JP2019006672A - Method for producing reproduced waste material composition and reproduced waste material composition - Google Patents

Abstract

To provide an effective technique that can make a processed product itself be a reusable useful composition through a simple and easy process, by being processed without using means for separating a required material from rubble including waste building materials almost regarded the same as wastes.SOLUTION: A production method for a reproduced waste material composition includes: an addition step (A) for an addition agent that is executed before a step (B) or after the step (B) and before a step (C); the heating step (B) that heats a waste gypsum board to obtain a heating treatment product; and the subsequent step (C) that is executed after the step (B). The mixed powder is obtained which has added to precursor powder containing an oxidation silicon component and a material containing a calcium component derived from another material different from the waste gypsum board, which reacts with an oxidation silicon component contained in the precursor powder, in the step (A); anhydrous gypsum is obtained as the heating treatment product in the step (B); and gypsum-tobermorite based material is obtained by hydrothermally treating a solidification body given from the mixed powder at the temperature of 120°C to 350°C in the subsequent step (C).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a recycled waste material composition and a recycled waste material composition. More specifically, the present invention separates a required material from rubble containing waste material composed of waste gypsum board and / or waste concrete (removing unnecessary materials). It is related with the technique which can be processed collectively without using the means to make the processed material itself into the useful recycled waste material composition which can be reused. Furthermore, from various waste materials that have been discarded as industrial waste, a recycling technology that enables the production of recycled waste material compositions containing gypsum-tobermorite materials that are useful as building materials, and that can provide materials with higher added value. About.

  For example, a building demolished by heavy machinery is made of rubble containing waste concrete and / or waste gypsum board used for building materials, and various deposits such as soil, wood, paper, cloth and plastic. Become a mountain. This pile of rubble is separated and partially reused, but most of it is treated as landfill or waste. Collecting and collecting necessary materials from rubble is a very troublesome work that is laborious and involves complicated processes. For example, waste concrete is often crushed and classified, washed with water, and mainly coarse aggregate is reused. In addition, waste gypsum board is finally used as a reusable raw material through physical and chemical processes after separating and removing attached paper, attached fibers, wood fragments and soil. As described above, the reuse of rubble often involves complicated and complicated processes, resulting in high costs, which hinders the reuse of rubble. Below, the situation of the reuse currently performed is demonstrated.

  The amount of waste concrete discharged is enormous, and some of it is reused as aggregate as described below. Specifically, the waste concrete is pulverized and divided into a coarse aggregate of 5 mm or more and a fine aggregate of 5 mm or less, and the coarse aggregate is mainly reused. When the fine aggregate is reused, lime, fly ash, or the like is added, and after component adjustment, the fine aggregate is heated and melted at a high temperature and reused as an aggregate (see Non-Patent Document 1). Others are sent to landfill.

  On the other hand, for example, since the recycling rate of waste gypsum board in FY2014 is about 40%, a large amount of industrial waste of about 500,000 tons / year is born. Recycling is broadly divided into board and cement. When reusing as board, paper, fiber, topsoil, iron rust, etc. are removed by crushing and sieving and then transferred to hemihydrate gypsum. However, this process is very complicated and expensive (see Non-Patent Document 2). In addition, as a method of reusing as a raw material for cement, there are a method of converting waste gypsum board to quick lime at about 1450 ° C., a method of melting treatment with plasma, etc., both methods have a problem in cost, It cannot be said that waste gypsum has been fully reused.

  As can be seen from the above examples, the reuse of these materials from debris including waste concrete and waste gypsum board has a problem that various miscellaneous mixtures must be separated and removed from the debris. . In addition to harmful asbestos, the inclusions in the rubble include a wide variety of items such as wood chips, sticky paper, cloth, and metals. It is extremely difficult to extract only the required materials from these. It must be a costly and time consuming process.

  In addition to the above, for example, processing waste powder of rocks such as anti-fluorite, Otani stone, diatomaceous earth, clay mineral powder mixed with topsoil, coal ash, clay mixed with topsoil, waste concrete, etc. It is discharged in large quantities and its effective use is desired. In addition, a large amount of materials derived from flush cakes containing calcium components, such as quick lime, slaked lime, digested dolomite, calcium carbonate, dolomite, and oyster shell powder, containing calcium components, are also produced in large quantities as industrial waste. Have been discharged.

Concrete waste recycling method, International Technology Development Center, News Guide No. 9553 Development of recycling technology for dismantled gypsum board, Gypsum board industry association, 2001

  In contrast to the current situation described above, the present inventors will be able to make the process for reuse extremely simple and easy if the required materials can be made into a reusable composition from rubble containing waste materials such as waste gypsum board and waste concrete. It was recognized that it was extremely useful because of the great economic benefits and effective utilization of resources. In other words, it is extremely effective if all the debris is regarded as a resource and the treated product itself can be reused, rather than taking out a reusable material from debris containing various materials. In addition, it will be a more useful technology if it can be used as processing materials for various rocks used as building materials and discharged as industrial waste, or materials derived from washing cake of industrial waste.

  Therefore, the object of the present invention is to obtain the necessary materials from the above-mentioned rubble, which has conventionally been mostly waste, as building materials containing tobermorite, solid materials for soft soil, materials for fixing harmful substances, It is to find an effective technique that can be made into a useful composition that can be reused as a radiation shielding material, and that can be produced by a simple and easy process. In addition, the object of the present invention is to convert a large amount of rubble, which is mostly treated as waste, and various materials regarded as industrial waste, into a reusable useful composition, which is novel and useful. Providing a new recycled waste material composition.

  The above object is achieved by the present invention described below. That is, in the first embodiment of the present invention, it is possible to obtain a useful gypsum-tobermorite-based material that can be expected to be reused in various applications such as building materials. The recycled waste material having the configuration [1] or [2] A method for producing the composition is provided. In the present invention, since crystal growth was observed in the treatment in the presence of high-temperature and high-pressure hot water, the treatment in the subsequent step (C) was referred to as “hydrothermal treatment”, but also referred to as “hydrothermal synthesis”. It is.

[1] A heating step (B) for heating the waste gypsum board to obtain a heat-treated product, a post-step (C) performed after the heating step (B), and before the heating step (B), or Production of a recycled waste material composition for obtaining a gypsum-tobermorite-based material after the heating step (B) and before the post-step (C), the step of adding the additive material (A). In the method, the heating temperature in the heating step (B) is set to 200 ° C. or more and 1200 ° C. or less, anhydrous gypsum is obtained as a heat-treated product in the step (B), and oxidation is performed in the additive material adding step (A). A raw material powder containing a silicon component and a material containing a calcium component derived from a material different from the waste gypsum board, which reacts with the silicon oxide component in the raw material powder, are added, and a solidified product of these mixed powders In the post-process (C), the solidified product is 120 And hydrothermal treatment at a temperature of 350 ° C. inclusive, gypsum - tobermorite system manufacturing method of reproducing waste composition, characterized in that to obtain a material.

[2] A heating step (B) for heating the waste gypsum board to obtain a heat-treated product, a post-step (C) performed after the heating step (B), and before the heating step (B), or Production of a recycled waste material composition for obtaining a gypsum-tobermorite-based material after the heating step (B) and before the post-step (C), the step of adding the additive material (A). It is a method, The heating temperature in the said heating process (B) shall be 70 degreeC or more and 220 degrees C or less, and hemihydrate gypsum is obtained as a heat processing thing in this process (B), In the addition process (A) of the said addition material, A raw material powder containing a silicon oxide component and a material containing a calcium component derived from a material different from the waste gypsum board that reacts with the silicon oxide component in the raw material powder are added and solidified with these mixed powders In the post-process (C), the solidified body 350 ° C. and hydrothermal treatment at a temperature below, gypsum - tobermorite system manufacturing method of reproducing waste composition, characterized in that to obtain a material.

Preferred requirements of the first embodiment of the present invention having the above-mentioned configuration [1] or [2] from which the gypsum-tobermorite-based material is obtained include the following.
[3] In the addition step (A) of the additive material, a raw material powder containing a silicon oxide component and a calcium component derived from a material different from the waste gypsum board that reacts with the silicon oxide component in the raw material powder. Adding the material to be contained so that the molar ratio of Si component / Ca component is 1.0 to 1.5;
[4] The raw material powder containing the silicon oxide component is at least one selected from the group consisting of rock processing waste powder, topsoil mixed clay mineral powder, waste concrete, coal ash, and topsoil mixed clay, The material containing a calcium component derived from a material other than the waste gypsum board is at least one selected from the group consisting of quick lime, slaked lime, digested dolomite, calcium carbonate, dolomite and oyster shell powder;
[5] The material containing a calcium component derived from a material different from the waste gypsum board is a material derived from a washed cake;
[6] When obtaining the solidified body, a calcium component derived from a material different from the heat-treated product, the raw material powder containing the silicon oxide component, and the waste gypsum board, which is a raw material constituting the solidified body. Miniaturize and uniformly mix the materials it contains;
[7] Hydrothermally treating the solidified body at a temperature of 170 ° C. or higher and 190 ° C. or lower in the subsequent step (C);
[8] As a material containing a calcium component derived from a material different from the waste gypsum board, digested dolomite is used, or quick lime or slaked lime is used in combination with magnesium oxide or magnesium hydroxide;
[9] As the raw material powder containing the silicon oxide component, at least one selected from the group consisting of anti-fluorite, kaolin, kibushi clay and waste cement is used, and the hydrothermal reaction in the post-process (C) To form a gypsum-zeolite material by adding sodium hydroxide during the treatment;
[10] The solidified body may be further mixed with monofilament hemp soot.

