JP2004315360A - Method for manufacturing hydraulic material utilizing waste material of ceramic-based building material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a novel hydraulic material with which the strength at ordinary temperature can be effectively assured by skillfully utilizing the characteristics of waste materials of ceramic-based building materials and with which handling quality can be improved and the final strength in ceramic-based products can be advantageously exhibited when the hydraulic material is used as a raw material for, for example, the ceramic-based products. <P>SOLUTION: The hydraulic material which contains Alite and cures at ordinary temperature is obtained by using the waste materials of the ceramic-based building materials as raw materials, adding auxiliary components containing calcium to the main raw materials and subjecting the mixture containing the main raw materials and the auxiliary components to firing treatment to react the main raw materials and the auxiliary components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a ceramic building material that realizes the reuse of waste materials generated when constructing, repairing, dismantling, etc., general houses and various buildings, for example, ceramics exterior materials such as houses and waste materials such as tiles as main raw materials. And a method for producing a hydraulic material using waste materials.

  Waste materials of ceramic building materials generated during construction, repair and demolition of general houses and other buildings are often landfilled. However, as the cost of processing increases as landfills decrease, arterial recycling is considered. I'm starting. For example, it is conceivable to produce a cement mineral (including cement clinker; the same applies hereinafter) by pulverizing and baking to reuse it as a hydraulic material.

  As a hydraulic material using such building material waste, for example, as shown in Patent Document 1, a hydraulic waste composition containing incineration of construction waste including concrete waste, Portland cement, and a calcium compound Alternatively, as shown in Patent Literature 2, water containing a calcium silicate-based mineral in which calcium oxide and a part of tobermorite are decomposed by heat-treating ALC building waste material at 600 to 1500 ° C. Hard calcium silicate-based raw materials are known.

  However, the hydraulic composition disclosed in Patent Literature 1 is only based on the premise that Portland cement is blended, and there is a problem that it is difficult to effectively utilize waste materials.

  Further, in the hydraulic calcium silicate-based raw material disclosed in Patent Document 2, the content of calcium oxide and calcium silicate-based minerals contained in the raw material manufactured by the heat treatment is adjusted according to the material of the ALC building waste material, the generation environment, and the like. The problem is that there is a risk that the strength may vary, so that it is difficult to realize a stable strength.

  In addition, a large amount of asbestos may be used for tiles and exterior materials of general houses and the like produced in the past. In such a waste material of ceramic building materials, there is a problem that it is more difficult to generate a cement mineral and reuse it as a hydraulic material. That is, asbestos is a mineral fiber containing a large amount of magnesium, and even in cementing, uniform dispersibility of asbestos becomes important when mixing various auxiliary components and the like with ceramic building materials as a main raw material. . In addition, if the asbestos content in the waste material is excessive, free magnesium oxide (f-MgO) that is not a compound remains in the hydraulic material, which may impair the function of the obtained hydraulic material. There is also.

JP-A-11-263659 JP 2001-199750 A

  Here, the present invention has been made in the background of the above-described circumstances, and the problem to be solved is to make use of the characteristics of waste materials of ceramic building materials to improve the strength at room temperature. Production of a new hydraulic material which can effectively ensure, for example, when used as a raw material of a ceramic product, can improve the handleability and can exert the final strength of the ceramic product advantageously. It is to provide a method and the like.

  In addition, the present invention is also effective in waste materials such as tiles and building exterior materials containing relatively large amounts of asbestos, in which asbestos is efficiently incorporated as a cement component, and exhibits excellent functionality and curing performance in the obtained hydraulic material. It is also an object to provide a method for producing a hydraulic material which can be obtained.

  Hereinafter, embodiments of the present invention made to solve such problems will be described. The components employed in each of the embodiments described below can be employed in any combination as possible. In addition, aspects or technical features of the present invention are not limited to those described below, but are described in the entire specification and drawings, or based on the invention ideas that can be understood by those skilled in the art from the descriptions. It should be understood that it is recognized on the basis of.

  That is, in order to solve the above-mentioned problems, the present inventor has conducted many experiments and studies on the reuse of waste materials of ceramic building materials, and as a result, the types and contents of chemical components contained in the waste materials of ceramic building materials. By focusing on the above, by adding a specific treatment to the waste materials of the ceramic building materials, it is possible to newly find a characteristic fact that alite as a cement mineral contributing to cement strength at room temperature can be effectively generated. Therefore, based on such knowledge, the present inventors have conducted intensive studies, and as a result, have completed the present invention.

  Here, the first aspect of the present invention is to use a waste material of a ceramic building material as a main raw material, add an auxiliary component containing calcium to the main raw material, and perform a sintering process on a mixture containing the main raw material and the auxiliary component. And reacting the main raw material with the auxiliary component to obtain a hydraulic material that contains arit and cures at room temperature.

According to the method of the present invention, calcium, silica, iron, and other chemical components contained in waste materials are effectively used as cement components of a target hydraulic material, and an auxiliary component containing calcium is used as a main raw material. by adding, are adjusted firing reaction of main material and the auxiliary components, Alit as contributing cement mineral cement strength (3 CaO · SiO ₂ etc.) than is favorably produced, than Te, at room temperature By hardening, the practical strength is sufficiently exhibited, and it becomes easy to manufacture ceramic products and the like.

In the present invention, “allit” is generally represented by C ₃ S, but as is well known, a form contained in known cement in addition to the ideal type 3CaO · SiO ₂ . This is a concept including various solid solutions, and for example, a solid solution containing Al ₂ O ₃ or Mg ₂ O ₃ may be used. Specifically, the alit being industrially treated is 54CaO.MgO.Al ₂ O ₃ .16SiO ₂ , and this solid solution also contained in cement is naturally included in the alit of the present invention. It is.

