Method for manufacturing cement-containing hydrophobic materials

Abstract

To solve the problem that it is difficult to control drying shrinkage cracking when kneading into a building structure because, even after combustion removal of an organic matter and removal of hydration water retained by CSH through thermal treatment of a particulate matter of a cement-containing material, it absorbs moisture in the air again.SOLUTION: The present invention has found that thermal treatment at a temperature of 900°C or higher while supplying a support combustible gas to a particulate matter of a cement-containing material mixed with an organic matter not only can remove the organic matter by combustion but also can reduce surface hydrophilicity and reduce moisture absorption. Accordingly, a unit water content of concrete can be reduced, and cracks associated with drying shrinkage can be suppressed. Furthermore, the present invention can be used in applications requiring low moisture absorption, such as a filler for a plastic molded product or an insulating powder used in an electrical / electronic component.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a method for producing a cement-containing hydrophobic material that can be used as a filler or aggregate. [Background technology]

[0002] (Regarding cement-containing materials) The main cement-containing materials that make up concrete, mortar, or ceramic siding used in the exterior walls and landscaping of buildings are made by adding fibrous raw materials, admixtures, and water to cement, and then molding and solidifying it into any desired shape.

[0003] The aforementioned cement contains inorganic components such as tricalcium silicate (alite, 3CaO·SiO2), dicalcium silicate (belite, 2CaO·SiO2), and calcium hydroxide (Ca(OH)2). These react with water to form cement hydrate (hereinafter referred to as CSH), which then hardens. In addition, the cement-containing material retains moisture from surface adsorbed water as well as water coagulated in the fine voids of CSH, and the amount of moisture retained changes reversibly depending on the relative humidity.

[0004] (Regarding the recycling of cement-containing materials) On the other hand, cement-containing materials are mixed with organic matter to provide functionalities such as improved mechanical strength, reduced weight, and enhanced water retention, as well as to enhance design. After such cement-containing materials are installed in buildings, the cement-containing materials generated during the demolition of buildings, or the scraps and powders generated during pre-cutting at factories, pose a pressing need for the establishment of technologies to reuse them, given the difficulty in securing landfill space for disposal and the need for effective resource utilization. However, in the case of cement-containing materials, especially ceramic siding, the proportion of organic matter is high, and separating CSH from organic matter is difficult. As a result, currently, they are hardly reused and are instead disposed of in landfills as industrial waste.

[0005] From such a background, as a method for recycling ceramic siding, which has been difficult to recycle due to its high organic content, a technique has been proposed in which combustible gas is introduced while heating at 500 to 600 °C to simultaneously remove organic substances by combustion and remove the water of hydration retained by CSH. For example, Patent Document 1 and Patent Document 2, etc. That is, it is also proposed that the water of hydration can be removed from CSH by heat treatment of the ceramic siding powder particles, and the moisture content can be reduced.

[0006] Also, according to Patent Document 1 and Patent Document 2, it has been proposed that for a cement-containing material from which organic substances have been removed, by mixing it as an aggregate when manufacturing concrete or mortar, it can contribute to suppressing heat generation during hardening and reducing manufacturing costs.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, even if organic substances are removed by combustion by heat treatment of the powder particles of the cement-containing material and the water of hydration retained by CSH is removed, since it absorbs moisture in the air again, it is often difficult to suppress drying shrinkage cracks even when used for building structures. From the above, there is a demand for powder particles of a cement-containing material with low surface hydrophilicity (high surface hydrophobicity) and a small amount of moisture absorption.

[0009] Therefore, in view of the above-mentioned problems, the present invention aims to provide a method for producing a cement-containing hydrophobic material that modifies the surface to be hydrophobic in order to suppress drying shrinkage cracks when used cement-containing material powder or granules are reused in concrete, mortar, or ceramic siding, and that maintains the aforementioned hydrophobicity for a long period of time. [Means for solving the problem]

[0010] Means 1 for achieving the above objective are: A method for efficiently heating a cement-containing material containing organic matter at a concentration of 50 wt.% or less in powder form, while supplying a combustion-supporting gas, within a temperature range of 900°C to 1200°C. The method for producing cement-containing hydrophobic material involves adjusting the feed rate within an appropriate range depending on the type of combustion-supporting gas. Specifically, when the combustion-supporting gas is air, the feed rate (mL / min) is in the range of 100 aW / T to 900 aW / T; when the combustion-supporting gas is selected from oxygen, ozone, or nitrogen dioxide, the feed rate (mL / min) is in the range of 20 aW / T to 180 aW / T; and when the combustion-supporting gas is selected from nitrous oxide or nitric oxide, the feed rate (mL / min) is in the range of 40 aW / T to 360 aW / T. In this method, W represents the weight (g) of the ceramic siding, a represents the weight percentage (wt.%) of organic matter contained in the ceramic siding, and T represents the heat treatment time (minutes). In other words, considering the effects and benefits, this invention is based on a completely different perspective from the prior art. By burning and heating the granular material in a manner that does not significantly deform its shape, the contained organic matter is burned and removed. As a result, this invention provides a method for producing a cement-containing hydrophobic material from which organic matter has been removed, at least from the surface of the granular material.

[0011] This method 1 was discovered through various experiments to recycle cement-containing materials, and by pursuing how to reduce the hydrophilicity of the surface of the powdered granules of cement-containing materials in a very simple way, the resulting invention is a method for manufacturing cement-containing hydrophobic materials. When cement-containing hydrophobic materials manufactured in this way are reused and used to make concrete, the unit water content can be reduced, and cracking due to drying shrinkage can be suppressed. Furthermore, it can be provided as a material that requires low hygroscopicity, such as insulating powder or filler for plastic molded products. Moreover, when the surface is made hydrophobic by the heat treatment in this invention, it is not necessary to use commonly used processing agents. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a method for producing a cement-containing hydrophobic material in which at least the surface of the powder or granules of the cement-containing material is made hydrophobic, and the hydrophobicity is maintained for a long period of time.

[0013] Furthermore, the heat-treated cement-containing material powder obtained by this invention can be molded into any shape by compression. For this reason, it can be used in applications such as exterior wall materials that are resistant to dirt, and moisture-proof and waterproof panels that suppress the penetration of moisture into the interior. Moreover, this invention can contribute to the effective utilization of cement-containing materials such as concrete, mortar, and ceramic siding that have been discarded until now, thereby reducing the amount of construction waste.

[0014] (Other means to solve the problem) In means 2 for achieving the above objective, In the aforementioned method 1, the granular material containing cement is a cement-containing hydrophobic material that contains at least one of the following: ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, moderate-heat Portland cement, low-heat Portland cement, sulfate-resistant Portland cement, blast furnace cement, silica cement, fly ash cement, and eco-cement.

[0015] According to the invention of the above-described method 2, it is possible to provide a method for producing a cement-containing hydrophobic material that is applicable to all types of Portland cement, enhances the hydrophobicity of the surface, and allows the hydrophobicity to be maintained for a long period of time.

[0016] Also, Means for achieving the above objective 1 Therefore, a method for producing a cement-containing hydrophobic material can be provided, wherein the aforementioned combustion-supporting gas contains at least one type from the group consisting of air, oxygen, ozone, nitrous oxide, nitric oxide, and nitrogen dioxide. 1 According to the report, heating can be efficiently achieved using various gases, including air. In particular, air can be used as is, keeping costs low. Furthermore, if any of the following atmospheres are available, oxygen, ozone, nitrous oxide, nitric oxide, or nitrogen dioxide, they can be used as is.

