JP2001342688A - Carbonized raw material for building material and the like, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide carbonized raw material for novel-structured building materials and the like and a novel method of manufacturing the same, which can convert cellulosic fiber body such as old paper sheets, waste, bark, or chaff and straw which are agricultural by-products into raw material with ease, at very low cost and effectively. SOLUTION: This carbonized raw material for building materials and the like comprises carbonized raw material which is made in such a way that a cellulosic fiber body impregnated with liquid additive comprising either phosphorus compound such as phosphoric acid or mixture thereof is heated at a temperature ranging from 65 to 400 deg.C, or if possible, 80 to 300 deg.C, under active atmosphere for required time according to the concentration of the liquid additive, and carbonized residue is increased by promoting dehydration and carbonization while restricting the flammable gas generation caused by heating and flame until the weight reduction rate of it becomes at least a little over 40%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-combustible functional material, for example, a carbonized material suitable as a material for a building material, such as a heat insulating material, a sound insulating material, and a moisture absorbing material. It is possible to easily use raw materials from waste paper, waste materials, bark, and cellulosic fibrous materials such as rice husks and straw as agricultural by-products in a large amount of waste, which can be said as one symbol of a society that has become a raw material. It can be produced very inexpensively and efficiently, and can be used for heat insulating materials, soundproofing materials, moisture absorbing materials, etc. for building materials, and it can be considerably advantageous in workability. An object of the present invention is to provide a carbonized material for use and a novel production method therefor.

[0002]

2. Description of the Related Art As an environment that is rich in economy and culture is being prepared, a large amount of materials is consumed every day without distinction between corporate management and family life, and various waste generated in the process is Now, the handling is becoming an extremely large social problem from the viewpoint of natural environment conservation, not the problem of economic burden. In particular, looking at the handling of large volumes of waste paper, which is often referred to as a barometer in a high-economic society, newspapers and some magazines use recycled paper that uses recycled paper. Recycled paper itself is not only made of 100% recovered paper, but virgin pulp is added at a certain percentage and reused as a means of stabilizing quality. However, even with the cooperation of the industry actively using recycled paper, it is impossible to meet the requirements of the used paper market at all.

[0003] Such surplus waste paper that has no way of reuse or waste paper that is discarded without being collected is burned in an incinerator together with other combustible garbage and the like. It is believed that harmful dioxins are released into the atmosphere and destroy the natural environment.They are forced to invest a large amount of social capital to construct high-performance incinerators, which are less likely to occur. In order to secure them, they will have to deal with various policy issues such as planning for various difficulties.
The problem of this disposal is that, apart from waste paper, construction sites, sawmills,
A similar problem is encountered with other cellulosic fibrous bodies in general, such as waste wood and wood chips generated in large quantities from woodworking plants and timber landing piers, and rice husks and straw from rice farmers.

Techniques for processing and processing cellulosic fibrous materials by means other than incineration include, for example,
〓Japanese Patent Laid-Open No. Sho 62-15645 "Method for producing fibrous activated carbon"
(Toho Rayon), JP-A-4-231314, "Production method of activated carbon with high surface area" (Eukar Carbon Technology Co .: USA), JP-A-6-56416, "Production method of activated carbon" (West Vacco Co., Ltd.) : U.S.A., etc., which will be activated carbonized and used as a basic material in fields that require the excellent chemical treatment function of activated carbon, that is, deodorization function, filtration function, anion generation function, etc. Technology has been established for a long time.

However, in the case of activated carbon produced by these various activated carbonization techniques, the use of the activated carbon is related to a very special area, and high quality and performance are required as a material meeting the demand. In addition to the fact that the quality of the target raw materials is limited, in addition to the fact that considerable initial investment must be prepared for the maintenance of high-performance equipment, for example, in the case of Toho rayon technology described in ① above, In order to shorten the time required for the oxidation process, the oxidation process is divided into two parts, a preliminary oxidation treatment at 300 to 400 ° C. under an inert atmosphere having an oxygen content of 0.5 to 5%, and a steam and carbon dioxide gas atmosphere. Below, a two-stage oxidation treatment step of a main oxidation treatment in a high temperature range of 700 to 1000 ° C. is required. In the technology, a cellulose-based material is treated with an additive solution such as phosphoric acid, carbonized under an inert atmosphere at 450 to 1200 ° C., and further activated under an oxidizing atmosphere with steam or the like at 700 ° C. or more. And also
ウ エ ス ト West Vaco Co. As in the technology, for wood (lignocellulose), the treatment process is complicated and involves high operability, such as finely pulverizing and carbonizing them, and then molding the carbonized powder again. For example, waste paper and waste materials that are generated in large quantities every day and vary widely in quality are treated as cellulosic fibrous materials to be treated because of the quality and economics. Must also be made almost impossible.