  In addition, in this embodiment, since waste materials of the ceramic building material contain impurities such as an appropriate extender and a reinforcing agent in addition to the aggregate, there is a possibility that environmental problems may occur when the waste is reused. However, according to the method of the present invention, these impurities are eliminated or, in combination with the action of the addition of auxiliary components, may transform into another useful substance. Can be eliminated.

  In addition, as an adjustment method of adding an auxiliary component containing calcium to waste material (main raw material) of ceramic building materials, for example, after measuring various components included in the waste material in advance, adding an appropriate amount of auxiliary component, Alternatively, it can be realized by adding an auxiliary component to waste materials of various ceramic building materials based on experimental data obtained by measuring and evaluating the strength and the like of a hydraulic material manufactured according to the method of the present invention. The ordinary temperature in this embodiment refers to a temperature which can be usually obtained indoors or outdoors without heating, and is generally 20 ± 15 ° C.

  Further, in the present embodiment, it is desirable that the main raw material and the auxiliary component are sufficiently kneaded before firing, for example, they are mixed as they are in a wet or dry system, or mixed while being pulverized using a mixing machine such as a ball mill. It is also possible. In particular, it is desirable that these main raw materials and auxiliary components are in the form of a fine powder at the stage of the mixture, so that, during the firing treatment, the reaction between various components including silica and the like and the auxiliary components in the waste materials of ceramic building materials. Thus, the hydraulic properties can be improved, and the hydraulic properties can be further improved and stabilized, and the strength at room temperature to which water has been added can be effectively exerted in the production of ceramic products.

  Further, in the present embodiment, generally, a cement clinker is generated by firing the mixture, and it is possible to provide the cement clinker to the market as it is as a hydraulic material. In order to be easily used without being subjected to processing such as crushing at the time, and to be able to easily perform handling and transport operations, it is desirable that crushing and crushing processing be provided to the market, Further, gypsum, an appropriate auxiliary agent, an extender, and the like can be appropriately added.

The specific surface area of the particles in the mixture obtained by grinding the waste materials and auxiliary components of these ceramic building materials is not particularly limited, but is preferably 3000 to 5000 cm ² / g in consideration of the above-described reasons.

Further, as the calcium contained in the auxiliary component, for example, calcium oxide, calcium hydroxide, calcium carbonate, or the like can be adopted, or a waste containing a calcium component consisting of shell scraps such as oyster shells is used alone. Alternatively, the waste may be used in combination with another material containing a calcium component. Further, iron, which is also effective for dusting and C ₃ A content reduction adjustment, may be added as an auxiliary component.

  Here, in this embodiment, as the calcium component of the auxiliary component, preferably, calcium carbonate, more preferably, calcium hydroxide, and more preferably, calcium oxide is employed, so that arit is more efficiently generated. Has been confirmed by the present inventors.

In a second aspect of the present invention, in the method for producing a hydraulic material according to the first aspect, the molar ratio of CaO / SiO ₂ in the mixture is 2.5 to 4.0, and the calcination is performed. The sintering temperature in the treatment is 1300 to 1400 ° C.

  In this embodiment, the calcination treatment at a low temperature of 1300 to 1400 ° C. is compared with the calcination treatment at a high temperature of 1450 ° C. or more as the industrial production temperature considered to be necessary for the conventional cement production. Is adopted, equipment such as an incinerator is simplified, and energy costs are reduced, so that cost reduction can be realized.

Further, in this embodiment, the auxiliary component is added to the waste material of the ceramic building material, and the molar ratio of CaO / SiO ₂ in the mixture containing the waste material and the auxiliary component is set to 2.5 to 4.0, so that firing is performed. The alit content in the hydraulic material after the treatment can be effectively secured. That is, when the molar ratio of CaO / SiO ₂ becomes too small, calcium becomes insufficient for silica (SiO ₂ ) contained in the waste material of the ceramic building material, and the arit is not effectively generated. Also, if the molar ratio of CaO / SiO ₂ becomes too large, the amount of CaO that does not react with the SiO ₂ in the waste material during the sintering process increases, and as a result, f-CaO (free lime) remains in the hydraulic material. Therefore, for example, when such a hydraulic material is used as a building material, the free lime reacts with carbon dioxide at room temperature to become CaCO ₃ , and shrinkage of the base material occurs, and it is difficult to effectively secure dimensional accuracy. .

Therefore, according to the present embodiment, by adding and adjusting the auxiliary component so that the molar ratio of CaO / SiO ₂ in the mixture is included in the range, it is set to a low temperature region in general cement production. Even in the firing treatment at 1300 to 1400 ° C., the arit is favorably formed, so that the practical initial strength can be exhibited more advantageously.

  In addition, the lump hydraulic material manufactured according to this embodiment has a lower hardness than the lump (cement clinker) obtained by baking at a high temperature of 1450 ° C. or more, and therefore after the baking processing. When a powdery material is obtained by crushing and pulverizing, there is an advantage that the processing is easy and the equipment cost can be reduced.

  Further, a third aspect of the present invention is the method for producing a hydraulic material according to the first or second aspect, wherein, as a pretreatment of the firing treatment, waste material of the ceramic building material or the mixture It is characterized by performing a calcination treatment.