[0017] Furthermore, In the aforementioned method 1, if W is the weight of the ceramic siding (g), a is the weight percentage of organic matter contained in the ceramic siding (wt.%), and T is the heat treatment time (minutes), then a method for producing a cement-containing hydrophobic material can be provided in which the feed rate is in the range of 100 aW / T to 900 aW / T when the selected combustion-supporting gas is air, the feed rate is in the range of 20 aW / T to 180 aW / T when the selected combustion-supporting gas is oxygen, ozone, or nitrogen dioxide, and the feed rate is in the range of 40 aW / T to 360 aW / T when the selected combustion-supporting gas is nitrous oxide or nitric oxide. According to this method 1, the present invention can be carried out in various environments while making use of the combustion-supporting gas present therein.

[0018] Thus, the present invention can contribute to the effective utilization of cement-containing materials such as concrete, mortar, and ceramic siding that have been discarded until now, and will also lead to a reduction in the amount of construction waste. [Brief explanation of the drawing]

[0019] [Figure 1] This diagram schematically represents a heat treatment apparatus used for heat treatment of cement-containing molded products, specifically one that uses air as the combustion-supporting gas. [Figure 2] This diagram schematically represents a heat treatment apparatus used for heat treatment of cement-containing molded products, specifically one that utilizes a combustion-supporting gas other than air. [Modes for carrying out the invention]

[0020] This invention relates to a heat treatment process that involves supplying a combustion-supporting gas while heat-treating at a temperature of 900°C or higher. This process not only burns and removes organic matter but also modifies the surface to be hydrophobic, further reducing moisture absorption. Moreover, it has been found that this reduction in surface hydrophilicity and moisture absorption can be sustained over a long period of time.

[0021] A preferred embodiment of the method for producing a cement-containing hydrophobic material according to the present invention will be described below. Note that the embodiments described below do not limit the scope of the present invention as defined in the claims.

[0022] (Types of cement) The types of cement contained in the powder or granules of the cement-containing material applicable to the present invention will be described. First, ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, moderate-heat Portland cement, low-heat Portland cement, sulfate-resistant Portland cement, blast furnace cement, silica cement, fly ash cement, eco-cement, etc. are preferred. Ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, moderate-heat Portland cement, low-heat Portland cement, and sulfate-resistant Portland cement are more preferred. Ordinary Portland cement is the most preferred. On the other hand, Portland cements such as ordinary Portland cement and rapid-hardening Portland cement have the least variation in composition between lots and offer the best handling properties.

[0023] (Suitable size for cement-containing material) The size of the cement-containing material of the present invention is such that it can pass through a sieve with a nominal mesh size of 32 μm as specified in JIS Z8801. without , passing through a sieve with a nominal mesh opening of 2 mm do The size is preferable, and it passes through a sieve with a nominal mesh opening of 45 μm. without , passing through a sieve with a nominal mesh opening of 1 mm do A larger size is preferable. Furthermore, it should pass through a sieve with a nominal mesh size of 63 μm. without It passes through a sieve with a nominal mesh size of 106 μm. do The size is most preferable. If the material is large enough to pass through a sieve with a nominal mesh size of 32 μm, it is prone to scattering, making it difficult to handle and raising concerns that it may get into gaps in parts used in heat treatment equipment, potentially causing equipment failure. On the other hand, if the material is too large to pass through a sieve with a nominal mesh size of 2 mm, there is a concern that the inside of the cement-containing material's powder granules may not be sufficiently hydrophobic, and there is also a concern that the moldability in compression molding may be reduced.

[0024] (Types of organic matter mixed into the powdered or granular material of cement) The organic materials mixed in the granular cement-containing material of the present invention include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyvinyl chloride, polyvinyl acetate, polycarbonate, phenolic resin, acrylic, acrylonitrile-butadiene-styrene copolymer, polyacetal, polyphenylene ether, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polyphenylene sulfide, polyvinylidene chloride, polytetrafluoroethylene, and polymethyl methacrylate. The material contains one or more of the following: ethylene-vinyl acetate copolymer, polyurethane, polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, styrene-butadiene rubber, silk, wool, feathers, wood, cotton, hemp, lyocell, Tencel, pulp, rayon, cupro, acetate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, glyceric acid, tartaric acid, malic acid, tartaric acid, citric acid, salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, trovaic acid, etc. These organic substances are removed by thermal decomposition through heat treatment at 900°C or higher, so even if they are contained in the powder or granules of the cement-containing material, they do not affect the surface hydrophobicity after heat treatment. These organic substances may be mixed into the cement-containing material beforehand, or added during compression molding.

[0025] (Proportion of organic matter mixtures) The proportion of organic matter in the cement-containing material of the present invention is preferably 50 wt.% or less, more preferably 35 wt.% or less, and most preferably 25 wt.% or less. If the proportion of organic matter in the cement-containing material exceeds 50 wt.%, there is a concern that a large amount of tar generated during heat treatment will remain, making cleaning and other operations complicated.

[0026] (Overview of the heat treatment process for cement-containing molded products) This document outlines the heat treatment process for the cement-containing material molded product of the present invention. In the heat treatment process, the ceramic siding is heat-treated at 900°C or higher while supplying a combustion-supporting gas. However, the temperature is not allowed to exceed 1200°C. This promotes the thermal decomposition and removal of organic matter contained in the powder and granules of the cement-containing material, as well as the dehydration of the hydration water of CSH. The heat treatment process is described in detail below.

[0027] The cement-containing molded product is heat-treated using a heat treatment apparatus as schematically shown in Figure 1. Specifically, the cement-containing molded product 1 is placed inside a quartz tube 2. When air is used as the combustion-supporting gas, air is supplied from a compressor 3 to the quartz tube 2 through piping 4. A heat supply device 5 is used to raise the temperature, and the temperature inside the quartz tube 2 is monitored by a thermocouple 6 and a temperature controller 7. The temperature controller 7 and the heat supply device 5 are connected by wiring 8, and when the temperature inside the quartz tube 2 reaches a predetermined temperature, the heat supply from the heat supply device 5 stops.

[0028] Furthermore, in order to prevent the cement-containing material molded product 1 from moving due to the combustion-supporting gas during heat treatment and being released outside the quartz tube 2, quartz wool 9a and quartz wool 9b are placed inside the quartz tube 2.

[0029] Furthermore, in order to ensure that all the air from the compressor 3 is introduced into the quartz tube 2, the quartz tube 2 and the piping 4 are connected by a stopper 10 made of heat-resistant material. In addition, the flow rate of the combustion-supporting gas is regulated by a mass flow controller 11.

[0030] If a gas other than air is used as the combustion-supporting gas, a pressure regulator 12 and a high-pressure gas cylinder 13 filled with the combustion-supporting gas should be connected to the piping 4 instead of the compressor 3, as schematically shown in Figure 3.

[0031] (Heat treatment temperature) The heat treatment temperature for the powdered cement-containing material of the present invention is preferably 900°C or higher and 1200°C or lower, more preferably 900°C or higher and 1000°C or lower, and most preferably 900°C or higher and 950°C or lower. Below 900°C, there is a high possibility that the surface of the powdered cement-containing material will not be sufficiently hydrophobic after heat treatment, and the surface hydrophobicity may decrease (become hydrophilic) due to repeated wetting and drying. Furthermore, at temperatures higher than 1200°C, the cement component may melt, and the shape of the powdered material may not be maintained.

[0032] (Heat treatment time) In this invention, the heat treatment time is preferably 15 minutes or more and 60 minutes or less, more preferably 20 minutes or more and 40 minutes or less, and most preferably 25 minutes or more and 35 minutes or less. If the heat treatment time is less than 15 minutes, there is a concern that organic matter and moisture will not be sufficiently burned off, or that the hydrophobicity of the surface will not progress sufficiently. Furthermore, if the heat treatment time is longer than 60 minutes, no change will be observed in the combustion and removal of organic matter or the hydrophobicity of the surface, and the industrial significance will be diminished.