On the other hand, instead of being used in such advanced fields, treatment by a traditional carbonization means for use as a fuel, soil improvement material, moisture proof material, heat insulation material, sound absorbing material, etc., that is, charcoal burning and charcoal (sumi) ). This charcoal burning technology burns wood materials at high temperature, and then
It is based on a production method in which oxygen is cut off and a steamed state is formed by a dehydration action at high temperature, and cellulose is decomposed and carbonized. This technology has not changed since ancient times.

However, the process of burning in a high temperature range,
After that, in the charcoal baking treatment, in which all of the processes of shutting off oxygen and incompletely burning are indispensable, a large amount of carbon dioxide and carbon monoxide are generated in any process, which directly leads to air pollution. And the fact that it is a completely unsuitable treatment means for carbonizing film-like or granular cellulosic fibrous materials such as waste paper and wood chips.

[0008] Further, disadvantageously, the charcoal produced by this traditional means has a solid structure in which the carbon chains in the composition are cut, and thus naturally has properties such as flexibility and elasticity. If you do not have it, therefore, if you intend to use it as a moisture proof material, a heat insulating material, a sound absorbing material, etc. on the uneven surface or curved surface of the building frame or equipment, etc., once crush the solid charcoal, Use by applying and bonding the carbon powder, kneading it in a binder such as resin, and re-molding, or mixing and adhering it to fibers etc. as appropriate, and molding it into a flexible material as a whole The disadvantage is that secondary processing is indispensable for use, and extra consideration and cost are required for measures against dust and coal generated in the secondary processing. Also comes with Therefore, so far, it has not been found that this traditional charcoal-based carbonization process has been applied and put to practical use as a technology for treating cellulosic fibrous bodies such as waste paper and waste materials generated in large quantities every day. .

In view of the above situation, the present invention has been effectively used only within a very limited range so far, and a considerable amount of the invention is incinerated or landfilled at a large cost. In addition to paying attention to the cellulosic fibrous body that has been sent to disposal, especially waste paper, it is also noted that carbon (that is, carbonized cellulose) has nonflammability with an oxygen index of 65 and high heat insulation. As a result of repeated trial and error, such as initiating development and research, and trying many trials and experiments, in order to pursue the possibility of application to building materials, etc. It is possible to efficiently carbonize the cellulosic fibrous body such as waste paper, etc., and to ensure that the carbonized material for building materials and the like having a new structure that maintains the flexibility of used paper, and the carbonized material for building materials etc. Sutra Which has led to the completion of the manufacturing process of new construction materials for carbide materials makes it possible to produce a manner.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The carbonized material for building materials and the like according to the present invention basically has the following structure. That is, cellulosic fibers impregnated with a phosphorus compound such as phosphoric acid, or an additive liquid comprising a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. Body at approximately 65 ° in an active atmosphere
The heat treatment is performed within a temperature range of about C to about 400 ° C., preferably about 80 ° C. to about 300 ° C., for a required time according to the concentration of the additive liquid, thereby suppressing generation of combustible gas due to heating or flame. This is a carbonized material for building materials and the like made of a carbonized material that promotes dehydration and carbonization while increasing the carbonization residue and at least reaching a weight reduction rate of just over 40%.

[0011] In the carbonized material for building materials and the like having the basic structure, the more preferable structure is a phosphorus compound such as phosphoric acid, or a phosphorus compound and any one of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. A cellulosic fiber sheet impregnated with either one or a mixture of two or more of them is placed in an active atmosphere at about 65 ° C. to 400 ° C., preferably about 80 ° C. Or within a temperature range of about 300 ° C.
A heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing the generation of flammable gas due to heating or flame, thereby increasing the amount of carbonized residue. By keeping the carbon chain in the middle of dehydration carbonization, and keeping the sheet body shape and flexibility as a carbonized material, it can be used alone or in combination with other materials to keep a single-layer or laminated structure It includes a sheet-like carbonized material for building materials and the like that can be handled as a material.