  In such an embodiment, the waste material or mixture of the ceramic building material before the firing treatment is included in the waste material of the ceramic building material by performing a heat treatment at a temperature of, for example, 500 to 800 ° C. as a calcining treatment. Impurities are efficiently removed, and the reactivity of waste materials and auxiliary components of ceramic building materials in the firing process of the mixture is improved, so that arit is well generated and the intended hydraulic performance is further improved. Improvement can be achieved.

  The impurities contained in the waste materials of the ceramic building materials include, for example, an organic packaging material according to a tenth embodiment described below in addition to an organic material such as pulp. It is presumed that these impurities become carbon and oxidize into carbon dioxide gas by the calcination treatment. Furthermore, it is presumed that by performing the calcination treatment, the decarbonation effect of the waste material of the ceramic building material is also achieved, and the impurities in the reaction can be efficiently removed. The calcination time is preferably 30 to 180 minutes, more preferably 90 to 180 minutes, depending on the size and processing capacity of the processing equipment, the material and amount of waste material, and the like.

  Further, a fourth aspect of the present invention is the method for producing a hydraulic material according to any one of the first to third aspects, wherein the waste material of the ceramic building material contains asbestos, and the asbestos is removed from the hydraulic material. It is characterized in that it is used as a raw material for materials.

In this embodiment, in addition to the effect of removing impurities by the calcination treatment according to the above-described third embodiment, a special effect can be obtained particularly in the burning treatment of waste materials of ceramic building materials including asbestos. That is, the SiO ₂ in the asbestos is used in the composition of Alit solid solution with CaO, which is one of the main components of Alit, a substitution solid solution of MgO in asbestos is replaced with a portion of CaO solid solutions Then, Fe ₂ O ₃ in the asbestos is incorporated into the hydraulic material as C ₄ AF.

  As a result, the structure of asbestos can be advantageously destroyed and rendered harmless, and since some of the main components of asbestos are used in the composition of arit, cost reductions associated with environmental conservation and effective use of raw materials are achieved. Can be achieved at the same time to a high degree.

Further, in this embodiment, the amount of C ₃ A causing a quick setting (pseudo-setting) action in the hydraulic material is reduced, and the temperature of the liquid phase reaction during the firing treatment is reduced and the solidification is reduced by Fe ₂ O ₃ and MgO. The effect of accelerating the dissolution reaction has the advantage that the curing characteristics of the hydraulic material can be further stabilized.

Furthermore, in the present embodiment, although not particularly limited, the present inventors have fired chrysotile, which is a kind of asbestos, to obtain powder X-ray diffraction (XRD) and SEM.
As a result of analysis by observation, it was confirmed that structural destruction due to crystallization water desorption occurred at about 700 ° C. and vitrification occurred at 1200 ° C. From these results, in this embodiment, it is assumed that asbestos reacts with calcium or the like as a material for the solid solution forming reaction to become another component.

  In a fifth aspect of the present invention, in the method for producing a hydraulic material according to the fourth aspect, the temperature at which crystal water in the asbestos is separated after adding the auxiliary component to the main raw material. The preheating is performed by heating the asbestos, the stress for pulverizing the asbestos is supplied, and then the firing is performed.

In this embodiment, in addition to the same effect as in the fourth embodiment, the SiO ₂ and MgO in asbestos are more efficiently consumed and taken into the hydraulic material. .

In other words, asbestos is a combination of SiO ₂ , MgO and H ₂ O, and when adding and mixing an auxiliary component containing calcium to the main raw material consisting of the waste material of ceramic building materials, the asymmetry of the component is reduced. , Difficult to avoid. Also, when such ceramic building materials are pulverized and then mixed, it is considered that handling becomes difficult because asbestos dust becomes toxic. In this regard, according to this embodiment, after adding calcium as an auxiliary component to the ceramic building material as the main raw material, the crystallization water in the asbestos is decomposed, so that the asbestos loses the bound water and efficiently removes the fiber. This makes it possible to more efficiently cause a solid solution reaction by the subsequent sintering, and a hydraulic material having a good function and curing performance even when asbestos-containing waste material is used as a main raw material. Can be obtained.

  More specifically, when producing a hydraulic material according to the present embodiment, an auxiliary component such as calcium carbonate is added to the asbestos-containing waste material, which is a main raw material, and mixed, then calcined at 700 ° C. or more, and then pulverized. It is desirable to mix by applying the following stress. First, calcium carbonate or the like is mixed with an asbestos-containing waste material at an appropriate ratio, and calcining is performed at 700 ° C. or more. More preferably, the temperature is set to about 1000 ° C. The time is preferably 10 minutes or more, and more preferably about 30 minutes. As a result of such a calcination treatment, asbestos loses bound water, and when shear (an external force that generates shear stress) is applied, the fibers are easily broken.

  In addition, before adding the auxiliary component such as calcium carbonate, the asbestos-containing waste material may be temporarily calcined alone, but as in this embodiment, after the auxiliary component consisting of a calcium source such as calcium carbonate is added, the preliminary firing is performed. It is better to do. By doing so, the asbestos component reacts with calcium to make it easier to grind.

In addition, the pulverization after firing in this embodiment is performed by, for example, mixing and pulverizing with a ball mill or the like. The particle size after the pulverization is better as the specific surface area is smaller as long as the processing time and handleability are permissible, so that the solid solution reaction by the subsequent baking treatment can be performed more efficiently. Specifically, in consideration of the processing time, the pulverizing effect, and the like, a pulverization treatment of, for example, several minutes to several tens of minutes by a ball mill or the like is preferably employed. That is, given a crushing stress, becomes the SiO ₂ and MgO asbestos lost bound water (H ₂ O) by calcination is uniformly dispersed in the main raw material, as a result, unreacted during sintering SiO ₂ decreases, for example, the solid solution reaction proceeds efficiently even at around 1300 ° C., and arit, which is a main component of cement (hydraulic material), is generated. As a result, the amount of f-CaO and f-MgO (free CaO and MgO that is not a compound) generated during the non-reaction is reduced. By producing the hydraulic material according to the manufacturing method of the embodiment, it is possible to more advantageously obtain a hydraulically stable material as a functionally stable recycled cement.