[0033] (Heat source of heat supply device 5) For the heat treatment of the cement-containing material powder of the present invention, electric, gas boilers using city gas or LPG, or liquid fuel boilers using kerosene or heavy oil are all preferably used, but heat treatment by electricity is most preferred. This is because the temperature rise of the molded product of the cement-containing material is uniform.

[0034] (Types of combustion-supporting gases) The combustion-supporting gas of the present invention is preferably air, oxygen, ozone, nitrous oxide, nitric oxide, or nitrogen dioxide, more preferably air and oxygen, and most preferably air. This is because air can be easily supplied using a compressor, is easy to handle, and is low-cost. Oxygen is relatively easy to obtain and can efficiently remove organic matter in ceramic siding through thermal decomposition, making it the next most preferred option after air. Furthermore, although ozone, nitrous oxide, nitric oxide, and nitrogen dioxide are corrosive gases and pose a risk of corrosion to metal components of the heat treatment device, they have the advantage of being able to remove organic matter in ceramic siding through thermal decomposition more efficiently than air. The above combustion-supporting gases may be supplied individually or as a mixture of two or more types.

[0035] (Amount of combustion-supporting gas supplied during the heat treatment process) The amount of combustion-supporting gas supplied during the heat treatment process is determined by the weight of the granular material containing the cement, the weight percentage of organic matter contained in the granular material containing the cement, and the heat treatment time.

[0036] When air is used as the combustion-supporting gas in the heat treatment process, the combustion-supporting gas supply rate preferably satisfies the following equation 1. Here, A represents the combustion-supporting gas supply rate (mL / min), W represents the weight of the cement-containing material powder (g), a represents the weight percentage of organic matter contained in the cement-containing material powder (wt.%), and T represents the heat treatment time (minutes).

[0037]

number

[0038] The air supply rate is preferably 100 aW / T to 900 aW / T, more preferably 200 aW / T to 700 aW / T, and most preferably 400 aW / T to 500 aW / T. If the combustion-supporting gas supply rate is less than 100 aW / T, there is a concern that organic matter will not be completely combusted and will not be sufficiently removed. On the other hand, if it is more than 900 aW / T, there is no difference in the effect of removing organic matter, surface hydrophilicity, or hygroscopicity, but there is a concern that the energy required to heat the combustion-supporting gas itself will increase, leading to increased processing costs.

[0039] Furthermore, when using oxygen, ozone, or nitrogen dioxide as the combustion-supporting gas in the heat treatment process, it is preferable that the combustion-supporting gas supply rate satisfies the following equation 2. Note that, as in equation 1, A represents the combustion-supporting gas supply rate (mL / min), W represents the weight of the cement-containing material powder (g), a represents the weight percentage of organic matter contained in the cement-containing material powder (wt.%), and T represents the heat treatment time (minutes).

[0040]

number

[0041] In this case, the supply rate of the combustion-supporting gas is preferably 20 aW / T or more and 180 aW / T or less, more preferably 60 aW / T or more and 140 aW / T or less, and most preferably 80 aW / T or more and 100 aW / T or less. If the supply rate of the combustion-supporting gas is less than 20 aW / T, there is a concern that organic matter will not be completely combusted and will not be sufficiently removed. On the other hand, if it is more than 180 aW / T, no difference is observed in the effect of removing organic matter, surface hydrophilicity, or hygroscopicity, and the industrial significance becomes weak.

[0042] Furthermore, when using either nitrous oxide or nitric oxide as the combustion-supporting gas in the heat treatment process, it is preferable that the combustion-supporting gas supply rate satisfies the following equation 3. Note that, as in equation 1, A represents the combustion-supporting gas supply rate (mL / min), W represents the weight of the cement-containing material powder (g), a represents the weight percentage of organic matter contained in the cement-containing material powder (wt.%), and T represents the heat treatment time (minutes).

[0043]

number

[0044] In this case, the supply rate of the combustion-supporting gas is preferably 40 aW / T or more and 360 aW / T or less, more preferably 80 aW / T or more and 240 aW / T or less, and most preferably 120 aW / T or more and 150 aW / T or less. If the supply rate of the combustion-supporting gas is less than 40 aW / T, there is a concern that organic matter will undergo incomplete combustion and will not be sufficiently removed. On the other hand, if it is more than 360 aW / T, no difference is observed in the effect of removing organic matter, surface hydrophilicity, or hygroscopicity, and its industrial significance becomes weak.

[0045] (Formation of powders and granules in cement-containing materials after heat treatment) The granular form of the cement-containing material after heat treatment can be molded into any shape by compression molding or other methods. Furthermore, depending on the application, colorants such as dyes and pigments, and functional substances such as antibacterial agents and fragrances may be mixed into the granular form of the heat-treated cement-containing material. [Examples]

[0046] The following examples illustrate and will be explained in more detail how to obtain a suitable molded powder or granule of cement-containing material after heat treatment. Note that these examples are provided to illustrate the present invention in detail and should not be considered limiting.

[0047] [Example 1] (Powdered and granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a suitable size was used. Furthermore, qualitative analysis of the organic matter contained in the cement-containing material used in this example was performed by pyrolysis GC / MS analysis, and raw cotton and styrene-butadiene rubber were detected.

[0048] (Comparative sample) Limestone is used as a low-water-absorbent aggregate (hereinafter referred to as low-water-absorbent aggregate) for the purpose of suppressing drying shrinkage cracks in building structures. Therefore, as a comparative sample, it passes through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do We used limestone (manufactured by Yoneyama Pharmaceutical Co., Ltd.) that had been crushed to the required size.

[0049] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, thermogravimetric analysis was performed on the granular cement-containing material using a thermogravimetric differential thermal analyzer (MAC Science, DTM-2000) under the conditions of a temperature range from room temperature to 600°C and a heating rate of 10°C / min. The weight percentage of organic matter was calculated using the following four equations. Note that a is the weight percentage (wt.%) of organic matter contained in the granular cement-containing material, and W is the weight percentage of organic matter. R600 These represent the weight retention rate (wt.%) at 600°C when performing thermogravimetric analysis of the powdered or granular material containing cement.

[0050]

number

[0051] Thermogravimetric analysis revealed that the weight retention rate at 600°C was 75.3 wt.%, indicating that the weight percentage of organic matter contained in the powdered granules of the cement-containing material was 24.7 wt.

[0052] (Preparation of powders and granules in cement-containing materials involving heat treatment) 0.52 g of granular cement-containing material was placed inside the quartz tube 2 of the heat treatment apparatus shown in Figure 1. The diameter of the quartz tube 2 was 20 mm and the furnace length was 300 mm. A horizontal electric ring furnace (Koyo Co., Ltd., KTF030N1) was used as the heat supply device 16, and heat treatment was performed at 900°C for 30 minutes while supplying air as a combustion-supporting gas at 180 ml / min. After heat treatment, it was allowed to cool naturally to room temperature, and this was the granular cement-containing material after heat treatment in this embodiment.

[0053] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the resulting heat-treated cement-containing material powder and the inside of the heat-treated quartz tube 2 was evaluated based on the five-point scale shown in Table 1.

[0054] [Table 1]

[0055] (Appearance evaluation) When the granular material of the cement-containing material obtained in this embodiment after heat treatment was evaluated for its appearance, it received a rating of 5.

