method of absorbing water in the process of hydration of quicklime and lightly burned magnesium to form a hydroxide and, at the same time, strengthening the ground by utilizing volume expansion. However, this method does not achieve the formation of a water-resistant and heat-resistant solidified body, but takes in the moisture contained in the ground as compound water, lowers the water content, and enhances the ground strength by improving the solid content concentration. It is only for the purpose.

The deep mixing method is a solidification treatment method using cement as a hardening agent. Even though the method of injecting and mixing a cement slurry into soft ground has a novelty, there is no particular novelty as a solidification treatment agent. . In addition, the chemical solution injection method using inorganic materials is expected to form a solid by siloxane bonds formed by polymerization of silanol groups found in the acid neutralization reaction of alkali silicate. Can't expect.

[0031]

As will be understood from the above background and the present situation described in the section of the prior art, wastes and the like are disposed of without being consumed by a large amount of energy in disposal. Waste such as construction waste soil and incinerated ash, such as powdery or hydrous mud-like silicate compositions (incinerated ash, fly ash, slug, construction waste soil,
The establishment of technologies that enable the effective use of clayey soil, organic soil, sludge, soft soil, volcanic ash clayey soil, etc. is still immature, and the conventional room-temperature solidification treatment technology remains a major subject.

As a method for solving the problem, there has been proposed a method of solidifying wastes and the like with a cement-based hardener. However, even if solidification of wastes and the like is carried out with a cement-based hardening agent, not only the harmful substances of the heavy metals contained therein cannot be immobilized in a water-insoluble manner, but also the chromium elution of the heavy metals contained in the cement causes environmental pollution (2000). (Refer to the Ministry of Construction Notice on March 24, 1998)). Therefore, in the solidification disposal using cement, it is not possible to treat and dispose of harmful substances such as wastes without causing environmental pollution.

In addition, rivers, bays, dams and other barriers constructed of concrete structures and fishing reefs set on the sea floor tend to suppress the growth of microorganisms, algae, and fish and shellfish. There is a tendency to eliminate concrete structures such as bays and dams. Furthermore, Portland cement and the like require a firing process at a high temperature of 1400 ° C., consume a lot of energy, generate a large amount of carbon dioxide due to decomposition and combustion of raw limestone, and have a negative effect on global warming. Giving a great deal.

On the other hand, there is a proposal to adopt a silica-based curing agent as a curing agent and to produce a solid by a room-temperature solidification treatment technique. However, there are various problems in the conventional technology of the silica-based curing agent, and a product trouble actually occurs.
The main cause of the trouble is that the free alkali component that is by-produced during the formation of the solidified product from the alkali silicate, which is the main raw material of the silica-based curing agent, remains in the solidified product and causes the efflorescence phenomenon. There is a basic problem as a solidified body that is hindered and the generated solidified body collapses.

As a means for solving these problems, a silanol group forming a siloxane polymer which effectively exerts a binder effect is determined for a clay mineral mainly composed of a ferrosilicate compound, and an alkali component is reacted with the clay mineral. The present inventors have at least prepared a silica-alkali composition, and have developed a binder technology using the silica-alkali composition as a main material of a silica-based binder and a technology related to a water-resistant and heat-resistant solidified body employing the silica-based binder. Have already been developed (JP-A-11-263661).

However, the specified ferrosilicate compound is used as a curing agent raw material, and a dangerous and complicated reaction step between the ferrosilicate compound and an alkali component such as caustic soda is required in advance. The cost of manufacturing has risen sharply, and the cost competitiveness of the curing agent has been drastically reduced, and technology development for further cost reduction is needed.

Further, it is necessary to control the work time by ensuring a workable work time of the silica-based curing agent composed of the silica-alkali composition and the aluminate. It is necessary to provide an adjusting agent capable of adjusting the pot life, and it is necessary to study the effect of the barium salt on the working time and the solidified physical properties when the pot life adjusting agent is adopted. Further, if possible, it is necessary to provide a product that can ensure the pot life in the use of the curing agent without using these pot life adjusting agents.

[0038]

SUMMARY OF THE INVENTION An object of the present invention is to establish an environment-friendly solidification technique at room temperature, which is intended to solidify easily reactive silicate-based materials, and has a conventional cement or alkali silicate-based binder. To provide a pollution-free alkaline hardener that can solve the problems that have been solved, and then subject the deformable admixture prepared with the silicate-based material and alkali-based hardener to solidification at room temperature to achieve water resistance and heat resistance The solidified solid material that stabilizes the heavy metals contained in the raw material to prevent environmental pollution by making it insoluble in water and reduces waste such as silicate-based waste at low cost and safely. By providing it as a product, it contributes to the reuse of waste without imposing a load on global warming.

[0039]

According to the present invention, according to the present invention, a silicate-based material (A) to be solidified is added to a calcium-based composition (B).
A) and an alkaline composition (BB) and an aqueous composition (B)
C) to prepare a deformable admixture (C) by adding an alkali-based curing agent (B) composed of the three components, and then subject the deformable admixture (C) to a room temperature solidification treatment to cure the mixture. In the step of transforming the body (E) to form a water-resistant and heat-resistant solidified body;

[0040] The silicate-based material (A) is dry solid basis silica SiO ₂ oxide criteria expressed by 20 wt% or more, the alumina expressed in _Al 2 _{O 3} oxide basis 2 wt%
A silicate compound which is easily reactive to the ionic alkali metal contained above;

The calcium composition (BA) is represented by the following composition formula (1): CaO.wH ₂ O ‥‥‥‥‥‥ (1) (where w is a number of 10 or less including zero). A calcium standard composition (BA1) containing 50% by weight or more of a calcium component composed of one or a combination of two or more selected from the group of calcium oxides, based on CaO oxide;

The above-mentioned alkali composition (BB) is obtained by oxidizing an alkali metal oxide composed of lithium, sodium or potassium alone or in combination of two or more of them with M ₂ O (M is Li, Na, K). 50 on a product basis
Weight percent or more of a standard alkaline composition (BB
1) is;

The above-mentioned aqueous composition (BC) is water (BC1) containing 70% by weight or more of water; and the above-mentioned alkaline curing agent (B) is 100% calcium hydroxide composition (BA).
1 to 3 parts by weight of alkali composition (BB)
0 parts by weight, and 1 to 300 parts of the aqueous composition (BC).
There is provided an alkali-based curing agent comprising a weight ratio of parts by weight.

According to the present invention, the silicate-based material (A) contains silica in an amount of not less than 20% by weight in terms of dry matter in terms of SiO ₂ oxide and alumina in terms of Al ₂ O ₃ oxide. 2% by weight or more, particle size of 100μ
Sand grains mainly composed of a silicate compound composed of a natural material, a synthetic material, a waste recycle material or a filler group, or a combination of two or more, which are easily reactive to an ionic alkali metal at a distance of 7 mm or less Body silicate material (A
An alkaline curing agent when S) is provided.

According to the present invention, the silicate-based material (A) contains 25% by weight or less of water, 20% by weight or more of silica in terms of dry matter in terms of SiO ₂ oxide, and Volcanic ash clay, clay mineral, organic soil, incineration ash, dry distillation ash, fly ash, slag, construction which is easily reactive to ionic alkali metal containing 2% by weight or more based on ₂ O ₃ oxide When it is a powdery silicate-based material (AP) mainly composed of a silicate compound composed solely or in combination of two or more of waste soil, sludge dry matter, and silicate waste group Is provided.

According to [0046] the present invention, the silicate-based material (A) is, moisture 26% by weight or more, the silica on a dry solid basis expressed as SiO ₂ oxide basis 20% by weight or more, the alumina Al _A hydrous muddy mud, a hydrous clayey or organic soil, a dredged soil, a sludge, a muddy soil, which is easily reactive to an ionic alkali metal contained in an amount of 2% by weight or more based on ₂ O ₃ oxide. Alkali curing agent for hydrated silicate-based material (AW) containing a silicate compound as a main component composed solely or in combination of two or more of soil, clayey soil or volcanic ash soil group Is provided.

According to the present invention, it said Karushiya composition (BA) is represented by the following formula _{(2) Ca n TO m ·} wH 2 O ..................... (2) ( wherein: T is boron , Aluminum, silicon, nitrogen, phosphorus, or an element consisting of a combination of two or more elements of the sulfur element, n is a number of 1.0 to 20.0, m is a number of 0.5 to 6.0, w is Alkali which is an oxyacid salt composition (BA2) composed of one or a combination of two or more of the normal salt or basic salt compound group of calcium oxyacid salts represented by 28.0 or less including zero) A system curing agent is provided.

According to the invention, said Karushiya composition (BA), the following composition formula _{(3) Ca n Z · wH} 2 O .................. (3) ( wherein: Z is halogen, n is 1.0 to 20.0
, And w is a number of 10.0 or less including zero), and an alkali-based curing agent which is a halogen salt composition (BA3) composed of one or a combination of two or more calcium halide salts. Is done.

According to the present invention, the above-mentioned calcium composition (BA) contains waste limestone, waste gypsum, ceramic waste, and the like, containing at least 20% by weight or more of a calcium component based on CaO oxide. Provided is an alkaline hardener which is a waste powder composition (BA4) composed of a powder group consisting of blast furnace slug or incineration ash wastes alone or in combination of two or more.

According to the present invention, the calcium composition (BA) comprises one or a combination of two or more selected from the group consisting of Portland cement, blast furnace cement, silica cement, fly ash cement and alumina cement. An alkaline hardening agent which is a cement powder composition (BA5) composed of cement is provided.

According to the present invention, there is provided the above-mentioned calcium carbonate modified composition (BA6), wherein the calcium carbonate modified composition (BA6) is a calcium carbonate modified composition having a calcium component modified with calcium carbonate as a main component; (BA7) is a natural aragonite, calcite, marble, etc. and calcium carbonate (Ca)
CO ₃ ) 100 parts by weight of powder and, if necessary, an amount of 50 parts by weight or less of an acid radical composed of one or a combination of two or more of hydrochloric acid, sulfurous acid, sulfuric acid, nitrous acid or nitric acid group, and added at 1000 ° C. or less The calcium component which has been denatured by contacting with a temperature of
There is provided an alkali-based curing agent which is a carbon-cal-modified composition containing 0% by weight or more.

According to the present invention, the above-mentioned calcium composition (BA) is a magnesium mixture mainly containing a calcium component containing at least 10% by weight of magnesium oxide or magnesium hydroxide alone or in combination of two types. An alkaline curing agent which is a composition (BA7) is provided.

According to the present invention, the above-mentioned calcia composition (BA) is replaced with the above-mentioned calcia standard composition (BA).
1), oxyacid salt composition (BA2), halogen salt composition (BA3), waste powder composition (BA4), cement powder composition (BA5), coal-calcium modified composition (BA6) and magnesium mixture Calcium composite composition (BA) composed of two or more combination compositions of the composition (BA7) group
8) is provided.

According to the present invention, the above-mentioned alkali composition (BB) has the following composition formula (4): M _n TO _m · wH ₂ O (4) (where M is lithium , An element comprising a single or a combination of two or more of the sodium or potassium element group,
T is an element composed of one or a combination of two or more of boron, aluminum, nitrogen or phosphorus, n is a number of 1.0 to 20.0, m is a number of 0.5 to 6.0, and w is zero. Or a number of 28.0 or less), which is an alkali-oxyacid composition (BB2) composed of one or a combination of two or more of a normal salt or a basic salt compound group of an alkali metal oxyacid salt. An alkaline curing agent is provided.

In accordance with the present invention, the alkaline composition (BB) is the following formula _{(5) M n Z · wH} 2 O .................. (5) ( wherein: M is lithium, sodium Or an element consisting of one or a combination of two or more of the potassium elements,
Z is a halogen element, n is a number from 1.0 to 20.0, w
Is an alkali-hardening composition (BB3) composed of one or a combination of two or more alkali metal halide salts represented by the following formula: .

According to the present invention, the above-mentioned alkali composition (BB) is converted into an easily reactive silicic acid-containing composition (BBS) in a solution in which an alkali metal compound is dissolved in an aqueous composition (BC) in advance. In the coexisting solution-silicate-alkali solution composition (BB4);

The above silicic acid-containing composition (BBS) is composed of an amorphous silica composition (BBS1) and a layered clay composition (BB).
S2) a silicic acid or silicate easily reactive with an ionic alkali metal composed of one or a combination of two or more of a hydrous muddy mud composition (BBS3) or an alkali silicate composition (BBS4) group; A silicic acid-containing composition as a main component;

The above amorphous silica composition (BBS1)
Is an amorphous silica composition containing amorphous silicic acid as a main component; the layered clay composition (BBS2) is 2: 1
A layered clay composition composed of a hydrous ferrosilicate clay having a layered dioctahedral or trioctahedral smectite group clay mineral as a main component;

The above-mentioned hydrous muddy mud composition (BBS3)
Is a hydrous muddy mud composition mainly containing aluminosilicate, which is the hydrous silicate-based material (AP); the above alkali silicate composition (BBS4) has the following composition formula ( _{6) M 2 O · bSiO 2} · wH 2 O .................. (6) ( wherein: M is the number of lithium, the alkali metal element as sodium or potassium, b is to no 1.0 3.5, w Is a deliquescent or liquid alkali silicate group alone or in combination of two or more kinds, having a silanol group represented by a number of 1.6 to 50.0);

The above-mentioned silicate-alkali solution composition (BB)
4) is based on 100 parts by weight of the silicic acid-containing compound (BBS), the alkali metal hydroxide is M (OH) (M is L
i, Na, K) A silicic acid-alkali solution composition obtained by adding 1 to 200 parts by weight of hydroxide and 1 to 200 parts by weight of water and reacting at room temperature or under heating conditions. Certain alkaline curing agents are provided.

According to the present invention, the above-mentioned alkali composition (BB) is mixed with an alumina-containing composition (BB) in a solution in which an alkali metal compound is previously dissolved in an aqueous composition (BC).
In the solution-aluminate-alkali solution composition (BB5) coexisting with A); the above-mentioned alumina-containing composition (BBA) is obtained by converting an aluminum compound or an aluminate to an oxide (Al ₂ O ₃ ). An alumina-containing composition containing, as a main component, an aluminum-containing compound which is easily reactive to an ionic alkali metal containing not less than 20% by weight;

The aluminate-alkali solution composition (BB5) was prepared by oxidizing an alkali metal hydroxide with M ₂ O (M is Li, Na, K) per 100 parts by weight of an alumina-containing compound (BBA). 1 to 200 parts by weight of water and 1 to 200 parts by weight of water, and an alkali-based curing agent, which is an alkali-aluminate solution composition, which is subjected to a reaction treatment at room temperature or under heating conditions. Is done.

According to the present invention, the above-mentioned alkali composition (BB) is added to a solution in which an alkali metal compound is previously dissolved in an aqueous composition (BC), and a sulfate group-containing composition (BBR) is used.
In the form of a solution of sulfuric acid-alkali solution (B)
In B6): the above-mentioned sulfate group-containing composition (BBR)
Is a sulfate group-containing composition composed of an oxyacid salt of sulfur alone or in combination of two or more of an elemental group of alkali metals, alkaline earth metals, iron and aluminum;

The above sulfuric acid-alkali solution composition (BB)
6) converts an alkali metal hydroxide to M ₂ O (M is Li, N) with respect to 100 parts by weight of a sulfate group-containing compound (BBR).
a, K) 1 to 200 parts by weight expressed on an oxide basis;
There is provided an alkaline curing agent which is a sulfuric acid-alkali solution composition containing an alkaline sulfur oxyacid salt, which is mixed by adding water in an amount of 1 to 200 parts by weight.

According to the present invention, the above-mentioned alkali composition (BB) is replaced with the above-mentioned standard alkali composition (B
B1), alkali-oxyacid composition (BB2), alkali-halogen salt composition (BB3), silicic acid-alkali solution composition (BB4), aluminate-alkali composition solution (BB5) and sulfuric acid-alkali composition Solution (BB
6) An alkaline curing agent which is a composite alkaline composition (BB7) composed of a plurality of compositions composed of a combination of two or more of the groups is provided.

According to the present invention, the alkaline curing agent (B) is a three-component alkaline curing agent comprising a calcium composition (BA), an alkaline composition (BB) and an aqueous composition (BC). A four-part alkaline curing agent (B) obtained by further adding a curing auxiliary composition (BD) to (B);

[0067] curing auxiliary composition above (BD) is represented by the following formula _{(7) EO n / 2 ·} eB 2 O 3 · wH 2 O ............... (7) ( wherein: E is lithium, sodium Or an alkali metal element of potassium, or an alkaline earth metal element of magnesium, calcium or zinc, e is a number of 1.0 to 2.0, and w is a number of 10 or less including zero). A buffer band forming composition (BD1) composed of one or a combination of two or more oxyacid salt compounds of a class of metal borons;

The above alkaline curing agent (B) is used in an amount of 1 to 30 parts by weight of the alkali composition (BB) and 100 parts by weight of the alkali composition (BC) with respect to 100 parts by weight of the calcium composition (BA).
Is added in the range of 1 to 300 parts by weight, and the curing auxiliary composition (BD) is further added in an amount of 50 parts by weight or less to provide an alkaline curing agent composed of four components.

According to the present invention, the above-mentioned curing auxiliary composition (BD) has the following unit cell chemical composition formula (8): M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · wH ₂ O 8... (8) (where M is a metal cation having a valence of n, and x + y is a tetrahedral number per unit cell) A crystal growth seed composition comprising an aluminosilicate zeolite ( BD2) is provided.

According to the present invention, the above-mentioned curing auxiliary composition (BD) has the following composition formula (9): M ₂ O · fSO _n · wH ₂ O (9) (where M is An alkali metal element of lithium, sodium or potassium, f is a number of 1.0 to 2.0, w is a number of 4 or less including zero, and n is a number of 2 or 3) There is provided an alkaline curing agent which is a curing accelerator composition (BD3) composed of a single salt group or a combination of two or more salts.

According to the present invention, the above-mentioned curing auxiliary composition (BD) has the following composition formula (10): BaO.gSiO ₂ .wH ₂ O (10) (where g is 4. A hardening adjusting composition (BD4) comprising a barium salt compound powder group soluble in an alkaline solution alone or in combination of two or more, represented by the following formula (BD4): ) Is provided.

According to the present invention, the above-mentioned curing auxiliary composition (BD) has the following composition formula (11): hSiO ₂ .P ₂ O ₅ (11) (where h is 1. An alkali-based hardening reinforcing composition (BD5) composed of a single or a combination of two or more powdered silicon phosphates having a sustained release of phosphoric acid represented by the following formula: A curing agent is provided.

According to the present invention, the above-mentioned hardening auxiliary composition (BD) is used as the buffer zone forming composition (BD)
1), a composite auxiliary composed of a combination composition of two or more of a crystal growth seed composition (BD2), a curing accelerating composition (BD3), a curing adjusting composition (B45) and a curing reinforcing composition (BD5). An alkaline curing agent that is a composition (BD6) is provided.

According to the present invention, the alkaline curing agent (B) comprises a calcium composition (BA) and a three-component alkaline curing agent of an alkaline composition (BB) and an aqueous composition (BC). (B) or a four-part alkaline curing agent (B) obtained by adding a curing auxiliary composition (BD) to the three-part alkaline curing agent (B) as necessary;

A liquid alkali-based curing agent having a slurry or fluid liquid state having a pH value of 10 or more even after the combined composition of the constituted alkaline-based curing agent (B) is integrated. There is provided an alkaline curing agent which is the agent (BL).

According to the present invention, the alkaline curing agent (B) is a three-component alkaline curing agent consisting of a calcium composition (BA) and an alkaline composition (BB) and an aqueous composition (BC). (B) or a four-part alkaline curing agent (B) obtained by adding a curing auxiliary composition (BD) to the three-part alkaline curing agent (B) as necessary;

The alkali-based curing agent (BP), which is a powdered alkali-based curing agent (BP), which reacts when the composition of the constituted alkali-based curing agent (B) is integrated and is transformed into a one-pack powder state. A curing agent is provided.

According to the present invention, the above-mentioned claims 1 to 2
4. A deformable admixture (C) prepared by adding the alkaline curing agent (B) according to any one of (4) to the silicate-based material (A) to be solidified and solidified at room temperature. In the step of forming a water-resistant and heat-resistant solidified body by subjecting the cured body (E) to a treatment to transform the cured body (E);

The above-mentioned deformable admixture (C) is composed of 100 parts by weight of the silicate-based material (A) and 20 to 500 parts by weight of the alkali-based curing agent (B). A mixture which is homogeneously mixed to ensure flowability or plastic processability;

The above-mentioned room temperature solidification treatment is a solidification treatment step of releasing the deformable admixture (C) into the atmosphere or water at least at room temperature to allow the reaction and curing to proceed, thereby transforming it into a cured product (E). Yes; a water- and heat-resistant solidified body in which the above-mentioned cured body (E) simultaneously exhibits water resistance and heat resistance is provided.

According to the present invention, the above-mentioned deformable admixture (C) is a two-component deformable admixture (C) of a silicate-based material (A) and an alkali-based curing agent (B). And a three-component mixed deformable admixture (C) further added with a functional addition composition (D);

The above functional addition composition (D) comprises a pigment,
Addition of functionality to solids composed of powder or granules having a particle size of at least 100 μm or less composed of a colorant, an activator, a filler and a group of functionalizing agents alone or in combination of two or more. Additive material composition (D1);

The above-mentioned deformable admixture (C) is composed of 100 to 100 parts by weight of the silicate-based material (A), 20 to 500 parts by weight of the alkali-based curing agent (B), and a functional additive composition. A water-resistant and heat-resistant solid which is a composite-type deformable admixture in which fluidity or plastic workability is ensured by homogeneously mixing the three components obtained by adding (D) to an amount of 1000 parts by weight or less is provided. You.

According to the present invention, the functional additive composition (D) is a silicate-based material (A) composed of iron hydroxide containing a divalent or trivalent iron hydroxide as a main component. Alternatively, there is provided a water-resistant and heat-resistant solid that is an arsenic-fixing composition (D2) for fixing an arsenic element contained in a calcium composition (BA).

According to the present invention, the functional additive composition (D) is a silica, alumina, silicate, carbon, zeolite-based adsorbent alone or in combination of two or more, and has a particle size of 100 μm or more. The present invention provides a water-resistant and heat-resistant solid that is an adsorptive material composition (D3) that exhibits an adsorptive function in a gas or solution composed of a powder or a granular material having a size of 8 mm.

According to the present invention, the functional additive composition (D) is represented by the following formula (12): ZO _y .hDO _x .wH ₂ O (12) Monovalent or divalent silver, copper, zinc or nickel element, D is calcium, magnesium, boron, aluminum, carbon, silicon, nitrogen, phosphorus or sulfur element, h is a number of 3.5 or less including zero, w is 24 including zero
0 or less, y is a number from 0.5 to 1.0, x is 0.5
Or a number of compounds containing silver, copper, zinc or nickel represented by the following formula (D3), which is an antimicrobial composition (D4) consisting of a single or a combination of two or more compounds. Provided.

According to the present invention, the above-mentioned functional additive composition (D) is a solid product formed from a water-repellent compound of an organosiloxane alone or a water emulsion group of an organosiloxane alone or in combination of two or more. A water- and heat-resistant solidified body, which is a liquid water-repellent additive composition (D5) for imparting water repellency to water.

According to the present invention, the functional additive composition (D) is used alone or in combination of two or more of a fiber group of metal fiber, glass fiber, carbon fiber, aramid fiber, vegetable fiber and mineral fiber. A fibrous reinforcing composition (D) that reinforces the solidified body strength of the resulting solidified body composed of a fibrous reinforcing agent
6) A water- and heat-resistant solidified product is provided.

According to the present invention, the functional additive composition (D) has a particle size in the range of 100 μm to 7 mm and a bulk specific gravity in the range of 0.5 to 2.5 g / cc. There is provided a water-resistant and heat-resistant solidified body which is an aggregate composition (D7) capable of supplementing the solidified body with sand particles.

According to the present invention, the functional additive composition (D) comprises the additive material composition (D1), the arsenic-immobilized composition (D2), and the adsorptive material composition (D3). ,
Antimicrobial composition (D4), water repellent additive composition (D
5) A water- and heat-resistant solidified body which is a multiple auxiliary composition (D8) composed of a combination of two or more of the fibrous reinforcing composition (D6) and the aggregate composition (D7) is provided. You.

According to the present invention, the above-mentioned room temperature solidification treatment comprises:
A water-resistant and heat-resistant solid which is a room-temperature solidification treatment step of transforming the deformable admixture (C) into a cured product (E) by reaction and curing released in an atmosphere of 400 ° C. or lower is provided.

According to the present invention, the cured product (E) is
The cured product (E), which is obtained by subjecting the deformable admixture (C) to a solidification treatment at room temperature to be transformed, has a property of at least 4
A water-resistant and heat-resistant solid which is a solid having a cured body strength of 50% or less even when left in an atmosphere of 00 ° C. is provided.

According to the present invention, the cured product (E) is
The cured product (E) for transforming the deformable admixture (C) into a solid by subjecting it to room temperature solidification treatment has a hardness of 2 kg / cm ² or more, preferably 10 kg or more.
Kg / cm ² or more, more preferably 90 Kg / cm ²
A water- and heat-resistant solidified body that exhibits the above uniaxial compressive strength is provided.

According to the present invention, the cured product (E) is
The cured product (E) which transforms the deformable admixture (C) by subjecting it to room temperature solidification treatment to convert heavy metals contained in the silicate-based material (A) or the calcium composition (BA) to be solidified to aluminosilicate The present invention provides a water- and heat-resistant solid which is a solid obtained by taking in a salt of zeolite or a zeolite precursor to immobilize heavy metals contained therein in a water-insoluble state.

According to the present invention, the cured product (E) is
A water- and heat-resistant solidified body is provided, in which a cured body (E) for transforming the deformable admixture (C) by subjecting it to a room-temperature solidification treatment and being a solidified porous body having a specific surface area of 500 cm ² / g or more is provided. Is done.

According to the present invention, the cured product (E) is
The deformable admixture (C) is secured to a columnar, granular, or granular granular material (EG) and subjected to room temperature solidification treatment to obtain the granular material (E).
G) A water- and heat-resistant solidified body that is a solidified body composed of a cured body (E) that has been transformed into a shape is provided.

According to the present invention, the cured product (E) is
A cured product which is formed into a specific structure (EU) by shaping the deformable admixture (C) into a specified moldable shape, subjected to room temperature solidification treatment, and transformed into a specific structure (EU) shape ( A water- and heat-resistant solid which is a solid comprising E) is provided.

According to the present invention, the cured product (E) is
When the deformable admixture (C) is coated, coated, adhered, bound, or dusted on the surface or inner surface of the substrate, the cured product (E)
B) and then subjected to room temperature solidification treatment to obtain an adhered and cured body (E
B) A water- and heat-resistant solidified body which is a solidified body composed of a cured body (E) that has been transformed into a shape is provided.

According to the present invention, the cured product (E) is
The deformable admixture (C) is coated, coated, adhered or dusted on the surface or the inner surface of a base material composed of 0.5 to 12 mmφ granular spheres to obtain a heterogeneous granular material (ED), which is then solidified at room temperature. There is provided a water- and heat-resistant solidified body which is a solidified body made of a cured body (E) which has been transformed into a heterogeneous granule (ED) shape.

According to the present invention, the cured product (E) is
From the cured product (E) which has been transformed into the unspecified form (EU) by securing the deformable admixture (C) to the unspecified form (EU) which is not limited to the specified shape and being subjected to room temperature solidification treatment The present invention provides a water-resistant and heat-resistant solid which is a solidified product.