  In a sixth aspect of the present invention, in the method for producing a hydraulic material according to the fourth or fifth aspect, the amount of the asbestos contained in the ceramic-based building material as the main raw material is the main raw material. And before the calcination, after addition of the auxiliary component, is 2.7% by weight or less.

  In this embodiment, in addition to being able to exhibit the same effects as those of the fourth embodiment or the fifth embodiment, the remaining of f-MgO generated in the unreacted state in the hydraulic material is more effectively achieved. In addition, it is possible to further stabilize the function of the obtained hydraulic material.

  That is, as described above, MgO, which is a main component of asbestos, is taken in as a part of the arit during firing as described above. However, in the raw material before temporary firing (after mixing the auxiliary component with the main raw material), If the amount of asbestos is 2.7% by weight or less, MgO in the asbestos component can be almost completely incorporated into the arit during firing. On the other hand, when a raw material containing asbestos exceeding 2.7% by weight is used, although it depends on the variation in the amount of generated arit, it exceeds the limit of MgO that can be taken into the arit, and the generated water is Excess MgO is present alone as f-MgO in the hard material. As a result, the presence of f-MgO results in an unstable hydraulic material in which expansion after construction and a resulting decrease in strength are concerned.

  In particular, building materials 20 to 30 years ago, in which demolition will increase in the future from now on, may contain a large amount (about 20%) of asbestos. However, even if it is possible to uniformly disperse, the excessive MgO component remains in the cement clinker as f-MgO, which is a problem that cannot be ignored in practice.

  Therefore, in the present embodiment, it is possible to obtain a functionally excellent hydraulic material by selectively using only waste materials in which the asbestos content is 2.7% by weight or less in the raw material state before calcining, Alternatively, when the asbestos content of the waste material is so large that the asbestos content exceeds 2.7% by weight, the asbestos-containing exterior material-based waste material is preliminarily mixed with the asbestos-free waste material to thereby reduce the amount of asbestos in the main material. By reducing the asbestos content and adjusting the asbestos content in the raw material before calcining to 2.7% by weight or less, it is possible to stably produce a hydraulic material excellent in functionality.

  Further, a seventh aspect of the present invention is the method for producing a hydraulic material according to the fourth or fifth aspect, wherein the amount of the asbestos contained in the ceramic building material as the main raw material is the main raw material. In the case where the content exceeds 2.7% by weight before the calcination after the addition of the auxiliary component, fly ash is added to the main raw material and mixed to reduce the asbestos content to 2%. It is characterized in that it is adjusted to 0.7% by weight or less.

  In this embodiment, in addition to the effect similar to that of the fourth embodiment or the fifth embodiment, even if the asbestos contained in the main raw material is large, the amount of f-MgO The function in the obtained hydraulic material can be stabilized by suppressing the residual in the hydraulic material.

  That is, even when the amount of asbestos in waste materials such as tiles and exterior materials as raw materials is large, by adding and mixing fly ash according to the present invention, the content of asbestos in the main raw material to which such fly ash is added is reduced. By controlling the asbestos content in the raw material before the preliminary calcination after adding the auxiliary component to 2.7% by weight or less, the excess MgO component can be reduced in the same manner as in the fifth embodiment of the present invention. Thus, it is possible to stably produce a hydraulic material excellent in functionality by suppressing the residual as f-MgO.

  Moreover, in the present embodiment, there is a great feature in using fly ash generated in a thermal power plant as waste similar to building materials, and the fly ash, which is waste, is mixed with asbestos excess waste. Thereby, it can be effectively used as one of the hydraulic materials.

  When fly ash is added in this manner, not only does the ratio of the MgO amount decrease, but also because fly ash contains amorphous Si, it also forms a solid solution during sintering after the addition of an auxiliary component containing calcium. It can be a waste material in which the reaction easily occurs, and it becomes possible to obtain a hydraulic material having high functionality and curing performance.

  Further, an eighth aspect of the present invention is directed to the method for producing a hydraulic material according to any one of the first to seventh aspects, wherein the waste material of the ceramic building material is subjected to crushing treatment, and And adding water to the water.

  In this embodiment, particularly when crushing waste materials of ceramic building materials containing asbestos and other harmful substances, scattering of harmful substances based on such crushing processing is reduced or prevented. Thereby, the safety of the working environment can be improved.

  In addition, as the water of the present embodiment, for example, water such as river water or purified tap water is used, and an aqueous solution in which an appropriate substance is dissolved in water is also used. Further, in the present embodiment, as a method of adding water when performing crushing treatment on the waste material of the ceramic building material, for example, when the waste material and the auxiliary component are put into a mixing machine such as a ball mill and the two materials are kneaded, water is used. It is realized by adding it appropriately, or adding an appropriate amount of water at the time of pulverizing before mixing the waste material with the auxiliary component. Further, preferably, the facility for crushing the waste material is provided with a protective wall or is installed separately, so that the safety can be further improved.

  Further, a ninth aspect of the present invention is the method for producing a hydraulic material according to any one of the first to eighth aspects, wherein the waste material of the ceramic building material is subjected to crushing treatment, , A wet pellet is obtained by subjecting the pellet to water injection, and the pellet is used as the main raw material.