[0056] (Weight retention rate of cement-containing material in powder form after heat treatment) Thermogravimetric analysis of the heat-treated cement-containing material powder obtained in this embodiment showed that the weight retention rate at 600°C was 99.8%. This confirmed that the heat-treated cement-containing material powder in this embodiment contained almost no organic matter.

[0057] (Calculation of N2 specific surface area) In this embodiment, the powdered cement-containing material obtained after heat treatment and a multi-sample gas adsorption measurement device (Anton Paar, Autosorb-iQ2-XR-VP) were used to perform adsorption isotherm measurements at liquid nitrogen temperature with nitrogen as the adsorbed gas species. Furthermore, the specific surface area was calculated from the nitrogen adsorption amounts at relative pressures of 0.1, 0.2, and 0.3 using the BET method, and this was defined as the N2 specific surface area. In addition, the N2 specific surface area was calculated for the powdered cement-containing material before heat treatment and for limestone as comparative samples.

[0058] (Water vapor adsorption isotherm measurement and calculation of H2O specific surface area) For the heat-treated cement-containing material powder obtained in this embodiment, adsorption isotherm measurements were performed at 25°C using the multi-sample gas adsorption amount measuring device described above, with water vapor as the adsorbed gas. The relative pressure range was set to 0 to 0.9, and the amount of water vapor adsorbed was measured at 0.05 relative pressure intervals. Furthermore, the specific surface area was calculated from the amount of water vapor adsorbed at relative pressures of 0.1, 0.2, and 0.3 using the BET method, and this was defined as the H2O specific surface area. In addition, the H2O specific surface area was calculated for the cement-containing material powder and limestone as comparative samples.

[0059] (Evaluation of surface hydrophilicity in granular cement-containing materials) To evaluate the surface hydrophilicity of the granular material in the heat-treated cement-containing material obtained in this embodiment, the specific surface area of ​​N2 was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C. The value obtained by dividing the specific surface area of ​​H2O by the specific surface area of ​​N2 (hereinafter referred to as H2O specific surface area / N2 specific surface area) was used as the surface hydrophilicity index of the granular material in the heat-treated cement-containing material.

[0060] (Specific surface area of ​​N2 in granular cement-containing materials) First, regarding the granular cement-containing material before heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and it was found to be 20.7 m². 2 It was / g.

[0061] (Specific surface area of ​​H2O in granular cement-containing materials) Furthermore, when the specific surface area of ​​H2O in the granular material containing cement was calculated from the water vapor adsorption isotherm at 25°C, it was found to be 106.0 m². 2 It was / g.

[0062] (Surface hydrophilicity index of granular materials containing cement) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the powdered material containing cement before heat treatment was 5.12.

[0063] (Specific surface area of ​​N2 in limestone) Furthermore, regarding limestone, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and it was found to be 1.7 m². 2 It was / g.

[0064] (Specific surface area of ​​H2O in limestone) Furthermore, when the specific surface area of ​​H2O in the granular material containing cement was calculated from the water vapor adsorption isotherm at 25°C, it was found to be 1.5 m². 2 It was / g.

[0065] (Surface hydrophilicity index of limestone) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the granular material containing cement before heat treatment was 0.88.

[0066] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) On the other hand, when the N2 specific surface area of ​​the granular material containing heat-treated cement obtained in this embodiment was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, it was found to be 2.0 m². 2 It was / g.

[0067] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular material containing heat-treated cement obtained in this embodiment, it was found to be 1.7 m². 2 It was / g.

[0068] (Surface hydrophilicity index of the powder of the cement-containing material after heat treatment) From this, the H2O specific surface area / N2 specific surface area of the powder of the cement-containing material after heat treatment obtained in this example was 0.85.

[0069] (Water vapor adsorption amount in a humid environment) The water vapor adsorption amounts per 1 g of the powder of the cement-containing material before heat treatment, limestone, and the powder of the heat-treated cement-containing material obtained in this example at a relative humidity of 90% were 90.3 mg, 1.9 mg, and 1.8 mg, respectively.

[0070] (Dry-wet repeated treatment) To evaluate the changes in the N2 specific surface area and H2O specific surface area of the powder of the cement-containing material after heat treatment by repeating drying and wetting, a thermo-hygrostat (manufactured by Tokyo Rika Kikai Co., Ltd., KCL-2000W) was used, and after standing for 12 hours under dry conditions of 25°C and a relative humidity of 40%, standing for 12 hours under wet conditions of 40°C and a relative humidity of 90% was taken as one cycle, and this cycle was repeated 180 times (180 days).

[0071] (N2 specific surface area and H2O specific surface area of the powder of the cement-containing material after heat treatment after dry-wet repeated treatment) After measuring the N2 specific surface area and H2O specific surface area of the powder of the heat-treated cement-containing material obtained in this example after 180 cycles of dry-wet repeated treatment, they were 2.0 m 2 / g and 1.8 m 2 / g, respectively.

[0072] (Evaluation criteria) 1) Regarding the appearance of the powder of the cement-containing material after heat treatment, it was determined that the standard was met if it was 4 or more in the five-level evaluation shown in Table 1. 2) If the H2O specific surface area / N2 specific surface area ratio, which is the surface hydrophilicity index of the granular cement-containing material after heat treatment, is lower than the H2O specific surface area / N2 specific surface area ratio of the granular cement-containing material before heat treatment (5.12), it indicates that the surface hydrophilicity has decreased due to heat treatment, that is, the surface hydrophobicity has increased. However, considering its use as an aggregate to suppress drying shrinkage cracks in concrete, as well as as an insulating powder and a filler for plastic molded products, the standard for the surface hydrophilicity index is set at a value of less than 1.05 for the H2O specific surface area / N2 specific surface area ratio of the granular cement-containing material after heat treatment. Note that a value of 1.05 is equivalent to 1.2 times the H2O specific surface area / N2 specific surface area ratio of limestone (0.88). 3) If the amount of water vapor adsorbed per gram of heat-treated cement-containing material at 90% relative humidity is smaller than the amount of water vapor adsorbed per gram of the powder-containing material before heat treatment at 90% relative humidity (90.3 mg), it indicates that the hygroscopicity has decreased due to the heat treatment. However, considering its use as an aggregate to suppress drying shrinkage cracks in concrete, as an insulating powder, and as a filler for plastic molded products, the standard for water vapor adsorption was set at less than 2.28 mg per gram of heat-treated cement-containing material at 90% relative humidity. Note that the value of 2.28 mg is equivalent to 1.2 times the amount of water vapor adsorbed per gram of limestone at 90% relative humidity (1.9 mg). 4) If the increase rate of N2 specific surface area and the increase rate of H2O specific surface area due to 180 cycles of wet-dry treatment are both less than 10% of the initial value before the wet-dry treatment, the criteria for the change in N2 specific surface area and H2O specific surface area due to wet-dry treatment are met. A comprehensive evaluation was given as "suitable" when all of the above evaluation criteria 1) to 4) were met. Furthermore, meeting all of these evaluation criteria demonstrates that, although it is a recycled material, it is an excellent material that can be used as a filler or aggregate.

[0073] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material obtained in this embodiment was 0.166 times that of the untreated cement-containing material and 0.966 times that of limestone. Furthermore, the amount of water vapor adsorbed by the heat-treated cement-containing material at a relative humidity of 90% was 0.020 times that of the untreated cement-containing material and 0.947 times that of limestone. Thus, it is considered that the cement-containing material was sufficiently surface-hydrophobic by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0074] [Example 2] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, a qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and pulp was detected.

[0075] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the cement-containing material was calculated using the same method as in Example 1, and it was found to be 5.4 wt.%.