[0012] The carbonized material for building materials and the like having the desirable constitution may be a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. The cellulosic fiber sheet impregnated with the additive liquid is placed in an active atmosphere at about 65 ° C. to 400 ° C., preferably about 8 ° C.
Within a temperature range of about 0 ° C. to 300 ° C., heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing generation of flammable gas due to heating or flame, and carbonization residue is generated. And at least a weight loss of 4
By reaching a little over 0%, leaving the carbon chain in the middle of the dehydration carbonization of cellulose, and making it a carbonized material while maintaining the sheet body shape and flexibility, it can be used alone or in combination with other materials, It can be handled as a single-layer or laminated shape-retaining material, and can also be shown as a sheet-like carbonized material for building materials and the like, which is used as a non-combustible heat insulating material, a moisture absorbing material, a sound absorbing material, and a deodorizing material.

Further, the carbonized material for building materials and the like according to the above-mentioned basic structure and a desirable structure among them includes carbonized materials for building materials and the like which can be shown by the following structures, respectively. It is. Cellulose-based fiber sheet body impregnated with a phosphorus compound such as phosphoric acid, or an additive liquid comprising a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. At about 65 ° C. to 4 ° C. in an active atmosphere.
About 00 ° C, preferably about 80 ° C to 300 ° C
Within the temperature range of about, heat treatment for the required time according to the concentration of the additive liquid, promote dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame, increase carbonization residue, increase weight loss rate It reaches over 40%, leaving the carbon chain in the middle of the dehydration carbonization of cellulose, making it a carbonized material while maintaining the shape and flexibility of the sheet body, and then performing boric acid treatment for wood coating. This is a carbonized material for building materials or the like, which is also provided with a function of preventing insects such as termites.

The most typical cellulosic fibrous materials are used paper such as newspapers and magazines, and used corrugated paper, and the like. Other examples include building sites, sawmills, woodworking plants, and the like. Other cellulosic fibrous materials, such as waste materials and wood chips generated in large quantities from timber landing wharves and rice husks and straw from rice farmers, can also be targeted. As raw materials to be used for materials, sound absorption, hygroscopic materials, etc., for example, those made specially in a bulky structure such as paper towels, and those with roll structure toilet paper with roll structure Of course, those provided for other applications as they are, or those which are appropriately processed, etc., are of course also intended to be of interest. , Sheets, laminated structures, blocks, boxes or cylinders, granules or powders, straws, rods, etc. It is intended for cellulosic fibrous bodies of various types and properties for no particular reason.

The additive liquid exerts an effect of suppressing any of generation of incombustible gas at the time of thermal decomposition of cellulose, masking action by vitrification, and generation of combustible gas due to chemical change (esterification), and dehydration of cellulose. Must be able to fulfill the function of promoting carbonization and increasing the amount of carbonized residue, and a phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
It shall consist of either ammonium sulfate, boric acid, or a mixture of any one or more of these derivatives.

[0016] The cellulosic fibrous body impregnated with the above-mentioned additive solution is subjected to a temperature of approximately 65 ° C to 400 ° C under an active atmosphere.
Heat treatment within a temperature range of about 80 ° C. to about 300 ° C. for a required time according to the concentration of the additive solution to achieve a weight reduction rate of more than 40%, thereby obtaining a carbonized residue. Is increased and the predetermined carbonization is terminated, and the carbonized material for building materials and the like is formed from a carbonized material with the carbon chain remaining in the middle of the dehydration carbonization of cellulose in the material composition.

Even at a predetermined heat treatment temperature within a temperature range of about 65 ° C. to 400 ° C., when the impregnated amount of the additive liquid is small, the carbonized material is harder than that of the impregnated amount. This causes a difference in flexibility. This is due to the difference in the residual ratio of the carbon chains of the polysaccharide in the treated cellulose with the amount of the additive liquid, and the small amount of the additive liquid impregnated, as a result of decomposition into simple carbon, its flexibility, that is, It is considered that the flexibility is lost. Therefore, it can be said that the flexibility of the obtained carbonized material can be adjusted by controlling the amount of the impregnated liquid.