  In this embodiment, by performing the water injection treatment on the waste material, for example, in addition to effectively preventing the scattering of harmful substances such as asbestos contained in the waste material at the time of the pulverization treatment, in addition to these pulverization treatment and water injection By using wet pellets obtained as a main raw material, scattering of harmful substances during transportation of materials and mixing with auxiliary components can be effectively prevented. Further improvements can be achieved.

  Note that the water injection treatment of this embodiment is advantageously realized by adding water as shown in the eighth embodiment to waste material. In addition, dry or wet pulverization is employed as the pulverization of the waste material. In this case, when a dry pulverization treatment is adopted, the pulverization treatment and the water injection treatment of this embodiment are completed by adding an appropriate amount of water to the powder obtained by subjecting the waste material to a pulverization treatment with a pulverizer or the like. . When a wet pulverization process is adopted, the waste material is put into a pulverizer to which water has been injected in advance, and the waste material is subjected to the pulverization process, whereby the pulverization process and the water injection process of this embodiment are completed. Also, wet pellets, for example, in addition to being realized as a lump by performing crushing treatment and water injection treatment of waste materials of ceramic building materials, while performing water injection treatment on the powder that has been subjected to crushing treatment of the waste materials, It can be realized by hardening into a dumpling or the like by tumbling, or by adding a binder or the like at the time of performing water injection treatment on the powder and hardening into a bulk.

  Further, in the eighth and ninth aspects, by maintaining the waste material of the ceramic building material to which water is added at an appropriate humidity, when the waste material contains asbestos, the waste material and auxiliary components in the asbestos are physically removed. The effect of adsorption is improved, and it can be expected that the solid solution reaction during firing proceeds more effectively. Further, the water content (water content) in the fifth and sixth aspects is not particularly limited, but preferably, the water content is 0.2 to 2.0 by weight of water / waste material. You. If the water content is too low, the dust diffuses into the air, while if the water content is too high, the energy loss required for water volatilization in the firing treatment of the mixture of the waste material and the auxiliary component increases.

  Further, a ninth aspect of the present invention is the method for producing a hydraulic material according to any one of the first to eighth aspects, wherein after subjecting the waste material of the ceramic building material to a crushing treatment, And packaging the waste material with an organic packaging material and mixing the waste material with the auxiliary component to obtain the mixture.

  In this embodiment, the handleability of the mixture can be improved during the baking treatment, and the use of the organic packaging material causes the packaging material to be burned off during the baking of the mixture, thereby simplifying the working process. Can be advantageously achieved.

  Furthermore, an eleventh aspect of the present invention is characterized in that a waste material of a ceramic building material is used as a main raw material, an auxiliary component containing calcium is added to the main raw material, and a baking treatment is performed on a mixture containing the main raw material and the auxiliary component. And reacting the main raw material with the auxiliary component, which is characterized by containing an arit and hardening at room temperature.

  In the hydraulic material according to the present aspect, by adjusting the amount of the auxiliary component containing calcium, the amount of arit that contributes to the cement strength is appropriately adjusted, so that the desired strength is exhibited. It can be done.

The hydraulic material of the present embodiment contains not only the above-mentioned arit (C ₃ S) but also berit (2CaO · SiO ₂ ), 3CaO · Al ₂ O ₃ (C ₃ A), 4CaO · Al ₂ O ₃ · Fe ₂ O ₃ (C ₄ AF), CaO ₂ , and an alitite appropriately containing a substituted solid solution in which Al ₂ O ₃ and Mg ₂ O ₃ are partially substituted. In addition, the shape of the hydraulic material is not particularly limited, and a powdery or lump-like shape is appropriately adopted in consideration of a form provided on the market, handleability, and the like.

  In the case of manufacturing a ceramic product using such a hydraulic material, it is possible to manufacture a ceramic product by kneading the hydraulic material with sand or water and curing at room temperature, or After hardening a mixture containing a hydraulic material, sand, water, etc., the mixture is subjected to high-temperature and high-pressure curing according to the required strength and the like, thereby realizing a ceramic product.

  Furthermore, in this embodiment, it is basically unnecessary to add a cement material such as ordinary Portland cement. That is, although the hydraulic material according to the present embodiment does not deny the addition of a cement material, it is mainly a waste material of a ceramic building material, and the cement material is used for the hydraulic material. It does not exceed 20% by weight. This is because the hydraulic material of the present embodiment can be cured at room temperature without using a cement material to obtain practical strength.

  Furthermore, a twelfth aspect of the present invention is characterized by a ceramic admixture using the hydraulic material according to the eleventh aspect.

  A thirteenth aspect of the present invention is characterized by a ceramic product manufactured by performing high-temperature and high-pressure curing using the hydraulic material according to the eleventh aspect.

  Further, a fourteenth aspect of the present invention is characterized by a ceramic product manufactured using the ceramic admixture according to the twelfth aspect.

  The ceramic products according to the thirteenth and fourteenth aspects are applied to various ceramic products, depending on the material of the hydraulic material and the production conditions of the intended product, and the like. For example, it is advantageously applied to concrete-based exterior materials and roof tiles.

  In a fifteenth aspect of the present invention, the waste material of the ceramic building material is subjected to a crushing treatment and a water injection treatment to form a lump, and the water according to any one of the first to tenth aspects is used. It is characterized by a wet pellet used as a main raw material in a method for producing a hard material.

  In such wet pellets according to the present embodiment, handling such as transportation of waste material is facilitated, and safety in operation is improved due to prevention of scattering of harmful substances by the wet process. It can be advantageously employed as a raw material.