The present invention, as another embodiment using the first embodiment of the present invention having the above-described configuration,
[11] A regeneration comprising the gypsum-tobermorite-based material obtained by the method for producing a recycled waste material composition having the above-mentioned configuration [1] or [2] from which the gypsum-tobermorite-based material is obtained. A waste material composition is provided.

The following is mentioned as a preferable requirement of the recycled waste material composition of this invention of the said [11] structure.
[12] The gypsum-tobermorite-based material includes particles having at least one shape selected from the group consisting of scale-like particles, columnar particles, needle-like particles, and plate-like particles;
[13] The gypsum-tobermorite material comprises at least one of plagioclase, feldspar, orthoclase, silica, silicate, and aluminosilicate.

In addition, as a second embodiment, the present invention can be reused collectively without separating required materials from rubble containing waste materials such as waste gypsum board or waste concrete (removing unnecessary ones), A method for producing a recycled waste material composition having the following constitution [1] or [3], which can be used as a useful composition that can be reused as a solidifying material for soft soil, a fixing material for harmful substances, a radiation shielding material, etc. I will provide a.
[1] At least a heating step (B) for heating a rubble containing waste materials made of waste gypsum board and / or waste concrete to obtain a heat-treated product, and a post-step (C) performed after the heating step (B) And the heating temperature in the heating step (B) is 200 ° C. or more and 1200 ° C. or less, and in the post-process (C), 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the heat treatment product. In the range, at least one selected from the group consisting of quick lime, slaked lime, digested dolomite, magnesium oxide and magnesium hydroxide is added to the heat-treated product as a binder (c1), or A method for producing a recycled waste material composition, comprising hydrothermally treating (c2) a solidified product obtained by adding a silicon oxide component and a calcium oxide component to a heat-treated product.

  As a preferable form of the method for producing a recycled waste material composition of [1] above, [2] Further, there is a post-process (D) performed after the heating process (B) different from the post-process (C). In the post-process (D), activated carbon, zeolite, hydroxy acid as an adsorbent is added to the heat-treated product within a range of 10 to 50 parts by weight with respect to 100 parts by weight of the heat-treated material. Examples include adding at least one selected from the group consisting of apatite (d1) and / or adding barium sulfate (d2).

[3] A heating step (B) for obtaining a heat-treated product by heating debris containing waste materials made of waste gypsum board and / or waste concrete, and a pre-step (A) performed before the heating step (B) And in the preceding step (A), the rubble is mixed with at least one selected from the group consisting of calcium carbonate, dolomite and magnesium carbonate, and the heating temperature in the heating step (B) is 200 A method for producing a recycled waste material composition, wherein the method is at a temperature of from ℃ to 1200 ℃.

As a preferable embodiment of the method for producing a recycled waste material composition of [3] above, the following configuration may be mentioned.
[4] A solidified body further comprising a post-process (C) performed after the heating process (B), wherein a silicon oxide component and a calcium oxide component are added to the heat-treated product in the post-process (C). Hydrothermally treating (c2);
[5] In the preceding step (A), at least one selected from the group consisting of activated carbon, zeolite, and hydroxyapatite is further added;
[6] Further, as a post-process (D) performed after the heating process (B), in the post-process (D), in any case, 10 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the heat-treated product. Within the range of at most parts, at least one selected from the group consisting of activated carbon, zeolite, and hydroxyapatite is added (d1) as the adsorbent to the heat-treated product, and / or barium sulfate. Is added (d2).

A preferable embodiment of the method for producing a recycled waste material composition according to the above [1] or [4] includes the following configuration.
[7] The silicon oxide component is at least one selected from the group consisting of silicon oxide, antifluorite and Otani stone;
[8] The calcium oxide component may be at least one selected from the group consisting of quick lime, slaked lime, and digested dolomite.

A preferable embodiment of the method for producing a recycled waste material composition of the above [1] to [8] includes the following configuration.
[9] The heating temperature in the heating step (B) is 300 ° C. or higher and 700 ° C. or lower;
[10] The heating time in the heating step (B) is 1 hour or more and 24 hours or less;
[11] The heating time in the heating step (B) is 1 hour or more and 5 hours or less.

  As another embodiment, the present invention includes [12] a heat-treated rubble containing waste material composed of waste gypsum board and / or waste concrete, and a group consisting of quick lime, slaked lime, digested dolomite, magnesium oxide and magnesium hydroxide. And at least one selected binder, and the binder is included in a range of 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the heat-treated product. A recycled waste material composition is provided.

As a preferable form of the recycled waste material composition of the above [12], there is a configuration as follows.
[13] The binder is at least one of quick lime and magnesium oxide;
[14] Further, it includes at least one kind of adsorbent selected from the group consisting of activated carbon, zeolite, and hydroxyapatite, and 5 mass of the adsorbent with respect to 100 parts by mass of the heat-treated product. In a range of not less than 50 parts by weight and not more
[15] Furthermore, barium sulfate is contained in a range of 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the heat-treated product;
[16] Further, tobermorite is included.

  According to the present invention, a means for separating (removing unnecessary materials) a required material from rubble including waste materials made up of waste gypsum board, waste concrete, etc., which has conventionally been mostly waste. Useful composition that can be processed together and reused as a building material containing tobermorite, a solid material for soft soil, a fixing material for harmful substances, a radiation shielding material, etc. In addition, there is provided an effective method for producing a recycled waste material composition that can be made into a product and can be produced by a simple and easy process. In addition, according to the present invention, it is converted into a useful composition that can be reused by treating a large amount of rubble that is mostly treated as waste and various materials that are treated as industrial waste. Provision of a new and useful recycled waste material composition can be realized. For this reason, according to the present invention, various resources that have been regarded as waste can be made reusable by an economical method, and thus there is extremely great value in terms of effective use of limited resources.

It is an X-ray diffraction pattern of three types of solidified bodies obtained by the method for producing a recycled waste material composition of the present invention. It is a figure which shows the SEM photograph of the anhydrous gypsum-anti-fluorite-slaked lime system solidified body obtained with the manufacturing method of the recycled waste material composition of this invention. It is a figure which shows the SEM photograph of the gypsum-tobermorite type | system | group raw material obtained with the manufacturing method of this invention using the anhydrous gypsum-anti-fluorite-slaked lime type | system | group material. FIG. 4 is an X-ray diffraction diagram of the gypsum-tobermorite material of FIG. 3. It is a figure which shows the SEM photograph of the gypsum-tobermorite type | system | group raw material obtained with the manufacturing method of this invention using the anhydrous gypsum-Otani stone-slaked lime type | system | group material. It is a figure which shows the SEM photograph of the gypsum-tobermorite type | system | group raw material obtained with the manufacturing method of this invention using the anhydrous gypsum-kaolin-slaked lime type | system | group material. It is a flowchart which shows the outline of the manufacturing method of the recycled waste material composition of this invention.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
As a result of earnestly examining the above-mentioned method for making a composition that can be reused together without separating (removing unnecessary materials) from the required materials, the following results were obtained. I found it.
(1) Waste lime, slaked lime, digested dolomite, etc., alone, on waste concrete and waste gypsum board used as building materials, rubble heat-treated material consisting of various deposits such as soil, wood and paper Alternatively, it has been found that a mixture containing any ratio of these can be used as, for example, a softening material for soft soil, a fixing material for harmful substances, a neutralizing material for acidic soil, a herbicidal material, etc. It was. According to the study by the present inventors, quick lime, slaked lime, digested dolomite, etc. added to the heat-treated rubble supplement the solidification strength that is lacking in the heat-treated rubble. It is considered that the heat-treated product was able to function as a solidifying material such as the soft soil listed above.

(2) Waste concrete and waste gypsum board used as building materials, rubble heat-treated products consisting of various deposits such as soil, wood and paper, zeolite, hydroxyapatite, carbon powder alone Alternatively, it has been found that a mixture containing a mixture of any ratio thereof can be used as a fixing material for soft soil or a fixing material for harmful substances. According to the study by the present inventors, by adding zeolite, hydroxyapatite, carbon powder to the debris heat-treated product, the components derived from these materials are contained in the debris heat-treated product. It is thought to function as a material immobilization material.

(3) Barium sulfate alone or barium sulfate on heat-treated rubble made of various deposits such as soil, wood and paper, waste concrete and waste gypsum board used as building materials It has been found that a mixture obtained by adding a mixture of lime, quick lime, slaked lime, digested dolomite and the like in an arbitrary ratio to be plastered can be effectively used as a radiation shielding material. According to the study by the present inventors, in particular, the radiation shielding performance is exhibited by a component derived from barium sulfate.