[0076] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.81 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that oxygen was used as the combustion-supporting gas, the combustion-supporting gas introduction rate was 10 ml / min, the heat treatment temperature was 1000°C, and the heat treatment time was 35 minutes.

[0077] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0078] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the granular cement-containing material heat-treated in this embodiment contained almost no organic matter.

[0079] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.8 m². 2 It was / g.

[0080] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this embodiment after heat treatment, it was found to be 1.5 m². 2 It was / g.

[0081] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the H2O specific surface area / N2 specific surface area of ​​the heat-treated cement-containing material obtained in this example was 0.83.

[0082] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.5 mg.

[0083] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder and granule material obtained in this example was carried out in the same manner as described in Example 1.

[0084] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O of the heat-treated cement-containing material obtained in this example was measured, and both were 1.9 m². 2 / g and 1.6m 2 It was / g.

[0085] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this embodiment was 0.163 times that of the untreated cement-containing material powder described in Example 1, and 0.947 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this embodiment was 0.017 times that of the untreated cement-containing material powder described in Example 1, and 0.789 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobic by the heat treatment according to this embodiment. Moreover, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0086] [Example 3] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and pulp was detected.

[0087] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 15.7 wt.%.

[0088] (Preparation of powdered or granular cement-containing materials through heat treatment) 1.22 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The combustion-supporting gas was nitrous oxide, and the combustion-supporting gas introduction rate was 50 ml / min, the heat treatment temperature was 1000°C, and the heat treatment time was 20 minutes. The preparation was carried out in the same manner as described in Example 1.

[0089] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0090] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.6%. From this, it was concluded that the granular cement-containing material heat-treated in this embodiment contained almost no organic matter.

[0091] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.8 m². 2 It was / g.

[0092] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the powdered material containing heat-treated cement obtained in this embodiment, it was found to be 1.5 m².2 It was / g.

[0093] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the H2O specific surface area / N2 specific surface area of ​​the heat-treated cement-containing material obtained in this example was 0.83.

[0094] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.5 mg.

[0095] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this example was carried out in the same manner as described in Example 1.

[0096] (Specific surface area of ​​N2 and H2O in granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 1.8 m², respectively. 2 / g and 1.5m 2 It was / g.

[0097] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the cement-containing material powder obtained in this embodiment after heat treatment was 0.163 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.947 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the cement-containing material powder obtained in this embodiment after heat treatment was 0.018 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.842 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobicized by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0098] [Example 4] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0099] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the cement-containing material was calculated using the same method as in Example 1, and it was found to be 24.9 wt.%.

[0100] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.55 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that oxygen was used as the combustion-supporting gas, the combustion-supporting gas introduction rate was 20 ml / min, and the heat treatment time was 60 minutes.

[0101] (Visual evaluation of granular cement-containing materials after heat treatment) In this embodiment, the appearance of the cement-containing material powder and granules after heat treatment, as well as the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0102] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.7%. From this, it was concluded that the granular cement-containing material obtained in this embodiment after heat treatment contained almost no organic matter.

[0103] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) In this embodiment, the N2 specific surface area of ​​the heat-treated cement-containing material was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 2.0 m². 2 It was / g.

[0104] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the heat-treated cement-containing material powder obtained in this embodiment, it was found to be 1.8 m². 2 It was / g.

[0105] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the H2O specific surface area / N2 specific surface area of ​​the heat-treated cement-containing material obtained in this example was 0.90.

[0106] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of the heat-treated cement-containing material at a relative humidity of 90% was 1.8 mg.

[0107] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder and granule material obtained in this example was carried out in the same manner as described in Example 1.

[0108] (Specific surface area of ​​N2 and H2O in granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 2.1 m², respectively. 2 / g and 1.9m 2 It was / g.

[0109] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the cement-containing material powder obtained in this embodiment after heat treatment was 0.176 times that of the cement-containing material powder before heat treatment described in Example 1, and 1.023 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the cement-containing material powder obtained in this embodiment after heat treatment was 0.020 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.947 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobicized by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0110] [Example 5] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0111] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 11.4 wt.%.

[0112] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.27 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 100 ml / min, the heat treatment temperature was 950°C, and the heat treatment time was 15 minutes.

[0113] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0114] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the granular cement-containing material obtained in this embodiment after heat treatment contained almost no organic matter.

[0115] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.9 m². 2 It was / g.

[0116] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the heat-treated cement-containing material powder obtained in this embodiment, it was found to be 1.6 m².2 It was / g.

[0117] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the H2O specific surface area / N2 specific surface area of ​​the heat-treated cement-containing material obtained in this example was 0.84.

[0118] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.7 mg.

[0119] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder and granule material obtained in this example was carried out in the same manner as described in Example 1.

[0120] (Specific surface area of ​​N2 and H2O in granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 1.9 m², respectively. 2 / g and 1.7m 2 It was / g.

[0121] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the cement-containing material powder obtained in this embodiment after heat treatment was 0.164 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.957 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the cement-containing material powder obtained in this embodiment after heat treatment was 0.019 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.895 times that of limestone. Thus, it was considered that the cement-containing material powder was sufficiently surface-hydrophobic by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0122] [Example 6] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and pulp was detected.

[0123] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 50.0 wt.%.

[0124] (Preparation of powdered or granular cement-containing materials through heat treatment) 2.11 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 360 ml / min and the heat treatment temperature was 1000°C.

[0125] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0126] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the granular cement-containing material obtained in this embodiment after heat treatment contained almost no organic matter.

[0127] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.7 m². 2 It was / g.

[0128] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the heat-treated cement-containing material powder obtained in this embodiment, it was found to be 1.4 m². 2 It was / g.

[0129] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, it was found that the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the granular material of the cement-containing material after heat treatment obtained in this example was 0.82.

[0130] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.5 mg.

[0131] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this example was carried out in the same manner as described in Example 1.

[0132] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 1.8 m², respectively. 2 / g and 1.5m 2 It was / g.

[0133] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this embodiment was 0.161 times that of the untreated cement-containing material powder described in Example 1, and 0.936 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this embodiment was 0.017 times that of the untreated cement-containing material powder described in Example 1, and 0.789 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobicized by the heat treatment according to this embodiment. Moreover, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0134] [Example 7] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton was detected.

[0135] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 10.9 wt.%.

[0136] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.53 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that oxygen was used as the combustion-supporting gas, the combustion-supporting gas introduction rate was 20 ml / min, and the heat treatment time was 45 minutes.

[0137] (Appearance evaluation of powdered or granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0138] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the granular cement-containing material obtained in this embodiment after heat treatment contained almost no organic matter.

[0139] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.9 m². 2 It was / g.

[0140] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the heat-treated cement-containing material powder obtained in this embodiment, it was found to be 1.8 m². 2 It was / g.

[0141] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this example was 0.95.

[0142] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.9 mg.

[0143] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this example was carried out in the same manner as described in Example 1.

[0144] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O of the heat-treated cement-containing material obtained in this example was measured, and both were found to be 2.0 m². 2 / g and 1.8m 2 It was / g.

[0145] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the cement-containing material powder obtained in this embodiment after heat treatment was 0.185 times that of the cement-containing material powder before heat treatment described in Example 1, and 1.077 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the cement-containing material powder obtained in this embodiment after heat treatment was 0.021 times that of the cement-containing material powder before heat treatment described in Example 1, and 1.000 times that of limestone. Thus, it was considered that the cement-containing material powder was sufficiently surface-hydrophobicized by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0146] [Example 8] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0147] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 25.1 wt.%.

[0148] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.52 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 300 ml / min, the heat treatment temperature was 950°C, and the heat treatment time was 20 minutes.