  As is clear from the above description, according to the method for producing a hydraulic material of the present invention, by adding an auxiliary component containing calcium to waste materials of ceramic building materials, various components contained in the waste materials and auxiliary materials are added. The components react to produce good arit as a cement mineral that contributes to the cement strength.As a result, sufficient initial strength is secured, and the workability of ceramic products etc. is improved. It can be improved effectively.

  Hereinafter, in order to clarify the present invention more specifically, a hydraulic material manufactured according to the method for manufacturing a hydraulic material according to the present invention will be described, but the present invention is limited to only these examples. Not.

First, a waste material of a ceramic exterior material as a ceramic building material is calcined at 500 ° C. for 2 hours. Then, calcium carbonate as an auxiliary component is added to the waste material to adjust the molar ratio of CaO / SiO ₂ : r to r = 3.3, and the value of the internal ratio in the waste material is 0%, 10%, 20%. % Asbestos is added separately to obtain three compositions. Further, each composition was put into a mill containing water, and wet-milled and mixed to obtain three kinds of mixtures. Each mixture in a wet state was put into an electric furnace, and kept at 1300 ° C. for 1 hour. By firing under the conditions, three types of cement clinkers are obtained. Further, each cement clinker was pulverized at 200 rpm for 1 hour by using a ball mill to obtain a 0% asbestos hydraulic material as Example 1 and a 10% asbestos hydraulic material as Example 2. As a third embodiment, a hydraulic material having 20% asbestos is obtained. At this time, the hydraulic materials of Examples 1 to 3 did not show a dusting phenomenon considered to be caused by γ-2CaO · SiO ₂ (γ-C ₂ S) and the like. In this example, the hydraulic materials of Examples 1 to 3 were analyzed by an X-ray diffractometer. The result is shown in FIG. Further, the result of analyzing a commercially available ordinary Portland cement with an X-ray diffractometer is shown in FIG.

In this connection, in this example, the chemical composition of the waste material of the ceramic exterior material after the calcination treatment was as follows. However, asbestos is not contained in the waste material.
_{CaO: 30.2%, SiO 2:} 41.8%, Al 2 O 3: 12.3%, Fe 2 O 3: 3.7%, MgO: 1.1%, TiO 2: 0.6%, K 2 O: 0.6%, P 2 O 5: 0.2%, MnO: 0.06%, Na 2 O: 0.4%

  Table 1 shows the compounding ratios of the compositions in the hydraulic materials of Examples 1 to 3. In addition, in the hydraulic material of Example 2 and Example 3 to which asbestos was added, since iron oxide was contained in asbestos, iron oxide was not added.

  FIG. 1 also shows that the hydraulic materials of Examples 1 to 3 have a large arit composition ratio based on the peak intensity of Comparative Example 1 using ordinary Portland cement in which the contents of various minerals are known. In addition, it is recognized that a simple treatment of the waste material of the ceramic building material advantageously produces a hydraulic material containing a lot of arit.

  Further, in this example, the residual of asbestos in the hydraulic material of Example 3 obtained as described above was confirmed by confirming the peak of the hydraulic material with an X-ray diffractometer. The result is shown in FIG. The result of analyzing the asbestos raw material with an X-ray diffractometer is shown in FIG. In the present embodiment, in the analysis using an X-ray diffractometer, the hydraulic material of Example 3 was previously treated with an acid to remove the cement minerals and the like which are not necessary for the analysis and to clarify the analysis result. On the other hand, since the asbestos raw material of Comparative Example 2 hardly changed even after the acid treatment, it was analyzed with an X-ray diffractometer.

  From the results shown in FIG. 2, it is recognized that in the hydraulic material having 20% asbestos in Example 3, no asbestos peak was observed, and asbestos was lost by the firing treatment at 1300 ° C., It is also assumed that asbestos disappears in the hydraulic materials of Examples 1 and 2 in which the asbestos content is lower than the hydraulic material of Example 3.

Further, in the present embodiment, similarly to the embodiment 2, etc., the waste material of the ceramic-based exterior material, calcium carbonate and 10% asbestos are included, and the molar ratio of CaO / SiO ₂ : r is r = 2. Two of the mixtures adjusted to 5 were prepared, and one of the mixtures was subjected to the baking treatment at 1100 ° C., while the other mixture was subjected to the baking treatment at 1300 ° C., whereby the baking treatment was performed at 1100 ° C. as in Example 4. A hydraulic material and a hydraulic material fired at 1300 ° C. as Example 5 were obtained. Then, the hydraulic materials of Examples 4 and 5 were each analyzed by an X-ray diffractometer. The result is shown in FIG.

As shown in FIG. 3, the hydraulic material of Example 5 contains more arit (3CaO.SiO ₂ ) than the hydraulic material of Example 4, so that the CaO / SiO 2 ₂ molar ratio: by a mixture of r was adjusted to r = 2.5 to baked at 1300 ° C., be permitted to effectively generate Alit.

  Further, in this example, after each of the hydraulic materials of Examples 1 to 3 was wet-mixed and stirred with various admixture materials shown in Table 2, dehydration and press molding were performed to obtain three types of molded articles. . Further, after holding these molded bodies at 40 ° C. for 8 hours for initial curing, the temperature was raised to 80 ° C. and pre-cured under the conditions of holding for 16 hours, whereby the molded bodies of Examples 1 ′ to 3 ′ were obtained. obtain. Then, the bending strengths of the molded bodies of Examples 1 'to 3' were measured. Table 3 shows the results. Further, using the ordinary Portland cement of Comparative Example 1, a molded article was produced under the same conditions as in Examples 1 'to 3', and the bending strength of the molded article was measured. The results are shown in Table 3 as Comparative Example 1 '. In addition, the bending strength in this example is a three-point bending strength performed under the following conditions, and is represented by the following equation.