(4) The silicon oxide component and calcium oxide component were added to the heat-treated rubble made up of various deposits such as soil, wood and paper, and waste concrete and waste gypsum board used as building materials. According to the study of the present inventors, the solidified body partially produces tobermorite (5CaO.6SiO ₂ .5H ₂ O, abbreviation for C ₅ S ₆ H ₅ ) by such a hydrothermal reaction. It has been found that tobermorite can be partially manufactured and can be reused as building materials.

  More specifically, a raw material powder such as a rock processing waste powder containing a silicon oxide component, many of which are treated as industrial waste, such as rubble including waste gypsum board, Hydrothermal treatment is performed on a solidified body that is added and mixed with a material containing a calcium component derived from a material different from the waste gypsum board that reacts with the silicon oxide component in the raw material powder, for example, a material derived from a washed cake such as slaked lime. Thus, it has been found that there is a great merit in terms of industrial waste treatment, and that a useful gypsum-tobermorite-based material that can be reused in various applications such as building materials can be obtained. Hereinafter, a material containing a calcium component derived from a material different from the waste gypsum board is simply one of the representative examples of “a material derived from a washed cake containing a calcium component” or “washed cake”. Also called “derived material”. Many of the “materials derived from a washed cake containing a calcium component” are often regarded as industrial waste, and the use thereof meets the purpose of the present invention.

  Tobermorite is a calcium silicate hydrate as described above, and various studies have been made since it is useful as a building material. The product is identified by X-ray diffraction on the (220) plane near 29 °. This is performed using a strong diffraction peak and a peak on the (222) plane near 30 °. In the present invention, the production of tobermorite was confirmed in the same manner.

  As a method for stably obtaining a gypsum-tobermorite-based material having a large amount of tobermorite in the production method of the present invention, the following two methods may be mentioned. In the first method, the anhydrous gypsum obtained by heat-treating the waste gypsum board is derived from the raw material powder containing the silicon oxide component, and the water-washed cake containing the calcium component that reacts with the silicon oxide component in the raw material powder. For example, the material is added and mixed so that the ratio of Si component / Ca component is 1.0 to 1.5, a solidified body made of the mixed powder is formed, and the formed solidified body is hydrothermally treated. A gypsum-tobermorite-based material is obtained. In the second method, the hemihydrate gypsum obtained by heat-treating the waste gypsum board contains a raw material powder containing a silicon oxide component and a calcium component that reacts with the silicon oxide component in the raw material powder. The material derived from the washed cake is added and mixed, for example, so that the ratio of Si component / Ca component is 1.0 to 1.5, a solidified body composed of these mixed powders is formed, and the formed solidified body is water. A gypsum-tobermorite material is obtained by heat treatment.

Furthermore, in the manufacturing method for obtaining the above-described gypsum-tobermorite-based material found by the present inventors, more useful requirements will be described.
(A) Gypsum constituting the gypsum-tobermorite-based material functions as nucleation, crystal generation, and aggregate of tobermorite particles in the production method described above. The amount of gypsum used in the solidified body used in the present invention is preferably 50% by mass or less, for example, about 15% by mass. Since the strength of the gypsum-tobermorite-based material depends on the amount of tobermorite in the material, the amount of gypsum used may be appropriately determined according to the application in consideration of this point.

  Moreover, the said raw material powder is used in order to supply the silicon oxide which comprises tobermorite, and the said material derived from a washing cake is used in order to supply the calcium oxide which comprises tobermorite. For perfect tobermorite, the Si / Ca ratio is 1.2. Therefore, in the present invention, for the purpose of obtaining a gypsum-tobermorite-based material having a larger amount of tobermorite, the usage ratio of the raw material powder containing the silicon oxide component and the material derived from the washing cake containing the calcium component is Si It is preferable to add and mix such that the ratio of component / Ca component is 1.0 to 1.5.

  Therefore, any material can be used as long as these objects can be achieved. Since the present invention is intended for effective use of industrial waste, the processing materials of various rocks, clay mineral powder mixed with topsoil, waste concrete (waste cement), coal ash and topsoil are used as materials for supplying silicon oxide. Using raw powder containing silicon oxide components such as mixed clay and supplying calcium oxide, materials derived from washing cake such as quick lime, slaked lime, digested dolomite, calcium carbonate, dolomite, oyster shell powder It is preferable to use it. Examples of the rock include anti-fluorite (main components are quartzite and plagioclase), Otani stone (main components are calcite), diatomaceous earth, and kaolin.

(A) In the above-described production method, when the raw material powder containing the silicon oxide component contains an aluminum component, for example, when kaolin, clay or waste cement is used, Na ₂ O or NaOH is added to perform hydrothermal treatment. Then, zeolite is produced by the reaction of Al ₂ O ₃ .Na ₂ O.SiO ₂ . Therefore, what is necessary is just to set the material to be used and the usage-amount suitably according to the intended purpose.

(C) In the manufacturing method described above, it was found that the effect of temperature was greater than time as the hydrothermal treatment condition for obtaining a good gypsum-tobermorite material. Suitable temperature conditions are 170-190 degreeC, More preferably, it is 180 degreeC-190 degreeC. The reaction time may be 300 hours or less, for example, 48 to 96 hours.

(D) Preparation of the solidified body used in the manufacturing method for obtaining the gypsum-tobermorite-based material described above is a method in which the mixed powder is formed into a hydrogenated slurry and then solidified using a mold, or the mixed powder is hydrogenated. The solidified body may be used. When using a hydrogenated slurry, for example, 50 to 60% of water may be added and mixed with respect to the total amount of the mixed powder. When hydrogenating, for example, about 15% of water is added to the mixed powder, What is necessary is just to shape | mold with the arbitrary shaping | molding pressure of about 5 Mpa, and to make a solidified body.

(E) As a material derived from a washing cake such as slaked lime containing a calcium component, used in the production method for obtaining the gypsum-tobermorite-based material described above, dolomite hydroxide, mixed use of magnesium hydroxide and slaked lime, Use of cement, use of magnesium hydroxide and hydraulic hemihydrate gypsum, and the like are preferable. The reason is that one of the disadvantages of tobermorite is the problem of strength deterioration due to carbonation, but carbonation can be suppressed by substituting calcium with sparingly soluble magnesium. On the other hand, since the solidification property of the molded body of magnesium hydroxide is low, it is necessary to partially stop the replacement of calcium with magnesium. Therefore, it is preferable to use the materials listed above.

(F) The gypsum-tobermorite-based material obtained in the above-described production method has different particle shapes depending on the location, and is composed of particles such as scales, columns, plates, and needles. Also, gypsum, tobermorite, plagioclase, etc. Consists of. Therefore, in order to obtain a better gypsum-tobermorite-based material, an anhydrous gypsum or hemihydrate gypsum which is a heat-treated product is mixed with raw material powder containing a silicon oxide component and a material derived from a washing cake containing a calcium component. When forming a solidified body from the mixed powder added and mixed, it is preferable to make the mixed powder finer and more uniformly mixed. In this way, when hydrothermal treatment is performed, high reactivity can be realized, and an excellent material free from pores and scratches with little fluctuation in composition can be obtained.

(G) The strength of the gypsum-tobermorite material depends on the amount of tobermorite particles produced. In order to make the gypsum-tobermorite material obtained by the above-described production method industrially usable, strength is an extremely important physical property. In order to obtain a material superior in strength, it is preferable that the manufacturing method is configured as follows. Since tobermorite is produced from a silicon oxide component and components such as slaked lime, as described above, it is effective to make the mixed powder used for forming a solidified body finer and more uniformly mixed. Moreover, when using an aluminosilicate for raw material powder, the more tobermorite is produced, the higher the strength of the raw material, the higher the proportion of silicon oxide. For this reason, when the content ratio of silicon oxide is low as in kaolin, it is effective to add fibers to the solidified body. Use of monofilament hemp suspension is simple. Hemp monofilament can be easily produced by boiling or hydrothermal treatment, and it can be kneaded into the solidified body by adding hemp soot up to about 30% of the total mass of the raw material.

  By skillfully utilizing the knowledge of (1) to (4) obtained above, the present inventors applied various kinds of materials such as soil, wood pieces, and paper pieces to waste concrete and waste gypsum boards used as building materials. For rubble made up of contaminants and deposits, various materials with various functions can be obtained by simple means by using various materials that have been discarded as industrial waste without using special materials. It was found that the material can be reused in the form, and the present invention has been achieved. FIG. 7 is a flowchart showing an outline of the method for producing the recycled waste material composition of the present invention.