According to the present invention, the cured product (E) is
The deformable admixture (C) is secured to a non-specific shape powder (EP) having a particle size of 10 to 2000 μ and subjected to room temperature solidification treatment to be transformed into a zeolite-containing powder (EP). There is provided a water-resistant and heat-resistant solid which is a solid comprising the cured product (E).

According to the present invention, the granules (EG) or the heterogeneous granules (ED) are integrated into granules (EG) or heterogeneous granules (ED) to form millet. In an aggregate cured product (EC) forming a molded product having a through-like void;

The above-mentioned aggregated cured product (EC) is a granular material (E)
G) or 100 parts by weight of heterogeneous granules (ED),
The surface of the granules (EG) or heterolamellar granules (ED) group is coated in an amount of 10 to 65 parts by weight of the deformable admixture (C), and then the coated granules (EG) or the heterogeneous granules (ED) are coated. In a molding process for integrating the layered granules (ED) assemblage, pouring into a disk of a specific thickness or subjecting to a room temperature solidification treatment in a state where the specific shape is secured in the spraying construction process,

Next, the aggregate hardened body (EC) composed of a group of millet-like granules (EG) or heterogeneous granules (ED) having through voids is secured, and the water-resistant material which is transformed into the hardened body (E) is obtained. -Heat-resistant solid.

[0105]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have established a room temperature solidification treatment technology which can solve various problems of conventional room temperature solidification treatment technology such as lath of cement and water, and at the same time, target wastes. Silicate-based material (A) is solidified at room temperature without impact on global warming to provide a water-resistant and heat-resistant solidified body, and immobilizes heavy metals contained in wastes to contaminate the environment. It was determined that it was important to prevent waste and enable the safe reuse of waste.

The present inventors have already developed, as a method of solidifying at room temperature, a hydraulic silica-based binder containing a specific silica-alkali composition and an aluminate composition and a water- and heat-resistant solidified product. Development (Japanese Unexamined Patent Application Publication No. 11-26
3661, hereinafter abbreviated as "prior application technology"), and commercialized and put to practical use, and has achieved results.

The inventors of the present invention have experienced the practical application of the prior application technology based on the room temperature solidification treatment technology constructed with the prior application technology, in order to make the object of the present invention more effective and to achieve at low cost. It has been determined that it is important to overcome various problems and to complete the room temperature solidification processing technology using inexpensive materials and simple processing methods and conditions.

On the basis of the above judgment, the present inventors based on the technology constructed with the hydraulic silica-based binder and the water-resistant and heat-resistant solidified body of the prior application, the silicate which solidifies wastes as well. A non-polluting alkaline hardener is added to the base material to prepare a deformable admixture, and at least at room temperature is released to the atmosphere or water at room temperature. We have conducted intensive studies and conducted experiments with the aim of developing a simple and inexpensive curing agent that enables formation and a processing step.

As a result, when the silicate-based material (A), which is easily reactive, is to be solidified, the present inventors have obtained a silanol group (-Si-OH) having a silanol group (-Si-OH), which exerted a binder effect by the prior application. The necessary alkali silicate can be solidified by adding an ionic alkali metal element to the easily reactive silicate-based material (A) to be solidified without causing the acid alkali to coexist with the curing agent in advance. It has been found that the alkali silicate produced in the material exerts a binder effect in the material to be solidified at room temperature.

[0110] In particular, in the present invention technology, in which a calcium composition (BA) containing calcium as a main component coexists at room temperature with alkali silicate generated in a material to be solidified, it is important to form a hydrated mineral. The formation of silica polymer enables "heat resistance" that was not possible with cement, and the "water resistance" that was impossible with water glass that produces soluble alkali as a water-insoluble alkali aluminosilicate ( And zeolite) have been found, and conditions for simultaneously exhibiting heat resistance and water resistance have been found.

That is, the silicate-based material (A) is targeted by the basic combination of the silicate-based material (A), the calcium composition (BA), the alkali composition (BB), and the aqueous composition (BC). As a result, a room temperature solidification technique that enables solidification at room temperature has been completed. Moreover, it is important to find solidified body forming conditions that can simultaneously exhibit water resistance and heat resistance, which were not possible when cement or water glass is used as a curing agent in the prior art.

Further, it is important that zeolite or a zeolite precursor is formed in the solidified product produced by the technique of the present invention. According to the technology of the present invention, when selecting a silicate-based material (A) or a cassia composition (BA) composed of waste containing hazardous heavy metals, the heavy metals contained are formed by the technology of the present invention. It has been found that water-insoluble salts are incorporated into the zeolite or zeolite precursor crystals, and that elution of heavy metals into water is prevented. Therefore, according to the present invention, heavy metals are immobilized in the solidified body, and an effect of preventing heavy metals from being diffused and contaminated in the environment can be exerted.

Therefore, the adoption of the room temperature solidification treatment technology of the present invention fixes heavy metals as harmful substances at room temperature treatment, and enables the solidification of wastes containing heavy metals without the use of large amounts of energy. The waste can be provided as a body, and the waste can be used as a valuable resource, rather than as troublesome garbage that must be disposed of in a specific management area. This suggests that the technology of the present invention can contribute to solving environmental problems.

Further, the inventors of the present invention have proposed a calcium-containing composition (B
Workability in deformable admixture (C) prepared from alkali hardener (B) composed of A), alkali composition (BB) and aqueous composition (BC) and silicate material (A) In addition, an auxiliary agent capable of exhibiting a supplemental effect was studied in response to various needs required for the cured product (E) to be formed. As a result, they have found that when various curing auxiliary compositions (BD) are used in combination with the alkaline curing agent (B) of the present invention, the respective auxiliary effects are exhibited in combination.

Furthermore, the present inventors, in order to add various additives, filling properties and functions to the deformable admixture (C) to be prepared, various additives and fillers, and also various kinds of additives. The function-imparting agent was studied. As a result, when the deformable admixture (C) of the present invention is adopted in combination with various functional addition compositions (D), the respective additive properties, filling properties, and functions are added to the solidified product of the present invention. I found that it can be added.

As described above, the present inventors have found that the alkaline composition (B
B) and the calcium composition (BA), and if necessary, the curing auxiliary composition (BD), and also the functional addition composition (D), are separately or simultaneously, or are pre-packed, and then solidified. When the deformable admixture (C) is prepared by homogeneously dispersing it in the target silicate-based material (A) and then subjected to room temperature solidification, the cured product (E) formed here is water resistant. It has heat resistance, has a certain strength, immobilizes heavy metals, has properties as an inorganic carrier, and can be processed into shapes and molded bodies according to the purpose of use Was found.

The basic reaction phenomena of the room temperature solidification treatment technology of the present invention found above are considered to be in the following three points. The reaction between the ionic alkali metal element constituting the alkali-based curing agent (B) and the easily reactive silicate-based material (A) in the object to be solidified causes the alkali silicate having a silanol group to be formed. Generate. A dealkalization reaction occurs in the alkali silicate generated by the coexisting calcium, and the contained silanol groups form a siloxane polymer composed of polysiloxane bonds. The alkali component by-produced in the dealkalization reaction reacts with coexisting silica or alumina to fix the alkali and produce zeolite or a zeolite precursor.

In any case, the solidified body prepared by the room-temperature solidification treatment technique of the present invention is not formed by solid reaction of alkali metal ions or calcium component of the curing agent component directly to form a solidified matrix, The silicic acid component and alumina component of the silicate-based material (A) become a solidified body through a chemical reaction with alkali metal ions to form an aluminosilicate compound (zeolite or zeolite precursor) and a siloxane polymer. There is a feature in what you do.

The present invention also provides a deformable admixture (C) obtained by uniformly mixing an alkali-based curing agent (B) with a silicate-based material (A) to be solidified, into a granular material (EG), and a specific structure. Body (EM), adhesion hardened body (EB), heterolamellar granule (ED),
Unspecified form (EU), powdered granule (EP), aggregated cured body (E
After securing the respective shapes of C), the solidified material which has been subjected to room temperature solidification treatment technology and transformed into a cured product (E) is formed into a solidified product which is effectively provided for each application used in each field. It is in.

What is important in the present invention is that the specified alkali-based curing agent (B) is selected, the silicate-based material (A) is solidified, and a deformable admixture (C) is prepared. By securing the deformable admixture (C) in various shapes and subjecting it to room temperature solidification treatment conditions, it transforms into a cured product (E) that is suitable for applications of various shapes and produces various water-resistant and heat-resistant solids. It is being made possible to provide the product safely at low cost for the purpose and application.

In particular, in the present invention, a silicate-based material (AP) or a silicate-based material (AW) which is difficult to handle in a powdery or muddy state is intended to kill the properties of the silicate-based material (A). In addition, it can be processed into granular material (EG) that is easy to handle, and the silicate-based material (A) composed of waste can be effectively used as a recyclable product without waste.

Hereinafter, specific embodiments for carrying out the present invention will be described with reference to a silicate-based material (A) to be solidified; an alkali composition (BB) which is a component of an alkali-based curing agent (B); The calcium composition (BA), the curing auxiliary composition (BD), and the liquid alkaline curing agent (BL) and the powder alkaline curing agent (BP) prepared in advance will be described. Further, a functional additive composition (D) that is optionally blended with a silicate-based material (A) and an alkali-based curing agent (B), and a deformable admixture prepared by homogeneously mixing these materials. (C) will be described.

Furthermore, the prepared deformable admixture (C) was further converted into a granular material (EG), a specific structure (EM), an adhesion hardened product (EB), a heterogeneous granule (ED), and an unspecified shape (E).
U), granules (EP), aggregated cured bodies (EC), etc., are secured and cured by subjecting them to room temperature solidification treatment, which reacts and cures at least when released into the air or water at room temperature. A description will be given of the fact that it is a solidified body which is transformed into a body (E) and simultaneously exhibits water resistance and heat resistance.

The silicate-based material (A) which can be suitably employed in the present invention and which is to be solidified, has a water content of 25% by weight or less, and is an easily reactive and substantially powdery silicate-based material (A).
P); a sandy silicate material (A) having a water content of 25% by weight or less, an easy reactivity and a particle size of 100 μm to 7 mm
S): Three types of silicate compositions (AW) which are easily reactive and contain a hydrous mud-like aluminosilicate containing 25% by weight or more of free water as a main component.

The powdery silicate material (A) adopted in the present invention
P) is a natural or synthetic silicate or aluminosilicate containing 20% by weight or more of silicic acid based on SiO ₂ oxide and ₂ % by weight or more of alumina based on Al ₂ O ₃ oxide. A silicate-based compound powder that is easily reactive to the main ionic alkali metal element is preferable.
The powdery silicate-based material (AP) of the present invention does not need to be completely anhydrous, and may be in the form of water of crystallization, absorbed water, attached water, free water, or the like. 20% by weight powder
Moisture may be contained in the following amounts.

Representative examples of the powdery silicate-based material (AP) include natural or synthetic volcanic ash clay, layered clay mineral, clayey soil, organic soil, and powdery silicate material (AP).
Various natural soils, incineration ash, dry distillation ash (charcoal-silicate ash), fly ash, blast furnace slag, etc., various sludges, construction waste soil, sludge dry matter, rocks waste, ceramic products waste Examples of the powdery material mainly include a silicate compound composed of a single or a combination of two or more kinds of powders of waste and various wastes.

In particular, specific examples of the powdery wastes suitably adopted in the present invention include the following examples. Steel slugs (blast furnace slugs, steelmaking slugs) emitted from the steel industry Sludges emitted from metal smelters and ships, which are silicate-containing wastes Fly ash emitted from coal-fired power plants Emissions from the paper industry Organic waste discharged from agricultural, livestock and fisheries sites, food factories, paper industry, urban sludge, etc. and their carbonized ash (charcoal-silicate). Various incineration ash and sewerage Various incineration ash produced as a by-product from incineration Waste incineration ash and molten slag powder of incineration ash Dust powder emitted from the ceramic industry dealing with stone, clay and ceramics Emitted from dams, rivers, and various water treatment plants Sludge, sludge and dried products of sedimentary soil {10} Silicate-containing waste such as construction industrial waste and processed powder thereof.

However, the above powdery silicate material (A
The silicate-containing wastes adopted in P), such as various incineration ash, carbonized carbonized ash, and volcanic ash have undergone thermal history, and many fine pores and pores are present on the particle surface of the powder. It has a large specific surface area and a water absorption of 1000 cm ² /
g or more. In the silicate-based material (A1) having a large specific surface area and a large water absorption, the alkali-based curing agent to be blended is absorbed by the large surface area, and the effect as a curing agent is reduced, and a strong solidified body is formed. difficult. In such a case, the silicate material (AP) may be preliminarily subjected to an impregnation process for filling pores to reduce the specific surface area and adopted as the silicate material (AP) of the present invention. preferable.

A typical example of the silicate-based material (AS) preferably used in the present invention is a granular silicate-based material (AS), which is mainly composed of easily reactive silicate-based waste. Recycled materials that have been processed into waste, particle size-adjusted products such as construction waste soil, as well as heavy or light aggregates synthesized from various waste materials, and volcanic ash containing easily reactive silicate And silicate materials in the form of sand or granules of natural clays.

The sand-grained silicate-based material (AS) may include a granular silicate-based material having a particle size of 100 μm or more and 7 mm or less. Specific shapes of the sandy silicate-based material (AS) include various shapes such as sand, lump, needle, column, sphere, hollow, fiber, plate, flake, and deformation. Can be used as a sandy silicate-based material (A2).

The particle size of the sandy silicate material (AS) is generally preferably 7 mm or less as a material to be solidified to form a solidified body. When used in combination with (AP), a silicate-based material (AS) having a particle size of 7 mm or more may coexist.

Representative examples of the hydrous mud-like silicate-based material (AW) include construction sites such as construction and civil engineering, sea,
Clay soil, organic soil, muddy soil, soft soil, sludge, dredged soil, volcanic ash containing layered clay minerals such as construction by-products and dredging by-products generated as waste by lakes, swamps, rivers, dams, etc. A silicate-based compound in the form of hydrous mud containing silicate, which is a viscous soil, as a main component and containing at least 25% by weight of water.

Conventionally, when hardening these hydrated mud, for example, sludge, into a solidified body, a hardening agent for cement has been added. However, mixing of a large amount of powdered cement is inevitable, and hexavalent chromium contained in cement is
It was not effective due to the problem of elution from the solidified material using cement.

However, by adopting the alkaline hardener (B) according to the present invention, these problems of hexavalent chromium and the like can be solved, and a fluid mud-like silicate-based material (AW ) As solidification target soil, the solidified body formed here secures a certain strength at low cost, and when heavy metals are contained, the heavy metals are fixed,
In addition, there is a feature that a solid body having water resistance and heat resistance can be obtained.

In addition, even if conventional Portland cement or the like is adopted as an improved hardening agent for soft ground against soft mud of soft ground based on volcanic ash such as Kanto loam, the fineness of clay particles such as Kanto loam can be improved. Further, the hardening is inhibited by the organic substances contained in the Kanto loam and the like and the decayed substances of the organic components, and a solidified body having a secured strength cannot be realized, resulting in failure.

By adopting the alkaline hardening agent (B) in the present invention, an effective solidified body can be formed even on the above-mentioned hydrated muddy clay of volcanic ash such as Kanto loam, as shown in Examples described later. It shows that it is a hardening agent that makes it possible to exhibit an effective solidification ability even with hydrous mud such as soft ground.

In the present invention, a silicate which is easily reactive to an alkali corresponding to the silicate material (A) to be solidified is replaced with an alkali composition constituting an alkali-based curing agent (B) as described later. Material (BB) and calcium composition (BA)
Can coexist in advance, and specifically,
Silicic acid-alkali composition (B) of alkali composition (BB)
B2) and the waste powder composition (BA5) of the calcium composition (BA).

When a calcium composition (BA) or an alkali composition (BB) is adopted in the presence of a silicate,
Even if the above-mentioned silicate-based materials (A) are not selected as solidification targets, the silicate materials are already present in the adopted alkali-based curing agent (B). Therefore, even if a more deformable admixture (C) of only an alkali-based curing agent (B) coexisting with silicate is prepared, this deformable admixture (C) is subjected to room temperature solidification treatment. Thus, the cured product (E) of the present invention
It is possible to provide a water-resistant and heat-resistant solid for the purpose of the present invention.

The alkaline curing agent (B) of the present invention comprises a calcium composition (BA), an alkaline composition (BB) and an aqueous composition (BC), and if necessary, a curing auxiliary composition (BD). ) Is added. In particular, in order for the calcium composition (BA) of the alkali-based curing agent (B) to react with the silicate-based material (A) to be solidified to form a cured product, first, the water-based composition (BC) must be used. It is important to form an alkali silanol group of the silicic acid by the coexistence of the alkali composition (BB) in the presence of.

The aqueous composition (BC) coexisting in the alkali-based curing agent (B) of the present invention originally functions as a solvent for dissolving the alkali component of the alkali composition (BB) ionically, and at the same time, the calcium composition It is important that the water help the dispersion of the substance (BA). Therefore,
This water-based composition (BC) is prepared in advance by a calcia composition (B
The dispersing medium of A) may be mixed with the calcium composition (BA), or may be a dissolving medium as a solution of the alkaline composition (BB) in advance, such as water containing sodium chloride such as seawater.

The aqueous composition (BC) of the present invention is a powdery alkaline curing agent (BP) prepared by combining and reacting water with a calcium composition (BA) and an alkaline composition (BB). Is mixed with the silicate-based material (A) to form the deformable admixture (C), the powdered alkali-based curing agent (BP) may be adopted as a dispersion aqueous medium for slurrying.

Further, when a hydrated mud silicate-based material (AW) is adopted as the silicate-based material (A),
The water contained in the hydrous mud silicate-based material (AW) can also be used as the water-based composition (BC) of the present invention. Furthermore, in the alkali composition (BB), a silicate-alkali solution composition (BB4) and an aluminate-alkali solution composition (B
B5), water in the sulfuric acid-alkali solution composition (BB6) and the composite alkali composition (BB7) can also be used as the aqueous composition (BC) of the present invention.

In the alkali-based curing agent (B) of the present invention, the silicate-based material (A) to be solidified and the alkali composition (BB) are first reacted by making full use of room-temperature solidification treatment technology. An alkali is generated, and then the alkali silanol group of the generated alkali silicate is transformed into a cured product (E) having a polysiloxane bond as a base by the action of the calcium composition (BA), and at the same time, by-produced. It is important to be able to immobilize a free alkali component as zeolite or the like, which is a water-insoluble aluminosilicate.

As the composition suitable as the calcium composition (BA) adopted in the present invention, the following eight kinds can be suitably mentioned. Calcium standard composition (BA1) which is an oxide / hydroxide of calcium Oxyacid salt composition which is an oxyacid salt compound (BA2) Halogen salt composition (BA3) which is a halogen compound of calcium Slug, Waste powder composition which is waste such as sludge and incinerated ash (BA4) Cement powder composition which is Portland cement and alumina cement (BA5) Charcoal which is a heat-treated denatured product of natural marble and shells Modified composition (BA6) Magnesium or magnesium mixed composition containing magnesium hydroxide (BA7) Two or more calcium composite compositions (BA8) of the above-mentioned calcium composition (BA) group

The calcium composition (BA) in the present invention
Depending on the use, purpose, workability, etc. of the solidified product to be produced, natural mineral resources mainly composed of calcium compounds, synthetic chemicals, industrial chemicals, commercially available hydraulic cements,
It is possible to appropriately select from shells such as scallops and oysters, further wastes containing calcia, etc., and to use these single-piece compositions or combination compositions, and furthermore, process-modified compositions using these as raw materials. .

The calcium composition (BA) of the present invention generally has a calcium component of 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight, based on the CaO oxide. It is preferably a powdered calcium composition (BA) containing calcium oxide having high reaction activity as a main component. Alternatively, it is preferably calcium hydroxide obtained by reacting water with this calcium oxide.

In general, it is preferable that the calcium as a main component constituting the calcium composition (BA) is a natural or synthetic calcium oxide or hydroxide. However, these calcium compounds are sensitive to the reaction with carbonic acid and water present in the air, and generally form a carbonate, but generally contain a variety of impurities. Therefore, when the alkali-based curing agent (B) is adopted, it is desirable to appropriately select the solidified body according to the present invention according to the intended use and application thereof, and to purify the solidified body as necessary before adopting.

It is important that the alkali composition (BA) of the alkali curing agent (B) employed in the present invention contains calcium having high activity as a main component. Various kinds of calcium salts or basic salt compounds of calcium which can release calcium ions in the coexistence are easily reactive silicate-based materials (A) in the alkaline curing agent (B) of the present invention. Any calcium compound that can effectively act as a polymerized curing agent can be suitably selected.

Of course, the calcium composition (BA) adopted in the present invention contains, as a mixed component, magnesium, zinc, strontium, barium, and the like, which are other alkaline earth metal elements belonging to the same family as the calcium element. The coexistence does not impair the basic chemical reaction of the calcium composition (BA) in the present invention.

A typical composition of the calcium composition (BA) is represented by the following composition formula (1): CaO.wH ₂ O (1) (where w is a number of 2 or less including zero). Powdered calcium containing 50% by weight or more of a calcium component composed of one or a combination of two or more selected from the group consisting of calcium oxide and calcium hydroxide expressed in terms of CaO oxide. Calcium Standard Composition (BA1).

In general, calcium oxide and calcium hydroxide constituting the calcium standard composition (BA1) are produced or processed in large quantities as purified natural mineral products or decarbonated or digested products of calcium carbonates such as limestone and shells. So-called quick lime, which is an oxide of calcium, or slaked lime, which is a hydroxide of calcium, is suitable because it is an industrial chemical that is easily available and inexpensive.

Another embodiment of the calcium composition (BA) adopted as the alkaline curing agent (B) of the present invention is an oxyacid salt composition of calcium salt (BA2). Oxy acid salt composition of this calcium salt (BA2)
The following composition formula _{(3) Ca n TO m ·} wH 2 O ..................... (3) ( wherein: T is boron, aluminum, silicon, nitrogen, phosphorus or sulfur element group alone or 2 N is a number of 1.0 to 6.0, m is a number of 0.5 to 6.0, and w is a number of 28.0 or less including zero. The powder of the oxyacid salt composition of calcium salt composed of one or a combination of two or more selected from the group of oxyacid salts of salts or basic salts is preferred.

When the calcium oxyacid salt compound coexists with the alkali composition (BB), the calcium oxyacid contained therein reacts with the alkali composition (BB) and the silicate material (A) to be solidified. And can be suitably adopted as the calcium composition (BA) of the present invention. Moreover, since the calcium oxyacid salt compound used as the oxyacid salt composition (BA2) is generally easily available as a natural product or a synthetic industrial chemical, it is used as a raw material of the alkaline hardener (B) of the present invention. It is suitable.

When calcium silicate is adopted as the oxyacid salt composition (BA2) of the calcium composition (BA) of the present invention, the calcium silicate is modified without reducing the silica concentration of the modified admixture (C) to be prepared. It is preferable because the fluidity or plasticity of the water-soluble mixture (C) can be ensured. Further, calcium silicate is a hydratable compound, and is also preferable from the viewpoint of reducing the free moisture of the formed solid to secure the solid and improving the strength of the solid.

Specific examples of the readily reactive calcium silicate employed in the present invention include wollastonite, natural calcium silicate having an amorphous structure, and synthetic calcium silicate. Furthermore, powdery materials such as calcium silicate contained in blast furnace slag and the like, which are industrial wastes, are inexpensive and easily available, so that they can be suitably selected appropriately.

Further, when calcium aluminate is adopted as the oxyacid salt composition (BA2) of the calcium composition (BA) of the present invention, an aluminum component which is a zeolite component indispensable for the solidification is simultaneously supplemented. It is also preferable from the point of view. Moreover, it is a hydratable compound as in the case of calcium silicate, and is suitable for reducing the free moisture of the formed solid to secure the solid and improving the strength of the formed solid.

The oxyacid salt composition (B) adopted in the present invention
Compounds suitable as A2) can be appropriately selected from commercially available industrial chemicals and reagents of calcium salt compounds and purified natural mineral products. However, with regard to the selection of the anion component bound to calcium, a preliminary experiment should be carried out as necessary, taking into account the workability, purpose of use, application, price, etc. of the alkaline hardener (B). There is a need.

Further, when a calcium normal salt or a basic salt containing a sulfur oxyacid is adopted as the oxyacid salt composition (BA2) of the calcium composition (BA) of the present invention, coexisting silicic acid or It is preferable because a hydratable mineral is generated by the reaction with aluminate and the strength of the generated solid is improved.

As the normal salt or basic salt of calcium containing a sulfur oxyacid, a sulfur oxide (SO _n :
n is a number of 2 or 3) At least 2
Sulfur oxyacid salt of a basic salt of calcium or calcium sulphate of a normal salt (so-called gypsum) containing by weight or more
It is preferable to be constituted by. Generally, gypsum has water of crystallization as dihydrate or hemihydrate, but in the present invention, any of these gypsums can be suitably adopted.

Gypsum, which is calcium sulfate, is generally supplied also as natural gypsum, but gypsum by-produced in processes such as wastewater treatment in the chemical industry and flue gas desulfurization when using petroleum as fuel is also used as calcium gypsum. It can be suitably adopted as the oxyacid salt composition (BA2) of the product (BA). In particular, by-product gypsum is low in cost in terms of cost and is suitable.

Further, the oxyacid salt composition of the present invention (BA
2) As another specific example, a powder composed of an anhydrous or hydrated normal or basic salt such as calcium borate, calcium nitrite, calcium nitrate, and calcium phosphate can be mentioned. Needless to say, these compounds may contain other alkaline earth metal compounds of the same family as long as the object of the present invention is not impaired.

Another embodiment of the calcium composition (BA) adopted as the alkaline curing agent (B) of the present invention is a halogen salt composition (BA3). As the halogen salt composition (BA3), the following composition formula (4): CaZ.wH ₂ O (4) (where D is a calcium element of magnesium, calcium or zinc, and Z is a halogen group) The element, w is a number of 10 or less including zero), a calcium halide salt composition (BA3) composed of one or a combination of two or more selected from the group of halogenated compounds of basic salts of calcium. It is.

A calcium salt composition (BA)
As 3), calcium chloride, which is an abundant industrially produced and inexpensive chloride, can be mentioned. Other examples include calcium fluoride. However, regarding the adoption of the halogen component bound to calcium, the workability of the alkali-based curing agent,
It is necessary to take into account the price etc. and adopt it. Needless to say, other alkaline earth metal compounds of the same family may be present as long as the object of the present invention is not impaired.

[0164] As another embodiment of the calcium composition (BA) employed in the alkaline curing agent (B) of the present invention, slag such as blast furnace slag by-produced in a steel mill or the like, lime produced by-product in the papermaking industry. Gypsum such as sum sludge, waste gypsum board,
And various waste powders such as incineration ash discharged from various incinerators, etc., which are rich in calcium oxide or salt compounds, which are in shortage for disposal, as 20% by weight or more in terms of calcium oxide. The waste powder composition (BA4) contained therein can be exemplified.

In particular, blast furnace slag which is a by-product of steelmaking and various metallurgy industries, which are representatives of wastes; incinerated ash of lime neutralized paper sludge discharged from the papermaking industry; organic-containing wastes (thinning materials, Agricultural, livestock and fishery wastes, various fermentation residues, food processing residues, etc.) and their carbonized incineration ash, which are dry-distilled products; incineration ash of various garbage including general waste: lime neutralized The waste powder composition (BA4) which has received heat history such as incinerated ash of sewage sludge and various other sludges can be suitably adopted.