The reason why carbonization with the flexibility remaining is possible is that the specimen (charcoal) treated with cellulose in a normal inert gas atmosphere and the liquid impregnated with an additive solution are used. A specimen of the present invention heated and carbonized in air,
Fig. 1 shows a comparison of X-ray diffraction data with virgin pulp (Kim towel ... paper) as a raw material of each specimen.
As shown in Fig. 1, ordinary paper (virgin pulp)
It is characterized by a broad peak of 2 ° and a peak near 23 °, whereas the specimen (charcoal) has a weak broad peak of 20 ° to 30 ° (expressed as peak). In the case of the test specimen of the present invention, although the peak does not become as high as that of virgin pulp, a clear peak appears, so that it is impregnated with the additive liquid. In the carbonized material obtained, a part of the carbonized chain of cellulose remains in the carbonized material, while slightly retaining the characteristics of paper as the raw material, and this is considered to contribute to the flexibility remaining close to the raw material.

On the other hand, in the carbonized material for building materials and the like according to the present invention, the chart (carbonized layer) has an oxygen index (oxygen index: oxygen concentration required for combustion) of 65, and that of the raw material is 18
In comparison to being a flammable substance, it is a material with much higher non-combustibility and high heat insulation, and naturally it can be used as a non-combustible material, and its chart has a large specific surface area In addition, since it has a high adsorptive power, it can also function as a moisture absorbent and deodorant, it can also be expected to adsorb gas, and the chart contains a large amount of air and has high insulation performance, so it is non-combustible insulation In addition to having the performance as a material, sound absorbing characteristics can be obtained by the damping effect between carbon fibers.

[0020]

[Related Invention] The present invention relates to a carbonized material for a building material or the like of the present invention having the above-described structure as a gist. The present invention includes a method for producing a carbonized material for a building material or the like having the following structure. I have. That is, a cellulose compound, a phosphorus compound such as phosphoric acid, a phosphorus compound and sulfuric acid, ammonium sulfate, boric acid,
Or a step of impregnating an additive liquid consisting of any one or a mixture of two or more of the derivatives thereof, the cellulosic fibrous body impregnated with the additive liquid is subjected to approximately 65 ° C. in an active atmosphere. The heat treatment is performed within a temperature range of about C to about 400 ° C., preferably about 80 ° C. to about 300 ° C., for a required time according to the concentration of the additive liquid, thereby suppressing generation of combustible gas due to heating or flame. While dehydrating,
The step of promoting carbonization to increase the carbonization residue, the step of increasing the carbonization residue, and stopping the heat treatment when the weight reduction rate reaches at least over 40%. This is a method for producing a carbonized material for a building material or the like in which a carbonized material is obtained while leaving a carbon chain.

As a more desirable structure, a cellulose compound is added to a phosphorus compound such as phosphoric acid or a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. A step of impregnating the additive liquid composed of any one of the mixtures with the cellulose-based fibrous body impregnated with the additive liquid in an active atmosphere at about 65
The heat treatment is performed for a required time according to the concentration of the additive liquid within a temperature range of about 400 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C., thereby suppressing generation of flammable gas due to heating or flame. A step of promoting dehydration and carbonization to increase the amount of carbonized residue; a step of increasing the amount of carbonized residue and stopping the heat treatment when the weight reduction rate reaches at least over 40%; A step of removing or removing as much as possible the additive liquid component, a step of drying the carbonized material from which the residual additive liquid component has been removed, and by the above steps, to obtain a carbonized material while leaving the carbon chain in the middle of dehydration and carbonization of cellulose. A method for producing a carbonized material for a building material or the like having the above configuration as a gist.

In the method for producing a carbonized material for building materials and the like according to the present invention having the above-described structure, an old newspaper or an old newspaper is used as a pretreatment step of a step of impregnating a cellulosic fiber sheet body with an additive liquid. A myriad of perforations that penetrate through the thickness direction of the cellulosic fibrous sheet body, which is made up of laminated paper and other paper materials such as magazines, with a thickness of up to about 2 cm, in an averaged arrangement over the entire plane. And a method for producing a sheet-like carbonized material for building materials and the like, which is obtained by incorporating a step of perforating a laminated sheet to obtain a carbonized sheet laminate in a thick plate shape while maintaining flexibility.