  First, when the present inventors heat-treat waste concrete and waste gypsum board-containing rubble in a specific temperature range, it becomes a heat-treated product as a mixture of anhydrous cement or anhydrous gypsum, and the obtained heat-treated product is It has been found that functions such as hydraulic properties can be fully utilized for reuse as a solidifying material for soft soil. In the present invention, based on this knowledge, first, the rubble is heated in the heating step (B) or, as described later, the heating step after the previous step (A) in which calcium carbonate or the like is mixed with the rubble. (B) was provided and heated to obtain a heat-treated product. In the heating step (B), in an oxidizing or neutral or reducing atmosphere, at 1200 ° C. or lower for 24 hours or shorter, 200 ° C. or higher and 1200 ° C. or lower, preferably 300 ° C. to 700 ° C., more preferably 400 ° C. to 600 ° C. Then, heat for about 1 to 5 hours.

  For example, when the waste gypsum board-containing rubble is heat-treated at the above-described temperature in the heating step (B), anhydrous gypsum is obtained as a heat-treated product. In addition, the production method of the present invention is not limited to the above, and as described above, in the heat treatment step (B), the waste gypsum board-containing rubble is heat-treated at 70 ° C. or more and 220 ° C. or less. A gypsum-tobermorite-based material can also be obtained by obtaining hemihydrate gypsum as a heat-treated product and using the obtained hemihydrate gypsum. Therefore, a gypsum-tobermorite-based material useful as a building material or the like can be obtained even by heat treatment at such a low temperature, depending on the type of rubble (the type of impurities contained together with gypsum).

  In the reuse of waste concrete and waste gypsum board, the conventional method has a problem of separating and removing various mixed materials. The mixed material may contain harmful asbestos or the like depending on the case. For example, the mixed material includes a wide variety of materials such as a piece of wood, attached paper, cloth, and metals. It is difficult, expensive, and time consuming to extract only the required material from these. On the other hand, in the present invention, the debris composed of waste concrete, waste gypsum board, mixture or deposits is 1200 ° C. or less, preferably 300 ° C. to 700 ° C., or 70 ° C. depending on the type of debris. Heat treatment is performed at 220 ° C. or lower. As a result, a heat-treated product made of anhydrous cement, anhydrous gypsum, hemihydrate gypsum, ash or the like is obtained. According to the study by the present inventors, the ash contains a large amount of calcium oxide, but there is no problem in using the heat-treated product. In addition, it is known that even if asbestos or the like is mixed in the rubble, it can be rendered harmless by heat treatment at a temperature of 750 ° C. or higher. For this reason, it is possible to treat the rubble together and heat the treated material as it is at a high temperature without using any means for separating (removing unnecessary ones). Therefore, it is effective because a complicated separation work can be eliminated.

  The present inventors may use a heat-treated product made of anhydrous cement, anhydrous gypsum or hemihydrate gypsum, ash, etc., obtained as described above, as it is when the previous step (A) is carried out. However, it has been found that a material that can be reused for various purposes can be obtained by adopting a configuration in which the following steps are performed.

  Specifically, the following method is exemplified as the post-process (C). As a post-process (c1), in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the heat-treated product obtained above, the heat-treated product has quick lime, slaked lime, digested dolomite, At least one selected from the group consisting of magnesium oxide and magnesium hydroxide is added. In addition, in the case of the heat-processed material obtained by implementing the pre-process (A) mentioned later, this process does not need to be performed. The heat-treated product obtained by adding and mixing slaked lime and the like obtained by carrying out the post-process (c1) as described above is, for example, a soft soil solidifying material, a mold solidifying material, or an acidic soil neutralizing material. It can be reused as soil improvement materials such as fertilizers and plaster materials.

  Soft soils in lowlands and wetlands may carry eutrophication ammonia and toxic substances such as lead, arsenic, cadmium, cobalt, chromium, copper, mercury or manganese. In some cases, radioactive cesium discharged in the nuclear accident is carried by wind and rain and may accumulate in soft soils in lowlands and wetlands. In this case, it is necessary to fix the harmful substances mentioned above and solidify the soft soil at the same time. According to the study by the present inventors, in response to such a request, first, the post-process (c1) in which slaked lime or the like is added and mixed to the heat-treated product obtained in the heating process (B) described above is performed. It has been found that it is effective to use a composition having an obtained structure. That is, the solidification function exhibited by the anhydrous cement or anhydrous gypsum hydraulic material constituting the heat-treated product and the slaked lime added and mixed in (c1) can be effectively utilized for solidifying soft soil.

  Furthermore, according to the study by the present inventors, in addition to the implementation of (c1), which is a subsequent process to the heat-treated product, 10 masses as a further post-process (D) with respect to 100 parts by mass of the heat-treated product. In a range of not less than 50 parts by mass and not more than 50 parts by mass, at least one selected from the group consisting of activated carbon, zeolite, and hydroxyapatite is added to and mixed with the heat-treated product as an adsorbent (d1 It is effective to use a composition having a structure obtained by performing the above. With this configuration, the ion exchange and adsorption functions of zeolite, hydroxyapatite, charcoal, etc. coexisted in the heat-treated product are exhibited, and the harmful substances as mentioned above are immobilized. If the granular solidified product of the heat-treated product is used as a fluidized bed, harmful substances can be easily fixed.

  Moreover, in addition to the implementation of (d1), in addition to the implementation of (d1) described above, in addition to the implementation of (d1), in addition to the implementation of (c1), which is a subsequent process to the heat-treated product, Addition of barium sulfate (d2) is also a preferred form. That is, if barium sulfate is made into a plaster-like coating material by utilizing the curability of anhydrous cement or anhydrous gypsum in the heat-treated product, it can be used as a radiation shielding material. In this case, if a reinforcing material such as wollastonite, slaked lime, digested dolomite or a mixture of any proportion, or wollastonite or carrageenan is added, the coating film becomes a strong and smooth barium sulfate-containing plaster. When using a reinforcing material to coat the base material like plaster, add / mix 5wt% or less wollastonite, carrageenan and other substances, and knead to make it plaster-like. It is preferable.

  In the present invention, it is effective to add a silicon oxide component and a calcium oxide component to the heat-treated product and perform hydrothermal treatment as a post-process (c2). As described above, the solidified product obtained by adding the silicon oxide component and the calcium oxide component to the heat-treated product made of anhydrous cement, anhydrous gypsum, ash, etc. causes the hydrothermal reaction between the calcium oxide component such as slaked lime and the silicon oxide component. As a result, tobermorite was partially produced. Thus, by partially manufacturing tobermorite, it can be made reusable for building materials. The feature of the production method in this case is that the hydrothermal reaction can proceed while maintaining the shape of the solidified body. As a silicon oxide source involved in the hydrothermal reaction, not only silicon oxide itself but also materials having silicon oxide as an end component such as anti-fluorite, Otani stone, clay, topsoil, etc. can be used. It is a feature.

The present inventors further examined the point that tobermorite could be partially produced in the solidified body in the post-process (c2) after the hydrothermal treatment described above, and examined suitable treatment conditions. . As a result, it is obtained by adding and mixing 500 parts by mass or less of calcium oxide and 500 parts by mass or less of silicon oxide which reacts sufficiently and sufficiently to 100 parts by mass of the heat-treated product obtained by heat-treating rubble. It was found that tobermorite can be partially produced in the solidified body more effectively by hydrothermally treating the solidified body in a temperature range of 150 ° C to 300 ° C for an arbitrary time.
Details regarding this point have been described above as the method for obtaining the gypsum-tobermorite-based material of the first form, and the outline thereof is as follows. First, in the heat treatment step (B), rubble including waste gypsum board is heat-treated to obtain anhydrous gypsum or hemihydrate gypsum as a heat-treated product. Next, the obtained anhydrous gypsum or hemihydrate gypsum is appropriately used with a raw material powder containing a silicon oxide component and a material derived from a washing cake containing a calcium component that reacts with the silicon oxide component in the raw material powder. In a proportion, preferably, the Si component / Ca component is added and mixed at a use proportion such that the molar ratio of the Si component / Ca component is 1.0 to 1.5, and a solidified body is formed with the mixed powder composed of these. The solidified body is hydrothermally treated at a temperature of 120 ° C. or higher and 350 ° C. or lower, more preferably 170 to 190 ° C., thereby realizing a better gypsum-tobermorite-based material containing a large amount of tobermorite. it can.

  Moreover, in this invention, when performing the heating process (B) which heats the debris containing the waste material which consists of an above-mentioned waste gypsum board and / or waste concrete, and obtains a heat processing thing, as the previous process (A), It is also effective to mix at least one selected from the group consisting of calcium carbonate, dolomite and magnesium carbonate into the rubble, and then perform the heating step (B). Specifically, for example, calcium carbonate, dolomite, and magnesium carbonate are added to and mixed with 100 parts by mass of rubble, alone or in an arbitrary ratio, in an amount of 100 parts by mass or less. Heat treatment at 1200 ° C. or less for 24 hours or less, preferably 300 ° C. to 700 ° C. for 1 to 5 hours. Thus, when it is set as the structure which provided the previous process (A), a heat processing thing becomes a thing of the structure which consists of anhydrous cement, anhydrous gypsum, quicklime, magnesium oxide, an inorganic substance, etc. Also when comprised in this way, it can utilize as a plaster, a herbicide, etc. as a solidification material of a soft soil as mentioned above, as a mold solidification material, as a fixing material of a harmful substance.