These wastes generally tend to contain harmful heavy metals. However, as described above, when the alkaline curing agent (B) in the present invention is adopted as a curing agent for wastes, zeolite or a zeolite precursor is generated during the solidification reaction step, and the zeolite formed there is produced. Immobilize the harmful heavy metals contained in these wastes to form water-insoluble salts, prevent the diffusion of harmful substances into the environment, and enable the reuse of wastes. Is important.

In another embodiment of the calcium composition (BA) adopted as the alkaline curing agent (B) of the present invention, a powder containing a calcium component as a main component is industrially mass-produced. Powdered Cement Powder Composition (BA)
5).

As the cement powder composition (BA5),
It can be appropriately selected from known and publicly used hydraulic cement powders. Specific examples include Portland cement (ordinary, fast strength, super fast strength, moderate heat, sulfate resistance) and mixed cement (blast furnace cement, silica cement, fly ash cement) specified in JIS R 5200. Various special cements (white Portland cement,
Alumina cement, super-rapid setting cement, colloidal cement, oil well cement, geothermal well cement, swelling cement,
Preferred examples thereof include powders of hydraulic cement minerals such as other special cements.

These hydraulic cement mineral powders themselves form hydrates by mixing with water to form solids. However, the cement powder composition of the present invention (B
With respect to A5), the formation of a solidified body by hydration of the cement itself is not expected, and the silanol group generated by the reaction between the silicate-based material of the solidification target of the present invention and the alkali composition (BB) is not expected. It is expected to be effective as a reaction accelerator for alkali silicates.

Another embodiment of the calcium composition (BA) adopted as the alkaline hardener (B) of the present invention is natural calcium carbonate (C) such as aragonite, calcite, marble or shell.
aCO ₃ ) powder is brought into contact with a hot atmosphere of 1000 ° C. or lower to decarboxylate and modify the calcium component to form an oxide (C)
aO) A carbon-calcium-modified composition (BA6) containing calcium oxide as a main component and containing at least 50% by weight or more in terms of standard conversion.

Further, 100 parts by weight of calcium carbonate (CaCO ₃ ) powder such as natural aragonite, calcite, marble, shells and the like are used alone or in combination of two or more of hydrochloric acid, sulfurous acid, sulfuric acid, nitrous acid or nitric acid. In an amount of not more than 50 parts by weight of an acid radical consisting of a ferrosilicate clay containing 2: 1 octahedral or 3 octahedral smectite clay mineral as a main component in a 2: 1 layer type. , Calcium carbonate containing at least 50% by weight or more of a calcium carbonate (CaO) component modified by decarboxylation by contacting at a temperature of 1000 ° C. or less, and having calcium oxide as a main component, and further containing an acid radical and a silicic acid component Can be exemplified by a modified coal-calcium composition (BA6).

In particular, shells of shellfish such as scallops and oysters are abandoned in large quantities while being left unused because calcium carbonate-containing treasure trove, but the main component of the shell is calcium carbonate stable. And it is in trouble for its disposal. By adopting the shell of the shellfish as a raw material of the modified carbon-calcium composition (BA6) of the present invention, the shellfish that are in short supply for disposal are effectively used. In particular, when the seabed mud is to be solidified, it is preferable to improve the sea environment by using raw materials recovered from the sea as raw materials.

As another embodiment of the calcium composition (BA) adopted as the alkaline curing agent (B) of the present invention, a compound of a magnesium element belonging to the second group, which is the same as the calcium element on the periodic table, is used. And the above-mentioned calcium composition (B)
A magnesium mixture composition (BA7) mixed in A) at least in an amount of at least 10% by weight can be selected.

As the magnesium element compound selected here, magnesium oxide, which is magnesium oxide, is most preferable, but magnesium hydroxide or another magnesium oxyacid salt may be used. The compounds of these magnesium elements are preferable because they exhibit substantially the same action as that shown by Calcia in forming the solidified body of the present invention and contribute to the formation of the solidified body.

In another embodiment of the calcium composition (BA) employed in the alkaline curing agent (B) of the present invention,
The standard alkaline earth composition (BA1), the oxyacid salt composition (BA2), the halogen salt composition (BA3), and the waste powder composition (BA4), which have been shown for the respective calcium compositions (BA) described above. , Cement powder composition (BA5),
There may be mentioned a calcium composite composition (BA8) comprising a combination of two or more types in the composition group of the coal-calcium modified composition (BA6) and the magnesium mixture composition (BA7).

It is preferable that each calcium composition (BA) adopted as the above-mentioned alkaline curing agent (B) is generally provided in a powder state in terms of work and handling when forming a solid. Further, it is preliminarily mixed and mixed in a one-pack state with an alkali composition (BB) or an aqueous composition (BC), which is another component constituting the alkali-based curing agent (B), to form a liquid state or a powder state. It is also preferred that it be processed and adopted.

As the calcium composition (BA) to be adopted as the alkaline curing agent (B) of the present invention, in general, quick lime or waste mainly composed of lime is preferred from the viewpoint of easy availability and cost. It is. However, when the quicklime is adopted as the calcium composition (BA), a large amount of heat (15 moles per 1 mole of reaction) is caused by the reaction between quicklime and water.
540 cal. ) Must be handled with care.

The basic composition of the alkali composition (BB) adopted as the alkali-based curing agent (B) in the present invention is the oxidation of an alkali metal composed of lithium, sodium or potassium alone or in combination of two or more. Are expressed as M ₂ O (M is Li, Na, K) oxide based on 30
It is generally preferred that the hydroxide be an alkali metal hydroxide containing at least 50% by weight, preferably at least 50% by weight.

However, the alkaline curing agent (B) of the present invention
The alkali composition (BB) adopted in (1) may be in a solution state in which an alkali metal ion is dissolved in the aqueous composition (BC) to maintain an alkaline state. It may be composed of a solution in which aluminum or alumina or a sulfate group is reacted or dissolved, and may be appropriately selected and adopted from the physical properties required for the solidified material, the workability of the work, and the like.

The alkali composition (BB) preferably adopted as the alkaline curing agent (B) in the present invention includes a standard alkali composition (BB1), an alkali-oxyacid composition (BB2), and an alkali-halogen composition. (BB3), silicate-alkali solution composition (BB4), aluminate-alkali solution composition (BB5), sulfuric acid-alkali solution composition (BB6), and composite alkaline composition (BB7). .

As the standard alkali composition (BB1) classified as the alkali-based curing agent (B) of the present invention, lithium, sodium, or potassium alone or 2
An alkali metal oxide composed of a combination of at least three kinds is expressed as M ₂ O (M is Li, Na, K) oxide standard and 3
Alkali metal hydroxides containing 0% by weight or more, preferably 50% by weight or more are preferred.

These standard alkaline compositions (BB1)
It is also possible to adopt a solid alkali metal hydroxide as it is at the time of adoption, but the aqueous composition (B
C) It can be adopted as a solution in which at least 1 part by weight of an alkali metal hydroxide is dissolved per 100 parts by weight, or when handling alkali metal hydroxide which is a dangerous substance, It is also suitable from above.

The alkali metal element ions generally adopted in the alkali composition (BB) are most preferably selected from sodium hydroxide because they are easily available and inexpensive. However, it is effective to select the type and amount of the alkali metal element according to the workability at the time of forming the solidified material and the application and purpose, and also to select the concentration, and to select these in combination to effectively use the solidified material of the present invention. It is suitable for forming.

When the aqueous component (BC) is added to the standard alkali composition (BB1) and the alkali component concentration is lower than 1 part by weight, the silicate material (A) to be solidified and the alkali are used. The amount of the alkali silanol groups generated in the reaction with the composition (BB) is small, so that it is difficult to secure the amount of the alkali silanol groups necessary for forming the solid, and it is expected that the formed solid has high strength properties. Can not.

In the present invention, the alkali composition (B
The alkali component concentration in B) may be increased, but it is reasonable to treat the solubility of the alkali component in water at room temperature as the upper limit. The total amount of the alkali component in the alkali-based curing agent (B) of the present invention depends on the required amount of the alkali silanol group required depending on the use, purpose, performance, and the like required for the formed solid.

The concentration of the alkali component of the alkali composition (BB) of the present invention is basically limited to the solubility of a hydroxide of an alkali metal element in water at room temperature as described above. As in the case of the solution composition (BB2) and the like, when selecting the hydrous mud silicate material (A3) which is the silicate material (A) to be solidified as the silicate, the hydrous mud silicate is used. An alkali metal element is selected from solid alkali metal element hydroxides in such an amount that alkali metal element ions can be dissolved in the water content of the base material (A3), and the alkali component is directly hydrated with a solid hydroxide containing hydrous muddy silica. It is advantageous to mix it with the acid salt-based material (A3).

However, the alkali composition (BB) of the present invention
When the alkali concentration in the above becomes, for example, 5% by weight or more as a NaOH concentration, the "Poisonous and Deleterious Substances Control Law" is applied, and therefore, it is necessary to pay sufficient attention to its handling. However, when the NaOH concentration is 5% by weight or less, it is excluded from the application of the law, and from the standpoint of the "Poisonous and Deleterious Substances Control Law", from the standpoint of handling the alkali composition (BB) of the present invention. Also alkaline component (NaOH)
Is preferably 5% by weight or less.

The alkali-oxyacid composition (BB2) classified as the alkaline curing agent (B) of the present invention has the following composition formula (4): M _n TO _m · wH ₂ O 4) (wherein, M is an element composed of one or a combination of two or more of lithium, sodium or potassium elements;
T is an element composed of one or a combination of two or more of boron, aluminum, nitrogen or phosphorus, n is a number of 1.0 to 20.0, m is a number of 0.5 to 6.0, and w is zero. Is preferably an alkali metal oxyacid compound composed of a single or a combination of two or more alkali metal oxyacid salt normal or basic salt compounds represented by the following formula: It is.

When an alkali metal oxyacid compound is adopted as the alkali-based curing agent (B) of the present invention, when a normal salt or a neutral salt of these alkali metal oxyacid compounds is adopted, a combined calcium salt is used. Composition (B)
It is important to select calcium oxide, calcium hydroxide, or the like in which A) sufficiently secures a basic component. Choosing a normal salt or a neutral salt as the calcium composition (BA) is an alkaline hardening method. This is important for sufficiently exhibiting the curing agent effect as the agent (B).

Specific examples of the alkali-oxyacid composition (BB2) employed in the present invention include lithium borate, sodium borate, potassium borate, sodium aluminate, potassium aluminate, sodium nitrite, sodium nitrite, and the like. Powders consisting of anhydrous or hydrated normal or basic salts such as potassium nitrate, lithium nitrate, sodium nitrate, potassium nitrate, sodium phosphate, potassium phosphate, etc., or a combination of two or more powdered compounds. Can be. Needless to say, these compounds may contain other alkali metal compounds of the same family as long as the object of the present invention is not impaired.

[0191] alkali constituting the present invention an alkaline curing agent (B) - halogen composition (BB3) is represented by the following formula _{(5) M n Z · wH} 2 O .................. (5) ( wherein : M is an element composed of one or a combination of two or more of lithium, sodium or potassium elements,
Z is a halogen element, n is a number from 1.0 to 20.0, w
Is preferably a number of alkali metal halides represented by 10.0 or less including zero) or alkali metal halides composed of a combination of two or more alkali metal halides.

When a halogen compound of an alkali metal is adopted as the alkali-based curing agent (B) of the present invention, when a normal salt or a neutral salt of these alkali metal halides is adopted, the above-mentioned alkali metal oxyacid is used. As in the case of the compound, the combined calcium composition (B
It is important to select calcium oxide, calcium hydroxide, or the like in which A) sufficiently secures a basic component. By selecting a halogen compound for the constitution of the alkaline curing agent (B) of the present invention, a halogen element is brought into the solidified product, but the halogen element does not hinder the curing mechanism.

Specific examples of the alkali-halogen composition (BB3) employed in the present invention include sodium fluoride, potassium fluoride, lithium chloride, sodium chloride, potassium chloride, sodium bromide, and the like. Two or more combinations of halogen compounds can be given. Needless to say, these compounds may contain other alkali metal compounds of the same family as long as the object of the present invention is not impaired.

Further, the alkaline curing agent (B) of the present invention
As another embodiment of the alkali composition (BB) constituting (BBS1), a layered clay composition (BBS1) which is a silicate-based composition (BBS) and contains a silicic acid or a silicate which is easily reactive to an alkali. A silicate-based composition comprising a hydrous muddy mud composition (BBS2) or an alkali silicate composition (BBS3) alone or in combination of two or more is dissolved in an alkali composition (BB) or an alkaline solution in advance. Silicic acid-alkali solution composition (BB4).

The layered clay composition (BBS1) of the silicate composition adopted in the present invention comprises a 2: 1 layer type hydrous ferrosilicate mineral of the smectite group, which is a hydrous ferrosilicate mineral. Layered clay minerals are preferred. These layered clay minerals of hydrous ferrosilicate minerals have abundant silanol groups in the polysiloxane bond, and are easy to react with alkali,
It is effective for forming a silica polymer to be a composite matrix of the solidified product of the present invention.

Generally, the hydrous phyllosilicate mineral is Si-
A clay composed of a water-containing layered silicate compound based on a layered silicate structure bonded to each other around a tetrahedron of O is a general term, and a natural layered clay mineral corresponds to this. These phyllosilicate minerals are roughly classified into a hexagonal mesh layer and a square mesh layer, and most ferrosilicate compounds are formed from a hexagonal mesh layer.

The units constituting the phyllosilicate mineral are classified into three types: face, sheet, and layer, and the sheet includes a tetrahedral sheet and an octahedral sheet. Unit layers consisting of tetrahedral and octahedral sheets overlap in layers to form phyllosilicate minerals, with water molecules between the layers, and with various cations, and a stable charge. It is secured and forms a water-containing state.

According to the classification of the layered clay mineral which is a hydrous ferrosilicate mineral, kaolinite of 1: 1 layer type is classified into a dioctahedral type and a trioctahedral type. On the other hand, the 2: 1 layer type includes groups such as pyrophyllite, talc, smectite, vermiculite, mica, and chlorite.
It is classified into an octahedral type and a trioctahedral type.

Among them, layered clay minerals such as 2: 1-layer type smectite group octahedral montmorillonite and beidellite have a higher bond between aluminum and silicon than layered clay minerals such as 1: 1 layered kaolinite. It is unstable and rich in reactivity, has a large specific surface area, has high adsorption performance, and is excellent in exhibiting the binder effect in the present invention. Moreover, saponite, hectorite, and sauconite are classified into the trioctahedral type, and these layered clay minerals also suitably exert the binder effect of the present invention.

In particular, montmorillonite is easily reactive with alkali, easily available, and suitable. Montmorillonite is (Na, Ca _1/2 ) _0.33 (Al
_{It is represented by} the composition structural formula of _1.67 Mg _0.33 ) Si ₄ O ₁₀ (OH) ₂ (however, interlayer water is omitted). In this montmorillonite, the distance between positive and negative charges is large, the interaction force is weak, and cation exchange is easily caused to form an alkali silanol group exhibiting a binder effect, which is preferable.

The content and amount of the metal element partially substituted and the amount of water coordinated between the layers depend on the place of production and the environment at the time of clay formation. May change, and the distance between the bottom surfaces tends to change depending on the metal element to be replaced and water or organic substances interposed between the layers, which tends to affect the development of the swelling property. Montmorillonite is classified into bentonite and sub-bentonite (acid clay), whose swelling property is not so large.

However, since hydrous ferrosilicate minerals are naturally occurring minerals, they generally contain various impurities. Therefore, in the present invention, in the case of a water-containing layered clay mineral coexisting with impurities, if the clay mineral contains at least 50% by weight or more of an active ingredient as a clay mineral, for example, montmorillonite, the object of the present invention is considered. Can be adopted as a clay mineral without deteriorating.

In general, phyllosilicate clay contains water in an amount range of not more than 20% by weight even in a dried product. But,
The hydrous phyllosilicate employed in the present invention is preferably a dry powder. The dry powder has a water content of 20% by weight or less, preferably 18% by weight or less, and has a fineness of at least 80% or more which has been crushed and classified into a powder that passes through at least 80%. Are preferred in terms of handling such as reactivity and workability.

The silicate composition (B) adopted in the present invention
As the hydrous muddy mud composition (BBS2) of (BS), the hydrous muddy silicate material (AS) adopted as the silicate material (A) to be solidified of the present invention can also be suitably selected. . Specifically, construction sites, seas, lakes, swamps, rivers,
Natural clay minerals such as construction by-products and dredging by-products that are generated as waste by-products in dams, clay, organic soil, sludge, volcanic ash clay, weathered rock, silica such as clay in rice fields and fields, etc. Examples include hydrated muddy mud, such as earth and sand, mud, dredged soil, and hydrated clayey soil, containing silica-alumina as a main component and containing at least 25% by weight of water.

In the present invention, the hydrous muddy mud composition (B)
The significance of selecting BS2) is important when selecting a hydrous mud silicate material (AS) as the silicate composition (A) to be solidified. That is, it is possible to procure the raw material of the binder component at the site where the silicate-silicate material (A) to be solidified exists. as a result,
There is no need to prepare the curing agent in another place in advance, and it is not necessary to spend distribution costs on at least the silicic acid content, which is the main raw material of the curing agent, and the alkali-based curing agent (B) of the present invention can be prepared on site. This is very advantageous in terms of cost.

The silicate composition (B) adopted in the present invention
BS) Silicic acid-alkali solution composition (BBS3)
As we are all are composed mainly of alkali silicate, as a basic composition that collectively this, the following composition formula _{(6) M 2 O · bSiO} 2 · wH 2 O ..................... (6) ( Wherein M is an alkali metal element of lithium, sodium or potassium, b is a number of 1.0 to 3.5, w is a number of 1.6 to 50.0), and has a deliquescent property. You can mention an alkali silicate composition (BBS4) composed of one or a combination of two or more selected from the group of liquid alkali silicates.

Silicic acid-alkali solution composition (BBS3)
As the alkali metal element (M) in the composition formula (1), sodium (Na) is preferable because it is generally easily available and inexpensive. So-called water glass that is industrially mass-produced according to JIS is suitable as a basic raw material for an alkali silicate composition (BBA3). However, depending on the application field and purpose of the solidified material, the workability and the physical properties of the solidified material, potassium (K) and lithium (Li) are combined with the alkali metal element alone or in combination including sodium. It is preferable that the composite alkali silicate is appropriately selected and used.

Silicic acid-alkali solution composition (BBS3)
In the composition formula (6), the number of a and w differs slightly depending on the kind of the selected calcium composition (BA), but generally, a is in the range of 1.8 to 3.5. In particular, a deliquescent or liquid alkali silicate having a in the range of 2.0 to 3.2 and w in the range of 1.6 to 50.0 is preferably a silicate-alkali solution composition. It is suitable as (BBS3). At this time, when a in the composition formula (6) is smaller than 1.8, the hardening rate of the solidified product is retarded due to too much alkali component, or the formed solidified product develops a whitening phenomenon to provide water resistance. Tend to be inferior. On the other hand, when a is larger than 3.5, the amount of the reactive silanol group becomes small, and the formation of an effective polymer composed of siloxane bonds is not expected, so that a solid having a high hardness tends not to be obtained.

Silicic acid-alkali solution composition (BBS3)
When w in the composition formula (6) is in the range of 3.0 to 50.0, the alkali silicate is a liquid, and is suitable as a raw material of the alkali silicate composition (BBS3). When sodium silicate is a so-called liquid water glass, JI
It is an industrial chemical converted to S and is suitable as a raw material of the present invention because it is inexpensive. W of the composition formula (6) is 50.0
If it is larger than the liquid alkaline hardener (BL)
, The effective concentration of the active ingredient tends to be low, and the binder effect tends to be extremely reduced.

In the silicic acid-alkali solution composition (BB4) adopted in the present invention, the silicic acid already has an alkali silanol group in the alkali composition (BB), and the reactivity of the object to be solidified is high. A siloxane polymer can be formed in the easily reactive silicate-based material (A) to be solidified without waiting for a reaction with the silicate-silicate material (A);
Since it has an immediate effect on the formation of a solid, it is suitable for allowing room temperature solidification to proceed smoothly.

The preparation of the silicate-alkali solution composition (BB2) comprises one or a combination of two or more of a layered clay mineral (BBA1), a hydrous muddy mud composition (BBA2) and an alkali silicate (BBA3). 1 to 200 parts by weight of alkali metal hydroxide expressed as M (OH) (M is Li, Na, K) hydroxide based on 100 parts by weight of the silicate-based composition (BBS); Water 1-2
The silicic acid-alkali solution composition in which the alkali silanol group is formed by reacting at room temperature or under heating conditions in addition to the range of 00 parts by weight is effective in efficiently proceeding the formation of a solid. is there.

Further, the alkaline curing agent (B) of the present invention
In another embodiment of the alkali composition (BB), the alumina-containing aluminate composition (BBA), which is easily reactive to alkali, is dissolved in the alkali composition (BB) or alkali solution in advance, and the reaction Cured aluminate-alkali solution composition (BB5) may be mentioned.

Specific examples of the aluminate composition (BBA) preferably adopted in the present invention include aluminum oxide, aluminum hydroxide, normal salt or basic aluminum sulfate which is easily reactive to alkali. Examples thereof include aluminum chloride, aluminum phosphate, aluminum borate, aluminum silicate, etc., furthermore, sodium aluminate prepared by dissolving aluminum metal in an alkali, etc., and calcium aluminate and alumina cement.

Further, as the aluminate composition (BBA) adopted in the present invention, the waste powder composition (BA4) or the cement powder composition (BA5) mentioned above for the calcium composition (BA) Further, in a group of natural mineral powders, a composite type aluminate composition containing at least 15% by weight of an aluminum-containing compound that is easily reactive to alkali, based on Al ₂ O ₃ oxide, is selected and adopted. can do.

As the alkaline composition (BB) of the present invention,
By preparing an aluminate-alkali solution composition (BB5) in which alumina which is easily reactive to alkali is dissolved in advance, the alumina component necessary for forming zeolite or a zeolite precursor is modified into alkali aluminate in advance. It is effective because it can be replenished. Therefore, the formation of zeolite or a zeolite precursor can be efficiently promoted during the formation of the solidified product of the present invention, which is effective in fixing an alkali component.

Aluminic acid-alkali solution composition (BB
5) Preparation of alkali metal hydroxide is expressed as M ₂ O (M is Li, Na, K) oxide based on 100 parts by weight of alumina-containing compound (BBA), and 1 to 200 parts by weight. In order to effectively form a zeolite or a zeolite precursor, a composition of an aluminate-alkali solution, which is obtained by adding 1 to 200 parts by weight of water and reacting at room temperature or under heating conditions, is preferred. .

Further, as another embodiment of the alkali composition (BB) constituting the alkali-based curing agent (B) of the present invention,
A sulfuric acid group-containing composition (BBR) comprising a compound containing a sulfur oxyacid is previously dissolved in an alkali composition (BB) or an alkali solution, and the sulfuric acid is reacted and cured.
An alkaline solution composition (BB6) can be mentioned.

The sulfuric acid-alkali solution composition of the present invention (BB
In 6), since the sulfate group-containing composition (BBR) containing the oxyacid of sulfur is dissolved in the alkali composition, the sulfuric acid-alkali solution composition (BB6) and the calcium composition (BA) are dissolved. In the alkaline hardener (B) of the present invention, which is composed of the following components, hydraulic calcium sulfate is secured in the alkali composition (BB), and the alkaline component in the alkaline hardener (B) is zeolite or the like. To form hydrated and hydrated calcium sulfate by the formation of
This is advantageous because the solidified body of the present invention is advantageously exhibited and a solidified body with high strength can be formed.

As the sulfate group-containing composition (BBR) preferably adopted in the present invention, the above-mentioned calcium composition (BA) is used.
Oxyacid composition (BA2) and calcium sulfate as waste powder composition (BA4), and sodium sulfate as sulfur oxyacid alkali of the hardening promoting composition (BD3) described later. it can.

The sulfate group-containing composition (B) adopted in the present invention
Specific examples of BR) include calcium sulfate dihydrate, hemihydrate and anhydrous salt, magnesium sulfate, lithium sulfate, sodium sulfate, calcium sulfite, potassium sulfate, aluminum sulfate, basic aluminum sulfate, and iron sulfate. Gypsum recovered from a waste gypsum board can be used.

The preparation of the sulfuric acid-alkali solution composition (BB6) is performed by adding an alkali metal hydroxide to M ₂ O (M is Li, N) with respect to 100 parts by weight of the sulfate group-containing compound (BBR).
a, K) 1 to 200 parts by weight expressed on an oxide basis;
An alkaline sulfuric acid-alkali solution composition containing an oxyacid salt of sulfur mixed with water in the range of 1 to 200 parts by weight is effective in securing the strength of a solidified body to be formed.

Further, in the present invention, each of the above-mentioned alkali compositions (BB) [standard alkali composition (BB1),
Oxy acid salt composition (BB2), halogen salt composition (BB
3), silicate-alkali solution composition (BB4), aluminate-alkali solution composition (BB5), sulfuric acid-alkali solution composition (BB6)]. Can be.

The composite alkali composition (BB7)
In consideration of the performance and workability required for the alkali-based curing agent (B) of the present invention, the economic efficiency, and the properties and applications of the solidified product to be formed, preliminary experiments are performed as necessary.
It is possible to determine the type, composite content and proportion of the selected silicate-based composition (BBS), aluminate composition (BBA) and sulfate group-containing composition (BBR).

In particular, when the composite alkali composition (BB7) is adopted as the alkali-based curing agent (B) of the present invention, the components of silicic acid, aluminate or sulfate required for forming the solidified product of the present invention are used. It is possible to selectively mix each of them independently or in combination, to secure the alkali of the reaction system in the deformable admixture (C) for forming the solid, and to form silicic acid, aluminate or sulfate necessary for forming the solid. It is preferable because each required component can be secured on the alkaline side to enable formation of a solidified body.

When the deformable admixture (C) of the present invention is secured to a specific shape and subjected to room temperature solidification treatment to form a cured product (E), the purpose, application, workability and workability of each product are determined. The formation conditions of the cured product corresponding to the physical properties and performance of the solidified product are required. As the conditions for forming the cured body, auxiliary improvements of each condition such as formation of a buffer zone, promotion of crystal growth, acceleration of curing, adjustment of the curing speed, and improvement of the strength of the cured body are also required, and the auxiliary improvement can be coped with. As the compounding material, an appropriate curing auxiliary composition (BD) can be selected.

Each curing auxiliary composition (BD) selected here
May be separately compounded and used together during the preparation of the deformable admixture (C), but the alkali-based curing agent (B)
Is previously mixed with the alkali composition (BB) or calcium composition (BA), or the mixture / blend of the alkali composition (BB) and the calcium composition (BA). Adoption as the curing agent (B) is also preferable from the viewpoint of work efficiency.

The curing assistant composition (BD) preferably adopted as the alkaline curing agent (B) of the present invention includes the following 6
Types can be mentioned. Buffer zone forming composition comprising a boron-containing compound soluble in an alkaline solution (BD1) Crystal growth seed composition comprising aluminosilicate zeolite (BD2) Hardening promoting composition comprising a oxyacid salt of alkali metal sulfur (BD3) ) Curing preparation composition comprising a barium salt compound soluble in an alkaline solution (BD4) Curing reinforcing composition comprising powdered silicon phosphate having a sustained release of phosphoric acid (BD5) Curing auxiliary composition (BD) Are mixed and mixed, but a plurality of auxiliary compositions (BD6)

In the present invention, a buffer zone forming composition (BD1) can be selected as the hardening assisting composition (BD) so as not to leave a strain in the matrix of the formed solid. The silica polymer comprising a siloxane bond in the solidified product formed by the use of the alkali-based curing agent (B) of the present invention basically comprises tetravalent silicon (Si) and divalent oxygen (O) arranged regularly. Constructs a polymer matrix. However, the silica polymer produced from the alkali silicate tends to shrink in the polymerized matrix due to dehydration, and the strain energy resulting from the shrinkage tends to accumulate in the solidified body.