As described above, the cellulosic fibrous body is intended to cover various types and properties of the cellulosic fibrous body as described above in the carbonized material for building materials and the like, which is the basis of the present invention. In addition, it exerts an inhibitory effect on the generation of non-combustible gas during the thermal decomposition of cellulose, the masking effect by vitrification, and the generation of flammable gas due to chemical change (esterification), and promotes the dehydration and carbonization of cellulose to promote carbonization It must be able to perform the function of increasing the amount of the residue, and a phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
Ammonium sulfate, boric acid, or a mixture thereof with any one or more of the derivatives thereof, and may be formed by any appropriate means, such as dipping, coating or spraying, and the like. The additive liquid is impregnated into the entire cellulosic fibrous body by an appropriate means capable of impregnating the inside of the thickness direction as uniformly as possible.

In the case where the target cellulosic fibrous body is a sheet body, the additional liquid impregnating step can be performed collectively so that a plurality of sheets are laminated. At that time, in order to increase the permeation efficiency of the additive liquid and to realize a homogeneous permeation state inside the thickness direction, the entire plane of the laminated cellulose fiber sheet was averaged as much as possible. The pretreatment step of forming an infinite number of perforation holes penetrating in the thickness direction in the arrangement should be performed before the addition liquid impregnation processing step, and further, the heat treatment step following the addition liquid impregnation processing step In, the heating temperature is uniformly transmitted within a short time from the surface side of the laminated cellulosic fiber sheet body to the depth direction in the laminated state, and uniform carbonization is realized on both the surface side and the depth. Progress, elementary To allow the overall quality stabilized, it is desirable to a restricted limit of lamination thickness of about approximately 2 cm.

The cellulosic fibrous body thus uniformly impregnated with the additive liquid is heated as it is in a wet state or once in a dry state. Normal thermal decomposition of cellulose starts at about 300 ° C., and the cellulose having the molecular structure shown in FIG. 1 is converted into repoglucosan (β-glucosan C6H10O5) in FIG.
Combustible gas (furfuryl alcohol C5H6O
2, furfural C5H4O2, methanol CH
4O, ethanol C2H6O, acetaldehyde C
2H6O, glyoxal C2H2O2, etc.).

In the production method of the present invention, the pyrolysis that does not generate levoglucosan in the usual pyrolysis process of cellulose proceeds, thereby suppressing the subsequent decomposition into combustible gas and increasing the carbonization residue. Things. Therefore, in the heating step of the present invention, the target cellulosic fibrous body requires the above-described additive liquid impregnating step in advance, and does not generate levoglucosan even during the thermal decomposition of cellulose. Efficient esterification reaction by acid such as phosphoric acid and decompose cellulose into hemicellulose and decompose to polysaccharide phosphate ester without decomposing cellulose. This is to perform carbonization.

This heating step must be continued at least until the weight reduction rate reaches a little over 40%, which is a standard for confirming that the carbonization has progressed to a predetermined degree in the above-mentioned process. In the heat treatment, dehydration and carbonization are promoted while suppressing generation of combustible gas due to heating or flame.

FIG. 3 shows the dehydration reaction from the esterification of cellulose with phosphoric acid, the dehydration position, and the resulting structure.
In the dehydration reaction from the esterification, the hemicellulose in FIG. 3-1 is esterified by phosphoric acid treatment as shown in FIG. Will be decomposed. As described above, cellulose is prevented from becoming levoglucosan by the dehydration reaction of phosphoric acid or the like, so that generation of combustible gas is suppressed, and efficient dehydration and carbonization is performed without involving a flame. It has been confirmed that this reaction can be realized even at a low temperature of 300 ° C. or lower, which is generally said to cause thermal decomposition of cellulose.

When phosphoric acid was added to cellulose and the endothermic reaction of the cellulose upon heating was measured by suggestive thermal analysis (DTA), as shown in FIG. 4, as the amount of added phosphoric acid increased, the endothermicity of the cellulose increased. It is known that the peak shifts to a lower temperature side, and from this fact, it is clear that the dehydration reaction of cellulose occurs in preference to the production of lepoglucosan and the like. Further, when a phosphate compound is added to cellulose and heated, as shown in FIG. 5, the heat generation rate decreases with an increase in the amount of phosphorus added, so that the combustion of cellulose is performed gently and an oxidation reaction without flame is performed. It turns out that it shifts to.