"Test condition"
Span: 100mm
Sample size (length x width x thickness): 160 x 40 x 12 mm
Test speed: 2mm / min
"formula"
k = 3 × s × m / (2 × h × w ² )
k: Bending strength (MPa)
s: Span (mm)
m: Flexural breaking load (N)
h: Width (width) (mm)
w: thickness (mm)
In addition, in the present embodiment, generally, if the bending strength is 1.5 MPa or more, the strength required for the production line is secured.

  From the results shown in Tables 2 and 3, the hydraulic materials of Examples 1 'to 3' were also compared with Comparative Example 1 'even when the same amount of cement as Comparative Example 1' was added to the molded body. Although the strength is somewhat inferior, it is recognized that the initial strength required for the molded body can be sufficiently secured.

  In the present embodiment, the molded bodies of Examples 1 ″ to 3 ″ were subjected to high-temperature and high-pressure curing under the conditions of holding at 170 ° C. for 4 hours to cure the molded bodies of Examples 1 ″ to 3 ″. Get the body. Then, the bending strengths of Examples 1 "to 3" were measured under the same conditions as in the bending test of the molded articles of Examples 1 'to 3'. Table 4 shows the results. Further, using the molded body of Comparative Example 1 ', a molded body was produced under the same conditions as in Examples 1 "to 3", and the bending strength was measured. The results are shown in Table 4 as Comparative Example 1 ″.

  From these results, the molded articles of Examples 1 ′ to 3 ′ exhibit sufficient initial strength that can withstand a high-temperature and high-pressure atmosphere, and further reaction proceeds in this curing stage, and more effective strength is obtained. It is clear that the molded articles of Examples 1 ″ to 3 ″ having the above are realized, and thus, in the production of ceramic products and the like, the hydraulic material produced according to this example has excellent practical performance. It is presumed that it can be demonstrated.

  Although it is not the purpose of the present invention to clarify such technical reasons, for example, in the production of ceramic products, etc., in the case of ordinary cement, since hydration proceeds mainly in arit, gelation proceeds, While the reaction in high-temperature and high-pressure curing with other admixtures is hindered, the hydraulic material of this example has a little less arit than ordinary cement, but has a good gelation balance during hydration, It is presumed that the reactivity between the hydraulic material and the admixture material is further improved in the high-temperature and high-pressure curing, and a high strength product is realized.

Furthermore, in this example, the hydraulic material obtained in Example 1 was kneaded with water and standard sand, demolded after one day (one day old), and subjected to steam curing at 65 ° C. for 24 hours. Thus, a molded body A is obtained. Then, a compression strength test was performed on the molded body A in accordance with JIS R5201, thereby measuring the compression strength. As a result, a strength of 24.3 N / mm ² was confirmed. In addition, as manufacturing conditions of the molded object A, the hydraulic material is 445 parts by weight, the standard sand is 1350 parts by weight, and the water is 225 parts by weight.

Furthermore, in the present embodiment, the above-mentioned molded article A is steam-cured at 180 ° C. for 8 hours to obtain a molded article A ′. Then, a compression strength test was performed on the molded article A ′ in accordance with JIS R5201, thereby measuring the compression strength. As a result, a strength of 59.8 N / mm ² was confirmed.

  Next, several examples in the case of producing a hydraulic material using a main raw material containing asbestos will be described below. In addition, in each of the following Examples, in order to compare the asbestos content in the main raw material, instead of the asbestos-containing waste material, a material obtained by adding asbestos to an asbestos-free waste material in an appropriate amount was mainly used. Used as raw material.

  First, limestone as an auxiliary component containing calcium, iron oxide which promotes the reaction, and the like were added to the main raw material containing asbestos in appropriate amounts, thereby obtaining a raw material whose components before firing were adjusted. In such a raw material, by adjusting the blending amount of asbestos in the main raw material in consideration of the blending amount of waste materials and auxiliary components constituting the main raw material, the asbestos content is reduced at the stage of the raw material in which the component is adjusted before firing. As shown in the following [Table 5] and [Table 6], those prepared from 1.8% by weight to 6.9% by weight were prepared.

  Further, as shown in [Table 7], when the asbestos content in the main component (waste material + asbestos) was set to be as large as 20% by weight, the raw material to which fly ash of the same weight as the waste material was added was also used. Prepared.

Further, in each of these asbestos-containing waste materials (main raw materials), as shown in the following [Table 5], [Table 6], and [Table 7], the ratio of CaO and SiO ₂ forming an arit is all low. And the molar ratio was such that C / S = approximately 3.25. Then, a baking treatment was performed using an electric furnace at a baking temperature of 1300 ° C. for 1 hour. As a result, Examples 6 to 11 shown in Tables 5 to 7 were obtained as hydraulic materials according to the present invention using the main raw materials having various asbestos contents.

  In this case, in order to confirm the effect of the intermediate pulverization after the preliminary calcination, the preliminary calcination and the intermediate pulverization were not performed in Examples 6 and 7; In Example 10 and Example 11, during the heat treatment (firing treatment) as described above, the material was temporarily removed at 700 ° C. in the middle to form a temporary calcination treatment, and the removed material was subjected to ball mill pulverization to apply stress for pulverizing asbestos. After the pulverization treatment, the mixture was put into an electric furnace again and subjected to a baking treatment under the same conditions (1300 ° C.). The pulverization by a ball mill was performed at a rotation speed of 200 rotations / minute for 20 minutes.