In addition, since the polymer matrix is regularly formed, there is no room in the matrix structure, and there is no escape for the generated strain energy, and the strain energy tends to accumulate more and more. As a method for eliminating the strain energy accumulated here, there is a tendency to generate cracks and cracks in the solidified body to eliminate the strain energy. The occurrence of such cracks and cracks causes the commercialized product to be destroyed and causes troubles that impair the commercial value.

[0230] In the present invention, as the buffer strips forming composition allowed to form a buffer zone us to eliminate the distortion generated in the generation solidified (BD1), the following composition formula _{(7) EO n / 2 ·} eB 2 O 3 · wH ₂ O ‥‥‥‥‥‥ (7) (wherein, E is an alkali metal element of lithium, sodium or potassium, or an alkaline earth metal element of magnesium, calcium or zinc, and e is 1.0 to 2.0) Wherein w is a number of 10 or less, including zero) a buffer band forming composition which is a single or a combination of two or more selected from the group of oxyacid compounds of boron of alkali metals or alkaline earth metals. Can be suitably mentioned.

The buffer band forming composition (B) selected in the present invention
As a specific example of D1), a boron-containing compound containing boron having a valence of 3 and being easily soluble in an alkaline solution and easily reactive with a siloxane bond serving as a skeleton of a silica polymer is preferable. . Specifically, an alkali salt that is an alkali borate is preferable, and the alkali element is preferably potassium or sodium, and examples thereof include potassium borate and sodium borate.

Further, since the alkali borate is in the form of a powder, it is preferable to select from an anhydrous salt, a trihydrate, a pentahydrate, a heptahydrate, and a hydrate. Further, as another boron-containing compound, various borate compounds can be appropriately selected in place of the alkali salt. Examples of the borate compound include industrial chemicals such as boron oxide, boric acid,
Examples include boron phosphate, zinc borate, calcium borate, zinc borate, and aluminum borate.

The curing auxiliary composition (B) adopted in the present invention
As another form of D), as a crystal growth seed for rapidly accelerating the crystal growth of zeolite or a zeolite precursor, which is an aluminosilicate which is formed in the solidified product of the present invention and constitutes a matrix, is a member. It is effective to coexist an aluminosilicate.
A crystal growth seed composition (BD2) composed of an aluminosilicate zeolite can be cited as the crystal formation seed.

The crystal growth seed composition (BD2) effective as the above-mentioned hardening auxiliary composition (BD) is obtained by the following chemical composition formula of the unit cell (8): M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) ) _Y ] · wH ₂ O (8) (where M is a metal cation having a valence of n and x + y is the number of tetrahedrons per unit cell) and is a zeolite structure of aluminosilicate. Is effective as a crystal growth seed composition (BD2). These zeolites
Both natural mineral zeolites and artificially synthesized zeolites are effective.

In particular, a natural product can be selected as the crystal growth seed composition (BD2) in the present invention, but the most commonly synthesized 4A type synthetic zeolite is used as the crystal growth seed. is there. In order to further produce crystalline seeds, these synthetic zeolite seeds are:
Fine particles having a particle size of 10 μm or less, preferably 5 μm or less are preferred.

The curing auxiliary composition (B) adopted in the present invention
As another form in D), a hardening property for rapidly forming a sandy, powdery or hydrous mud-like silicate composition (A) into a water-resistant and heat-resistant solid by adopting an alkaline hardening agent. It is effective to use an oxyacid salt of an alkali metal sulfur exhibiting a function together with an alkaline curing agent as a curing acceleration composition (BD3).

The hardening promoting composition (BD3) comprising a sulfur oxyacid salt adopted in the present invention has a function of accelerating hardening of a solidified product and contains a sulfate group as a sulfur oxyacid salt. This is effective because it acts in the same manner as the sulfate composition (BA4), which is a calcium salt composition (BA), to form hydraulic calcium sulfate in the course of the reaction and exerts a reinforcing effect on the strength of the solidified body.

As the curing accelerating composition (BD3), which is the curing auxiliary composition (BD), the following composition formula (9): M ₂ O · fSO _n · wH ₂ O (9) : M is an alkali metal element of lithium, sodium or potassium, f is a number of 2.0 to 2, w is a number of 4 or less including zero, and n is a number of 2 or 3). Curing accelerator composition (B) consisting solely or in combination of two or more selected from the group of acid salts
D3) is effective.

The curing auxiliary composition (B) adopted in the present invention
As another form in D), deformable admixture in which an alkali-based curing agent (B) composed of an alkali composition (BB) and a calcium composition (BA) is homogeneously admixed with the silicate composition (A). When preparing the product (C), the fluidity or plasticity required for the working operation of the deformable admixture (C) is ensured,
There is a need for a curing control composition (BD4) that exhibits auxiliary functionality that enables adjustment of the work life.

Curing modifier selected in the present invention (BD4)
As the barium salt compound, a powdery barium salt compound having a soluble component in an alkali solution capable of adjusting a gelling reaction of an alkali silicate is preferable. As the barium salt compound, the following composition formula (10): BaO.gSiO ₂ .wH ₂ O ‥‥‥‥‥‥ (10) (where g is a number including zero of 4.0 or less, and w is 9.
A hardening adjusting composition (B) comprising a barium salt powder having a soluble content in an alkaline solution represented by the following formula (B) and a barium salt compound alone or in combination of two or more kinds;
D4) is preferred.

In the present invention, the curable composition (BD)
“Soluble in alkaline solution” that specifies the powdery barium salt compound adopted as 4) is the barium salt compound 1
0 g at 25 ° C. in 100 ml of 1N caustic soda solution.
After stirring and dispersing for 1 minute, the barium ion (Ba ⁺⁺ ) of the solution obtained by filtering the sample solution was quantified, and eluted in a 1N caustic soda solution based on the total (100) barium element (Ba) in the collected sample. Barium (Ba) amount (%).

The soluble matter of the barium salt compound of the present invention in an alkaline solution is preferably at least 10% in order to secure the fluidity or plasticity of the deformable admixture (C). When a barium salt compound having a solubility in an alkali solution of 10% or less is adopted, a pot life in which a fluid necessary for the work of applying an alkaline curing agent can be secured cannot be obtained. On the other hand, in the case of a barium salt compound having a soluble content of 90% or more in an alkaline solution, the working life of the deformable admixture (C) is ensured, but the hardening of the deformable admixture (C) is prolonged to form. The formation of a silica polymer is impaired, and the formation of a strong solid is hindered.

In general, the barium salt compound which satisfies the content soluble in the above-mentioned alkaline solution, is easily available and is inexpensive is a chemical formula Ba (OH) which is commercially available as an industrial product.
Barium hydroxide represented by ₂ · 8H ₂ O are preferred.
It is also effective to adopt barium oxide of the formula BaO. However, since the amount of the soluble component in the alkali solution can be controlled, the fluidity or plasticity of the alkali-based curing agent during the work is secured, and the workable time of the work can be adjusted and managed. The use of barium silicate, which can exert a mild activity, is more preferable.

As the barium silicate adopted here, a mixture of barium hydroxide and readily reactive silicic acid as raw materials is treated with an alkali solution prepared by a low-temperature (preferably 100 to 200 ° C.) treatment. Simple powdered barium silicate having a soluble content of 10% or more is preferable because it can ensure the fluidity or plasticity of the deformable admixture (C) during operation and can control the pot life and the curing time.

The simple barium silicate powder in this case is as follows:
The number of the composition formula (8) g is preferably not more than 4.0, and if it is not less than 4.0, the activity of barium ions cannot be effectively used. Further, the number of the composition formula (9) w is preferably not more than 9.0, and when the number is not less than 9.0, the storage stability of the barium salt compound in a one-pack product is particularly ensured in the present invention. Therefore, the object of the present invention cannot be achieved.

When the amount of the barium salt compound is less than 0.1 part by weight, it becomes difficult to secure a usable life suitable for workability and fluidity or plasticity of the alkaline curing agent. When the compounding amount of the barium salt compound is more than 12 parts by weight, the pot life of the workability is sufficient but the curing speed is 46%.
It tends to be slow, impairing the productivity and practicality of the solidified product.

The curing assistant composition (B) adopted in the present invention
As another form in D), deformable admixture in which an alkali-based curing agent (B) composed of an alkali composition (BB) and a calcium composition (BA) is homogeneously admixed with the silicate composition (A). A hardening reinforcing composition (BD5) which promotes and reinforces the hardening of a solidified product formed via the product (C), reinforces the formation of a high-strength solidified product, and exhibits functionality is required.

The cured reinforcing composition (BD) selected in the present invention
The 5), the following formula _{(11) hSiO 2 · P 2} O 5 .................. (11) ( wherein: phosphoric acid h is represented by 1.0 to a number of 8.0) Powdered silicon phosphate composed of silicon phosphate alone or in combination of two or more types having a sustained release property of at least one minute can be suitably mentioned as the hardening reinforcement (BD5).

The “sustained release of phosphoric acid content” of the powdered silicon phosphate of the present invention is represented by the following formula (11-b): Y = aX + b (11-b) Represents the elapsed time (minutes) up to 120 minutes of a sample solution obtained by stirring and dispersing 1 gram of powdered silicon phosphate in 100 cc of 4N caustic soda at 25 ° C., and Y represents the amount of phosphoric acid eluted in the sample solution ( P ₂ O ₅ elution amount b of the initial phosphate content of the sample solution represented by elution integrated amount (mg a / 100 cc)) of) is not less than 200, the average hydrolysis rate constant a is the range of 0.2 or more In the state.

The silicon phosphate in the present invention is desirably a stable compound which releases phosphoric acid in the deformable admixture (C) and does not easily hydrolyze in the alkaline composition. Therefore, silicon phosphate is represented by the composition formula (9-
b) the number of h in the range of 1.0 to 8.0, and
Sintering in a temperature range of 0 to 1200 ° C. is preferred from the viewpoint of controlling the sustained release of phosphoric acid. h
Is smaller than 1.0 and when calcined at 700 ° C. or lower, it tends to show deliquescence and lack stability as silicon phosphate. Further, the number of h is larger than 8.0 and 1
When firing at 200 ° C. or higher, the content of phosphoric acid decreases, and the function as a 23 agent is poor.

The powdery silicon phosphate of the present invention can be surface-treated in advance with a coating agent known and used in the art in order to secure stability during storage and sustained release of phosphoric acid. . As the coating agent in this case, an organic fatty acid (such as stearic acid) or a fatty acid salt (such as calcium stearate or barium stearate) soluble in an alkaline aqueous solution, and a coupling agent (organosiloxane monomer or polymer silane, titanium Coupling agent) is 0.0
It is preferable that the coating is applied in the range of 1 to 6%.

The curing auxiliary composition (B) adopted in the present invention
As another embodiment of D), the above-mentioned buffering band forming composition (BD1), crystal growth seed composition (BD2), curing accelerating composition (BD3), and curing preparation composition (BD) which are the above-mentioned curing auxiliary composition (BD) BD4) and a hardening reinforcing composition (BD
A composite auxiliary composition (BD6), which is a composition obtained by combining two or more of the composition groups in 5), can be given.

The composite auxiliary composition (BD6) in the present invention
In accordance with the purpose and application required for the solidified product of the present invention, and the auxiliary improvement, each of the curing auxiliary compositions (BD) is used in combination to promote the combined use of the auxiliary improvement, The effect can be expected. At this time, the combination content and quantitative ratio of each curing auxiliary composition (BD) can be determined by preliminary experiments performed in advance.

The alkali-based curing agent (B) adopted in the present invention includes an alkali-based curing agent (B) having a three-part composition of an alkali composition (BB), a calcium composition (BA), and an aqueous composition (BC). ). However, in the present invention, a three-part alkaline curing agent (B) is used as a compounding material to supplement and replenish the three-part alkaline curing agent (B) in view of the formation conditions required for the solidified material, performance, physical properties, and the like. In addition, if necessary, a hardening auxiliary composition (BD) may be added as needed to enable a four-part alkaline curing agent (B). The alkaline curing agent (B) is largely composed of three parts and four parts. There are two types of configurations.

In the alkaline curing agent (B) of the present invention,
The basic three-part alkaline curing agent (B) is composed of 1 to 30 parts by weight of the alkali composition (BB) and 100 parts by weight of the alkali composition (BB) based on 100 parts by weight of the calcium composition (BA). Is a three-part alkaline curing agent (B) in which (BC) is mixed in an amount of 1 to 300 parts by weight.

The four-component alkaline curing agent of the present invention (B)
Is obtained by adding 1 to 30 parts by weight of the alkali composition (BB) and 1 to 300 parts by weight of the aqueous composition (BC) with respect to 100 parts by weight of the calcium composition (BA).
Further, it is preferable to use a four-component alkaline curing agent (B) which is blended in an amount ratio of 300 parts by weight or less of the curing auxiliary composition (BD).

The components constituting the alkaline curing agent (B) in the present invention [the alkaline composition (BB), the calcium composition (BA), the aqueous composition (BC), the curing auxiliary composition (B)
The composition ratio of D)] depends on the type including the water-containing state of the silicate-based material (A) to be solidified, the purpose, the use and application of the solid to be formed, and the required functionality, performance and physical properties. Because of the differences, it is necessary to select the content and conditions of the alkaline curing agent (B) having a three- or four-part configuration from the above-described ranges through sufficient preliminary experiments.

In the alkaline curing agent (B) of the present invention, the constituents of the three- or four-part alkaline curing agent (B) are mixed with the silicate-based material (A) to be solid. When preparing the deformable admixture (C) by heating, the respective components of the alkali-based curing agent (B) are not integrated as a calcium-based solidifying agent (B) beforehand, and the alkali composition (BB) and the calcium-based composition ( It is also possible to prepare the deformable admixture (C) by separately adding and mixing the BA) and the curing auxiliary composition (BD) directly into the silicate-based material (A).

On the other hand, in the alkaline hardener (B) of the present invention, the alkaline hardener (B) having a three- or four-component constitution is preliminarily integrated at each mixing ratio. It is also preferable from the viewpoint of workability of forming a solidified body that the hardening agent (B) is mixed with the silicate-based material (A) to be solidified to prepare a deformable admixture (C).

In preparing the alkaline hardener (B) in which the components of the three- or four-component alkaline hardener (B) were previously integrated, the components were integrated and mixed and cured. Later, the alkali composition (B
The alkaline hardener (B) in which the liquid state of B) is ensured and the slurry state or the fluid liquid state is ensured can be adopted as the liquid alkaline hardener (BL).

The liquid alkali-based curing agent (BL) which has been prepared and integrated in advance has the alkali-based curing agent (B) as an integral component since the alkali-based curing agent (B) is integrated. The alkali composition (BB), the calcium composition (BA) and the hardening auxiliary composition (BD) are separately transported to the work site, and each is weighed to determine the site where the solid target silicate-based material (A) is used. This is desirable because the complexity of mixing must be eliminated.

However, the integrated liquid alkaline curing agent (BL) is used in the step of preliminarily integrating the components of the alkaline curing agent (B) in the alkaline composition (BB) and the calcium composition It is necessary to pay attention to the fact that the reaction progresses between the constituent components of the product (BA) and the curing auxiliary composition (BD), making it difficult to ensure a liquid state.

In particular, when the calcium standard composition (BA1) containing calcium oxide as a main component is selected as the calcium composition (BA), when the calcium standard composition (BA1) calcium oxide is mixed with the water of the alkaline composition (BB). The exothermic hydration reaction produces calcium hydroxide. It should be noted that the heat generated by the exothermic reaction causes the silica-based sol having a coexisting silanol group to gel, making it difficult to ensure a liquid state.

Therefore, the liquid alkaline curing agent (B
In the preparation of L), the contents and the mixing ratio of each component to be used are thoroughly examined, and the time required to maintain the liquid state is confirmed by preliminary experiments conducted as necessary, and the deformable admixture (C) is obtained. It is necessary to confirm the preparation conditions of the liquid alkaline curing agent (BL) that can smoothly carry out the blending preparation of ()).

Furthermore, in the alkaline curing agent (B) of the present invention, when the three- or four-part alkaline curing agent (B) is integrated at each mixing ratio, at least the alkali composition (B) is used. A non-fluid powdery alkali which is made to actively progress between BB) and the calcium composition (BA), and is transformed into a one-pack powdery state in which the alkali-based curing agent (B) is integrated. The preparation of the deformable admixture (C) is performed by mixing it with the silicate-based material (A) to be solidified to form the deformable admixture (C) after the preparation of the deformable admixture (C). It is suitable from the top, especially in field work.

In particular, a powdery alkaline curing agent (B
Preparing P) means that when the silicate-based material (A) to be solidified and the alkali-based curing agent (B) are mixed, the alkali-based curing agent (B) is packed in a single package in the same manner as a cement product. The two components, the liquid alkali composition (BB) and the powdered calcium composition (BA), are separately carried into the mixing site and mixed with the curing agent locally. There is no need to perform complicated operations, which is very preferable in terms of workability.

Further, when the powdered alkaline hardening agent (BP) in a one-pack form is adopted, the silicate-based material (A) is not mixed with the silicate-based material (A) to be solidified. When it is an aqueous material, water is added at the site to form a slurry, and when it is a hydrous silicate material (A), it is mixed with a hydrous silicate material (A) to which no water is added. Thus, each of the deformable admixtures (C) can be prepared, and the workability is suitable without complexity.

In the present invention, the deformable admixture (C) obtained by mixing two components is basically a three-component or four-component alkali based on 100 parts by weight of the silicate-based material (A) to be solidified. It is prepared by uniformly mixing 20 to 500 parts by weight of the system hardener (B) to form a two-part mixture which ensures fluidity or plastic processing and workability. At this time, even if the mixture is powdery and lumpy, it is effective as the deformable mixture (C) of the present invention as long as the mixture is integrated by external pressure and plasticity is obtained.

Further, in the present invention, the conditions for preparing the deformable admixture (C), the conditions for solidification at room temperature, the functions, performances and physical properties required for the target solidified product, and further the use and purpose, etc. In order to add various performances, addition properties, filling properties, and functions to the deformable admixture (C) and the cured product (E) as necessary, various functional addition compositions (D) are used. Deformable admixture (C) mixed with triad
Can be prepared.

In the present invention, the deformable admixture (C) prepared by mixing the functional addition composition (D) together with the three-component admixture is:
100 parts by weight of the silicate-based material (A) to be solidified, 20 to 500 parts by weight of a three-part or four-part alkaline curing agent (B), and a functional addition composition (D) It is prepared by homogenously mixing the three components in an amount of 1000 parts by weight or less to form a three-component blend which ensures fluidity or plastic processability.

Each of the functional additive compositions (D) to be co-blended in the present invention can be separately blended with the silicate-based material (A) to be solidified. ), The alkaline solution (BA), and the calcium composition (B)
B), a water composition (BC), a curing auxiliary composition (BD), and if necessary, a pre-mixed and mixed with another functional addition composition (D) to form a one-pack, and then a deformable mixture. Preparation of (C) is also possible in terms of work efficiency.

As the functional addition composition (D) preferably adopted in the present invention, the following eight types can be mentioned. Additive material composition such as pigment, colorant, activator, filler, etc. (D1) Arsenic-immobilized composition that makes harmful element made of iron salt arsenic element insoluble in water (D2) Adsorbability of silica, zeolite, charcoal, etc. Adsorbent material composition that exhibits (D3) Antimicrobial composition that exhibits antibacterial and antifungal properties of silver and zinc compounds (D4) Water-repellent additive composition containing organosiloxane as a main component (D5) Metal, Fiber-reinforced composition composed of fibrous materials such as glass, carbon, and aramid (D6) Aggregate composition used as a filler aggregate such as sand, lightweight aggregate, and pearlite (D7) Each of the above-mentioned functional additive compositions (D) ) Is a complex-mixed functional composite composition (D8)

As the functional additive composition (D) of the present invention,
It is effective that the solidified product of the present invention is a material that adds coloring property, activity, filling property, and functionality to the solidified product of the present invention. At least one kind of combination additive material composition (D1) can be mentioned. The co-combination of these additive material compositions (D1) is preferable because various special properties and various functions can be added to the solidified product prepared in the present invention.

The shape of the additive material composition (D1) is preferably a powder or a powder having a particle size of less than 50 μm. Specific shapes include powder, sand, lump, needle, column, column, sphere, granule, hollow, fibrous, plate, flake, petal, crushed, deformed or various shapes. A powder or a granule can be preferably used.

As the additive material composition (D1),
Generally, processing of paints, paints, adhesives, various processing agents, cement processing, etc., as well as pigments, colorants, activators, fillers or functionalizing agents known and used in the art. It can be appropriately selected from among them. Preferred examples of the additive material composition (D1) adopted in the present invention are shown below, and the additive material composition (D1) adopted in the present invention is shown below.
1) is not limited to the example shown here.

As the pigment, various extenders generally known and used in the art can be used. Inorganic pigments include carbon black, titanium oxide, zirconium oxide, various iron oxides, iron hydroxide, red iron oxide (iron oxide),
Fired pigments such as magnetic substances, chromium oxide, lead chromate, graphite, ultramarine, various metal oxides, inorganic colored pigments, and powders such as metals, alloys, non-oxides (nitrides, carbides, etc.). be able to.

Further, oxides such as silica fine powder, white carbon, fused silica, silicate, clay powder, alumina, fused alumina, calcium, calcium carbonate, magnesium, zinc oxide, magnetic iron oxide, etc. It can be selected according to the purpose from pigments such as carbonate compounds such as shell powder and non-oxides such as boron nitride and silicon carbide.

The organic pigments include, for example, insoluble azo pigments, soluble azo pigments, condensed polycyclic pigments, quinacridone pigments, isoindolinone pigments, and blue and green pigments generally used in red and yellow. And cyanine blue and cyanine green used in the above. Among them, pigments having strong alkalinity are preferred.

As the coloring agent, the above-mentioned inorganic pigments and organic pigments can be used. Known organic coloring compounds widely used in the art, inks of each color, natural or synthetic dyes, etc., alone or in combination of two or more may be used. By selecting from the combinations, it becomes possible to impart a desired hue to the solidified product.

As the activator, boric acid-containing compounds (zinc borate, calcium borate, etc.), lead-containing compounds, chromic acid-containing compounds or phosphoric acid-containing compounds (iron phosphate, zinc phosphate, silicon phosphate, etc.) Etc. can be selected. These activators are used as the alkaline curing agent (B) of the present invention.
When a metal such as iron is selected as a coating substrate, the adhesion between the adherend of the present invention as a coating material and a binder and the substrate is improved, and the anticorrosion property is improved. Can be expected. When these acid salts are selected, they can also be expected as a neutralizing agent for neutralizing the alkali component of the alkali composition (BB).

Examples of the filler include flakes, pastes and powders of metals and alloys such as stainless steel, silicon, zinc, aluminum, nickel and iron, glass powder, glass cullet, ceramic powder, cullet of ceramics, diamond powder, and oxidized powder. Silicon (silica sand powder, silica stone powder, silica powder, silica fume, fused silica powder, etc.), magnesia powder, shell powder, zircon sand, rock powder (serpentine, andesite, vermiculite, etc.), various clays (bentonite, smectite, gailome) , Kibushi clay, etc.), calcined clay (baked products such as bauxite, montmorillonite, kaolin), gypsum, calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate , Barium carbonate, barium hydroxide, ke Aluminum, iron ore,
It can be appropriately selected from powders having a particle size of 200 μm or less, such as glazes of various compositions, talc, mica, fly ash and the like.

As the function-imparting agent, any material capable of imparting various functions to the solidified product of the present invention, which is composed of an inorganic material or an organic material known and used in the art, and a treating agent thereof can be used. . When these functionalizing agents are liquid, these liquids are prepared in advance into a specific powder and a composite powder supported on a porous carrier prepared by the technique of the present invention, and the present invention is used. Can be adopted as a function imparting agent.

Specific examples of the function-imparting agent include a rust inhibitor, an antioxidant, an anti-slip agent, a blocking material, a non-combustible
Flame retardants, ultraviolet / infrared absorbers, far infrared ray generators, antifogging agents, repellents, insecticides, luminescent pigments, luminous bodies, photocatalysts, heat conductors, conductors, dielectrics, electromagnetic wave absorbers / shielders, Insulating pigments, heating elements, expanded bodies, water absorbing agents, elastic bodies, antistatic agents, activators, adsorbents, deodorants, deodorants, fragrances, anti-condensation agents, snow melting agents, freeze-thaw agents, fertilizers, various types Examples include species of plants and microorganisms, various drugs and chemicals, and the like.

As another form of the functional addition composition (D) adopted in the present invention, wastes are selected as the silicate-based material (A) or the calcium composition (BB) to be solidified, When this waste contains arsenic and chromium elements, it has the function of identifying arsenic and chromium elements, converting them into water-insoluble compounds, and immobilizing them, thereby preventing arsenic and chromium elements from contaminating the environment. The composition (D2) can be mentioned.

In the present invention, zeolite or a zeolite precursor is formed during the formation of a solidified product,
Water-soluble heavy metals mixed in the raw material can be fixed as water-insoluble aluminosilicate. However, the method of using the arsenic-immobilizing composition (D2) of the present invention is effective as a method for immobilizing arsenic and chromium elements in materials, wastes and sludges containing a large amount of arsenic and chromium elements among harmful heavy metals. It is.

The arsenic-immobilized composition (D) adopted in the present invention
As 2), divalent or trivalent iron ions are effective, and the arsenic or chromium element contained therein reacts with a divalent or trivalent iron compound in an alkaline state to form a water-insoluble iron salt compound. Therefore, arsenic and chromium elements can be immobilized. Specifically, iron salt compounds such as divalent or trivalent iron hydroxide, iron chloride, and iron sulfate which are easily available and have high water solubility are suitable.

The arsenic fixing composition (D) adopted in the present invention
It is sufficient that the divalent or trivalent iron hydroxide compound or iron salt compound (2) is mixed and mixed when preparing the deformable admixture (C). However, in the case of iron salt compounds such as iron chloride and iron sulfate having high water solubility, these iron salt compounds are added together with an alkaline hardening agent (B), and the iron salt compound is mixed with a deformable admixture (C). There is also a method in which iron hydroxide is changed to form a water-insoluble salt with arsenic element.

As another embodiment of the functional additive composition (D) adopted in the present invention, the cured product (E) of the present invention
An adsorptive material composition (D3) consisting of a single or a combination of two or more selected from the group of adsorbents such as silica gel, alumina gel, zeolite, and charcoal having an adsorptive function to add adsorptivity to Can be mentioned.

The adsorptive material composition (D
3) are collected, produced, processed or discharged in the fields of animals and plants containing various organic compounds and organic materials, and in the fields of agriculture, livestock and fisheries,
Natural products to be discarded, products produced by subjecting these natural products to the fermentation process, organic-containing materials such as residues, and waste products discharged from manufacturers of paper, pulp, fiber cloth, and processing Organic-containing material, an organic-containing material containing a high-molecular-weight organic compound, which is a plastic or a processed product thereof, is mainly composed of charcoal subjected to dry distillation at 400 to 1000 ° C., and contains silica or alumina depending on the case. Carbon-silicates.