[0149] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0150] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the powdered cement-containing material obtained in this embodiment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the powdered cement-containing material in this embodiment after heat treatment contained almost no organic matter.

[0151] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.7 m². 2 It was / g.

[0152] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this embodiment after heat treatment, it was found to be 1.7 m². 2 It was / g.

[0153] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the H2O specific surface area / N2 specific surface area of ​​the heat-treated cement-containing material obtained in this example was 1.00.

[0154] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.7 mg.

[0155] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder and granule material obtained in this example was carried out in the same manner as described in Example 1.

[0156] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 1.8 m² each. 2 / g and 1.8m 2 It was / g.

[0157] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this embodiment was 0.195 times that of the untreated cement-containing material powder described in Example 1, and 1.136 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this embodiment was 0.019 times that of the untreated cement-containing material powder described in Example 1, and 0.895 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobic by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0158] [Example 9] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0159] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 24.7 wt.%.

[0160] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.53 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 200 ml / min and the heat treatment temperature was 1200°C.

[0161] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this embodiment were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0162] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it can be concluded that the granular cement-containing material obtained in this embodiment after heat treatment contains almost no organic matter.

[0163] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this embodiment after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 1.7 m². 2 It was / g.

[0164] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this embodiment after heat treatment, it was found to be 1.5 m². 2It was / g.

[0165] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this example was 0.88.

[0166] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 1.6 mg.

[0167] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder and granule material obtained in this example was carried out in the same manner as described in Example 1.

[0168] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 1.7 m², respectively. 2 / g and 1.6m 2 It was / g.

[0169] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the cement-containing material powder obtained in this embodiment after heat treatment was 0.172 times that of the cement-containing material powder before heat treatment described in Example 1, and 1.003 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the cement-containing material powder obtained in this embodiment after heat treatment was 0.018 times that of the cement-containing material powder before heat treatment described in Example 1, and 0.842 times that of limestone. Thus, it was considered that the cement-containing material powder was sufficiently surface-hydrophobic by the heat treatment according to this embodiment. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0170] [Example 10] (Powdered or granular material containing cement) The cement-containing material in this embodiment consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A material of a specific size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0171] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this embodiment, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 20.5 wt.%.

[0172] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.52 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 170 ml / min and the heat treatment time was 25 minutes.

[0173] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the powder and granular material containing the heat-treated cement in this embodiment, as well as the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0174] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this embodiment after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that the granular cement-containing material obtained in this embodiment after heat treatment contained almost no organic matter.

[0175] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) In this embodiment, the N2 specific surface area of ​​the heat-treated cement-containing material was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 2.0 m². 2 It was / g.

[0176] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the powdered material containing heat-treated cement obtained in this embodiment, it was found to be 1.9 m². 2 It was / g.

[0177] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this example was 0.95.

[0178] (Amount of water vapor adsorbed in a humid environment) In this example, the amount of water vapor adsorbed per gram of the heat-treated cement-containing material at a relative humidity of 90% was 1.8 mg.

[0179] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this example was carried out in the same manner as described in Example 1.

[0180] (Specific surface area of ​​N2 and H2O of granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this example was measured and found to be 2.1 m², respectively. 2 / g and 2.0m 2 It was / g.

[0181] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this embodiment was 0.186 times that of the untreated cement-containing material powder described in Example 1, and 1.080 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this embodiment was 0.020 times that of the untreated cement-containing material powder described in Example 1, and 0.947 times that of limestone. Thus, it is considered that the cement-containing material powder was sufficiently surface-hydrophobicized by the heat treatment according to this embodiment. Moreover, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was 10% or less compared to before the wet-dry treatment. From the above, the overall evaluation of this embodiment was satisfactory.

[0182] [Comparative Example 1] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0183] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this comparative example, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 20.7 wt.%.

[0184] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.52 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 200 ml / min, the heat treatment temperature was 500°C, and the heat treatment time was 25 minutes.

[0185] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the granular material in the cement-containing material after heat treatment and the appearance inside the quartz tube 2 after heat treatment in this comparative example were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 3.

[0186] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this comparative example after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 97.2%. From this, it was considered that a small amount of organic matter remained in the granular cement-containing material after heat treatment in this comparative example.

[0187] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this comparative example after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and it was found to be 14.5 m². 2 It was / g.

[0188] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this comparative example after heat treatment, it was found to be 27.6 m².2 / g.

[0189] (Surface hydrophilicity index in the powder of the cement-containing material after heat treatment) From this, the H2O specific surface area / N2 specific surface area in the powder of the heat-treated cement-containing material obtained in this comparative example was 1.90.

[0190] (Water vapor adsorption amount in a humid environment) The water vapor adsorption amount at a relative humidity of 90% per gram of the powder of the heat-treated cement-containing material obtained in this comparative example was 31.4 mg.

[0191] (Dry-wet repeated treatment) The dry-wet repeated treatment of the powder of the heat-treated cement-containing material obtained in this comparative example was carried out in the same manner as the method described in Example 1.

[0192] (N2 specific surface area and H2O specific surface area in the powder of the heat-treated cement-containing material after dry-wet repeated treatment) When the N2 specific surface area and H2O specific surface area in the powder of the heat-treated cement-containing material obtained in this comparative example were measured after 180 cycles of dry-wet repeated treatment, they were 18.5 m 2 / g and 53.2 m 2 / g, respectively.

[0193] (Comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 0.372 times that of the untreated cement-containing material powder described in Example 1, and 2.163 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was 0.348 times that of the untreated cement-containing material powder described in Example 1, and 16.526 times that of limestone. Thus, although the surface hydrophilicity index and the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example were lower than those of the untreated cement-containing material powder, they were more than 1.2 times higher than those of limestone. In addition, the increase rate of N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. For the above reasons, the overall evaluation was unsatisfactory according to the evaluation criteria described in Example 1. It was speculated that this was due to a low heat treatment temperature, resulting in residual carbon, and insufficient N2 and H2O specific surface area due to the heat treatment.

[0194] [Comparative Example 2] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and pulp was detected.

[0195] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this comparative example, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 21.2 wt.%.

[0196] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.31 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 200 ml / min and the heat treatment time was 1 minute.

[0197] (Visual evaluation of powders and granules containing heat-treated cement) The appearance of the cement-containing material powder and granules after heat treatment in this comparative example, as well as the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 2.

[0198] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this comparative example after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 77.4%. From this, it was concluded that organic matter remained in the granular cement-containing material after heat treatment in this comparative example.

[0199] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this comparative example after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 17.4 m². 2 It was / g.

[0200] (Specific surface area of ​​H2O in powdered or granular materials containing heat-treated cement) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25 degrees Celsius for the granular cement-containing material obtained in this comparative example after heat treatment, it was found to be 95.3 m². 2 It was / g.

[0201] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this comparative example was 5.48.

[0202] (Amount of water vapor adsorbed in a humid environment) In this comparative example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 85.4 mg.

[0203] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this comparative example was carried out in the same manner as described in Example 1.

[0204] (Specific surface area of ​​N2 and H2O in granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this comparative example was measured and found to be 19.7 m², respectively. 2 / g and 102.5m 2 It was / g.