  Also in the embodiment in which the above-described pre-process (A) is performed, it is preferable to perform the post-process as described above for the heat-treated product obtained above, depending on the intended use of the final processed product (composition). . Specifically, the post-process (c2) of hydrothermally treating a solidified product obtained by adding a silicon oxide component and a calcium oxide component to the obtained heat-treated product, or for 100 parts by mass of the heat-treated product A post-process of adding at least one selected from the group consisting of activated carbon, zeolite, and hydroxyapatite as an adsorbent to the heat-treated product within a range of 10 parts by weight to 50 parts by weight (D1) is performed, or a post-step (d2) is performed in which barium sulfate is added in an amount within the above range.

  As described above, in the present invention, the construction waste material that has been treated as waste until now is used as a solidifying material for soft soil, as a fixing material for harmful substances, or as a radiation shielding material by simple means. Alternatively, it is an industrially extremely useful technique that can be used effectively as a building material containing a lot of tobermorite and can be reused as a valuable material.

Next, the present invention will be described more specifically with reference to study examples, examples, and comparative examples. In the text, “part” or “%” is based on mass.
The function as a solidifying material such as soft soil was evaluated, and the correlation with the difference in heating temperature for obtaining a heat-treated product was examined. The soft soil for evaluation (hereinafter simply referred to as “soft soil”) used was hydrogenated to the top soil of the schoolyard. At that time, the topsoil was separated by a sieve to remove coarse stones, etc., dried at 100 ° C. for 24 hours, and allowed to cool. For the simulated rubble for testing, a mixture of waste concrete, waste gypsum board, the above-mentioned topsoil, wood pieces, and adhered paper was used. In some tests, waste concrete and waste gypsum board were used alone.

[Examination example 1-Examination about heating process (B)]
Using a heating furnace, the debris containing the above-mentioned waste concrete and waste gypsum board is heat-treated at different temperatures of 300 ° C, 400 ° C, 500 ° C, 700 ° C, 900 ° C, 1000 ° C, and 1100 ° C for 1 hour, respectively. Thus, heat-treated products having different heating temperatures were obtained. The obtained heat-treated product was allowed to cool in a furnace, and then pulverized and mixed with an automatic pulverizer, and used as a sample of the example.

  As a result, it was confirmed that even when heated at any of the above temperatures for 1 hour, the heat-treated product obtained contains anhydrous cement derived from waste concrete and anhydrous gypsum derived from waste gypsum board. In addition, it was confirmed that these heat-treated products were solidified by water kneading and standing for ˜24 hours alone or as a mixture at an arbitrary ratio. This indicates that, as described above, the heat-treated product obtained by treating the debris in the heating step (B) defined in the present invention has hydration curability.

  In addition, it was confirmed that the obtained heat-treated product can be formed into a solidified body by adding and mixing the above-mentioned soft soil, zeolite, carbon powder alone or in a mixture at an arbitrary ratio and kneading the mixture with water. . As a result, it is shown that the heat-treated product obtained as described above functions as a solidifying material for solidifying the additive used in the test.

  From the state of solidification in the above test, a heat treatment test was performed using waste concrete and waste gypsum board respectively. As a result, the anhydrous gypsum obtained as a result of heat treatment at 300 ° C., 350 ° C., 400 ° C., and 500 ° C. for 1 hour has strong hydraulic properties. All the solidified bodies did not collapse even when immersed in water after 24 hours. In particular, anhydrous gypsum obtained by treatment at 300 ° C. for 1 hour can solidify 4 times or more amount of soft soil compared to heat-treated products obtained by heat treatment at higher temperature conditions. It was. However, in the heat treatment for 1 hour, the ashing of the adhered paper from the waste gypsum board is not sufficient, and in this respect, in the heating step (B) defined in the present invention, at 300 ° C. for 2 hours or more, or 350 It was found that it is preferable to perform a heat treatment at about 1 hour for about 1 hour.

  It was also found that when the heat treatment temperature was raised, the hardening ability of anhydrous cement was improved, but the hardening ability of anhydrous gypsum was decreased. For example, anhydrous gypsum obtained by heat treating waste gypsum board at 700 ° C. for 1 hour has low hydraulic properties, and anhydrous gypsum heated at 900 ° C. or higher for 1 hour is inferior to hydraulic properties at 700 ° C. I understood. Presumably, anhydrous gypsum that was heat-treated for 1 hour at a high temperature of 900 ° C. or higher turned into anhydrous gypsum that was difficult to hydrate, and hydraulic properties were lowered. From the above, it was found that the heat treatment temperature is preferably 700 ° C. or lower for the rubble mainly composed of waste gypsum board, and the heat treatment temperature is preferably 700 ° C. or higher for the rubble mainly composed of waste concrete.

  Moreover, the case where the debris containing a waste gypsum board was made lower than the heat processing temperature examined above by the heating process (B) was also examined. As a result, when the heating temperature in the heating step (B) is set to 70 ° C. or higher and 220 ° C. or lower, hemihydrate gypsum is obtained as the heat-treated product. It was found that the above-mentioned gypsum-tobermorite-based material can also be obtained. Of course, when a mixture of anhydrous gypsum and hemihydrate gypsum is used as the heat-treated product, a good gypsum-tobermorite material can be obtained in the same manner. Therefore, depending on the type of rubble, a useful recycled waste material composition can be obtained without heat treatment at a high temperature.

[Examination Example 2—Examination of addition of binder (c1) as a post-process (C)]
Here, the content of cement mortar derived from waste concrete contained in the rubble is quantitatively as low as 15% by mass or less. Therefore, as described above, the rubble heat-treated product exhibits hydraulic properties, but the hydraulic properties are limited. To compensate for this problem, at least one selected from the group consisting of quicklime, slaked lime, digested dolomite, magnesium oxide and magnesium hydroxide is added to the heat-treated product (c1). Is effective. These substances may be added alone, or two or more of them may be selected from the above and added as a mixture in an arbitrary ratio, but in any case, they function as a binder. As described above, in the case of waste gypsum board, heat treatment is preferably performed at 300 ° C. for 2 hours or more, or at 350 ° C. for about 1 hour, and when heat treated at 700 ° C., the hydraulic properties are inferior. On the other hand, in the case of rubble mainly composed of waste gypsum board, when asbestos is mixed in the rubble, it is necessary to treat it at 700 ° C. or higher for detoxification. When the heat treatment is performed at 700 ° C. or higher, the solidification performance by anhydrous gypsum is lowered. Therefore, it is extremely effective to add (c1) a substance that functions as a binder to the heat-treated product as a means to compensate for this. . Specifically, for example, when the same amount of slaked lime as the anhydrous gypsum contained in the heat-treated product is added, the solidification performance is remarkably improved, and soft soil more than 5 times the amount when no slaked lime is added can be solidified. It becomes like this. And the obtained solidified body does not collapse even if immersed in water, and becomes an effective solidified material. According to the study by the present inventors, such an effect of adding slaked lime is similarly exhibited even when the above anhydrous gypsum is replaced with anhydrous cement or a mixture of anhydrous cement and anhydrous gypsum in an arbitrary ratio. . Moreover, it was confirmed that the same effect was exhibited even when replaced with quicklime, digested dolomite, magnesium oxide and magnesium hydroxide as defined in the present invention.

  The actual composition of rubble is not uniform, and the desired solidification performance can be achieved even with heat-treated rubble heated at the temperature specified by the present invention due to various miscellaneous contaminants and other causes. It may be impossible. For this reason, it is preferable to add the binder (c1) as described above even when the heat-treated product obtained has a low solidification performance. According to the study by the present inventors, for example, even when a mixture in which the mass ratio of the heat-treated product to the soft soil is 1: 1 does not solidify, slaked lime of about 10% by mass with respect to the heat-treated product, etc. When the binder defined in the present invention is added, it easily solidifies. Among the binders defined in the present invention, addition of slaked lime is effective. The reason for this is that the addition of hydrogen bonds or the formation of fine ettringite or monosulfate may be involved in solidification. In addition, since the peak of ettringite and monosulfate was not confirmed by X-ray diffraction, even if they are formed, there is a high possibility that they are extremely fine.

[Examination Example 3—Examination of Preprocess (A)]
According to the study by the present inventors, at least one selected from the group consisting of calcium carbonate, dolomite and magnesium carbonate is added to and mixed with the rubble, and this mixture is heated in the heating step (B) described above. It was found that the heat-treated product can also solidify the soft soil. Specifically, a mixture of waste concrete, waste gypsum board, and calcium carbonate adjusted to a mass ratio of 1: 1: 1 to a piece of wood having a ratio of about 0.2 on a mass basis with respect to waste concrete, 0 A paper having a ratio of about 1 was used as simulated rubble, which was heat-treated at 900 ° C. for 1 hour in the air, allowed to cool in the furnace and pulverized to obtain a heat-treated product. This heat-treated product was found to be able to solidify soft soil having a weight four times or more that of the waste concrete. And even if the obtained solidified body was immersed in water, it confirmed that it did not collapse.