Specific examples of the organic-containing material suitable for the present invention include the following. In particular, adoption of these wastes as the adsorptive material composition (D3) is also effective as a method for treating and disposing them. Examples of the animals and plants containing organic compounds and organic materials as wastes include red tides, planktons, algae and seaweeds, thinning materials, driftwoods, and pruning waste materials such as row trees.

Organic substances such as natural products collected or produced, processed, or discharged, and discarded in the fields of agriculture, livestock, and fisheries, and products produced by subjecting natural products to a fermentation process, and residues thereof. Ingredients include fruit waste, vegetable waste, rice hulls, grain waste after threshing, waste and waste clay discharged from food processing plants, and fermentation discharged from fermentation plants such as sake and soy sauce. Residues, manure of livestock such as chickens, pigs and cattle, waste products discharged from a meat processing plant, waste products discharged from a fish processing and testing laboratory, and the like can be given.

[0292] Examples of the organic-containing material discharged from paper / pulp / fiber cloth manufacturing and processing manufacturers include waste products discharged from paper / pulp / fiber cloth manufacturing and processing manufacturers, and waste pulp. Organic sludge containing paper sludge containing, rags and the like discharged from the processing of clothing and the like, and newspapers, telephone directories and waste documents discharged from office work.

The general main chemical composition (% by weight on dry matter basis) of the organic-containing material adopted in the present invention is Si
O ₂ : 5.0 to 30.0, Al ₂ O ₃ : 1.0 to 30.0, Fe ₂ O ₃ : 0.1 to 10.0, Mg
O: 0.1 to 8.0, CaO: 0.1 to 8.
0, a material having a burning loss of 10.0 to 85.0 is preferable. However, the composition is not limited to the composition described above from the standpoint of undergoing carbonization treatment for carbonization.

The general main chemical composition (% by weight) of the charcoal or charcoal-silicate raw material obtained by subjecting the organic-containing material of the present invention to dry distillation is 3.0 to 50.0 for C and 10.0 for SiO _2. To 40.0, Al ₂ O ₃ is 5.0 to 3
5.0, Fe ₂ O ₃ is 0.5 to 10.0, MgO is 0.1 to 8.0, and CaO is 0.1 to 8.0.
The powdered carbon-containing composition (B8) having a specific surface area (cm ² / g) of 2400 or more and a sieve residue of 45 μm of 40% or less is suitable.

What is important in the solidified body obtained by adding the adsorptive material composition (D3) to the solidified body of the present invention is that the surface activity of the adsorptive material composition (D3) during the formation of the solidified body is important. Are utilized without being killed by the adopted curing agent, and the adsorption performance is exhibited irrespective of the fact that the powder forms an integrated solidified body. Therefore, the powdery adsorptive material can be molded into a solid such as granules which can be easily handled when used.

That is, when the alkali-based curing agent (B) of the present invention is adopted and the adsorptive material composition (D3) is added and blended to form a solidified body, the solidified body prepared here will be described later. As shown in the examples, it is well understood that the adopted adsorptive material composition (D3) sufficiently exhibits the adsorptivity to form a solid.

When a general hardening agent or adhesive is used regardless of whether it is organic or inorganic, the adsorbent material composition (D3) is hardened or bonded to form a solidified body. The cured agent or adhesive covers and blocks the adsorbing surface of the adsorbent, losing the adsorbing effect, which is the adsorbing performance of the adsorbent. Tended to be unable to do so.

In another embodiment of the functional additive composition (D) adopted in the present invention, the water- and heat-resistant solidified product of the present invention has an antimicrobial action such as antibacterial property, antifungal property and antialgal property. An antimicrobial composition capable of adding a compound containing an ion or an element such as silver, copper, zinc, nickel or a halogen element such as chlorine, bromine or iodine capable of exhibiting an antimicrobial composition (D4) It can be mentioned as.

As the antimicrobial composition (D4), the following formula (12): ZO _y · hDO _x · w ₂ O (12) (where Z is monovalent or divalent silver) , Copper, zinc or nickel element, D is calcium, magnesium, boron,
23. element aluminum, carbon, silicon, nitrogen, phosphorus or sulfur, h is a number not greater than 3.5 including zero, and w is including zero.
0 or less, y is a number from 0.5 to 1.0, x is 0.5
Or a compound of the formula (1) or a combination of two or more powdery silver, copper, zinc or nickel compound compounds represented by Examples can be given.

The compound containing monovalent or divalent silver or copper can be selected from commercially available reagents and industrial chemicals. As a specific example, silver oxide [Ag
O], silver suboxide [Ag ₂ O] silver carbonate [Ag ₂ CO ₃ ],
Silver nitrate [AgNO ₃ ], silver nitrite [AgNO ₂ ], copper oxide [CuO], cuprous oxide [Cu ₂ O], copper carbonate [Cu ₂
CO _3], copper borate _{[Cu 2 B 4 O 7 ·} 4H 2 O], a composite oxide such as silicic acid copper [Cusio _3] can be preferably exemplified.

The zinc-containing compound selected for the antimicrobial composition (D4) can be selected from commercially available reagents and industrial chemicals. As a specific example, zinc oxide [Zn
O], zinc hydroxide [Zn (OH) ₂ ], zinc sulfite [Z
nSO ₃ · _2H 2 O], zinc sulfate [ZnSO ₄ · 2H ₂
O], zinc phosphate [Zn ₃ (PO ₄ ) ₂ .4H ₂ O],
Zinc nitrite [Zn (NO ₂ ) ₂ .H ₂ O], zinc nitrate [Zn (NO ₃ ) ₂ .6H ₂ O], zinc borate [ZnB
_{4 O 7 · 4H 2 O]} , zinc acetate _[Zn (CH 3 COO)
₂ · _{2H 2} O], Gerhard zinc _{[Zn (C 2 O 4)} · 2H
₂ O], various zinc-containing solid solutions (Mg _0.9 Zn _0.1
O, 3MgO.Al ₂ O ₃ .ZnO, etc.] or a combination of two or more zinc compounds.

The nickel-containing compound selected for the antimicrobial composition (D4) can be selected from commercially available reagents and industrial chemicals. Specific examples of nickel oxide [NiO], nickel hydroxide [Ni _(OH) 2], nickel sulfate _{[NiSO 4 · 2H 2 O]} , nickel nitrate [N
i (NO ₃ ) ₂ .6H ₂ O] and other organic nickel compounds, etc., alone or in combination of two or more.

Further, as the chlorine, bromine and iodine of the halogen element selected for the antimicrobial composition (D4), a solution in which the halogen element is present as an ion is supported on zeolite, charcoal, silica, alumina or the like having a high supportability. This can be used as an antimicrobial composition (D4). Of course, these various halogen compounds can be selected alone or in combination.

Further, as another antimicrobial composition (D4), calcium ions or hydroxides of calcium or magnesium are combined with zinc ions, or nickel ions or zinc ions and copper ions or silver ions to form a solid solution. Complex oxides that have been used can also be mentioned. In addition, an antimicrobial composition of a material in which these zinc-containing compounds are supported on a clay mineral composed of zeolite or ferrosilicate having a supporting property, zirconium phosphate having an adsorptive power, activated carbon, silica gel, or the like, alone or in combination ( D4) is also effective.

When the zinc compound of the antimicrobial composition (D4), especially a water-soluble zinc salt, is incorporated into the alkaline hardening agent (B) of the present invention, the zinc salt becomes an alkaline hardening agent. By the reaction that occurs in parallel with the action of (B), zinc silicate is formed and fixed in the solidified body, and slowly releases zinc ions capable of exhibiting an antibacterial effect, and the antibacterial effect is long-term in a water-resistant solidified body. It is effective and preferable because it exerts its effects.

The compounds such as copper, silver, zinc, nickel and the like to be used as the antimicrobial composition (D4) are not limited to these compounds. For example, halogen compounds of these metal elements and metals themselves may be used. Can be adopted as the antimicrobial composition (D4) of the present invention as long as it is a compound or metal powder that exhibits antimicrobial properties.

As another form of the functional additive composition (D) adopted in the present invention, there is a water repellent imparting composition (D5) for imparting water repellency to the solidified product. When water repellency is required in addition to water resistance and heat resistance to the solidified body formed in the present invention, a water repellent can be applied to the surface of the formed solidified body. It is effective and effective to add the functional additive composition (D), which is a water repellent agent, to the solidified body forming material in advance in terms of simplification except for the workability.

In particular, as the water repellent-providing composition (D5), the following composition formula (13) (R ¹ ) (R ² ) [OSiR ³ ] _n. [SiOR ⁶ ] (R ⁴ ) (R ⁵ ) (Wherein, R ¹ to R ⁵ are the same or different groups selected from a hydrogen atom, an OR ⁶ group or a monovalent hydrocarbon group, and R ⁶ is a hydrogen atom or a C ₁ to C ₅ An alkyl group, n is a number smaller than 15 including zero) or a water-repellent-providing composition obtained by transforming an organosiloxane composed of a single or a combination of two or more low-molecular-weight organosiloxanes into a water emulsion. Can be mentioned.

In another embodiment of the functional additive composition (D) adopted in the present invention, a metal fiber, a glass fiber, a carbon fiber, an aramid fiber is used in order to add strength reinforcement to the solidified product of the present invention. , A fibrous reinforcing agent which is a long fiber or a short fiber from plant fibers and mineral fibers, and a fibrous reinforcing composition (D
6) can be suitably mentioned.

[0310] In another embodiment of the functional addition composition (D) adopted in the present invention, the solidified product of the present invention has a particle size of 100 µm or more and 7 mm Sandy, lumpy, needle-like, columnar, cylindrical, spherical, hollow, plate-like, flake-like, crushed-stone, and bulky with a specific gravity of 0.5 to 2.5 g / cc in the following ranges: Aggregate compositions (D7) of various shapes or various shapes can be suitably mentioned.

In the present invention, it is suggested that it is preferable that a sandy silicate-based material (AS) can be selected as the silicate material (A) to be solidified. Of course, as the aggregate composition (D7) suitable for the functional addition composition (D) adopted in the present invention, a sandy silicate-based material (A2) selected as a solidification target can also be selected. .

[0312] Typical examples of the aggregate composition (D7) include sand and stone having various particle diameters that are commonly used, similar to those adopted for the sandy silicate-based material (AS). Processed and improved aggregates such as natural aggregates, crushed stones, etc., and light-weight fine bones which are processed aggregates such as perlite and vermiculite, etc. obtained by heating and processing vermiculite Wood, and coarse-grained volcanic ash. Furthermore, when the weight of the formed solid is required as a weight or a fishing reef, sandy or granular materials such as iron ore and manganese ore having a large specific gravity can be selected and adopted.

Also, wastes containing silicate as a main component and in the form of aggregate can be suitably adopted. For example, slug cullet in which waste incineration ash is slugged by the melting method, cullet-like glass waste in which waste glass bottles and waste glass plates are cullet, and ceramic products such as cement products and ceramics are refined. Recycled materials such as scrap waste, recycled materials whose waste is processed into granules, granularity-regulated products such as construction waste soil, and aggregates synthesized from various waste materials. .

[0314] As the aggregate composition (D6) of the present invention, "aggregates" to be mixed with concrete products and the like can be selected. The “aggregate” at this time is classified into “fine aggregate” made of sand and crushed stone having a particle size of 5 mmφ or less and “coarse aggregate” made of gravel and crushed stone having a particle size of 5 mmφ or more. In the present specification, `` coarse aggregate '' is regarded as pure expanded aggregate, and the effect of adopting coarse aggregate is common general knowledge in the industry, and does not impair the essential properties of the water-resistant and heat-resistant solidified body. Therefore, the adoption of "coarse aggregate" is not incorporated into the sandy silicate-based material (AS) of the present invention unless otherwise specified.

As another form of the functional additive composition (D) adopted in the present invention, the above-mentioned additive material composition (D)
1), arsenic fixing composition (D2), adsorptive material composition (D3), antimicrobial composition (D4), water repellent additive composition (D5), fiber replenishment composition (D6) or aggregate A mixed material composition (D8) comprising a combination mixture of two or more of the composition (D7) can be mentioned. This mixed material composition (D8) is preferable because a plurality of additional materials are composited, whereby the composite properties as an additional material, the mixing effect, and the composite / mixed synergistic effect are sufficiently exhibited.

The deformable admixture (C) of the present invention comprises a silicate-based material (A) to be solidified, a three- or four-component alkaline curing agent (B), and a function as required. By adding the water-imparting composition (D) and homogenously mixing, a two-component or three-component fluid or plastic deformable admixture (C) is prepared.

However, the calcium composition (BA) and the alkaline composition (BB) constituting the alkaline curing agent (B)
When an easily reactive silicic acid or silicate coexists, it is not necessary to coexist the silicate-based material (A).
It is also possible to prepare a deformable admixture (C) with a single or triple alkali curing agent (B) alone.

The preparation method at this time varies depending on the purpose and use of the solidified product of the present invention, the required performance and function, and the like, but is generally a well-known or officially used mixer commonly used in the art. This can be easily achieved by selecting from among methods capable of uniformly mixing the components of the raw materials using a stirrer, kneader, disperser, or the like.

In general, in the preparation of the deformable admixture (C) of the present invention, a kneading machine, a mixing machine and a dispersing machine, which are adopted when processing cement milk and concrete secondary products, are also preferably adopted. Can be. In addition, depending on the purpose, a device for injecting or filling a hardening agent such as a deep mixing method adopted in ground improvement or the like can also be suitably adopted.

In addition, at the time of preparing the mixture of the deformable admixture (C) of the present invention, by adding and blending water, the mixing conditions are improved, and the work efficiency of the mixing process is improved. But,
In general, it should be noted that increasing the water content in the deformable admixture (C) tends to lower the strength of the solidified product.

In order to transform the deformable admixture (C) prepared by mixing the alkali-based curing agent (B) of the present invention into a cured product (E), it is subjected to the room temperature solidification treatment step of the present invention. Is preferred. By subjecting the deformable admixture (C) to a room temperature solidification treatment step, the flowable or plastic deformable admixture (C) loses its deformability and changes into a hardened body (E) having hardness at least at room temperature. It is possible to do.

In the room temperature solidification treatment step of the present invention, the deformable admixture (C), which is a homogeneous admixture of the silicate-based material (A) and the alkali-based curing agent (B), is mixed with the mixture at a temperature of 10 to Release into the atmosphere or atmosphere at a temperature in the range of 400 ° C. or into water at a temperature in the range of 10 to 90 ° C. to promote the reaction and curing in the deformable admixture (C) and to cure. A solidification treatment step for transforming the body (E) is effective.

In this room temperature solidification treatment step, there is no special meaning to limit the treatment temperature to 10 ° C. or higher. However, when the treatment temperature is 10 ° C. or lower, the formation of the cured product (E) of the deformable admixture (C) is not possible. Although not impossible, it takes time to form the cured product (E), which is not preferable in terms of working efficiency. In addition, the processing temperature is set to 40
Although it is not impossible to perform the treatment at a temperature of 0 ° C. or higher, it is not preferable because there is no particular advantage and thermal energy is wasted.

[0324] However, when the quality of the cured product (E) is required to change under the conditions that require productivity or heating in the production line, the cured product (E) may be subjected to a solidification treatment in an atmosphere of 400 ° C or less. It does not hinder the formation of the composite cured matrix of the silica polymer or aluminosilicate formed under these conditions, but may be preferable in terms of improving productivity.

There is no particular advantage even if the solidification treatment conditions are set to 400 ° C. or higher. However, when processing a solidified product or the like produced on a production line, the raw material to be solidified contains an organic component, or When improving the performance, strength, etc. of the resulting solidified product, release of the product to a high temperature of 900 ° C or less can carbonize or decarbonate the contained organic components. It does not hinder the basic reactions and steps of the room temperature solidification treatment technology of the invention.

Further, the deformable admixture (C) of the present invention
At room temperature or at least 400 ° C. under normal conditions in the air, as well as under various conditions such as pressurization, decompression, vibration, pouring, pushing, casting, etc. Can be. In curing conditions, not only room temperature curing but also heat curing, steam curing, pressure curing,
Various conditions such as reduced pressure curing and specific gas replacement curing can be adopted.

Further, in the room temperature solidification treatment of the present invention, it is also possible to carry out the treatment in water. In particular, a hydrated mud silicate material (AW) is selected as the silicate material (A) to be solidified. It is important that the deformable admixture (C) prepared in (1) can be subjected to room temperature solidification treatment in the presence of sufficient water or in water.

In the present invention, the fluid or plastically deformable admixture (C) prepared with the hydrous mud silicate material (AW) as a solidification target is subjected to room temperature solidification treatment in the presence of sufficient water or in water. Forming a solidified body even when attached is effective for improving soft ground, hardening dredged soil on the seabed or riverbed, and solidifying muddy mud in sludge or drainage treatment of dams and the like.

According to the method of the present invention, the deformable admixture (C) prepared by adding the alkali-based curing agent (B) to the silicate-based material (A) and mixing the resulting mixture is subjected to a room temperature solidification treatment step. As a result, the deformable mixture (C) is transformed into a cured product (E). The cured product (E) altered here forms a composite matrix containing silica polymer and aluminosilicate as main components, and it is considered that this composite matrix forms a matrix constituting the cured product.

Therefore, the cured product (E) of the present invention, which is deteriorated by the solidification treatment at room temperature, exhibits a uniaxial compressive strength of at least ² kgf / cm ^{2, and} more than 10 kgf / cm ² depending on the composition and conditions. Demonstrate
Further, when selecting the composition and conditions mainly for developing the strength, 90 kgf / cm ² or more, preferably 150 kgf / cm ² or more.
A cured product having a strength of not less than ² cm ² can be provided as a water-resistant and heat-resistant solidified product.

Further, the cured product (E) which is altered here is:
Even when the silicate-based material (A) or the calcium composition (BA) to be solidified contains heavy metals, the solidified body is allowed to undergo the reaction and curing under the room temperature solidification treatment conditions of the present invention. The aluminosilicate zeolite or zeolite precursor formed in it is formed by taking in heavy metals, forming a water-insoluble salt compound, and the cured product in which the heavy metals contained are immobilized in a water-insoluble state is water-resistant. It is formed as a heat-resistant solid.

Furthermore, the cured product (E) produced here is
It is porous, has a specific surface area of 500 g / cc or more and has an adsorption performance, and exhibits performance as an adsorbent and a support. Therefore, even when the silicate material (A) having an adsorption performance containing silica, alumina, carbon, etc. is to be solidified, the adsorption active surface is utilized without hindering the adsorption performance of the solidification target material at this time. A cured body can be formed.

The deformable admixture (C) prepared by adopting the room temperature solidification treatment technique of the present invention has a certain strength, is fixed with heavy metals, is porous, has adsorptivity, and has water resistance. And has been transformed into a heat-resistant cured product (E),
Shapes represented by the following seven types can be ensured, and can be provided for the uses exemplified below. The use of the solidified product of the present invention is not limited to the following examples.

Granular Body (EG) Shape: Sand, Granular, Granular, Lump, etc. Use: Aggregate, roadbed material, filler, adsorbent, purification material, etc. Specific structure (EM) shape: Various specific shapes Applications: Bricks, furnace materials, sanitary ware, building materials, etc. Adhesion-hardened (EB) shapes: Surfaces and inner surfaces of various base materials (iron, ceramic products, etc.) Applications: coatings, coatings, coatings, Adhesion, glaze, etc. Different-layer granules (ED) Shape: core (light or heavy) and surface coating are different Use: multilayer granules, glaze granules, etc. Unspecified shape (EU) Shape: unspecified Indefinite form Applications: Backfilling materials for civil engineering work sites, soft ground improvement, etc. Improvement of basement in water, such as sea, rivers and dam bottoms, etc. Particles (EP) Shape: 10-2000μ powders, etc. Application: Zeolite-containing water treatment agent, filling auxiliary agent, etc. Aggregate cured product (EC) Shape: millet-like (granular material) The secondary processed products) APPLICATIONS: soundproofing material, thermal insulation material, greening floor, millet revitalization body, etc.

In the present invention, the deformable admixture (C) is
After granulation into sand, granules, spheres, columns, blocks, flakes, etc., having a particle size of 0.1 to 100 mm, the granules (EG) are cured by subjecting them to a room temperature solidification treatment step. A water-resistant and heat-resistant solid can be provided as the body (E).

The granulation of the granules (EG) can be performed by subjecting the deformable admixture (C) of the present invention to rolling granulation and extrusion granulation which are known and used in the art. , Stirring granulation,
Spray granulation, various pelletizers, spray granulation, mold-flow granulation, packing granulation, etc.
Granules such as crushed stones, spheres, columns, granules, and flakes can be formed. After granulation, each granule (EG) is released under an atmosphere of 10 to 400 ° C.
Can be transformed into a cured body (E) in which is secured.

Further, in the present invention, when a carbon-containing silicate or an organic-containing silicate is selected for the silicate composition (A), the granular material (EG) processed here is subjected to a temperature of 180 to 900 ° C. By performing a so-called incineration treatment at a high temperature, water, carbon, organic components, etc., held in the granular molded body are carbonized or burnt off, and the granular molded body is subjected to carbonization or sintering. EG), carbonized or hardened granular material (E
G) can be secured.

These granulated or heat-treated granules (EG) are used as substitute aggregates such as sand, gravel, crushed stones, fillers,
Various purification treatment agents, adsorbents, deodorants, liquid treatment materials, water treatment materials, oil treatment materials, water treatment agents for rivers and lakes, nitrogen as roadbed materials, landfill materials, and granular materials with various functions・ Adsorbents such as phosphorus, sound deadening materials, sound insulating materials, heat insulating materials, heat insulating materials,
Anti-microbial agents such as snow melting agents, shielding materials, antibacterial agents, greening base materials,
It can be effectively applied as a catalyst, a building material, a greening base material, and a support for various functional agents.

In the present invention, the deformable admixture (C) is
After molding into a specific structure suitable for each purpose, as seen in various concrete secondary products and pottery ceramic products, when the specific structure molded here is subjected to room temperature solidification treatment, it is water resistant Thus, a solidified body secured in the specific structure (EM) transformed into a heat-resistant cured body (E) can be provided.

The means for molding the deformable admixture (C) of the present invention into a specific structure can be obtained by using a slurry or a plastic material generally used in the industry, the secondary concrete product manufacturing industry and the ceramic product manufacturing industry. Molding means for molding
All molding methods and methods of the method can be adopted.

Of course, in these molding means, normal pressure,
Various means such as pressurizing, depressurizing, vibrating, pouring, pushing, and casting can also be applied. In the curing, not only room temperature curing but also various conditions such as heating curing, steam curing, pressure curing, reduced pressure curing, and specific gas replacement curing can be adopted.

The specific structure (EM) of the present invention can be used for all types of molded products adopted for concrete secondary products and ceramic products manufactured under high-temperature heating conditions. You can choose. Particularly, it is suitable from the standpoint of enabling energy saving as a substitute for pottery and so-called ceramic products which have required high energy.

As specific examples, various blocks,
Bricks, tiles, foundation stones, interlocking, tetrapots, fishing reefs, dividers, dividers, interior materials, outer wall materials,
Poles, pillars, steps, various building materials, U-shaped grooves, earthen pipes, fume pipes, pots, flowerbeds, decorations, ornaments, sleepers, benches, desks,
Examples include tiles, porcelain / porcelain, sanitary ware such as toilets, bricks, heat-resistant bricks, fire-resistant bricks, and various structures.

In particular, the concrete structure (EM) comprising the water-resistant and heat-resistant solidified body of the present invention does not contain harmful heavy metals such as chromium, unlike cement-based concrete products. There is no fear of elution and contamination, and for example, it can be adopted for agricultural water distribution channels, etc., and it may be adopted with confidence without polluting rice fields.

Furthermore, the alkali-based curing agent (B) of the present invention can form a solidified product at room temperature, as a general concrete slurry milk product is adopted for construction of structures at various construction sites. Therefore, the specific structure (EM) of the present invention can be effectively applied to the construction of structures at construction sites such as civil engineering, construction, and processing in various places.

In the present invention, the deformable admixture (C) is
When it is subjected to room temperature solidification after being attached to the surface or inside of the various base members, the water and heat resistant cured body (E) It is possible to provide a solidified body in which a cured coating (EB) formed in a coating or a coated state that has been transformed into a solidified state is secured.

[0347] Substrates which are the object of the adhered cured product (EB) include various structures, concrete structures such as quays, seawalls, dams, concrete products, secondary products made of various cements, and various metals. Processed products, processed products made of wood, bamboo, paper, cloth, nonwoven fabric, textile products, glass, pottery,
Porcelain products, various ceramic products, various coatings and films, rubber and plastics products, various composite products, various foams (such as pearlite) and lightweight aggregates, and processed products and moldings made from the solidified product of the present invention And the like.

Specific applications of the adhesive cured product (EB) include various adhesives, binders, binders, jointing materials, caulking materials, filling materials, cohesive materials, solidifying materials, backing materials, anchor materials, coatings, and the like. Wood, un-to-car coat, flooring,
Wall materials, waterproof materials, coating materials, waste containers, paints and coatings, antimicrobial coatings, anti-condensation materials and coatings, various functional materials, etc., and repair materials for various structures and products, etc. And a glaze material of a glaze granulated on the surface of the granule.

As a specific method of applying the adhered cured product (EB), the deformable admixture (C) prepared for the base material is dipped, flow-coated, brush-coated, sprayed, sprayed, roller-coated, iron-coated. After applying by known and public methods in the industry such as coating, infiltration method, lifting method, nozzle method, winding method, laying method, patching method, and spraying method,
It can be released at least to room temperature and processed into an adhered cured product (EB) product.

In the present invention, the surface of the granule composed of a lightweight or heavy foreign material is coated or dusted with the deformable admixture (C), using the core as a core.
When a layer of a foreign material and a layer different from the core of the core material are formed on the surface of the granule and then subjected to room temperature solidification treatment, the surface of the core substrate is made of a water-resistant and heat-resistant cured material (E). The solidified body in which the heterogeneous granules (ED) formed of the above materials are secured can be provided.

Examples of the heterogeneous base material serving as the core of the heterogeneous granules (ED) include various concrete products, cement products, various metallic products, wood, bamboo, paper products, cloth, nonwoven fabric, textile products, Glass, pottery and porcelain products, molten cullet of waste, various ceramic products, various coatings, rubber and plastic products, various composite products, various foams (such as perlite) and lightweight aggregates (Bermu Kirite).

Specific applications of the heterogeneous granules (ED) include various heat insulating materials, heat insulating materials, moisture absorbing materials, joint materials, caulking materials, filling materials, cohesive materials, solidifying materials, backing materials, anchor materials, Examples include coating materials, flooring materials, waterproofing materials, coating materials, and repair materials for various structures and products, as well as glaze granules.

As a specific method for applying the heterogeneous granules (ED), the deformable admixture (C) prepared for the base material is applied, flow-coated, brush-coated, sprayed, sprayed, and sprayed. Coating, granulation method, after the granules subjected to formation of a different layer by a method known and used in the art such as a recoating method,
It can be released to room temperature and processed into heterolamellar granules (ED).

In the present invention, the deformable admixture (C) is
When it is poured or backfilled into ground bases and structures in various places or gaps as it is, and then subjected to room temperature solidification treatment, it is made of a water-resistant and heat-resistant cured body (E) at the target location It is possible to provide a solidified body in which an unspecified shape (EU) is secured.

What is important in the room temperature solidification treatment technology of the present invention is that when a hydrous mud silicate material (AW) is selected as the silicate material (A), this hydrous mud silicate material is used. When the alkaline hardener (B) is mixed with (AW), the raw material retains a large amount of water, so that a mayonnaise-like deformable admixture (C) is prepared.