  The hydraulic materials of Examples 6 to 11 obtained as described above were analyzed by XRD, and as a result, the asbestos content in the raw material before calcining (after adding the auxiliary component to the main raw material) was 1 In the case of Example 6 at 2.8% by weight, peaks of f-CaO and f-MgO were not observed. In Example 7 in which the asbestos content in the raw material before the calcination was 2.7% by weight, the peaks of f-CaO and f-MgO were slightly detected.

  On the other hand, in Examples 8 to 10 in which calcination and pulverization were performed in the middle, in Example 8 in which the asbestos content in the raw material before calcination was 2.7% by weight, which is the same as in Example 7, f-CaO and f-CaO were also used. No MgO peak was observed. Also, in Examples 9 and 10 in which the asbestos content in the raw material before calcining was larger than that of Example 7 and was 3.5% by weight and 6.9% by weight, the peaks of f-CaO and f-MgO were also found. Was confirmed to be suppressed.

Further, in Example 11 in which the content of asbestos with respect to the waste material was set to be as large as that in Example 10, f-MgO was added by adding fly ash thereto.
No peak was observed, and the peak of f-CaO also sharply decreased.

  From the results of Examples 6 to 11, it is possible to suppress the asbestos content in the raw material before calcining to 2.7% by weight or less, so that the peak of f-MgO in XRD can be suppressed to about 0.10 or less. Therefore, it is very effective in maintaining the functionality of the obtained hydraulic material, and it is possible to provide a preliminary firing and an intermediate pulverization step after mixing the auxiliary component with the main raw material, thereby maintaining the functionality of the obtained hydraulic material. It was confirmed that the addition of fly ash was extremely effective when a main raw material having a large asbestos content was used. As a result, both f-CaO and f-MgO, which affect the functionality of the hydraulic material, can be effectively suppressed.

FIG. 2 is an X-ray diffraction diagram showing the results of analyzing the hydraulic materials obtained in Examples 1, 2, and 3 of the present invention with an X-ray diffractometer together with Comparative Example 1. FIG. 6 is an X-ray diffraction diagram showing, together with Comparative Example 2, a result of analyzing a hydraulic material obtained in Example 3 of the present invention obtained by acid treatment with an X-ray diffractometer. FIG. 4 is an X-ray diffraction diagram showing the results of analyzing the hydraulic materials obtained in Examples 4 and 5 of the present invention with an X-ray diffractometer.

Claims (15)

Using waste materials of ceramic building materials as main raw materials, adding auxiliary components containing calcium to the main raw materials, subjecting the mixture containing these main raw materials and auxiliary components to firing treatment to react the main raw materials with the auxiliary components A method for producing a hydraulic material, characterized by obtaining a hydraulic material containing arit and curing at room temperature. Wherein with the molar ratio of CaO / SiO ₂ is from 2.5 to 4.0 in the mixture, the production method of a hydraulic material according to claim 1 firing temperature is 1300-1400 ° C. in the baking process. The method for producing a hydraulic material according to claim 1 or 2, wherein a calcining treatment is performed on the waste material of the ceramic building material or the mixture as a pretreatment of the firing treatment. The method for producing a hydraulic material according to any one of claims 1 to 3, wherein the waste material of the ceramic building material contains asbestos, and the asbestos is used as a raw material of the hydraulic material. After adding the auxiliary component to the main raw material, while performing calcination by heating to a temperature at which the water of crystallization in the asbestos is separated, a stress for pulverizing the asbestos is supplied, and then the calcination treatment is performed. The method for producing a hydraulic material according to claim 4, which is applied. The amount of the asbestos contained in the ceramic building material as the main raw material is 2.7% by weight or less in a state before the preliminary firing after adding the auxiliary component to the main raw material. 3. The method for producing a hydraulic material according to 1.). When the amount of the asbestos contained in the ceramic building material as the main raw material exceeds 2.7% by weight in the state before the calcination after adding the auxiliary component to the main raw material, The method for producing a hydraulic material according to claim 4 or 5, wherein the content of the asbestos is adjusted to 2.7% by weight or less by adding fly ash to the mixture and mixing. The method for producing a hydraulic material according to any one of claims 1 to 7, wherein the waste material of the ceramic building material is subjected to a crushing treatment, and water is added during the crushing treatment. The waste material of the ceramic building material is subjected to a crushing process, and a wet pellet is obtained by performing a water injection process during the crushing process, and the pellet is used as the main raw material. Method for producing hydraulic material. The waste material of the ceramic building material is subjected to a pulverizing treatment, and after the pulverizing treatment, the waste material of the ceramic building material is packaged with an organic packaging material and mixed with the auxiliary component to obtain the mixture. The method for producing a hydraulic material according to any one of the above. Using waste materials of ceramic building materials as main raw materials, adding auxiliary components containing calcium to the main raw materials, subjecting the mixture containing these main raw materials and auxiliary components to firing treatment to react the main raw materials with the auxiliary components A hydraulic material, which is produced by allowing to cure at room temperature and contains arit. A ceramic admixture using the hydraulic material according to claim 11. A ceramic product manufactured by performing high-temperature and high-pressure curing using the hydraulic material according to claim 11. A ceramic product manufactured using the ceramic admixture according to claim 12. A waste material of a ceramic building material is subjected to a crushing process and a water injection process to form a lump, and is used as the main raw material in the method for producing a hydraulic material according to any one of claims 1 to 10. Features wet pellets.

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