  In addition, a piece of wood with a ratio of about 0.1 on a mass basis is added to a mixture of waste concrete, waste gypsum board, and dolomite in a mass ratio of 1: 1: 1, followed by heat treatment in air at 700 ° C. for 1 hour, The mixture was allowed to cool and then pulverized to obtain a heat-treated product. This heat-treated product was able to solidify soft soil having a weight more than three times that of the waste concrete. Moreover, even if the solidified body was immersed in water, it did not collapse.

  As described above, rubble containing calcium or magnesium is added regardless of the method of addition in the post-process (c1) of Study Example 2 or addition in the pre-process (A) of Study Example 3. It was confirmed that the solidified product of the heat-treated product can be effectively used as a solidified material for soft soil. Moreover, since the supernatant liquid obtained by immersing a heat-treated product containing slaked lime, quicklime, digested dolomite, etc. in water has a pH in the range of 12 to 13 and is alkaline, it is a neutralizer for herbicides and acidic soils. It can also be used effectively.

[Examination Example 4-Examination of immobilization of hazardous substances]
It is known that zeolite and carbon powder can immobilize harmful substances by ion exchange or adsorption. Therefore, it is considered that harmful substances such as radioactive cesium, ammonium ions, and heavy metal ions can be immobilized if the debris heat-treated product obtained as described above has a form containing zeolite or carbon powder. .

  The present inventors conducted an examination test on this point. As a result, the amount of zeolite or carbon powder added to the heat-treated rubble required to obtain the effect of immobilizing harmful substances is about 10% to 50%, and the amount added is relatively small. It was confirmed that the solidification performance of the heat-treated product was not a problem. Specifically, for example, the above-described waste gypsum board-based rubble heat-treated product may be solidified by adding slaked lime together with zeolite or carbon powder, or the waste gypsum board-based rubble, In (A), zeolite or carbon powder may be added and mixed together with calcium carbonate or the like, and heat-treated at 300 ° C. to 500 ° C. where they are thermally stable, and the solidified product may be used.

According to the study by the present inventors, for example, anhydrous gypsum obtained by heat treating a waste gypsum board at 300 ° C. for 1 hour, or anhydrous gypsum obtained above and waste concrete at 1 ° C. at 500 ° C. or higher. 3 parts of zeolite A (Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] 27H ₂ O) with respect to 10 parts of the heat-treated product composed of an arbitrary proportion of a mixture with anhydrous cement obtained by heat treatment for a period of time ) And kneaded with water to solidify. This solidified product does not collapse even when immersed in water and is stable. Also in this case, if a binder such as slaked lime described above is added in an amount of 3 parts or less to the heat-treated product, a more stable solidified product is obtained. In this case, the solidified product obtained by water kneading was stable even if the zeolite A was replaced with other zeolite or carbon powder, or a mixture of zeolite A and carbon powder.

  The following examination was performed about the utilization method of the heat processing thing (solidified body) containing the above-mentioned zeolite and carbon powder. The solidified body obtained above was filled into a columnar tube, and an aqueous solution containing ammonium ions, heavy metal ions, phosphate ions, hydrogen sulfide, or the like was allowed to flow from the tube bottom toward the tube. As a result, ammonium ions and heavy metal ions are ion exchanged with zeolite, organic substances are adsorbed with carbon powder, and phosphate ions react with the combined slaked lime to become hydroxyapatite and be immobilized. Was confirmed. If this kind of solidified body is used as a building material, like gypsum board, it is considered to function as a wall material for adsorbing and fixing the causative substance of sick house syndrome, and its use is expected.

  Addition and mixing of quick lime 0.5 and zeolite (clinoptilolite) 0.5 to waste gypsum board 1 on a mass basis, heat treatment in air at 400 ° C. for 1 hour, and cool in the furnace . To this heat-treated product, water was added and mixed at a ratio of 1.5 and left to solidify for 24 hours. X-ray diffraction of the heat-treated product obtained was a mixture composed of dihydrate gypsum, slaked lime, and clinoptilolite. The following test was conducted using this heat-treated product. The heat-treated product obtained above is suspended in an aqueous solution containing 0.1% non-radioactive cesium chloride, shaken for 24 hours (80 rpm), solid-liquid separated, and the separated liquid is diluted 500 times. Then, the cesium concentration was measured with an atomic absorption photometer. As a result, the adsorption amount of cesium was 23 mg / g to 27 mg / g, and it was confirmed that the heat-treated product fixed cesium ions.

  As described above, the solidified product of the heat-treated rubble containing zeolite or carbon powder is expected to be usefully used as a fixing material for harmful substances.

[Examination example 5-Examination 1 about utilization of heat-treated product]
The debris mainly composed of waste gypsum board was treated at 300 ° C. for 1 hour to obtain a heat-treated product. 50 parts of the obtained heat-treated product, 30 parts of barium sulfate, 20 parts of calcium hydroxide, 5 parts of wollastonite and 2 parts of carrageenan were added with water as a slurry to apply it to a plaster board. As a result, it was confirmed that the plaster-like surface had a smooth surface without cracks. 30 parts of the heat-treated product used above, 40 parts of barium sulfate, 20 parts of calcium hydroxide, 5 parts of wollastonite, and 2 parts of carrageenan were hydrogenated to form a slurry and applied on a gypsum board. Also in this case, the surface became plaster like a smooth surface without cracks. Similar results were obtained even when the calcium hydroxide was completely or partially replaced with magnesium hydroxide or dolomite hydroxide.

  In the above test, good results were obtained even when about 2% glue was dissolved in hot water instead of carrageenan used as a paste material. In the case described above, it is also effective to prevent cracking of the surface by adding a little hemp grass or a cloth piece instead of it.

  When the heat-treated product obtained in the same manner as described above was used instead of the rubble mainly composed of waste gypsum board as described above, the same result as above was obtained. This means that a similar plaster-like coating film can be obtained even if a heat-treated product obtained from actual rubble, which is expected to contain various proportions of anhydrous gypsum and anhydrous cement, is used. Since the barium sulfate-based plaster coating film using the heat-treated product defined in the present invention obtained as described above has a radiation shielding function, it is expected to be used as a radiation shielding material.

[Examination example 6-Examination 2 about utilization of heat-processed material]
The debris mainly composed of waste gypsum board or the debris mainly composed of waste concrete was heat-treated at 500 ° C. for 1 hour, respectively, to obtain heat-treated products mainly composed of anhydrous gypsum or anhydrous cement. In each of the obtained heat-treated products, as a silicon oxide component, in addition to silicon oxide itself, anti-fluorite and the above-mentioned topsoil are used, and as a calcium oxide component, slaked lime is used, and these are added to be anhydrous. Three types of solidified bodies were obtained: gypsum-silicon oxide-slaked lime system, anhydrous cement-anti-fluorite-slaked lime system, and anhydrous cement-topsoil-slaked lime system.

Each of the above solidified bodies was hydrothermally treated at 180 ° C. (−10 atm) for 7 days to cause hydrothermal reaction between the silicon oxide content and the calcium oxide content in the solidified body. FIG. 1 shows an X-ray diffraction diagram (XRD diagram) of the obtained reaction product. In each case, the diffraction line shows a peak presumed to be tobermorite (C ₅ S ₆ H ₅ ), which strongly suggests the production of tobermorite. The silicon oxide content of the anti-fluorite used above is approximately 76% from the analysis, and the silicon oxide content of the topsoil is approximately 65%, similar to the knot clay of the sedimentary clay mainly composed of kaolinite mineral. It was used for the synthesis | combination of the said solidified body. The mixing ratio of silicon oxide and slaked lime was a molar ratio of 1: 1 in each case.

  FIG. 2 is an SEM photograph in which the anhydrous gypsum-anti-fluorite-slaked lime solidified body obtained above was hydrothermally reacted at 180 ° C. for 7 days. Scaly or acicular particles suggest the production of tobermorite. Further, according to the result of energy dispersive X-ray analysis (EDX analysis), the locations where calcium and silicon are present are completely coincident with each other, indicating that the scaly particles are tobermorite. The same results were obtained even when the firestone was replaced with Kibushi clay or Otani stone. However, when the structure of the hydrothermally treated product is observed in detail, a part of the particle-like structure is observed locally instead of a plate-like shape. This is probably due to the non-uniformity of the mixing of the raw materials, indicating that uniform mixing is extremely important for hydrothermal treatment. The obtained hydrothermal reaction product of the solidified body is very strong and has a strong structure in which plate-like and needle-like crystals are entangled, and is expected to be used for building materials.

The composition of the cement (ordinary Portland cement) is, SiO ₂ is about 22%, Al ₂ O ₃ is about 5%, Fe ₂ O ₃ is about 3%, CaO about 65%, SO ₂ is about 2%, (Na , K) ₂ O is about 0.8%. On the other hand, the composition of concrete is about 13% for cement, about 27% for water, and about 60% for aggregate. Assuming that the aggregate is sand of silicon oxide and calculating the equivalent ratio of silicon oxide to calcium oxide required for the synthesis of tobermorite, calcium oxide is quantitative for silicon oxide in the heat-treated waste concrete. Shortage. Therefore, hydrothermal synthesis was attempted by making up for this shortage. As a result, flaky particles of tobermorite were obtained. This indicates that there is no particular problem in the synthesis of tobermorite as long as it is a substance containing silicon oxide, and that slaked lime may be solidified with anhydrous gypsum and hydrothermally reacted, and is defined in the present invention. It was confirmed that by using the heat-treated product, a solidified body on which tobermorite expected to be used for building materials can be obtained by a simple and easy method.