What is important in the mayonnaise-like deformable admixture (C) prepared here is that even when subjected to the reaction and curing of room temperature solidification treatment in water, the mayonnaise-like deformable admixture (C) is mixed. (C) is transformed into a non-fluid hardened body (E) which exhibits a certain strength in a solid state without being dispersed in water, and forms a solidified body.

Therefore, the specific adoption of the unspecified form (EU) of the present invention may be attributable to sludge at riverbeds, sea floors, swamp bottoms, dam bottoms, tunnels, etc., or sludge generated at construction sites where hydrous mud is deposited. Mud silicate-based material (AW) such as slag and hydrated mud, and even hydrated soil in soft ground, is transformed into a stable, water-resistant and heat-resistant cured product (E) to provide strength without deformation. It is possible to use it effectively as backfill soil or moldings.

What is important in the present invention is that, by adopting the alkaline curing agent (B) of the present invention, the alkaline curing agent (B) itself does not contain harmful substances such as hexavalent chromium, and There is no concern about the elution of water such as hexavalent chromium, which had been a problem when the cements were adopted as curing agents, and it was an effective method as a treatment technology in the effective reuse of construction waste soil and sludge. Therefore, it is very effective as a technology capable of solving the pollution problem caused by heavy metal contamination.

Further, by adopting the technology of the present invention, even when a fixed body is formed in an aqueous system using a material containing heavy metals as a component to provide a water-resistant and heat-resistant solid, for example, harmful substances contained in wastes may be used. Since the heavy metal of the substance can be immobilized by making it insoluble in water, it is possible to eliminate environmental pollution, which is a problem in the disposal of wastes, and to effectively reuse the wastes.

In the present invention, the deformable admixture (C) is
When the water content of the deformable admixture (C) is small, 10
After securing to a once-smooth powder of 1000 μm, by subjecting to solidification at room temperature, it is possible to transform into a powder-like, water-resistant, heat-resistant solid,
It is possible to provide a solidified body in which the shape of a powder (EP) that can be used as various functional materials is ensured.

Since the powder (EP) of the present invention contains lipophilic zeolite or a zeolite precursor in a complex form, the powder (EP) recovered here is simply mixed with water. It is effective not only as a treatment agent and an adsorption treatment agent but also as a water treatment agent in which oil components and oil classifications are mixed. Further, when a carbon component (for example, the above-described charcoal-zeolite component) is added to the powder (EP), it is very effective as a treating agent for water or a solution in which water and oil are mixed, and it is very effective in a living environment. It is suitable as a cleaning agent.

As another application example of the solidified product of the present invention, the above-mentioned granules having a particle size of 0.1 to 25 mm or heated granules (E
G) or a heterogeneous granule (ED) as an aggregate, and the deformable admixture (C) of the present invention prepared as the above-mentioned separately prepared adhesive cured product (EB) is adopted as a binder,・ After assembling a group of granules such as heated granules (EG) and heterogeneous granules (ED) into a specific aggregate shape such as a millet-like shape, use the same The adhesive binder is transformed into a water-resistant and heat-resistant cured product (E), and a permeable void formed by combining the granules such as granules / heated granules (EG) and heterogeneous granules (ED). Can provide a millet-like solidified body forming an aggregated cured body (EC) having the following.

In the processing of the aggregated cured product (EC) in the present invention, the silica-based curing agent (B) of the present invention or the specified binder is used with respect to 100 parts by weight of the granular material or the granular material. The binder is added in an amount of 5 to 65 parts by weight, and the surface of the granular material is coated with the binder. 40
It can be supplied as a millet-shaped aggregated cured product (EC) having through-holes at 0 ° C. with the binder portion as a cured product.

[0364] Specific uses of the millet-like aggregated cured product (EC) of the present invention include: building materials, soundproofing materials, heat insulating materials, heat insulating materials, water retaining agents, shielding materials, filtering materials, detergents, water treatment materials, Gas treatment materials, antimicrobial materials, blocks, fish reefs, seagrass seabeds,
Grass floor, river improvement materials, muddy or wet soil improvement materials,
It can be expected to be used in various fields for greening infrastructure.

Furthermore, the aggregate cured product (EC) of the present invention
In connection with the fact that can be processed at room temperature, depending on the purpose of use of the present invention, bring the granules or granules to the construction or use site, and transfer the granules or the group of granules to the situation at the site At the construction site, a binder composed of the alkali-based curing agent of the present invention (the adhesive cured product of the present invention (E
B)), and by applying a construction method such as spraying, pouring, and pressing to a form suitable for the on-site situation, in the same manner as when a concrete mill is constructed on the site, a millet-like set hardened body ( EC) can be constructed and completed.

Therefore, the millet-shaped aggregated cured product (E
C) does not need to be manufactured in advance as a collective cured product on a factory line, and the collective cured product (E) can be produced without wasting the labor and energy involved in transporting the molded product to the site.
C) can be performed at room temperature at the site according to the situation at the site, and there is an advantage that it can be adopted as a labor-saving product.

In particular, large-scale construction related to civil engineering and construction, for example, soundproofing on expressways and the like, heat insulation processing in large buildings, completion of greening floors in rivers and dams, and completion of processing materials of specific shapes in the purification process It can be suitably applied as a labor-saving type structural product.

Also, the millet-like aggregated cured product (E
Examples of C) construction on site include civil engineering dam construction, gulf construction, riverbed construction, river protection construction, road construction, railway construction, factory construction, ground construction, house construction, tank installation, pole installation, and park construction. Business, greening business, local construction structures, building materials, etc., which can be widely applied to various uses and are effective.

[0369]

EXAMPLES In the following Reference Examples and Examples,
For the silicate-based material (A) to be solidified in the present invention, the calcium composition (BA), the alkali composition (BB), the aqueous composition (BC), and the curing assistant composition (B) of the present invention are used.
About the alkali-based curing agent (B) composed of D), and about the deformable admixture (C) prepared by further adding the functional addition composition (D) to the alkali-based curing agent (B) as necessary. This will be described with a specific example.

Furthermore, the deformable admixture (C) of the present invention
A granular body (EG), a specific structure (EM), an adhesion hardened body (EB), a heterogeneous granule (ED), an unspecified form (EU),
After securing each shape of the granular material (EP) or the aggregated cured product (EC), the cured product (E) is transformed into a cured product (E) of each shape by subjecting it to the room temperature solidification treatment of the present invention. The water-resistant and heat-resistant solidified body (E) will be described with specific examples.

In the unspecified form (EU), the workability and physical properties required for the specific use of the unspecified form (EU) are not particularly different from the specified structure (EM) except for the purpose of use. Since they are common, the specific structure (EM) will be described in common in the examples. Note that the content of the present invention is not limited to the examples described in the following Reference Examples and Examples.

Hereinafter, the test methods and evaluation methods for evaluating the physical properties of the respective test specimens prepared in the present reference example and the present example are described below. In addition,
The test method conforms to the JIS standard in principle. However, some tests employ test methods and evaluation methods for specifically evaluating the content of the present invention.

[Physical Property Evaluation Test Method] Pot life of deformable admixture (C) Prepared deformable admixture (C) is about 500c in a 1 liter container
c) The sample was collected and left to stand in a constant temperature bath at 30 ± 2 ° C. in an open state, and the time until the sample did not deform even when an external pressure was applied to the sampled deformable mixture (C) was defined as the time from the start of standing. And the time was displayed as the limit of the workable time for work such as molding.

[0374] 2. Preparation of Standard Specimens for Evaluating Physical Properties (Cylindrical Specimen and Granular Specimen) As standard specimens in this example, two kinds of cylindrical specimens and granular specimens were used as standard specimens. The preparation conditions for each specimen are as follows. The cylindrical specimen is
The deformable admixture (C) prepared in a predetermined amount ratio was added to a φ50
After filling and filling into a cylindrical mold of × 100 mm, the surface is covered with a vinyl sheet and reacted and cured at room temperature (about 25 ° C) for a predetermined time (7 days or 28 days) in a sealed state or open state, and then demolded As a result, a cylindrical specimen was obtained. The granular test specimen is a deformable admixture (C) prepared at a predetermined ratio.
Is molded into granules of about 2 to 6 mm, and then room temperature (about 25 mm).
° C) or a predetermined time at a predetermined temperature [standard: 25 ° C x 48
Time] Reaction and curing were performed to obtain a granular test body.

[0375] 3. Evaluation of the water resistance of the resulting solidified product The prepared granular test sample was immersed in water maintained at about 20 ° C.
The specimen was immersed for a period of time and the strength was maintained without any change in the specimen after immersion.

[0376] 4. Evaluation of heat resistance of the resulting solidified body After drying the prepared granular specimen at room temperature, it was exposed to an electric oven at 400 ° C. for 2 hours.
% Was evaluated as "heat resistant", and the case where there was no test specimen strength after exposure was evaluated as "no heat resistance".

[0377] 5. Uniaxial Compressive Strength Test The prepared columnar specimen (n number = 3) was subjected to a uniaxial compressive crushing strength test using a crushing strength tester, and the breaking strength at that time was measured and expressed in Kgf / cm ² . In addition, the test specimen which was opened and cured on the 28th was 200 kgf /
cm ² or more is regarded as “pass”, and the test specimen cured underwater or sealed in a sealed state for 28 days is 10 kgf /
A case where the value was ² cm or more was evaluated as “pass”. However, depending on the use and purpose of use of the solidified body, it may be possible to adopt the solidified body without being restricted by the acceptable strength value.

[0378] 6. Evaluation of strength of granule The prepared granular specimen (n number = 5) having a diameter of about 5 mm
When sandwiched between two iron plates, a weight of 10 kg is gently placed on the top and pressurized, and when the granules are crushed by the 10 kg pressurization at this time, the granulated specimen is said to have "strength" in the granulated solid. evaluated.

[0379] 7. Water Dissolution Test of Heavy Metals The prepared granular specimens were subjected to a water dissolution test of heavy metals according to the method specified in Notification No. 13 of the Environment Agency in accordance with JIS K0102. The harmful heavy metals include hexavalent chromium, cadmium, lead, total cyanide, arsenic, and total mercury. In this example, lead element was selected and measured as a representative of these heavy metals. In displaying the results, those below the detection limit of the concentration of heavy metals in the water dissolution test were indicated as "ND".

[0380] 8. Adhesion Test A base steel plate and an asbestos plate having a thickness of 0.5 mm are cut into a test plate having a size of 30 × 25 cm according to the method described in JIS K 6852. The portion corresponding to the bonding surface of the steel plate is polished using a 240-degree paper to give a metallic luster, and the surface is washed with a mixed solvent and dried. On the other hand, the adhesive surface portion of the asbestos plate is washed with water and dried.

Next, the prepared deformable admixture (C) was applied to a rectangular asbestos test plate 25 × 25 cm area to a thickness of about 2 mm, and a rectangular steel plate test piece 25 × 25 cm area was further applied thereon. And glue them together.
At this time, the 5 × 25 cm portions that are not adhered are set so as to protrude in a straight line at opposite portions from each other.

Next, the test piece (test body) set by bonding
After standing at room temperature of about 20 ° C. for 7 days, a test piece (specimen) was erected in a vertical direction with an ear-shaped portion using a compression rupture tester. Kg / c
m ² ) to evaluate the adhesion. However, when the asbestos member as the base material was broken, not the bonded portion when the load was applied, the bonding strength was evaluated as exceeding the material strength of the base material.

[0383] 9. Antimicrobial (antibacterial) effect test of treated water and pH measurement Purification test of warm water mixed with E. coli Preparation of bacterial liquid: E. coli (E.
c. As a nutrient of -3), NB medium (bouillon) is 1/5
0 concentration (10 times the test standard concentration) at 27 ° C, 16
Escherichia coli cultured with shaking for hours is adjusted to pH 7 to a final concentration of 1 / 10,000. Preparation of treated water: Dispense 150 cc of the above E. coli solution into an Erlenmeyer flask, stopper tightly to obtain a blank solution (BL). A predetermined amount concentration (1 g / 150 cc and 0.5 g / 150
cc (2 levels of cc) is supplied, sealed and used as test treatment water. Test conditions: Test treated water is cultured for 72 hours in a constant temperature bath at 40 ° C., and the number of bacteria is measured. PH measurement of treated water Test treated water (1g / 150cc
Is measured with a pH meter.

[0384] 10. Measuring method of soluble content of barium salt compound in alkaline solution: powdered barium salt compound sample 10 g
Was stirred and dispersed in 100 ml of a 1N caustic soda solution at 25 ° C. for 10 minutes, and then the sample solution was filtered off to quantitatively analyze barium ions in the collected solution. The total amount of barium elements in the collected sample was defined as a reference (100). The amount of barium ion (Ba ⁺⁺ ) eluted in 1N caustic soda solution (mg /
1) was calculated.

[0385] 11. Sustained release of phosphoric acid: 1 g of sample
Stir and disperse in 100 ml of 4N caustic soda solution at 5 ° C. Then sampled 5 minutes elapsed and 120 minutes after dispersion, fractionated filtration, phosphoric acid in the filtrate fraction (P ₂ O ₅₎
Is plotted in mg / 100 ml, the elapsed time (minutes) is plotted on the horizontal axis of the graph, and the integrated elution amount (mg / 100 ml) of phosphoric acid (P ₂ O ₅ ) is plotted on the vertical axis. From the equation (13) Y = aX + b (13), the elution amount b of the initial phosphoric acid content and the average hydrolysis rate constant a were calculated.

[0386] 12. Evaluation method for easy reactivity to ionic alkali metal elements Silicate-based materials (A) and aluminate-based materials (BBA)
With respect to 100 parts by weight, 1000 parts by weight of an alkali solution having a concentration of 10% by weight based on Na ₂ O oxide is added at room temperature, and the mixture is reacted under stirring for 60 minutes. Was evaluated as being easily reactive to the ionic alkali metal element.

13. Test Method of Deodorizing Effect of Adsorbent 13-1 Deodorizing Effect on Representative Offensive Odor (Sensory Evaluation) The evaluation method is as follows. Ammonia, trimethylamine, hydrogen sulfide, E-mercaptan,
Methyl sulfide, isovaleric acid, acetic acid), 1 g of the adsorbent of the sample was added, the mixture was allowed to stand at room temperature for 6 hours, and then 0.1 liter of gas in the bottle was taken out. Was evaluated according to

13-2 Static Deodorization Capacity for Various Odors The evaluation method was as follows.
/ L) is charged with a predetermined amount of malodorous components (ammonia, trimethylamine, hydrogen sulfide), and then 1 g of the adsorbent of the sample is added and left at room temperature for 24 hours. After 24 hours, the maximum concentration point of the malodorous component at which no malodorous component was detected was evaluated as the static deodorizing capacity.

13-3 Dynamic Deodorizing Capacity for Various Odors The evaluation method was as follows.
The adsorbent of the sample is packed so as to have a length of m. Next, a gaseous malodorous component (ammonia, trimethylamine, hydrogen sulfide) adjusted to about 1% concentration is passed through the sample adsorbent in the column at a rate of 200 ml / min. With this operation, the dynamic deodorizing capacity was measured from the breakthrough point at which the malodorous component was not adsorbed on the sample adsorbent.

[Reference Example 1] In this reference example, eight types of easily-reactive sandy, powdery or hydrous mud-like silicate-based materials (A) to be solidified which can be adopted in this example Will be described.

The sandy silicate-based material (AS) includes granular Sakurajima volcanic ash (AS-1) and diatomaceous earth (A).
S-2); as a powdery silicate-based material (AP), powdered incinerated ash (AP-
1), fly ash discharged from thermal power plants (AP
-2), charcoal-silicate ash (AP-3) obtained by dry distillation of paper sludge, and blast furnace slag (AP-4) discharged from a steel mill; and a silicate-based material (AW ) Includes wet mud (AW-1) dredged from the sea floor (Osaka Bay), mud (AW-2) collected from the lower tunnel of the river (Sumida River), and sludge (AW) collected from the dam bottom of the hydroelectric power plant. -3), I chose volcanic ash clay (AW-4) from Kanto (Ibaraki Prefecture). The typical composition of these components is shown in Table 1 below.

[0392]

[Reference Example 2] In this reference example, a calcium standard composition (BA1), which is a calcium composition (BA) which can be used as the alkaline curing agent (B) of the present invention, and an oxyacid salt composition (BA) BA2), a halogen salt composition (BA3),
Waste powder composition (BA4), cement powder composition (B
A5), a modified carbon-calcium composition (BA6), a sulfate composition (BA7), and eight kinds of calcium composite compositions (BA8) will be described. Each calcium composition (BA) was selected from powders of commercially available reagents, industrial chemicals, wastes, and processed products such as wastes shown in Table 2. The calcium composite composition (BA
8) is shown in the actual formulation. These calcium compositions (B
The main components of A) are also shown in Table 2.

[0394]

Reference Example 3 In this reference example, the standard alkali composition (BB1), alkali-oxyacid composition (BB2) and alkali-halogen composition (BB3) constituting the alkali composition (BB) of the present invention were used. )) Or a single or composite alkali composition (BB7). Standard alkali composition (BB1), alkali-oxyacid composition (BB2) and alkali-halogen composition (BB
For 3), a composite alkali composition (BB7) was selected from commercially available reagents and industrial chemicals, in which the compounds were mixed with the respective alkali metal compounds shown in Table 3 in the amounts shown in Table 3.

[0396]

[Reference Example 4] In this reference example, an easily reactive silicate-based composition adopted as a raw material of a silicate-alkali solution composition (BB4) which is another embodiment of the alkali composition (BB) Silica (BB) which is a product (BBS)
S1), layered clay composition (BBS2), hydrous muddy mud composition (BBS3) and alkali silicate composition (BB
Step S4) will be described.

As the amorphous silica (BBS1), ultrafine powdered silica manufactured by using sodium silicate as a raw material (trade name “Mizukasil” manufactured by Mizusawa Chemical) was selected. As the layered clay composition (BBS2), a 2-octahedral montmorillonite family of 2-octahedral montmorillonite having a three-layer structure (2: 1 layer) of a natural clay mineral and a layered phyllosilicate smectite clay mineral is used. Acid clay (BBS2-1) selected as the salt-based material (A) and a three-layer structure (2: 1)
Layer) 3-octahedral talc talc (BBS2-2)
I chose two types.

The hydrous muddy mud composition (BBS3) is hydrous mud (AW-1) and volcanic ash clay dredged from the seabed (Osaka Bay) selected as the silicate material (A) to be solidified. Wet mud (AW-4) was selected.
Selected amorphous silica (BBS1), layered clay mineral (BB)
S4) and main constituent components of the hydrous muddy mud (BBS3) are also shown in Table 4.

[0400]

The alkali silicate composition (BBS4) is selected from powdery or liquid alkali silicates (lithium, sodium, potassium salts), which are industrial chemicals (JIS products) or commercially available reagents, and its main constituent components Are also shown in Table 5.

[0402]

[Reference Example 5] In this reference example, a silicate-alkali solution composition (BB4) which is another embodiment of the alkali composition (BB) constituting the alkali-based curing agent (B) will be described. Silicic acid-alkali solution composition (BB
For the preparation of 4), amorphous silica (BBS1) which is an easily reactive silicate-based composition (BBS) shown in Tables 4 and 5,
Layered clay composition (BBS4), hydrous muddy mud composition (B
BS3) and an alkali silicate composition (BBS4) were selected, and the alkali silicate or the standard alkali composition (BB1) (composite alkali) was added to these silicate-based compositions (BBS) in the amounts shown in Table 6. Including the composition)
And react at room temperature, cure for at least 7 days,
Twelve kinds of silicic acid-alkali solution compositions (BB4) were prepared and used as samples.

[0404]

[Reference Example 6] In this reference example, an aluminate containing a readily reactive alumina component to be a raw material of an aluminate-alkali solution composition (BB5) which is another embodiment of the alkali composition (BB) was used. The composition (BBA) will be described.

As the aluminate composition (BBA),
Aluminum oxide, aluminum hydroxide, basic aluminum sulfate, aluminum silicate, sodium aluminate, calcium aluminate, which are easily reactive aluminum-containing compounds from commercial industrial chemicals and commercial reagents,
Furthermore, fly ash powder discharged from a thermal power plant containing a readily reactive aluminum compound from waste, incinerated ash consisting of carbon-silicate incinerated paper sludge under dry distillation conditions, and commercially available alumina Chosen from cement. Each selected aluminate composition (BBA)
Are shown in Table 7.

[0407]

[Reference Example 7] In this Reference Example, an alkali-aluminate solution prepared from an aluminate composition (BBA), which is another embodiment of the alkali composition (BB), which is easily reactive to alkali, is used as a raw material. The composition (BB5) will be described.

The alkali-aluminate solution composition (BB)
In preparation of 5), each aluminate composition (BBA) containing an easily reactive alumina component shown in Table 8 was selected, and alkali hydroxide was added to these aluminate compositions (BBA) in the amount ratio shown in Table 8. Or standard alkaline composition (BB1)
(Including a composite alkaline composition) was added, reacted at room temperature, cured for at least 7 days, and 12 kinds of silicate-alkali solution compositions (BB4) were prepared and used as test samples.

[0410]

Reference Example 8 In this reference example, another embodiment of the alkali composition (BB), which is a sulfuric acid-alkali solution composition (BB6) exhibiting a reinforcing effect on the solidified product
The composite alkaline composition (BB7) will be described. Compounds containing a sulfuric acid oxyacid shown in Table 9 were selected for containing a sulfate group as a raw material of the sulfuric acid-alkali solution composition (BB6).

For the preparation of the sulfuric acid-alkali solution composition (BB6), each sulfate group-containing composition (BBR) which is a compound containing a sulfur oxyacid shown in Table 9 was selected. (BBR), alkali hydroxide or a standard alkali composition (BB1) (including a complex-type alkali composition) in an amount ratio shown in Table 9 was added thereto, reacted at room temperature, cured for at least 7 days, and silicic acid was added. Five kinds of alkali solution compositions (BB4) were prepared and used as samples.

Further, a sulfuric acid-alkali solution composition (BB
6) A composite alkali composition (BB) obtained by combining a silicate-alkali solution composition (BB4) or an aluminate-alkali solution composition (BB5) alone or in combination of two types.
7) Five types are prepared and are also shown in Table 9.

[0414]

[Reference Example 9] In this reference example, a three-membered calcium-based curing system composed of the calcium composition (BA), the alkali composition (BB), and the aqueous composition (BC) adopted in the present invention. Liquid curing agent (B)
L) and a powdery calcium curing agent (BP) will be described. The calcium composition (BA) was selected from the calcium compositions (BA) shown in Reference Example 2. The alkaline composition (BB) was selected from the alkaline compositions (BB) shown in Reference Example 3, Reference Example 5, Reference Example 6, Reference Example 7, and Reference Example 8.

[0416]

The liquid calcium curing agent (BL) composed of three components of the present reference example was prepared by mixing the components in the liquid state with the composition shown in Table 10 and then continuing stirring and mixing to ensure the fluidity. It was prepared by terminating the reaction in the state described above.
The liquid calcium curing agent (BL) prepared here
Confirmed that the liquid properties were maintained for at least 6 hours.

On the other hand, the powdery calcium-based curing agent (BP) of the three-membered composition of the present reference example was prepared by mixing the constituents with the contents shown in Table 10 and performing homogeneous stirring and mixing. The whole was recovered and prepared as a powdery powder by an exothermic reaction based on the sum reaction. When the calcination reaction was not accompanied, the reaction was allowed to proceed at least at a temperature exceeding 80 ° C., and the whole was recovered and prepared as a powdery powder.

[Reference Example 10] In this reference example, a curing auxiliary composition (BD) which is added to the calcium curing agent (B) of the present invention as necessary and has an auxiliary effect on curing will be described. Examples of the curing assisting composition (BD) include an impact band forming composition (BD1) composed of a boron oxyacid salt compound that imparts buffering properties to the solidified body, and a zeolite that promotes the growth of zeolite crystals formed in the solidified body. The three types of a crystal growth seed composition (BD2) and a curing acceleration composition (BD3) composed of a sulfur oxyacid salt compound that promotes the curing of the deformable admixture and improves the strength of the solidified body I chose.

As the buffer zone forming composition (BD1), sodium borate powder [Na ₂ B ₄ O ₇ · 10H _2] which is a boron-containing compound soluble in an alkaline solution from commercially available reagents was used.
O] (BD1-1) and potassium borate powder [K _{2
B 4 O 7 · 8H 2 O} ] chose (BD1-2). The crystal growth seed composition (BD2) is a commercially available industrial chemical aluminosilicate having an Al / Si atomic ratio of 4, 2 and a ring number of 8, and is referred to as a 4A type. 2
Synthetic zeolite (BD2-1) which is fine powder of 0 μ or less
I chose. As the curing promoting composition (BD3), sodium sulfate (BD3-1) and potassium sulfate (BD3-2), which are commercially available industrial chemicals, were selected.

[Reference Example 11] In this Reference Example, the curing time of the deformable admixture (C) can be adjusted in the direction of delaying the curing time of the deformable admixture (C) from the curing auxiliary composition (BD) to be blended as required in the present invention. The curing adjustment composition (BD4) composed of a barium salt compound will be described. Curing adjustment composition (BD
4) As the commercially available industrial chemical barium hydroxide (BD)
4-1) and a simple barium silicate (BD4-2) prepared by the following preparation method were selected.

As a raw material for preparing simple barium silicate (BD4-2), an acid-treated clay product [siliconite (trade name, manufactured by Mizusawa Chemical): main component (%) SiO ₂ 93.0, Al ₂
O ₃ 1.5, Fe ₂ O ₃ 0.3, MgO 0.3, CaO
0.2, Ig. Loss 3.7] and crystalline barium hydroxide [Ba (OH) ₂ ], which is an industrial chemical, were selected. The method for preparing barium silicate (BD4-2) is as follows.
After homogenous mixing so that the molar ratio of iO ₂ / BaO becomes 1.0 and drying at 200 ° C. for 60 minutes, the dried product is ground using a hammer impact type pulverizer, and the powder classified by 200 mesh is used as a sample. And

The barium silicate (BD4-2) prepared here was identified by X-ray diffraction to contain barium silicate as a main component. The soluble matter (Ba ⁺⁺ ) of the simple barium silicate (BD4-2) prepared in the alkaline solution was 800 mg / l as a result of measurement by the following method. In addition, the soluble matter (Ba) of the other barium salt compound in the alkaline solution
⁺⁺ ) is barium hydroxide [Ba (O
H) ₂ ], the value was 7300 mg / l, and barium oxide [BaO] was 15000 mg / l.

[Reference Example 12] In this reference example, a curing reinforcing composition (BD) containing silicon phosphate as a main component was selected from the curing auxiliary compositions (BD) adopted as necessary in the present invention.
5) will be described. As the hardening reinforcing composition (BD5), five specially prepared silicon phosphates (BD5-1 to 5) shown below were selected.

Examples of the silica raw material of silicon phosphate include acid-treated clay-treated silphonite [manufactured by Mizusawa Chemical: representative composition (%) SiO ₂ 93.0, Al ₂ O ₃ 1.5, Fe ₂ O
₃ 0.3, MgO0.3, CaO0.2, Ig. Los
s3.7], a commercial phosphoric acid solution [H ₃ PO ₄ concentration: 85.0%] was selected as a phosphoric acid raw material, and the molar ratio of both was 2.0 or 3.0 with SiO ₂ / P ₂ O ₅ . Mix homogeneously to 0. Then, after drying at 170 to 200 ° C. for 60 minutes, it is baked at 800 to 1100 ° C. for 30 minutes in a rotary kiln to synthesize silicon phosphate.