FIGS. 6 to 8 show the weight loss by the phosphoric acid treatment concentration of the cellulose and the heating temperature by the constant temperature drier, and FIGS. 9 to 11 show the reduction rate.
As can be seen from FIGS. 6 and 9, in the dryer set at 100 ° C., the change in the weight of the cellulose not treated with phosphoric acid (Kim towel white) is 72 hours after the change in weight within 1 hour, which is considered to be the attached moisture. No change in weight was observed (a slight change was slight moisture absorption until measurement). However, in the case of the heat treatment by phosphoric acid impregnation of the present invention, the weight loss increases with the treatment concentration of phosphoric acid.

Therefore, even at 100 ° C., which is lower than the normal decomposition temperature of cellulose (250 ° C.), a sufficient dehydration reaction occurs depending on the concentration of phosphoric acid. It has been confirmed that carbonization occurs even after 65 ° C., which is the ammonia desorption temperature.

As shown in FIG. 7 and FIG.
In a dryer set at 50 ° C., remarkable dehydration carbonization occurs at 100 ° C. or higher, and a large weight loss is observed even in a low-concentration phosphoric acid-treated product.
% To 40%, but 1% for untreated products
After the initial weight loss within hours, there is almost no change in weight. That is, it is understood that cellulose is not normally decomposed at 150 ° C., but dehydration carbonization is caused by the heat treatment after the impregnation of the additive liquid.

At 200 ° C., as shown in FIG. 8 and FIG. 11, the dehydration carbonization effect is remarkable, and the weight change within one hour is the largest, and the subsequent weight change is small with the amount of the additive liquid impregnated. Cellulose is larger. Also, the cellulose untreated with the additive liquid began to decompose after 24 hours, and after 72 hours, the weight was reduced to the same level as that of the treated article impregnated with the additive liquid. The surface of the product was almost brown and adhesion of tar was observed.
No change in the surface after time was observed, but a small amount of the impregnated solution (1.1% P) resulted in a hard and inflexible carbonized sheet as compared with a large amount of the impregnated solution. .

It is thought that the flexibility due to the residual carbon chains of the polysaccharide disappeared by the impregnation of the cellulose with the additive liquid as a result of the decomposition of the carbon into a simple substance in accordance with the small amount of the impregnation with the additive liquid. Can be From this fact,
It can be seen that the flexibility of the carbonized material can be adjusted by changing the amount of the impregnated liquid. From the results of X-ray diffraction data (FIG. 1) of the specimen treated with cellulose in a normal inert gas atmosphere and the specimen according to the present invention and virgin pulp (kim towel paper) as a raw material, the additive liquid was obtained. The fact that the carbonized material of the present invention, which has been impregnated and heat-treated, causes a part of the carbonized chain of cellulose to remain in the carbonized sheet and slightly retains the characteristics of paper is as described above.

[0035]

Example 1 Cellulose fibrous material such as paper and cotton was impregnated with an additive solution containing phosphoric acid as a main component, and then subjected to approximately 65 ° C.
To about 400 ° C., preferably about 80 ° C. to 3
Heat treatment is carried out within a temperature range of about 00 ° C., and the heat treatment is continued until the weight reduction rate, which is a measure of the progress of carbonization, reaches a little over 40%.
Sublimation or the like of phosphoric acid due to treatment such as neutralization suppresses removal and action of the residual additive solution, and produces a flexible carbonized sheet or carbonized felt at low cost.

[0036]

Embodiment 2 This embodiment shows a typical embodiment in which a cellulosic fibrous body is once defibrated and then formed into a board by appropriate means and carbonized.
A more specific description will be added according to the process diagram shown in FIG. First, in the defibration process, waste paper and rice straw, etc., which have been transported as raw materials, are subdivided by known means such as shredders and crushers, and in the case of books and magazines, clasps such as staples are crushed and mixed. In addition to the above, there is a possibility that foreign matter may enter the recovery stage. Therefore, a process of removing such foreign matter such as metal and stone by air classification or a magnetic separator should be performed in parallel. The defibrating means may be any known one such as a wet type, a semi-dry type, and a dry type.