  In order to promote the hydrothermal reaction described above, dissolution of silicon oxide is promoted, so the addition of an alkali component such as lithium hydroxide, sodium hydroxide, potassium hydroxide is preferable from the viewpoint of increasing the reaction rate. However, a calcium compound such as slaked lime is an end component of the reaction, and it may be sufficient to keep it slightly alkaline to keep the reaction solution alkaline. There is no particular problem in terms of ratio.

  As described above, by hydrothermal reaction of calcium and silicon oxide contained in the solidified body by heat-treated rubble containing waste gypsum board and / or waste concrete, in the solidified body, building materials, etc. Usable tobermorite can be partially produced, and as a result, waste gypsum board and waste concrete, which have been mostly discarded, can be reused as valuable resources.

[Examination Example 7-Examination on generation of gypsum-tobermorite-based material]
The debris mainly composed of waste gypsum board was heat-treated to obtain a heat-treated product mainly composed of anhydrous gypsum. A raw material powder containing a silicon oxide component and a material derived from a washed cake containing a calcium component were added to and mixed with the obtained heat-treated product to obtain a solidified product. At that time, each material was pulverized and mixed with an automatic stirrer to refine the material, and at the same time, a solidified body was produced using the mixed powder that was uniformly mixed. The solidified body was molded by adding a small amount of water to the mixed powder obtained as described above, and used for the next hydrothermal treatment. The solidified body was molded at a molding pressure of 5 MPa and water was added dropwise to promote solidification and left for 1 day. Moreover, the mixing ratio of the raw material powder containing the silicon oxide component and the material containing the calcium component derived from the water-washed cake in the mixed powder, which is the raw material for forming the solidified body, is the molar ratio of the Si component / Ca component of the active ingredient. Was set to 1.2. The amount of anhydrous gypsum as a heat-treated product was used so as to be 15% by mass in the mixed powder.

  As raw material powder containing silicon oxide component, when using anti-fluorite processing waste powder, which is industrial waste, when using Otani stone processing waste powder, and using diatomaceous earth processing waste powder The case of using kaolin processing waste powder, the case of using Kibushi clay, and the case of using waste cement powder were examined. As a material containing a calcium component, slaked lime derived from a water-washed cake was used for all.

(Anhydrous gypsum-anti-fluorite-slaked lime example)
EDX analysis of the anti-fire stone used is, SiO ₂ is 78.0%, Al ₂ O ₃ is 12.2%, Fe ₂ O ₃ is 1.1%, CaO is 1.7%, MgO 1.3 %, K ₂ O was 3.2%, and Na ₂ O was 2.5%. In addition, since the Si / Ca ratio in the complete tobermorite is 1.2, the amount of each material constituting the mixed powder used for the formation of the solidified body is determined and formulated using the EDX analysis value. . Specifically, 10 parts of waste gypsum heat-treated at 400 ° C. for 2 hours, 30 parts of anti-fluorite, and the amount of calcium component that reacts with the silicon oxide component of the used anti-fluorite can form tobermorite. The slaked lime was prepared in such an amount that the component / Ca component molar ratio was 1.2. Then, these materials are pulverized and mixed for 30 minutes with an automatic stirrer, and mixed uniformly to obtain a mixed powder used for forming a solidified body. Using the obtained mixed powder, hydrogenation molding is performed as described above. Thus, a solidified body was produced.

Using the solidified material obtained above, hydrothermal treatment was performed at different temperatures and times. Specifically, hydrothermal treatment was performed at 170 ° C. for 48 hours and 96 hours, 175 ° C. for 48 hours and 96 hours, 180 ° C. for 24, 48, 120, 168 hours, and 190 ° C. for 24 and 48 hours. . As a result, under any condition, scaly and needle-like particles were observed by SEM, and it was confirmed by X-ray diffraction that these particles were tobermorite. From the results of SEM observation, it was found that the increase in the reaction temperature was more effective than the reaction time for grain growth of tobermorite, and 180 ° C. and 190 ° C. were preferable to 170 ° C. and 175 ° C. . It was found that the reaction time is preferably about 48 to 96 hours. All of the obtained materials had a bulk specific gravity of 1.68 g / cm ³ . There was almost no shrinkage of the material by the hydrothermal reaction.

  FIG. 3 shows an SEM photograph of a gypsum-tobermorite material obtained by hydrothermal treatment at 190 ° C. for 48 hours. In FIG. 3, the figure of SEM in four places from which the obtained raw material differs was shown. It can be seen from the upper right diagram in FIG. 3 that the scaly particles are growing so as to fill the space between the particles. The columnar particles in the lower right diagram of FIG. 3 are gypsum. It was confirmed that gypsum was transformed into plate-like particles with a high aspect ratio by repeating dissolution and precipitation during the synthesis process. The gypsum was stable and functioned as an aggregate of a gypsum-tobermorite-based material and a nucleation site of tobermorite, and the tobermorite grew on the gypsum.

FIG. 4 is an X-ray diffraction diagram of a gypsum-tobermorite material obtained by hydrothermal treatment at 190 ° C. for 24 hours. It can be confirmed that the gypsum and tobermorite crystals are growing. As indicated by B in FIG. 4, the X-ray diffraction peak of tobermorite was split. This is due to Al ³⁺ , Na ⁺ , K ^+, etc. at the Si ⁴⁺ and Ca ²⁺ ion sites of tobermorite. Is due to the formation of substances with different lattice spacing. Moreover, when local elemental analysis was performed by EXD analysis, the Si / Ca ratio was different for each sample, and it was confirmed that there was location dependence.

(Anhydrous gypsum-Oya stone-slaked lime example)
EDX analysis of Oya is, SiO ₂ is 74.5% Al ₂ O ₃ is 14.2% Fe ₂ O ₃ is 1.3% CaO is 1.0% MgO 0.2% K ₂ O was 3.4% and Na ₂ O was 5.4%. A solidified body was prepared in the same manner as in the example using the anti-fluorite, and hydrothermally treated under the same conditions as in the example using the anti-fluorite. As a result, almost the same results as in the case of using anti-fluorite were obtained. Si / Ca molar ratio so that 10 parts of waste gypsum heat treated at 400 ° C. for 2 hours, 30 parts of Oya stone, and the amount of calcium component that reacts with the silicon oxide component of Oya stone used can form tobermorite. A mixed powder that was uniformly stirred and mixed was prepared using slaked lime in an amount of 1.2. FIG. 5 shows an SEM diagram of a gypsum-tobermorite-based material obtained by forming a solidified body from the prepared mixed powder and hydrothermally treating the solidified body at 190 ° C. for 48 hours. Although not shown, X-ray diffraction showed a diffraction peak on the (220) plane of tobermorite in the vicinity of 29 °. Further, the peak was split as in the case of using anti-fluorite. Minerals contained in Otani are silica, plagioclase, feldspar, mordenite and clinoptlite zeolite, and the others are amorphous silicon oxide. Among them, silica, feldspar, and amorphous silicon oxide are considered to react with slaked lime to produce tobermorite. Plagioclase is likely to become fibrous and is used for physical entanglement with gypsum and tobermorite, and is thought to contribute to the development of strength of the material.

(Examples using other raw material powders)
The influence on the composition of the gypsum-tobermorite-based material obtained by the difference in the composition of the raw material powder was examined. The raw material powder which consists of the following each material was examined.
・ Kaolin: Al ₂ Si ₂ O ₅ (OH) ₄
Diatomaceous earth: SiO ₂ 77.10%, Al ₂ O ₃ 14.50%, Fe ₂ O ₃ 4.56%, CaO 0.16%, MgO 1.50%, K ₂ O 1 51%, Na ₂ O 0.64%
Kibushi clay: SiO ₂ 47.69%, Al ₂ O ₃ 33.60%, Fe ₂ O ₃ 1.26%, CaO 0.60%, MgO 0.65%, K ₂ O 1.12%, Na ₂ O 0.10%, TiO ₂ 0.94%, H ₂ O 15.26%
- waste concrete: The composition of the ordinary Portland cement, SiO ₂ is through 22%, Al ₂ O ₃ is to 5%, Fe ₂ O ₃ is to 3%, CaO is to 65%, SO ₂ is 2%, ( Since Na, K) ₂ O is ~ 0.8% and the concrete composition is cement ~ 13%, water ~ 27%, aggregate ~ 60%, the amount of silicon oxide in the waste concrete is calculated The

  A gypsum-tobermorite-based material was obtained using each of the above raw material powders in the same manner as described above using hydrofluoric acid and hydrothermal treatment at 190 ° C. for 96 hours. Then, the properties of the materials obtained in the same manner as described above were examined. As a result, when diatomaceous earth powder was used, it was confirmed that scaly tobermorite was generated in the diatomaceous earth shell. Moreover, when kaolin was used, as shown in the SEM diagram of FIG. 6, a device in which scaly particles peculiar to tobermorite and acicular particles were mixed was obtained. When Kibushi clay was used, plaster particles of gypsum mixed with tobermorite scaly particles were found (not shown), similar to the case of using anti-fluorite and Otani stone. In the example using waste cement, fibrous and plate-like particles are characteristic, reflecting the characteristics of waste cement (not shown). It was confirmed that a gypsum-tobermorite-based material that can be used for building materials can be synthesized in any case.