The silicon phosphate synthesized by each of the firings was roughly pulverized, and then pulverized using a hammer impact type pulverizer through a 200-mesh sieve to collect powdered silicon phosphate (BD5-1). To 5) were used as test samples. Each silicon phosphate prepared here was identified by X-ray diffraction to be mainly composed of silicon phosphate of SiP ₂ O ₇ . Further, the sustained release properties (constants a and b) of each phosphoric acid at different molar ratios and calcination temperatures were measured, and the results are also shown in Table 10.

[0427]

[Reference Example 13] In this reference example, a composite auxiliary composition (BD6), which is a curing auxiliary composition (BD) adopted as needed in the present invention, will be described. As the composite auxiliary composition (BD6), a buffer band forming composition (BD
1), a crystal growth seed composition (BD2), a curing accelerating composition (BD3), a curing adjusting composition (BD4), and a curing auxiliary composition (BD5) shown in Table 12 composed of a group of curing reinforcing compositions (BD5). BD).

[0429]

[Reference Example 14] In this reference example, the calcium composition (BA), the alkali composition (BB), the aqueous composition (BC), and the curing assistant composition (B) adopted in the present invention were used.
The liquid calcium curing agent (BL) and the powder calcium curing agent (BP) of the four-membered calcium curing agent (B) composed of D) will be described.

As the calcium composition (BA), the calcium composition (BA) shown in Reference Example 2 was selected. As the alkali composition (BB), Reference Example 3, Reference Example 5,
It was selected from the respective alkali compositions (BB) shown in Reference Examples 6, 7 and 8. Curing aid composition (B
D) was selected from the group of curing auxiliary compositions (BD) shown in Reference Examples 10 to 13. The type and amount ratio are also shown in Table 13.

[0432]

[Reference Example 15] In this reference example, the additive material composition (D1), which is a functional addition composition (D), which is blended with the calcium curing agent (B) of the present invention as necessary, and further contains arsenic The immobilizing composition (D2) will be described.

The additive material composition (BD1) and the arsenic fixing composition (D2) are reagents or industrial chemicals, and are generally commercially available in the art as pigments, colorants, activators, fillers, and function-imparting agents. Among the additive materials that have been
Twelve elements were selected which can exhibit the functionality and the water-insoluble immobilization of arsenic suitable for the purpose and application of the water-resistant and heat-resistant solidified body of the present invention.

Each additive material composition selected here (BD1)
Are also shown in Table 14 together with the main components constituting the particles. In addition, the additive material composition (BD1) in the present invention
Is not limited to the additive material composition (BD1) selected here, but the additive material composition (B
D1) This is merely an example.

[0436]

[Reference Example 16] In this reference example, an aqueous or oily compound in a gaseous or liquid state having a supplementary function to be added to the alkaline curing agent (B) as required. Functional additive composition (D) that exhibits adsorptivity
The adsorptive material composition (D3) is described below. As the adsorptive material composition (D3), silica gel (D3-1) having adsorptivity from commercially available reagents or industrial chemicals,
Alumina gel (D3-2), zeolite 4A (D3-
3) and 0.5 or 2m of Bincho charcoal (D3-4)
Four types of fine powder or fine granules having mφ were selected.

As another adsorptive material composition (D3), a paper sludge cake discharged from the papermaking industry is prepared by subjecting it to a carbonization step at 400 to 1000 ° C., and is adopted as the silicate-based material (A). Carbon-silicate ash (AP-3 = D3-5) and waste clay containing waste oil by-produced from the oil and fat refining industry, similarly subjected to the carbonization process 2 of aluminum ash (D3-6)
I chose the type. Table 15 also shows these main compositions and specific surface areas.

[0439]

[Reference Example 17] In this Reference Example, a functionally added composition exhibiting antimicrobial properties such as antibacterial properties and anti-algal properties, which is added as necessary to the deformable admixture (C) of the present invention. The antimicrobial material composition (D4) that is (D) will be described.

The antimicrobial composition (D4) may be selected from commercially available reagents and industrial chemicals, and antimicrobial agents generally used as antimicrobial agents and antialgal agents in the art. Has 10 kinds of antimicrobial properties such as silver oxide, copper oxide, cuprous oxide, copper borate, copper oxalate, zinc oxide, zinc borate, zinc-containing solid solution, copper iodide, sodium hypochlorite, etc. Compounds were chosen as an example. The main chemical composition formula of the selected antimicrobial material composition (D4) is also shown in Table 16.

[0442]

[Reference Example 18] In this Reference Example, a functional addition composition (D) having a supplementary function and exhibiting water repellency, which is adopted as necessary for the alkali-based curing agent (B) of the present invention. )) Is described.

As the water-repellent additive composition (D5), a functional side chain OR group (R is a hydrogen atom) which is compatible with the alkaline effect agent (B) of the present invention as shown in Table 16 below from commercial products or chose alkyl group) four water emulsion alone or organosiloxane organosiloxane or organopolysiloxane is a organosilane containing a C ₁ or C _5. Table 17 shows their chemical names and manufacturer names.

[0445]

[Reference Example 19] In this Reference Example, a functional additive composition (D) having a supplementary function and exhibiting reinforcing properties, which is added to the alkali-based curing agent (B) of the present invention as necessary. )) Is described. As the fibrous reinforcing composition (D6), from among fibrous products generally adopted as a fibrous reinforcing agent in the art and marketed as industrial products, about 0.1 × 1-3.
mm stainless steel fiber (D6-1), glass fiber (D6
-2), carbon fiber (D6-3), cotton fiber (D6-4) and wood pulp (D6-5).

[Reference Example 20] In this Reference Example, a functionally added composition having a supplementary function to be added to the alkali-based curing agent (B) of the present invention as necessary and exhibiting a supplemental property and a reinforcing property. The filled aggregate composition (D7) which is the product (D) will be described.

The filled aggregate composition (D7) is a filled / aggregate / light-weight aggregate commercially available as an aggregate generally adopted in the civil engineering and construction industries, and has a particle size of 100.
It was selected from the range of μ to 7 mm and the bulk specific gravity in the range of 0.3 to 5.0 g / cc. Sand (D7-1), gravel (D) selected as the filled aggregate composition (D7)
7-2) Perlite (D7-3), vermiculite (D7-4), glass waste (D7-5) obtained by crushing and granulating glass products such as industrial waste glass bottles, and waste incineration ash are melted into slugs. The prepared granule (D7-6), the granule (D7-7) obtained by granulating fly ash powder discharged from a thermal power plant using the alkaline hardener prepared according to the present invention as a binder, specific gravity Table 18 shows eight types of coarse particles of natural iron ore having a large value.

[0449]

Example 1 In this example, a three-part or four-part alkaline curing agent (B) was adopted.
A deformable admixture (C) is prepared by two-way mixing with the silicate-based material (A) to be solidified, and then the deformable admixture (C) is subjected to a specific structure including an unspecified form, a granular substance, Each of the adhered bodies is molded and then subjected to room temperature solidification treatment conditions to obtain a cured body (E). The cured body (E) formed here
The water-resistant and heat-resistant solidified body will be described.

As the silicate-based material (A), Reference Example 1
Was selected as fly ash (AP-2).
Examples of the alkaline curing agent (B) include the calcium composition (BA) shown in Reference Example 2, the alkaline composition (BB) which is the standard alkaline composition (BB1) shown in Reference Example 3, and the aqueous composition (BC). ), And, if necessary, a four-part alkaline curing agent (B) to which the curing auxiliary composition (BD) shown in Reference Examples 11 and 13 is added.
Was selected from the alkaline curing agents (B) formulated and mixed in the proportions shown in Table 17.

In this example, the deformable admixture (C) was prepared by adding a three-part or four-part alkaline curing agent to each of the silicate-based materials (A) to be solidified as shown in Table 17. (B) was blended in the amount ratio shown in Table 17, and was homogeneously mixed using a kneader, and 14 kinds of deformable admixtures (C) were used as test samples. For the deformable admixture (C) prepared here, the pot life was measured in accordance with the physical property evaluation test method described above,
The results are shown in Table 18 together.

Further, the deformable admixture (C) prepared here was subjected to a room temperature solidification treatment shown in Table 18 in accordance with the above-described physical property evaluation test method, and a columnar test as a standard test body for physical property evaluation was performed. The body was prepared and subjected to a uniaxial compressive strength (Kgf / cm ² ) evaluation test for evaluation as a specific structure (EM). Similarly, a granular specimen of a standard specimen for evaluating physical properties was prepared and subjected to an evaluation test of heat resistance and water resistance as a granular substance (EP). Furthermore, an adhesion test specimen using an asbestos plate and a steel plate as a substrate was prepared, and subjected to an evaluation test of the adhesion as an adhesion-hardened body (EB). The above results are also shown in Table 18.

In order to compare and evaluate the technical effect of the present invention and the technical effect of the prior art, the following comparative examples were implemented, and the technology of the present invention was comparatively evaluated.
As a comparative example in the conventional technology, Portland cement and acid-curable water glass [No. 2 water glass + aluminum phosphate + water] were selected as curing agents that form a solidified body at normal temperature.
The silicate-based material (A) to be solidified is (AP-2) and (A)
W-2) was selected to prepare two types of deformable admixtures (C) (sample No. C1 series) with the composition shown in Table 17.

Further, as a comparative example in the present technology, in the case where the alkali composition (BB) was not added to the alkali-based curing agent (B) of the present invention, the silicate-based material (A) to be solidified was also added. Table 1 shows the case in which
Two kinds of deformable admixtures (C) (sample No. C1 series) were prepared with the composition shown in FIG.

In the comparative example, a columnar test specimen of a standard specimen for evaluating physical properties was prepared in the same manner as in this example, and an evaluation test of uniaxial compressive strength (Kgf / cm ² ) was conducted in order to evaluate it as a specific structure. Prepare a granular specimen of a standard specimen for evaluating physical properties, conduct an evaluation test of heat resistance and water resistance, and also prepare an adhesion specimen using asbestos plate and steel sheet as a base material, The test was performed to evaluate the adhesive force. The results are shown in Table 18.

As a result, in the solidified body prepared by the conventional technique shown in the comparative example, heat resistance and water resistance were not simultaneously exhibited, and the alkali-based curing agent (B) according to the present invention was adopted. It is well understood that, when the silicate-based material (A) is to be solidified, it is possible to form a solidified body with higher effectiveness than the prior art.

Further, an alkali-based curing agent (B) mainly comprising the calcium composition (BA) and the alkali composition (BB) according to the present invention for solidifying the silicate-based material (A) is adopted. When the deformable admixture (C) is prepared, molded, and subjected to room temperature solidification treatment, the solidified body formed here is water-resistant and heat-resistant enough to be effectively used for each purpose. The solidified physical properties of However, when the alkali composition (BB), which is a constituent component of the alkali-based curing agent (B), or the silicate-based material (A) to be solidified is missing, a good solid is not formed. Is well understood.

[0459]

[0460]

Example 2 In this example, a four-part alkaline curing agent (B) added with a three-part one-pack alkaline curing agent (B) or a curing auxiliary composition (BD) was added. ), A deformable admixture (C) is prepared by mixing the silicate-based material (A) to be solidified with the mixture as required, and then the deformable admixture (C) contains an unspecified form. After molding into a specific structure, a granular body, and an adhered body, the cured body (E) is subjected to room temperature solidification treatment conditions to obtain a cured body (E), which is a water-resistant and heat-resistant solidified body. Will be described.

As the silicate-based material (A), Reference Example 1
Among them, granular volcanic ash (AS-1), garbage incineration ash (AP-1), fly ash (AP-2), charcoal-silicate ash (AP-3), and hydrous soil at the river bottom ( AW-2) and six kinds of volcanic ash (AW-4) were selected.

As the alkaline curing agent (B), the calcium composition (BA) shown in Reference Example 2 and Reference Examples 3, 5,
A liquid alkaline hardener (BL) or a powdered alkaline hardener (BP) shown in Table 10 prepared with the alkali composition (BB) and the aqueous composition (BC) shown in 6, 7 and 8 It was selected from a certain three-part alkaline curing agent (B). Further, if necessary, the four-component alkaline curing agent (B) to which the curing auxiliary composition (BD) shown in Reference Examples 11 and 13 was added was blended and prepared in an amount ratio shown in Table 19. Agent (B).

[0464] In this example, the deformable admixture (C) was prepared by adding a three-part or four-part alkaline curing agent to each silicate-based material (A) to be solidified as shown in Table 19. (B) was blended in the amount ratio shown in Table 19, and was homogeneously mixed using a kneader, and 12 kinds of deformable admixtures (C) were used as test samples. For the deformable admixture (C) prepared here, the pot life was measured in accordance with the physical property evaluation test method described above,
The results are shown in Table 20.

Further, the deformable admixture (C) prepared here was subjected to room temperature solidification treatment conditions shown in Table 20 in the same manner as in Example 1 to prepare a columnar test body, and a specific structure (EM ) To evaluate as uniaxial compressive strength (Kgf
/ Cm ² ). Further, a granular test body was prepared and subjected to an evaluation test of heat resistance and water resistance as a granular body (EP). Furthermore, an adhesion test specimen was prepared and subjected to an evaluation test of adhesion as an adhesive cured product (EB). The above results are also shown in Table 20.

As a result, when the one-pack alkaline hardener (B) according to the present invention is adopted and various silicate materials (A) are to be solidified, the alkali hardener (B) is used. Is a one-pack, so that the workability of the work is good, and in particular, the powdery alkaline hardener (BL) was easy to handle in the work. Moreover, it is well understood that the solidified body produced here exhibits solidified physical properties that simultaneously exhibit water resistance and heat resistance, and is more effective than the solidified body prepared according to the prior art.

[0467]

[0468]

Example 3 In this example, a one-pack type alkaline hardener (B) having a three-part or four-part configuration was adopted, and a silicate-based material (A) was solidified. Further, a deformable admixture (C) is prepared by adding the function-adding composition (D) to the mixture of the three to form a deformable admixture (C), and then the deformable admixture (C) is molded into a specific structure including an unspecified form and a granular body. After processing, the cured product (E) is subjected to room temperature solidification treatment conditions, and the water-resistant and heat-resistant cured product of the cured product (E) formed here will be described.

As the silicate-based material (A), Reference Example 1
The fly ash (AP-2) or the blast furnace slug (AP-4) and the seabed hydrous soil (A)
W-1) or volcanic ash (AW-4) was selected.
As the alkali-based curing agent (B), a liquid alkaline-based curing agent (BL) prepared in a one-pack with a three- or four-member configuration shown in Reference Example 9 and Reference Example 14
Or from the powdered alkaline curing agent (BP)
The unpack type alkaline curing agent (B) shown in No. 1 was selected.

Further, in this example, as the functional additive composition (D) added to the deformable admixture (C), the additive material composition (D1) and the filled aggregate composition (D7)
Functional composite composition (D8) selected from the group consisting of:
The functional addition compositions (D) shown in Table 21 were selected and blended.

The preparation of the deformable admixture (C) in this example was carried out according to the silicate material (A) to be solidified shown in Table 21.
On the other hand, a functional addition composition (D) was further added to a three- or four-part alkaline curing agent (B) and water, as shown in Table 2.
The mixture was added at the ratio shown in No. 1 and blended, and the mixture was homogeneously mixed by using a kneader. 21 kinds of the deformable admixtures (C) of the three-member mixture were used as test samples.

The working life of each of the deformable admixtures (C) thus prepared was measured in the same manner as in Example 1, and the unconfined compressive strength (Kgf / Kgf / cm ² ) An evaluation test of a test and an evaluation test of heat resistance and water resistance were performed. The above test results are also shown in Table 22.

As a result, the composition was prepared by adding the functional additive composition (D) in which the additive material composition (D1) and the filler aggregate composition (D7) were combined with the alkaline curing agent (B) of the present invention. The deformable admixture (C) is subjected to a room temperature solidification treatment to obtain an unspecified form (EU) and a specified structure (E), respectively.
M) and a cured product (E) such as a granular material (EP), the functional additive composition (D) added to each of them.
It is well understood that the functionality of is effectively exhibited, and a solidified body effectively supplied for various uses is formed.

[0475]

[0476]

Example 4 In this example, a four-membered alkaline hardening agent (B) was adopted in the same manner as in Example 3, and the silicate material (A) was further solidified. A deformable admixture (C) is prepared by adding the function-adding composition (D) and mixing the three components, and then the deformable admixture (C) is combined with a specific structure (EM) containing an unspecified form (EU) and After each of the granules (EG) is molded and processed, it is subjected to room temperature solidification treatment conditions to obtain a cured body (E). The water-resistant and heat-resistant solidified body (E) formed here will be described.

As the silicate-based material (A), Reference Example 1
The blast furnace slug (AP-4) and the volcanic ash clay (AW-4) were selected from among those shown in (1). The alkaline hardener (B) is shown in Table 23 from among the four-part one-pack type liquid alkaline hardener (BL) or powdered alkaline hardener (BP) shown in Reference Example 14. The alkaline hardener (B) was selected.

Furthermore, in this example, the deformable admixture (C)
As the functional additive composition (D) added to the composition, the additive material composition (D1), the water repellency imparting composition (D5), the fibrous reinforcing composition (D6), and the filled aggregate composition (D7) are combined. The functional addition composition (D) shown in Table 23 was selected from the functional composite composition (D8) thus obtained.

The preparation of the deformable admixture (C) in this example was carried out according to the silicate-based material (A) to be solidified as shown in Table 23.
On the other hand, in a four-part alkaline curing agent (B) and water,
Further, the functional additive composition (D) was added in the amount ratio shown in Table 23, and each was blended and homogeneously mixed using a kneader to prepare 14 kinds of three-component deformable admixtures (C). A sample was used.

The working life of each of the deformable admixtures (C) prepared here was measured in the same manner as in Example 1, and the unconfined compressive strength (Kgf / Kgf / cm ² ) An evaluation test of a test and an evaluation test of heat resistance and water resistance were performed. The above test results are also shown in Table 24.

As a result, the alkali-based curing agent (B) of the present invention was added to the functional additive composition (D) [the additive material composition (D1), the water repellency imparting composition (D5), and the fibrous reinforcing composition] (D6), filled aggregate composition (D7)], and then subjected to room temperature solidification treatment to obtain an unspecified form (EU), a specified structure (EM), When a solidified body such as a granular body (EG) is formed, a solidified body in which the functionality of the functional composition (D) added to each of the solidified bodies is effectively exhibited is formed, and is effectively provided for each application. It is well understood that

[0483]

[0484]

Example 5 In this example, a silicate-based material (A) containing a heavy metal and a calcium composition (B) were used.
B), and further, if necessary, the arsenic-immobilized composition (D
2) and the adsorptive material composition (D3) are added to prepare a deformable admixture (C) of the present invention which is mixed with the three components, and the deformable admixture (C) is unspecified form (EU), specific structure After forming into a body (EM), a granular body (EP) and a granular body (EG),
The water-resistant and heat-resistant solid of the cured product (E) formed in the cured product (E) in which the heavy metals contained therein are immobilized in a water-insoluble state by being subjected to room temperature solidification treatment conditions will be described.

As the heavy metal-containing silicate-based material (A), incineration ash (AP-1) of general waste (garbage) and wet mud on the river bottom (AW-2) were selected. Waste gypsum board + quick lime (BA5-2) was selected as a calcium composition (BB) containing heavy metals. The heavy metal content (mg / Kg) of these heavy metal-containing materials (dry matter basis) was analyzed, and the results are shown in Table 26. As the alkaline curing agent (B), the liquid alkaline curing agent (BL) shown in Reference Example 14 or a powdered alkaline curing agent (BP) is used.
The alkaline hardener (B) having a four-part composition was selected.

Further, in this example, the deformable admixture (C)
As the functional additive composition (D) added to the composition, the additive material composition (D1), the arsenic-immobilized composition (D2), the adsorptive material composition (D3), the filled aggregate composition (D7), and these The functional addition composition (D) shown in Table 25 was selected from the functional composite composition (D8) in which was compounded.

The preparation of the deformable admixture (C) in this example is based on the fact that the silicate-based material (A) to be solidified is functionalized by adding a four-part alkaline curing agent (B) and water. The composition (D) was added in the amount ratio shown in Table 25, and the mixture was homogeneously mixed using a kneader to prepare six types of three-component deformable admixtures (C), each serving as a sample.

For each of the deformable admixtures (C) thus prepared, the pot life (min) was measured in the same manner as in Example 1, and the room temperature solidification treatment conditions (° C. × day) shown in Table 24 were used. To form a solidified body and subjected to an evaluation test of a uniaxial compressive strength (Kgf / cm ² ) test and an evaluation test of heat resistance and water resistance. Furthermore, the water dissolution test of heavy metals from the solidified body was examined in accordance with the method specified in Notification No. 13 of the Environment Agency for the water dissolution test of heavy metals. The above test results are also shown in Table 27.

[0490] In order to compare the situation in which heavy metals are immobilized and made water-insoluble in the solidified body prepared using the alkaline curing agent of the present invention, the results are shown in Example 1 below.
Similarly, two types of solidified bodies (Comparative Example Sample Nos. C4-1 and C4-2) were prepared using Portland cement adopted in the above, and the water elution status of heavy metals was determined in accordance with the method specified in Notification No. 13 of the Environment Agency. Was examined. Table 27 shows the above test results.
Are also shown. In addition, the heavy metal content of the cement used was separately analyzed and also shown in Table 26.

As a result, for the silicate-based material (A) containing heavy metals and the calcium composition (BB),
When the deformable admixture (C) prepared by admixing the alkali-based curing agent (B) of the present invention and mixing the three components is subjected to room temperature solidification treatment to obtain a cured product (E), each of the cured products formed here Body (E)
It is well understood that harmful heavy metals including arsenic contained therein are immobilized in the structure of the zeolite crystal, and water insolubilization of the heavy metals is achieved.

Therefore, when the alkali-based curing agent (B) of the present invention is selected to solidify a material containing heavy metals, the heavy metals contained therein are fixed in a water-insoluble manner, and the environment of heavy metals is fixed. It is understood that the alkali-based curing agent (B) of the present invention is a treating agent that can cope with environmental problems by preventing the diffusion of contamination to water.

[0493]

[0494]

[0495]

Example 6 In this example, an antimicrobial composition (D4), which is a functional addition composition (D), was used, and if necessary, an alkali added with a curing auxiliary composition (BD). The hardening agent (B) is blended with the silicate-based material (A) to prepare a deformable admixture (C) having a mixture of three components.
Structure (EM), granular material (EG), granular material (E) containing an unspecified form (EU)
P) After molding, the cured product (E) is subjected to a room temperature solidification treatment to obtain a cured product (E). The cured product having antimicrobial properties of the cured product (E) will be described.

As the silicate-based material (A), two types of fly ash (AP-2) and carbon-silicate ash (AP-3) shown in Reference Example 1 are selected. Alkali curing agent (B)
In the same manner as in Example 2, a liquid alkaline curing agent (BL) and a powdered alkaline curing agent (BP) of a three-component alkaline curing agent (B) are selected, and if necessary, a curing aid. The four-component alkaline curing agent (B) to which the composition (BD) was added was selected, and the alkaline curing agent (B) was prepared in the proportions shown in Table 28.

Further, in this example, the deformable admixture (C)
As the functional additive composition (D) added to the composition, an antimicrobial composition (D4) is first selected, and if necessary, an additive material composition (D1), an arsenic-immobilized composition (D2), It was selected from the functional material composition (D3), the filled aggregate composition (D7), and the functional composite composition (D8) in the proportions shown in Table 28.

In this example, the deformable admixture (C) was prepared by mixing a silicate-based material (A) to be solidified shown in Table 28 with a three-part or four-part alkaline curing agent. Table 28 further shows the functional addition composition (D) in addition to (B) and water.
The mixture was blended, and the mixture was homogeneously mixed using a kneader to prepare six types of three-component deformable admixtures (C).

For each of the deformable admixtures (C) thus prepared, the pot life was measured in the same manner as in Example 1, and the mixture was solidified under normal temperature solidification treatment conditions (° C. × day) shown in Table 29. A body was formed and subjected to a uniaxial compressive strength (Kgf / cm ² ) test and a heat resistance and water resistance evaluation test.

Further, the effect of the antimicrobial agent (antibacterial agent) when the solidified product composed of each cured product (E) including the granular material prepared from the deformable admixture (C) was adopted as a water treatment agent was examined. In order to evaluate, the properties of water treated with the sample solidified granules were evaluated at pH, and the antimicrobial effects were evaluated and tested. The above results are also shown in Table 29.

As a result, a cured product prepared by adding the antimicrobial composition (D4) to the alkaline curing agent (B) of the present invention and subjecting the deformable admixture (C) to a solidification treatment at room temperature (E) is a solidified material that can be usefully used as a granular material or the like that simultaneously exhibits water resistance and heat resistance, and the pH of water when this solidified material is treated as a water treatment agent is 8.3. In the following, the alkaline component (B) of the alkaline curing agent used is sufficiently fixed, harmful fungi such as Escherichia coli have disappeared, and it is recovered as water suitable as drinking water and the like. It can be clearly understood that the water-processed solid having microbial properties can be effectively supplied.

[0503]

[0504]

[Example 7] In this example, an adsorptive material composition (D3), which is a functional addition composition (D), was used, and if necessary, an alkali to which a curing auxiliary composition (BD) was added. The hardening agent (B) is blended with the silicate-based material (A) to prepare a deformable admixture (C) having a mixture of three components.
The deformable admixture (C) mixed with the mixture is subjected to room temperature solidification treatment to obtain a cured product (E). The cured product (E) formed here and having absorptivity will be described.

As the silicate-based material (A), two kinds were selected: granular diatomaceous earth (AS-2) and carbon-silicate ash (AP-3) shown in Reference Example 1. As the alkaline curing agent (B), a liquid alkaline curing agent (BL) and a powdered alkaline curing agent (BP) of the four-component alkaline curing agent (B) shown in Reference Example 14 were selected and further cured. The alkaline curing agent (B) to which the auxiliary composition (BD) was added was selected.

Furthermore, in this example, the deformable admixture (C)
As the adsorptive material composition (D3) which is the functional addition composition (D) added to the silica gel (D3-1), the alumina gel (D3-2), and the zeolite A4 (D3- 3), Bincho charcoal (D3-4), charcoal-silicate ash (D3-5) and charcoal-silicate aluminum ash (D3-6)
First, and if necessary, the additive material composition (D
1), a filled aggregate composition (D7) and a functional composite composition (D8).

The preparation of the deformable admixture (C) in this example was carried out according to the silicate-based material (A) to be solidified shown in Table 27.
On the other hand, a functional addition composition (D) was further added to a three- or four-part alkaline curing agent (B) and water, as shown in Table 3.
The mixture was added in the amount ratio shown in 0, blended, and homogeneously mixed using a kneader. Seven kinds of three-component deformable admixtures (C) were used as test samples.

For each of the deformable admixtures (C) prepared here, the pot life was measured in the same manner as in Example 1, and a solid was formed under normal temperature solidification treatment conditions (° C. × day). The test piece was subjected to a uniaxial compressive strength (Kgf / cm ² ) test and an evaluation test for heat resistance and water resistance. Further, in order to evaluate the effect of the solidified granular material prepared from the deformable admixture (C) as an adsorbent, the above-mentioned “Test method for deodorizing effect of adsorbent” was performed using the solidified sample. Therefore, three kinds of odor components (ammonia: NH, trimethylamine: T
M, hydrogen sulfide: HS) to evaluate the static deodorizing capacity and the dynamic deodorizing capacity. Table 31 shows the results.
Are also shown.