As the additive solution, a commercially available phosphoric acid solution, for example, a plating additive solution, or a fertilizer such as ammonium sulfate or phosphorous phosphorus can be used for economic reasons. What is necessary is just to select and employ | adopt suitably according to the usage purpose etc. of the carbonized material after a process. In addition, the use of inexpensive boric acid or borax is also effective for termite control, etc., and is sent to these additive liquid impregnation steps.

The additive solution used in this step may be a commercially available phosphoric acid solution such as a plating additive solution, ammonium sulfate,
It is also possible to use a fertilizer such as phosphorus phosphorus, and what kind of solution to which phosphoric acid is to be used may be appropriately selected and used depending on the purpose of use of the carbonized material after the treatment.
Use of inexpensive boric acid or borax is also effective for termite control, and the use of a mixture thereof is also effective.

The additive liquid treatment may be performed by a method such as spray coating or immersion, or by mixing the additive liquid powder and the defibrated fibers in a dry state, then blending them with steam, and further performing preheating. In the case of the wet method, a method of mixing a foaming agent, a foaming agent, and the like to collide with air may be considered. There is also a method in which dust scattering prevention and addition liquid impregnation are simultaneously performed by spraying with an aqueous solution or the like at the time of defibration in the opened defibration step.

The cellulosic fibrous body that has been subjected to the additive liquid impregnating treatment in this way continues to the heating step. This step is
In order to dehydrate and carbonize the treated cellulosic fibrous body, it is preferable to perform the drying in a dry state as much as possible, which leads to a loss of heating energy. In particular, in the case of a heat treatment in a low temperature range such as 65 to 100 ° C., this drying step is performed. Is a mandatory condition. If the heat source for the heat treatment is ammonium sulfate, a mixture of phosphorus and ammonium, or sulfuric acid, carbonization occurs from a low temperature range of around 65 ° C. Therefore, it is easy to use waste heat in addition to electricity, gas, petroleum, etc. In this case, since the reaction occurs slowly, it is possible to obtain a material which is in the process of decomposing cellulose, and to apply it to fertilizers and the like. In addition, even if it is directly heated by a flame, carbonization is performed while controlling the flammable gas by the effect of the additive liquid, so that there is less fear of fire. (If the concentration of the additive solution is low or the mixture does not contain a sulfate group, there is a risk of ignition at high temperatures, so that sufficient care must be taken in the formulation of the additive solution.)

The processing time required for this heating step depends on the concentration of the additive solution (1.5 to 15%) and the heating temperature (65 to 400 ° C.).
According to the correlation with C), it must be carried out continuously until the weight phenomenon rate reaches at least a little over 40%. If the heat source of the heat treatment is ammonium sulfate, a mixture of phosphorus and sulfuric acid, and carbonization occurs from 65 ° C,
In addition to electricity, gas, petroleum, etc., waste heat can be used,
In the heat treatment in the low temperature range, the reaction occurs slowly, so that the material can be used during the decomposition of cellulose,
Application to fertilizer and others is possible. In addition, even if it is directly heated by a flame, carbonization is performed while suppressing the flammable gas by the effect of the additive liquid, so that there is less fear of fire. (If the concentration of the additive solution is low or the mixture does not contain a sulfate group, there is a risk of ignition at high temperatures, so that sufficient care must be taken in the formulation.)

[0042]

Example 3 Waste paper fiber and inorganic fiber such as rock wool are mixed and molded, impregnated with the additive liquid used in Example 3, and then heated with a hot air dryer at 180 ° C. (heating at a high frequency is also possible). Yes) and carbonized to form a board with high shape retention strength and flexibility.

[0043]

The carbonized material for construction and the like of the present invention and the method for producing the same, which have the above-mentioned structure, pay attention to the thermal decomposition mechanism of cellulose and suppress the generation of combustible gas by chemicals to carbonize. It is based on the knowledge that it is possible to impregnate a cellulosic fibrous body with an additive liquid containing phosphoric acid as a main component, and to reduce the weight by more than 40%, which is a measure for confirming the completion of carbonization. Heat treatment is performed until the temperature reaches the limit, and dehydration and carbonization are promoted while suppressing the generation of flammable gas due to heating or flame. Therefore, in high-temperature air (in an inert gas atmosphere or without shutting off oxygen) Also does not produce levoglucosan (tar component), so there is no generation of flammable gas and dehydration carbonization does not involve a flame (reduces the risk of fire), and is therefore in the manufacturing process. , Risk causing air pollution or no, also possible to prevent the occurrence of a fire, work safety can be secured, it has a great feature that it is possible to efficiently produce carbon.