[0205] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 1.070 times that of the untreated cement-containing material powder described in Example 1, and 6.224 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was 0.946 times that of the untreated cement-containing material powder described in Example 1, and 44.947 times that of limestone. Thus, although the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was lower than that of the untreated cement-containing material powder, the surface hydrophilicity of the heat-treated cement-containing material powder increased compared to that of the untreated cement-containing material powder. In addition, the surface hydrophilicity and the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder were more than 1.2 times that of limestone. Furthermore, the increase in N2 specific surface area due to 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. Based on the above, the overall evaluation was unsatisfactory according to the evaluation criteria described in Example 1. This is presumed to be because the combustion-supporting gas flow rate was lower than the combustion-supporting gas flow rate range determined according to the amount of powder and granular material of the cement-containing material subjected to heat treatment and the heat treatment time, resulting in residual carbon.

[0206] [Comparative Example 3] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and raw cotton and styrene-butadiene rubber were detected.

[0207] (Amount of organic matter contained in the powder and granular material of cement-containing material) For the powder particles of the cement-containing material in this comparative example, when the weight ratio of the contained organic matter was calculated by the same method as in Example 1, it was 32.1 wt.%.

[0208] (Preparation of Powder Particles of Cement-Containing Material with Heat Treatment) 0.52 g of the powder particles of the cement-containing material were placed in the heat treatment apparatus shown in Fig. 1. Also, it was prepared by the same method as described in Example 1 except that the amount of the supporting combustible gas introduced was 5 ml / min and the heat treatment temperature was 950°C.

[0209] (Appearance Evaluation of Powder Particles of Cement-Containing Material after Heat Treatment) Regarding the appearance of the powder particles in the cement-containing material after heat treatment in this comparative example and the inside of the quartz tube 2 after heat treatment, when a five-level evaluation shown in Table 1 was conducted, the evaluation was 4.

[0210] (Thermogravimetric Measurement of Powder Particles of Cement-Containing Material after Heat Treatment) Regarding the powder particles of the cement-containing material obtained after heat treatment in this comparative example, when thermogravimetric measurement was conducted by the same method as in Example 1, the weight retention rate at 600°C was 89.4%. From this, it was considered that organic matter remained in the powder particles of the cement-containing material after heat treatment in this comparative example.

[0211] (N2 Specific Surface Area of Powder Particles of Cement-Containing Material after Heat Treatment) Regarding the powder particles of the cement-containing material obtained after heat treatment in this comparative example, when the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, it was 1.9 m 2 / g.

[0212] (H2O Specific Surface Area of Powder Particles of Cement-Containing Material after Heat Treatment) Also, regarding the powder particles of the cement-containing material obtained after heat treatment in this comparative example, when the H2O specific surface area was calculated from the water vapor adsorption isotherm at 25°C, it was 7.4 m 2 / g.

[0213] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this comparative example was 3.89.

[0214] (Amount of water vapor adsorbed in a humid environment) In this comparative example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 16.5 mg.

[0215] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this comparative example was carried out in the same manner as described in Example 1.

[0216] (Specific surface area of ​​N2 and H2O in granular cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this comparative example was measured, and both were 2.1 m². 2 / g and 8.9m 2 It was / g.

[0217] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 0.761 times that of the untreated cement-containing material powder described in Example 1, and 4.426 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was 0.183 times that of the untreated cement-containing material powder described in Example 1, and 8.684 times that of limestone. Thus, although the surface hydrophilicity index and the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example were lower than those of the untreated cement-containing material powder, they were more than 1.2 times higher than those of limestone. In addition, the increase in the H2O specific surface area due to 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. For the above reasons, the overall evaluation was unsatisfactory according to the evaluation criteria described in Example 1. This is presumed to be because the combustion-supporting gas flow rate was lower than the range of combustion-supporting gas flow rates determined by the amount of granular material in the cement-containing material subjected to heat treatment and the heat treatment time, resulting in residual carbon.

[0218] [Comparative Example 4] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and raw cotton was detected.

[0219] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this comparative example, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 22.5 wt.%.

[0220] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.52 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that the combustion-supporting gas introduction rate was 200 ml / min and the heat treatment temperature was 800°C.

[0221] (Visual evaluation of powders and granules containing heat-treated cement) The appearance of the cement-containing material powder and granules after heat treatment in this comparative example, as well as the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 5.

[0222] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this comparative example after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 99.8%. From this, it was concluded that almost no organic matter remained in the granular cement-containing material after heat treatment in this comparative example.

[0223] (Specific surface area of ​​N2 in powdered or granular materials containing heat-treated cement) For the powder-like material containing heat-treated cement obtained in this comparative example, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 4.8 m². 2 It was / g.

[0224] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this comparative example after heat treatment, it was found to be 4.4 m². 2 It was / g.

[0225] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this comparative example was 0.92.

[0226] (Amount of water vapor adsorbed in a humid environment) In this comparative example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 6.2 mg.

[0227] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing material powder obtained in this comparative example was carried out in the same manner as described in Example 1.

[0228] (Specific surface area of ​​N2 and H2O in powdered and granular materials containing heat-treated cement after repeated wet-dry treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this comparative example was measured, and both were 5.9 m². 2 / g and 5.6m 2 It was / g.

[0229] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 0.179 times that of the untreated cement-containing material powder described in Example 1, and 1.042 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was 0.069 times that of the untreated cement-containing material powder described in Example 1, and 3.268 times that of limestone. Thus, although the surface hydrophilicity index and the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example were lower than those of the untreated cement-containing material powder, they were more than 1.2 times higher than those of limestone. In addition, the increase rate of the N2 specific surface area and H2O specific surface area after 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. For the above reasons, the overall evaluation was unsatisfactory according to the evaluation criteria described in Example 1. This is presumed to be due to a low heat treatment temperature, resulting in residual carbon content, and insufficient N2 and H2O specific surface area due to the heat treatment.

[0230] [Comparative Example 5] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and raw cotton was detected.

[0231] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this comparative example, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 25.1 wt.%.

[0232] (Preparation of powdered or granular cement-containing materials through heat treatment) 15 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as described in Example 1, except that the combustion-supporting gas introduction rate was set to 450 ml / min.

[0233] (Visual evaluation of granular cement-containing materials after heat treatment) The powder and granular material containing the comment after heat treatment in this comparative example, and the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 3.

[0234] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this comparative example after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 98.1%. From this, it can be concluded that a small amount of carbon remained in the granular cement-containing material after heat treatment in this comparative example.

[0235] (Specific surface area of ​​N2 in granular cement-containing material after heat treatment) For the granular cement-containing material obtained in this comparative example after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 2.1 m². 2 It was / g.

[0236] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this comparative example after heat treatment, it was found to be 3.7 m². 2 It was / g.

[0237] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this comparative example was 1.76.

[0238] (Amount of water vapor adsorbed in a humid environment) In this comparative example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 5.2 mg.

[0239] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder granules obtained in this comparative example was carried out in the same manner as described in Example 1.

[0240] (Specific surface area of ​​N2 and H2O in the powdered and granular cement-containing material after repeated wet-drying and heat treatment) After 180 cycles of wet-dry treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material obtained in this comparative example was measured, and both were 2.3 m². 2 / g and 4.7m 2 It was / g.

[0241] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 0.344 times that of the untreated cement-containing material powder described in Example 1, and 2.002 times that of limestone. Furthermore, the amount of water vapor adsorbed at 90% relative humidity in the heat-treated cement-containing material powder obtained in this comparative example was 0.058 times that of the untreated cement-containing material powder described in Example 1, and 2.737 times that of limestone. Thus, although the surface hydrophilicity index and the amount of water vapor adsorbed at 90% relative humidity in the heat-treated cement-containing material powder obtained in this comparative example were lower than those of the untreated cement-containing material powder, they were more than 1.2 times higher than those of limestone. In addition, the increase in the H2O specific surface area due to 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. For the above reasons, the overall evaluation was unsatisfactory according to the evaluation criteria described in Example 1. This is presumed to be because the combustion-supporting gas flow rate was lower than the range of combustion-supporting gas flow rates determined by the amount of granular material in the cement-containing material subjected to heat treatment and the heat treatment time, resulting in residual carbon.