As a result of the above, the adsorbent material composition (D3), which is an adsorbent, was added to the deformable admixture (C) of the present invention, and the cured product (E) was formed by solidification at room temperature. )
Is a specific structure (E) that simultaneously exhibits water resistance and heat resistance.
M), a solid (EG), a solid that can be usefully utilized as a powder (EP), and the like, and when the solid is used as a deodorizing adsorbent, the alkali-based curing agent of the present invention ( B)
Exhibits an excellent deodorizing effect as a solidified body without killing the adsorption active surface, and it can be clearly understood that the solidified body is effective as an adsorbed solidified body.

[0511]

[0512]

[Example 8] In this example, a group of granular particles was selected as a skeleton raw material of the aggregated cured product, and the deformable admixture of the present invention was used as a binder for integrating the skeleton raw material into the aggregated cured product. C) is adopted to mold into a millet-shaped aggregated cured body (EC) having a through gap, and a solidified body in which this aggregated cured body (EC) is applied to a nonflammable soundproof plate will be described.

As the skeleton raw material for the aggregated cured product, the sample No. of Example 2 was used. A 1-5 mmφ granular granular material (EG) group prepared in (2-6) is selected. Sample N of Example 2 was used as a binder for integrating the skeleton raw material into the aggregated cured body.
o. A fluid paste-like deformable admixture (C) prepared with the alkaline curing agent (B) of (2-1) was selected.

The soundproofing plate was processed by adding about 10 kg of water to 100 kg of the sized granule (EG) group to wet the surface of the granule (EG) group, and then forming a fluid paste like a binder prepared as a binder. 15 kg of the deformable admixture (C) is added and mixed to uniformly wet the surface of the granular (EG) group with a binder. Next, the granules (E
G) The group is poured into a 300 mm × 300 mm formwork having a thickness of 30 mm and left at room temperature for at least 24 hours to develop the initial hardness.
C). Furthermore, it was left to stand at 80 ° C. for 1 hour to complete the curing, thereby obtaining a soundproofing material plate product made of a millet-shaped aggregated cured body (EC).

In order to evaluate the soundproofing effect of the soundproofing material plate product made of the collectively cured product (EC), a standard (representative item) shown in Table 32 below was evaluated according to JIS A 1416.
, And other test items were also evaluated by test. The results are shown in Table 32.

[0517] As a result, the binder for integrating the deformable admixture (C) of the present invention with the alkali-based curing agent (B) of the present invention as a raw material of the skeleton as a raw material of fly ash. In this case, it is well understood that an inorganic non-combustible soundproofing plate made of a millet-like aggregated cured product (EC) is prepared at room temperature and exhibits an efficient soundproofing effect.

[0518]

[0519]

According to the present invention, a silicate-based material (A) is used as an object to be solidified, an alkali-based curing agent (B) is adopted, and if necessary, a functional additive composition (D) is added to prepare a deformed admixture. In addition, the cured product (E) produced by the solidification treatment at room temperature simultaneously exhibits water resistance and heat resistance, and also fixes heavy metals in water-insoluble, and can be supplied to various uses in granular materials, specific structures, and attachments. Forms tangible, unspecified forms, powders and aggregates. Therefore, it is possible to produce an inorganic solid without polluting and consuming a large amount of energy, thereby making it possible to reuse waste.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C09K 17/02 C09K 17/02 P 17/06 17/06 P 17/12 17/12 P C09K 103: 00 C09K 103: 00

Claims (46)

[Claims] 1. A silicate material to be solidified (A)
To the mixture are added a calcium composition (BA) and an alkaline curing agent (B) composed of an alkaline composition (BB) and an aqueous composition (BC) to prepare a deformable admixture (C). And then subjecting the deformable admixture (C) to a room temperature solidification treatment to transform it into a cured product (E) to form a water-resistant and heat-resistant solidified product; A) easily reacts with an ionic alkali metal containing 20% by weight or more of silica on the basis of SiO ₂ oxide on a dry matter basis and ₂ % by weight or more of alumina on the basis of Al ₂ O ₃ oxide. Wherein the calcium composition (BA) is represented by the following composition formula (1): CaO.wH ₂ O ‥‥‥‥‥‥ (1) (where w is zero or less, including zero) Alone or selected from the group of calcium oxides represented by A calcium standard composition (BA1) containing 50% by weight or more of a calcium component composed of a combination of two or more thereof, expressed on the basis of CaO oxide; the above alkali composition (BB)
Contains 50% by weight or more of an alkali metal oxide composed of one or a combination of two or more of lithium, sodium, and potassium groups in terms of M ₂ O (M is Li, Na, K) oxide. The aqueous base composition (BC1) contains 70% by weight or more of water (BC1); and the alkaline hardener (B) contains: Calcia composition (BA)
An alkali-based curing composition comprising 1 to 30 parts by weight of an alkali composition (BB) and 1 to 300 parts by weight of an aqueous composition (BC) based on 100 parts by weight. Agent. Wherein said silicate based material (A) is a silica in a dry solid basis expressed as SiO ₂ oxide basis 20%
As described above, natural materials and synthetic materials containing alumina in an amount of 2% by weight or more based on Al ₂ O ₃ oxide and having a particle size of 100 μm to 7 mm and easily reactive to ionic alkali metals,
The silicate-based material (AS) in the form of a sand particle having a silicate compound as a main component composed of a single material or a combination of two or more kinds of a material for reusing waste or a filler material group. Alkaline hardener. 3. The silicate-based material (A) contains 25% by weight or less of water, 20% by weight or more of silica expressed on a dry matter basis in terms of SiO ₂ oxide, and alumina oxidizes Al ₂ O _3. Volcanic ash, clay minerals, which are easily reactive to ionic alkali metals containing 2% by weight or more in terms of
Organic materials, incineration ash, dry distillation ash, fly ash, slug, construction waste soil, sludge dry matter, silicate compounds composed of a single or a combination of two or more silicate wastes Powdery silicate material (A
The alkaline curing agent according to claim 1 when P). 4. The silicate-based material (A) has a water content of 26% by weight or more, a silica content of not less than 20% by weight in terms of dry matter in terms of SiO ₂ oxide, and an alumina oxide of Al ₂ O _3. Muddy mud, hydrated clayey or organic soil, dredged soil, sludge, muddy soil, soft soil, clayey material which is easily reactive to ionic alkali metal contained at 2% by weight or more in terms of material basis The alkaline hardening according to claim 1, wherein the silicate material is a hydrous silicate-based material (AW) containing a silicate compound as a main component, which is composed solely of a soil or a volcanic ash soil group or a combination of two or more types. Agent. Wherein said Karushiya composition (BA) is represented by the following formula _{(2) Ca n TO m ·} wH 2 O ..................... (2) ( wherein: T is boron, aluminum, silicon , Nitrogen, phosphorus or an element composed of a single or a combination of two or more elemental elements, n is a number of 1.0 to 20.0, m is a number of 0.5 to 6.0, and w is zero. 5. An oxyacid salt composition (BA2) composed of a single or a combination of two or more of the normal or basic salt compounds of calcium oxyacid salts represented by the formula (1). The alkaline curing agent according to any one of the above. Wherein said Karushiya composition (BA) is represented by the following composition formula _{(3) Ca n Z · wH} 2 O .................. (3) ( wherein: Z is halogen, n represents 1. 0 to 20.0
And w is a number of 10.0 or less including zero), and a halogen salt composition (BA3) composed of a single or a combination of two or more calcium halide salts. The alkaline curing agent according to any one of the preceding claims. 7. A waste limestone, waste gypsum, ceramic waste, blast furnace slag or incineration, wherein the calcium composition (BA) contains at least 20% by weight or more of a calcium component based on CaO oxide. 5. A waste powder composition (BA4) comprising a powder group consisting of ash wastes alone or in combination of two or more.
The alkaline curing agent according to any one of the above. 8. A cement powder comprising the calcium composition (BA) alone or in combination of two or more selected from the group consisting of Portland cement, blast furnace cement, silica cement, fly ash cement and alumina cement. The alkaline hardener according to any one of claims 1 to 4, which is a cement powder composition (BA5) composed of: 9. The above-mentioned calcium carbonate modified composition (BA7), wherein the above-mentioned calcium carbonate modified composition (BA7) comprises a calcium carbonate-modified composition (BA6) mainly containing a calcium component obtained by modifying calcium carbonate. Calcium carbonate (CaCO ₃ ) powder 10 for natural aragonite, calcite, marble, shells, etc.
0 parts by weight, if necessary, hydrochloric acid, sulfurous acid, sulfuric acid,
100 parts by weight or less of an acid radical consisting of nitrous acid or a nitric acid group alone or in combination of two or more,
5. The modified carbon-calcium composition according to any one of claims 1 to 4, comprising a calcium component modified by contacting at a temperature of 0 ° C. or lower and decarboxylation and denaturation in an amount of 50% by weight or more based on CaO oxide. Alkaline hardener. 10. A magnesium mixture composition (BA7) containing a calcium component as a main component, wherein the calcium composition (BA) contains at least 10% by weight or more of magnesium oxide or magnesium hydroxide alone or in combination of two types. 5) The alkaline curing agent according to any one of claims 1 to 4. 11. The above-mentioned calcia composition (BA) is the above-mentioned calcia standard composition (BA1), oxyacid salt composition (BA2), halogen salt composition (BA3), and waste powder composition. (BA4), cement powder composition (BA
5) A calcium composite composition (BA8) comprising a combination composition of at least two of the group consisting of a modified carbon-calcium composition (BA6) and a mixed magnesium composition (BA7). The alkali-based curing agent according to the above item. 12. The above alkaline composition (BB) is represented by the following composition formula (4): M _n TO _m · wH ₂ O (4) wherein M is lithium, sodium or potassium. An element consisting of a single element or a combination of two or more elements;
T is an element composed of one or a combination of two or more of boron, aluminum, nitrogen or phosphorus, n is a number of 1.0 to 20.0, m is a number of 0.5 to 6.0, and w is zero. Or a number of 28.0 or less), which is an alkali-oxyacid composition (BB2) composed of one or a combination of two or more of a normal salt or a basic salt compound group of an alkali metal oxyacid salt. The alkaline curing agent according to any one of claims 1 to 11. 13. The alkali composition (BB) is represented by the following composition formula (5): M _n Z · wH ₂ O (5) (wherein M is a lithium, sodium or potassium element group) An element consisting of one or a combination of two or more of
Z is a halogen element, n is a number from 1.0 to 20.0, w
Is an alkali-halogen composition (BB3) composed of one or a combination of two or more alkali metal halide salts represented by the following formula: The alkaline curing agent according to claim 1. 14. An easily reactive silicic acid-containing composition (BBS) coexists in a solution in which an alkali metal compound is previously dissolved in an aqueous composition (BC). Solution silicate-alkali solution composition (BB
In 4), the above-mentioned silicic acid-containing composition (BBS) is
Amorphous silica composition (BBS1), layered clay composition (B
BS2), a hydrous muddy mud composition (BBS3) or an alkali silicate composition (BBS4) alone or in combination with two or more ionic alkali metals. A silica-containing composition as a main component; the above-mentioned amorphous silica composition (BB
S1) is an amorphous silica composition mainly containing amorphous silicic acid; the above-mentioned layered clay composition (BBS2) is
A layered clay composition composed of a hydrous ferrosilicate clay mainly composed of a smectite group clay mineral of a 2: 1 layer type and a 2-octahedral or a 3-octahedral type smectite group clay; the above-mentioned hydrous muddy mud composition (BBS3) is a hydrous muddy mud composition mainly containing an aluminosilicate which is the hydrous silicate-based material (AP); the above alkali silicate composition (BBS4) is as follows: Composition formula (6) M ₂ O · bSiO ₂ · wH ₂ O (6) (wherein M is an alkali metal element of lithium, sodium or potassium, and b is 1.0 to 3.5) The number and w are silanol groups represented by 1.6 to 50.0), and an alkali silicate composition comprising a deliquescent or liquid alkali silicate group alone or in combination of two or more kinds. Yes; the above silicic acid- Alkali solution composition (BB4) is silicate-containing compound (BBS) with respect to 100 parts by weight, the alkali metal hydroxide M (OH) (M
Represents 1 to 20 on the basis of Li, Na, K) hydroxide.
The alkaline system according to any one of claims 1 to 11, which is a silicate-alkali solution composition obtained by adding 0 parts by weight and water in a range of 1 to 200 parts by weight and reacting at room temperature or under heating conditions. Curing agent. 15. A solution-type aluminate in which the alkali composition (BB) is prepared by co-existing an alumina-containing composition (BBA) in a solution in which an alkali metal compound is dissolved in an aqueous composition (BC) in advance. -Alkaline solution composition (BB5)
Wherein the alumina-containing composition (BBA) converts an aluminum compound or an aluminate to an oxide (Al
An alumina-containing composition mainly containing an aluminum-containing compound which is easily reactive to an ionic alkali metal containing not less than 20% by weight based on ₂ O ₃ ); the above-described aluminate-alkali solution composition (BB5) However, based on 100 parts by weight of the alumina-containing compound (BBA), 1 to 200 parts by weight of an alkali metal hydroxide is represented by M ₂ O (M is Li, Na, K) oxide, and water is 1 part by weight. 2. An alkali-aluminate-alkaline solution composition which has been subjected to a reaction treatment at room temperature or under heating conditions in the range of from 1 to 200 parts by weight.
12. The alkaline curing agent according to any one of items 11 to 11. 16. A solution of sulfuric acid in which the alkali composition (BB) is a solution in which a sulfate group-containing composition (BBR) coexists in a solution in which an alkali metal compound is previously dissolved in an aqueous composition (BC). The alkali solution composition (BB6); wherein the above-mentioned sulfate group-containing composition (BBR) is an alkali metal, alkaline earth metal, iron or aluminum element group alone or in combination of two or more sulfur oxyacid salts; The above-mentioned sulfuric acid-alkali solution composition (BB6) is obtained by adding an alkali metal hydroxide to M ₂ O (100 parts by weight of the sulfate group-containing compound (BBR)). M is Li, Na, K) containing 1 to 200 parts by weight, expressed on the basis of oxides, and an alkaline sulfur oxyacid salt which is mixed by adding water in the range of 1 to 200 parts by weight. Alkaline curing agent according to any one of claims 1 is an alkaline solution composition 11 - that sulfate. 17. The alkali composition (BB) is selected from the standard alkali composition (BB1), alkali-oxyacid composition (BB2), alkali-halogen salt composition (BB3), and silicic acid described above. -Alkaline solution composition (BB
4) A composite alkali composition (BB7) comprising a plurality of compositions comprising a combination of two or more of a group of an aluminate-alkali composition solution (BB5) and a sulfuric acid-alkali composition solution (BB6). 12. The alkaline curing agent according to any one of 1 to 11. 18. The alkaline curing agent (B) having a three-part structure of a calcium composition (BA), an alkaline composition (BB), and an aqueous composition (BC).
In addition, in a four-part alkaline curing agent (B) to which a curing auxiliary composition (BD) is further added; the above-mentioned curing auxiliary composition (BD) has the following composition formula (7): EOn _{/ 2} · eB ₂ O ₃ .wH ₂ O (7) (wherein E is an alkali metal element of lithium, sodium or potassium, or an alkaline earth metal element of magnesium, calcium or zinc, and e is 1.0 to 2) And w is a number of 10 or less including zero). A buffer-band-forming composition composed of one or a combination of two or more of the alkali metal or alkaline earth metal boron oxyacid salt compounds. (BD1); wherein the alkaline curing agent (B) is a calcium carbonate composition (BA) 1
The alkali composition (BB) is added in an amount of 1 to 30 parts by weight, the aqueous composition (BC) is added in an amount of 1 to 300 parts by weight, and the curing aid composition (BD) is added to 5 parts by weight.
The alkaline curing agent according to any one of claims 1 to 17, comprising four members added in an amount of 0 part by weight or less. 19. The above-mentioned curing auxiliary composition (BD) is composed of the following unit cell chemical composition formula (8): M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · wH ₂ O (8) (where M is a metal cation having a valence of n, and x + y is a tetrahedral number per unit cell) is a crystal growth seed composition (BD2) composed of an aluminosilicate zeolite. The alkaline curing agent according to claim 18. 20. The curing assisting composition (BD) has the following composition formula (9): M ₂ O · fSO _n · wH ₂ O (9) (wherein M is lithium, sodium or An alkali metal element of potassium, f is a number of 1.0 to 2.0, w is a number of 4 or less including zero, and n is a number of 2 or 3) 19. The alkaline curing agent according to claim 18, which is a curing acceleration composition (BD3) composed of a combination of two or more kinds. 21. The curing assisting composition (BD) has a composition represented by the following composition formula (10): BaO.gSiO ₂ .wH ₂ O (10) (where g is zero of 4.0 or less) , And w is a number including a zero of 9.0 or less), and is a curing control composition (BD4) composed of a barium salt compound powder group soluble in an alkali solution alone or in combination of two or more. Item 18. The alkaline curing agent according to Item 18. 22. The curing assisting composition (BD) has the following composition formula (11): hSiO ₂ .P ₂ O ₅ (11) (where h is 1.0 to 8. 19. The hardened reinforcing composition (BD5) comprising a powdery silicon phosphate group having a sustained release property of phosphoric acid represented by the formula (BD5) alone or in combination of two or more kinds. System hardener. 23. The curing assisting composition (BD) comprises the buffer zone forming composition (BD1), the crystal growth seed composition (BD2), the curing accelerating composition (BD3), and the curing adjusting composition. (B45) and a hardening reinforcing composition (BD
20. The alkaline curing agent according to claim 18, which is a composite auxiliary composition (BD6) composed of a combination composition of two or more of the groups. 24. The alkali-based curing agent (B) comprises a calcium composition (BA) and an alkali composition (BB).
And a water-based composition (BC), and a three-component alkaline curing agent (B), or a three-component alkaline curing agent (B) with a curing auxiliary composition (BD) added as necessary. In the composition of the alkaline curing agent (B) having the constitution, the slurry composition or the fluid liquid state having a pH value of 10 or more even after the composition of the composed alkaline curing agent (B) is integrated. The alkaline curing agent according to any one of claims 1 to 23, which is a secured liquid alkaline curing agent (BL). 25. The alkaline curing agent (B) comprises a calcium composition (BA) and an alkaline composition (BB)
And a water-based composition (BC), and a three-component alkaline curing agent (B), or a three-component alkaline curing agent (B) with a curing auxiliary composition (BD) added as necessary. In the alkaline curing agent (B) having the constitution, the powdered alkaline curing agent in which the composition of the composed alkaline curing agent (B) reacts when integrated and is transformed into a one-pack powder state. The alkaline curing agent according to any one of claims 1 to 23, which is an agent (BP). 26. The method according to claim 1, wherein
The deformable admixture (C) prepared by adding the alkali-based curing agent (B) described in (1) to the silicate-based material (A) to be solidified is subjected to room-temperature solidification treatment. In the step of forming a water-resistant and heat-resistant solid by transforming into a cured product (E) by heating, the above-mentioned deformable admixture (C) is added to 100 parts by weight of the silicate-based material (A). A mixture in which the alkali hardener (B) is mixed in a proportion of 20 to 500 parts by weight to homogenously mix the two to ensure fluidity or plastic workability; A solidification treatment step of releasing the deformable admixture (C) into the atmosphere or water at least at room temperature to allow the reaction and curing to proceed, thereby transforming it into a cured product (E);
A water- and heat-resistant solidified product, wherein the cured product (E) exhibits water resistance and heat resistance simultaneously. 27. The deformable admixture (C) is further modified into a deformable admixture (C) which is a mixture of a silicate-based material (A) and an alkali-based curing agent (B). In the composite deformable admixture (C) of the three-component mixture to which the addition composition (D) is added; the functional addition composition (D) is a pigment, a colorant, an activator, a filler, and a function imparting agent. An additive material composition (D1) that adds functionality to a powder or a solidified body composed of powder or granules having a particle diameter of at least 100 μm or less composed of a single or a combination of two or more agent groups;
The deformable admixture (C) is a silicate-based material (A) 1
The three components obtained by adding 20 to 500 parts by weight of the alkali-based curing agent (B) and 1000 parts by weight or less of the functional additive composition (D) to 00 parts by weight are homogeneously mixed. 27. The water- and heat-resistant solidified product according to claim 26, which is a composite-type deformable admixture in which fluidity or plastic workability is ensured. 28. The composition for functional addition (D), wherein
Arsenic-immobilizing composition for immobilizing arsenic element contained in a silicate-based material (A) or a calcium carbonate composition (BA) composed of iron hydroxide containing a trivalent or trivalent iron hydroxide as a main component The water- and heat-resistant solidified body according to claim 27, which is a product (D2). 29. The functional additive composition (D) may be silica, alumina, silicate, carbon, or a zeolite-based adsorbent alone or in combination of two or more, and has a particle size of 100.
28. The water- and heat-resistant solidified body according to claim 27, which is an adsorptive material composition (D3) that exhibits an adsorptive function in a gas or a solution composed of a powder or granules having a size of μ to 8 mm. 30. The functional addition composition (D) is represented by the following formula (12): ZO _y .hDO _x .wH ₂ O (12) (wherein, Z is monovalent or 2) Element of valence silver, copper, zinc or nickel, D is element of calcium, magnesium, boron, aluminum, carbon, silicon, nitrogen, phosphorus or sulfur, h is a number not more than 3.5 including zero, w is 24 including zero .
0 or less, y is a number from 0.5 to 1.0, x is 0.5
Or a combination of two or more of compounds comprising silver, copper, zinc or nickel represented by the formula (D4).
7. The water-resistant and heat-resistant solid according to 7. 31. The above-mentioned functional addition composition (D) imparts water repellency to a solidified product formed of a water repellent compound of an organosiloxane alone or a water emulsion group of an organosiloxane alone or in combination of two kinds. The water-resistant and heat-resistant solid according to claim 27, which is a liquid water-repellent addition composition (D5) to be added. 32. The above-mentioned functional additive composition (D), a metal fiber, a glass fiber, a carbon fiber, an aramid fiber, a vegetable fiber and a mineral fiber alone or in combination of two or more fiber reinforcing agents. 28. The water- and heat-resistant solidified body according to claim 27, which is a fibrous reinforcing composition (D6) for reinforcing the solidified body strength of the formed solidified body composed of: 33. The functional additive composition (D) is solidified with sand particles having a particle size of 100 μm or more and 7 mm or less and a bulk specific gravity of 0.5 to 2.5 g / cc. 3. An aggregate composition (D7) capable of supplementing the body.
7. The water-resistant and heat-resistant solid according to 7. 34. The above-mentioned functional additive composition (D) comprising the additive material composition (D1), the arsenic-immobilized composition (D2), the adsorptive material composition (D3), and the antimicrobial property A plurality of auxiliary compositions (D) composed of a combination composition of two or more of the composition (D4), the water-repellent additive composition (D5), the fibrous reinforcing composition (D6) and the aggregate composition (D7)
28. The water- and heat-resistant solidified body according to claim 27, which is 8). 35. The room temperature solidification treatment wherein the room temperature solidification treatment is a room temperature solidification treatment step of transforming the deformable admixture (C) into a cured product (E) by reaction and curing released in an atmosphere of 400 ° C. or less. Or the water resistance described in any one of 34.
Heat resistant solid. 36. A cured product (E), wherein the cured product (E) is subjected to room temperature solidification treatment to transform the deformable admixture (C).
35. The water-resistant material according to any one of claims 26 to 34, wherein the solidified material has a cured body strength of 50% or less even when poured into water or left in an atmosphere of at least 400 ° C. -Heat-resistant solid. 37. The cured product (E), which is obtained by subjecting the deformable admixture (C) to a solidification treatment at room temperature to transform the cured product (E).
But 2 kg / cm ² or more, preferably 10 kg / cm ²
A solidified material exhibiting a uniaxial compressive strength of 90 kg / cm ² or more, more preferably, 90 kg / cm ² or more.
The water-resistant and heat-resistant solid according to any one of the above. 38. The cured product (E), which is obtained by subjecting the deformable admixture (C) to a room temperature solidification treatment to transform the cured product (E).
Incorporates heavy metals contained in the silicate-based material (A) or the calcium composition (BA) to be solidified into zeolite or a zeolite precursor which is an aluminosilicate, and makes the contained heavy metals in a water-insoluble state. 35. The water- and heat-resistant solid according to any one of claims 26 to 34, which is a solidified solid. 39. The cured product (E), which is obtained by subjecting the deformable admixture (C) to a room temperature solidification treatment to transform the cured product (E).
35. The water- and heat-resistant solidified body according to any one of claims 26 to 34, wherein the solidified body is a porous body having a specific surface area of 500 cm ² / g or more. 40. The cured product (E) is obtained by transforming the deformable admixture (C) into a spherical, cylindrical, granular, or granular granular material (EG).
The water- and heat-resistant solidification according to any one of claims 26 to 39, wherein the solidification is made of a cured product (E) that has been subjected to room temperature solidification treatment and has been transformed into a granular material (EG) shape. body. 41. The cured product (E) is formed by molding the deformable admixture (C) into a specified moldability, securing it in a specified structure (EU), subjecting it to a room temperature solidification treatment, and specifying the same. The water- and heat-resistant solidified body according to any one of claims 26 to 39, wherein the solidified body is a solidified body composed of a cured body (E) that has been transformed into a structure (EU) shape. 42. The cured product (EB) in which the deformable admixture (C) is coated, coated, adhered, bound or dusted with the deformable admixture (C) on the surface or the inner surface of the substrate. 40. The water- and heat-resistant solidified body according to any one of claims 26 to 39, wherein the solidified body comprises a cured body (E) that has been subjected to room temperature solidification treatment and has been transformed into an adhered cured body (EB) shape. body. 43. The cured product (E) is formed by coating, coating, adhering or dusting the deformable admixture (C) on the surface or inner surface of a substrate composed of 0.5 to 12 mmφ granular spheres. 40. A solidified product comprising a cured product (E) which is secured to a layered granule (ED) and subjected to room temperature solidification treatment to be transformed into a heterolayered granule (ED) shape. The water-resistant and heat-resistant solid according to the item. 44. The unspecified shape (E) in which the cured product (E) is not limited to the deformable admixture (C) in a specified shape.
U) and subjected to room temperature solidification treatment to obtain an unspecified form (E
The water- and heat-resistant solidified body according to any one of claims 26 to 39, which is a solidified body composed of a cured body (E) that has been transformed into a shape U). 45. The cured product (E) is obtained by transforming the deformable admixture (C) into particles having a particle size of 10 to 2000 μm.
40. A solidified product comprising a cured product (E) which has been secured to the powdery granules (EP) and subjected to room-temperature solidification treatment to be transformed into a zeolite-containing powdery granules (EP).
The water-resistant and heat-resistant solid according to any one of the above. 46. The granular material (EG) or the heterogeneous granule (ED) becomes a group of the integrated granular material (EG) or heterogeneous granule (ED) and has a millet-like penetration. Aggregate cured product (E) forming a molded product having voids
In C), the above-mentioned aggregated cured product (EC) is used in an amount of 10 to 65 parts by weight of the deformable admixture (C) based on 100 parts by weight of the granular material (EG) or the heterogeneous granule (ED). A molding step of coating the surface of the granular body (EG) or the heterogeneous granule (ED) group with the above, and then integrating the coated granular body (EG) or the heterogeneous granule (ED) group, a specific thickness Is subjected to room temperature solidification treatment in a state where it has been secured to a specific shape in the casting or spraying process into a board shape. Then, from the group of millet-like granules (EG) or heterogeneous granules (ED) having through pores Set Cured Body (EC)
3. The cured product (E) having a secured shape.
40. The water- and heat-resistant solid according to any one of 6 to 39.