Claims (29)

A heating step (B) for heating the waste gypsum board to obtain a heat-treated product, a post-step (C) performed after the heating step (B), before the heating step (B), or the heating step ( A method for producing a recycled waste material composition for obtaining a gypsum-tobermorite-based material after B) and before the post-process (C), wherein the additive material is added (A). And
The heating temperature in the heating step (B) is 200 ° C. or more and 1200 ° C. or less, and anhydrous gypsum is obtained as a heat-treated product in the step (B).
A material containing a calcium component derived from a material different from the waste gypsum board that reacts with the raw material powder containing the silicon oxide component and the silicon oxide component in the raw material powder in the addition step (A) of the additive material To obtain a solidified body with these mixed powders,
In the subsequent step (C), the solidified body is hydrothermally treated at a temperature of 120 ° C. or higher and 350 ° C. or lower to obtain a gypsum-tobermorite-based material. A heating step (B) for heating the waste gypsum board to obtain a heat-treated product, a post-step (C) performed after the heating step (B), before the heating step (B), or the heating step ( A method for producing a recycled waste material composition for obtaining a gypsum-tobermorite-based material after B) and before the post-process (C), wherein the additive material is added (A). And
The heating temperature in the heating step (B) is 70 ° C. or higher and 220 ° C. or lower, and hemihydrate gypsum is obtained as a heat-treated product in the step (B).
A material containing a calcium component derived from a material different from the waste gypsum board that reacts with the raw material powder containing the silicon oxide component and the silicon oxide component in the raw material powder in the addition step (A) of the additive material To obtain a solidified body with these mixed powders,
In the subsequent step (C), the solidified body is hydrothermally treated at a temperature of 120 ° C. or higher and 350 ° C. or lower to obtain a gypsum-tobermorite-based material.   A material containing a calcium component derived from a material different from the waste gypsum board that reacts with the raw material powder containing the silicon oxide component and the silicon oxide component in the raw material powder in the addition step (A) of the additive material The method for producing a recycled waste material composition according to claim 1 or 2, wherein the Si component / Ca component molar ratio is 1.0 to 1.5.   The raw material powder containing the silicon oxide component is at least one selected from the group consisting of rock processing waste powder, topsoil mixed clay mineral powder, waste concrete, coal ash, and topsoil mixed clay, and the waste gypsum board The material containing a calcium component derived from another material is at least one selected from the group consisting of quicklime, slaked lime, digested dolomite, calcium carbonate, dolomite and oyster shell powder. A method for producing a recycled waste material composition according to item.   The method for producing a recycled waste material composition according to any one of claims 1 to 4, wherein the material containing a calcium component derived from a material different from the waste gypsum board is a material derived from a washed cake.   A material containing a calcium component derived from a material different from the heat-treated product, the raw material powder containing the silicon oxide component, and the waste gypsum board, which is a raw material constituting the solidified product when obtaining the solidified product The manufacturing method of the recycled waste material composition of any one of Claims 1-5 which refines | miniaturizes and mixes uniformly.   The method for producing a recycled waste material composition according to any one of claims 1 to 6, wherein the solidified body is hydrothermally treated at a temperature of 170 ° C or higher and 190 ° C or lower in the subsequent step (C).   The digested dolomite is used as a material containing a calcium component derived from a material different from the waste gypsum board, or quick lime or slaked lime is used in combination with magnesium oxide or magnesium hydroxide. A method for producing a recycled waste material composition according to item.   As the raw material powder containing the silicon oxide component, at least one selected from the group consisting of antifluorite, kaolin, kibushi clay and waste cement is used, and in the hydrothermal reaction in the post-process (C) The method for producing a recycled waste material composition according to any one of claims 1 to 8, wherein a gypsum-zeolite material is produced by adding sodium hydroxide.   The method for producing a recycled waste material composition according to any one of claims 1 to 9, wherein monofilament hemp soot is further mixed into the solidified body.   A recycled waste material composition comprising a gypsum-tobermorite-based material obtained by the method for producing a recycled waste material composition according to any one of claims 1 to 10.   The recycled waste material composition according to claim 11, wherein the gypsum-tobermorite-based material has particles having at least one shape selected from the group consisting of scale-like particles, columnar particles, needle-like particles, and plate-like particles. .   The recycled waste material composition according to claim 11 or 12, wherein the gypsum-tobermorite-based material comprises at least one of plagioclase, feldspar, orthoclase, silica stone, silicate, and aluminosilicate. At least a heating step (B) for obtaining a heat-treated product by heating debris containing waste material composed of waste gypsum board and / or waste concrete, and a post-step (C) performed after the heating step (B),
The heating temperature in the heating step (B) is 200 ° C. or more and 1200 ° C. or less,
In the post-process (C), quick lime, slaked lime, digested dolomite, oxidized as a binder to the heat-treated product within a range of 10 to 50 parts by weight with respect to 100 parts by weight of the heat-treated product. At least one selected from the group consisting of magnesium and magnesium hydroxide is added (c1), or a solidified product obtained by adding a silicon oxide component and a calcium oxide component to the heat-treated product is subjected to hydrothermal treatment (c2 A method for producing a recycled waste material composition. Furthermore, it has the post-process (D) performed after the said heating process (B) different from the said post-process (C),
In the post-process (D), within a range of 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of the heat-treated product, activated carbon, zeolite, and hydroxyapatite are used as the adsorbent. The method for producing a recycled waste material composition according to claim 14, wherein at least one selected from the group consisting of: (d1) and / or barium sulfate is added (d2). A heating step (B) for obtaining a heat-treated product by heating debris containing waste materials composed of waste gypsum board and / or waste concrete, and a pre-step (A) performed before the heating step (B),
In the previous step (A), the rubble is mixed with at least one selected from the group consisting of calcium carbonate, dolomite and magnesium carbonate, and
The method for producing a recycled waste material composition, wherein a heating temperature in the heating step (B) is 200 ° C or higher and 1200 ° C or lower. Furthermore, it has the post-process (C) performed after the said heating process (B),
The method for producing a recycled waste material composition according to claim 16, wherein in the subsequent step (C), a solidified product obtained by adding a silicon oxide component and a calcium oxide component to the heat-treated product is subjected to hydrothermal treatment (c2).   The method for producing a recycled waste material composition according to claim 16 or 17, further comprising adding at least one selected from the group consisting of activated carbon, zeolite, and hydroxyapatite in the previous step (A). Furthermore, as a post-process (D) performed after the heating process (B),
In any of the post-processes (D), activated carbon, zeolite, or adsorbent is used as an adsorbent in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the heat-treated product. And / or at least any one selected from the group consisting of hydroxyapatite is added (d1) and / or barium sulfate is added (d2). A method for producing the composition.   The method for producing a recycled waste material composition according to claim 14 or 17, wherein the silicon oxide component is at least one selected from the group consisting of silicon oxide, anti-fluorite, and Oya stone.   The method for producing a recycled waste material composition according to claim 14 or 17, wherein the calcium oxide component is at least one selected from the group consisting of quicklime, slaked lime, and digested dolomite.   The method for producing a recycled waste material composition according to any one of claims 14 to 21, wherein a heating temperature in the heating step (B) is 300 ° C or higher and 700 ° C or lower.   The method for producing a recycled waste material composition according to any one of claims 14 to 22, wherein the heating time in the heating step (B) is 1 hour or more and 24 hours or less.   The method for producing a recycled waste material composition according to any one of claims 14 to 22, wherein the heating time in the heating step (B) is 1 hour or more and 5 hours or less. Heat-treated rubble containing waste material composed of waste gypsum board and / or waste concrete;
And at least one selected from the group consisting of quicklime, slaked lime, digested dolomite, magnesium oxide and magnesium hydroxide, and
A recycled waste material composition comprising the binder in a range of 10 to 100 parts by mass with respect to 100 parts by mass of the heat-treated product.   The recycled waste material composition according to claim 25, wherein the binder is at least one of quick lime and magnesium oxide. And further comprising at least one adsorbent selected from the group consisting of activated carbon, zeolite and hydroxyapatite, and
27. The recycled waste material composition according to claim 25 or 26, wherein the adsorbent is contained in a range of 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the heat-treated product.   The recycled waste material composition according to any one of claims 25 to 27, further comprising barium sulfate in a range of 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the heat-treated product.   The recycled waste material composition according to any one of claims 25 to 28, further comprising tobermorite.