[0242] [Comparative Example 6] (Powdered or granular material containing cement) The cement-containing material in this comparative example consists of ceramic siding powder generated during exterior wall cutting and processing, which has passed through a sieve with a nominal mesh size of 63 μm as specified in JIS Z8801. without It passes through a sieve with a nominal mesh size of 106 μm. do A sample of the specified size was used. Furthermore, qualitative analysis of the contained organic matter in the granular cement-containing material used in this comparative example was performed using the same method as in Example 1, and pulp was detected.

[0243] (Amount of organic matter contained in the powder and granular material of cement-containing material) In this comparative example, the weight percentage of organic matter contained in the granular cement-containing material was calculated using the same method as in Example 1, and it was found to be 26.4 wt.%.

[0244] (Preparation of powdered or granular cement-containing materials through heat treatment) 0.56 g of granular cement-containing material was placed in the heat treatment apparatus shown in Figure 1. The preparation was carried out in the same manner as in Example 1, except that nitrogen was introduced as a non-combustible gas and the combustion-supporting gas introduction rate was set to 200 ml / min.

[0245] (Visual evaluation of granular cement-containing materials after heat treatment) The appearance of the cement-containing material powder and granules after heat treatment in this comparative example, as well as the appearance inside the quartz tube 2 after heat treatment, were evaluated on a 5-point scale as shown in Table 1, and the evaluation was 2.

[0246] (Thermogravimetric analysis of granular cement-containing materials after heat treatment) When the granular cement-containing material obtained in this comparative example after heat treatment was subjected to thermogravimetric analysis using the same method as in Example 1, the weight retention rate at 600°C was 86.1%. From this, it was concluded that carbon content remained in the granular cement-containing material after heat treatment in this comparative example.

[0247] (Specific surface area of ​​N2 in powdered or granular materials containing heat-treated cement) For the granular cement-containing material obtained in this comparative example after heat treatment, the N2 specific surface area was calculated from the nitrogen adsorption isotherm at liquid nitrogen temperature, and was found to be 2.0 m². 2 It was / g.

[0248] (Specific surface area of ​​H2O in granular cement-containing material after heat treatment) Furthermore, when the specific surface area of ​​H2O was calculated from the water vapor adsorption isotherm at 25°C for the granular cement-containing material obtained in this comparative example after heat treatment, it was found to be 13.6 m². 2 It was / g.

[0249] (Surface hydrophilicity index of granular cement-containing materials after heat treatment) From this, the ratio of the specific surface area of ​​H2O to the specific surface area of ​​N2 in the heat-treated cement-containing material obtained in this comparative example was 6.80.

[0250] (Amount of water vapor adsorbed in a humid environment) In this comparative example, the amount of water vapor adsorbed per gram of heat-treated cement-containing material at a relative humidity of 90% was 31.1 mg.

[0251] (Wet and dry repeated treatment) The repeated wet-drying treatment of the heat-treated cement-containing powder granules obtained in this comparative example was carried out in the same manner as described in Example 1.

[0252] (Specific surface area of ​​N2 and H2O in granular particles of cement-containing material after repeated wet-dry treatment and heat treatment) After 180 cycles of dry lacquer treatment, the specific surface area of ​​N2 and H2O in the heat-treated cement-containing material powder obtained in this comparative example was measured, and both were 2.1 m². 2 / g and 16.5m 2 It was / g.

[0253] (comprehensive evaluation) From the above results, the surface hydrophilicity index of the heat-treated cement-containing material powder obtained in this comparative example was 1.328 times that of the untreated cement-containing material powder described in Example 1, and 7.727 times that of limestone. Furthermore, the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was 0.344 times that of the untreated cement-containing material powder described in Example 1, and 16.368 times that of limestone. Thus, although the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder obtained in this comparative example was lower than that of the untreated cement-containing material powder, the surface hydrophilicity of the heat-treated cement-containing material powder increased compared to that of the untreated cement-containing material powder. In addition, the surface hydrophilicity and the amount of water vapor adsorbed at a relative humidity of 90% in the heat-treated cement-containing material powder were more than 1.2 times higher than those of limestone. Furthermore, the increase in the specific surface area of ​​H2O after 180 cycles of wet-dry treatment was greater than 10% compared to before the wet-dry treatment. Therefore, according to the evaluation criteria described in Example 1, the overall evaluation was unsatisfactory. This was presumed to be because carbon residue remained due to the supply of nitrogen, a non-combustible gas, instead of a combustion-supporting gas.

[0254] Table 2 shows the preparation conditions for the heat-treated cement-containing powders and granules in Examples 1-10 and Comparative Examples 1-6. Table 3 summarizes the appearance evaluation of the heat-treated cement-containing powders and granules, the weight retention rate at 600°C determined by thermogravimetric analysis, the specific surface area of ​​N2, the specific surface area of ​​H2O, the ratio of the specific surface area of ​​N2 to H2O, the amount of water vapor adsorbed at 90% relative humidity, the specific surface area of ​​N2 after 180 cycles of wet-dry treatment, the specific surface area of ​​H2O after 180 cycles of wet-dry treatment, and the overall evaluation.

[0255] [Table 2]

[0256] [Table 3] [Industrial applicability]

[0257] By making the surface of the granular material containing cement hydrophobic, the water content of concrete can be reduced, thereby suppressing cracking caused by drying shrinkage. This makes it possible to provide materials that require low hygroscopicity, such as aggregates that suppress drying shrinkage cracks in concrete, insulating powders, and fillers for plastic molded products.

[0258] Furthermore, the heat-treated cement-containing material obtained by this invention can be molded into any shape by compression. For this reason, it can be used in applications such as exterior wall materials that are resistant to dirt, and moisture-proof and waterproof panels that suppress the penetration of moisture into the interior. [Explanation of Symbols]

[0259] 1…Cement-containing material powders and granules 2…Quartz tube 3…Compressor 4…Piping 5...Heat supply device 6… Thermocouple 7…Temperature controller 8…Wiring 9a...Quartz wool 9b...Quartz wool 10... stopper 11…Mass flow controller 12… Pressure regulator 13… High-pressure gas cylinder

Claims

1. A method for producing a cement-containing hydrophobic material, comprising supplying a combustion-supporting gas to a granular cement-containing material containing organic matter in a proportion of 50 wt.% or less, and burning it at a temperature of 900°C to 1200°C using a heating means, thereby reducing the hydrophilicity of the surface of the granular cement-containing material, characterized in that when the combustion-supporting gas is air, the feed rate (mL / min) is in the range of 100 aW / T to 900 aW / T; when the combustion-supporting gas is selected from oxygen, ozone, or nitrogen dioxide, the feed rate (mL / min) is in the range of 20 aW / T to 180 aW / T; and when the combustion-supporting gas is selected from nitrous oxide or nitric oxide, the feed rate (mL / min) is in the range of 40 aW / T to 360 aW / T. However, in the unit symbol for the amount of combustion-supporting gas supplied, W represents the weight (g) of a type of cement-containing material, ceramic siding; a represents the weight percentage (wt.%) of organic matter contained in the ceramic siding; and T represents the heat treatment time (minutes).

2. A method for producing a cement-containing hydrophobic material according to claim 1, wherein the granular material of the cement-containing material contains at least one of the following: ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, moderate-heat Portland cement, low-heat Portland cement, sulfate-resistant Portland cement, blast furnace cement, silica cement, fly ash cement, and eco-cement.

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