When the concentration of phosphoric acid impregnated in the cellulosic fibrous body is less than 1%, carbonization hardly proceeds, and when the concentration exceeds 20%, a flexible carbonized material is obtained. Very subtle and impractical,
Therefore, the concentration is 1 to 20%, desirably 1.5 to 15
% Or more, and the heating temperature is practically 65 to 40.
Since the heat treatment is performed at a temperature range of 0 ° C., preferably around 80 to 300 ° C., a carbon chain can be left in the carbonized material, and a flexible carbonized material can be realized. In the case of manufacturing materials such as heat insulating materials, sound absorbing materials, underfloor moisture absorbing materials, and fire-resistant coating materials, powder scattering from carbonized materials is almost eliminated, workability is extremely improved, and efficient manufacturing is enabled. In addition, the use of inexpensive chemicals (ammonium sulfate and phosphorus ammonium are sold as fertilizers) as additive liquids, and also enables production with a simple heating device, and the use of high-performance building materials An excellent effect that it can be provided at a considerably low price can be expected.

Also, in the present invention,
Cellulosic fibrous materials that are buried as waste or incinerated or otherwise treated in an enormous amount, such as waste paper such as newspapers and magazines and used corrugated paper, or construction sites and Sawmill, woodworking shop,
It can be used as an effective waste disposal means because it can cover various cellulosic fibrous materials in general, such as waste materials and wood chips generated in large quantities from timber landing wharves and rice husks and straw from rice farmers. It has the advantage of being able to. In particular, in the case of the carbonized material for building material and the like and the method of manufacturing the material shown as a representative example of the present invention, it is necessary to ensure that these characteristics can be achieved and make it extremely practical. it can.

As described above, the carbonized material for building materials and the like having the novel structure of the present invention and the method for producing the same are intended to be able to achieve the intended purpose in general. In addition to being highly evaluated as an effective utilization means of cellulosic fibrous materials as wastes, as a means that can easily and reliably treat those wastes without generating harmful by-products such as dioxins, sufficient It is expected that it will gain trust and will be adopted and spread widely.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a comparison graph showing composition analysis of three types of raw material, cellulose (virgin pulp), charcoal treated by phosphoric acid, and charcoal heated in a normal inert atmosphere by X-ray diffraction.

FIG. 2 is a structural formula of cellulose.

FIG. 3 is a structural formula of a flammable gas generated by pyrolysis of levoglucosan (tar component), which is generated by ordinary pyrolysis of cellulose.

FIG. 4 is a structural formula of a phosphoric acid dehydration reaction of cellulose.

FIG. 4-1 is a structural formula showing a change due to dehydration of cellulose.

FIG. 4-2 is a structural formula illustrating a dehydrating action from esterification by phosphoric acid.

FIG. 5 is a graph comparing the change in heat absorption and heat generation due to the difference in concentration with the data of differential thermal analysis (measurement of heat absorption and heat generation) during heating of cellulose treated with phosphoric acid.

FIG. 6 is a graph showing a change in heat generation rate when burning cellulose (cotton) treated with a phosphate compound.

FIG. 7 is a graph showing a change in weight at a heating temperature of 100 ° C. due to a difference in the concentration of a phosphoric acid treatment of cellulose.

FIG. 8 is a graph showing a change in weight at a heating temperature of 150 ° C. depending on a difference in the phosphoric acid treatment concentration of cellulose.

FIG. 9 is a graph showing a change in weight at a heating temperature of 200 ° C. due to a difference in the concentration of phosphoric acid treatment of cellulose.

FIG. 10 is a graph showing a weight change rate at a heating temperature of 100 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 11 is a graph showing a weight change rate at a heating temperature of 150 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 12 is a graph showing a weight change rate at a heating temperature of 200 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 13 is a manufacturing process diagram of the third embodiment.

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[Procedure amendment]

[Submission date] October 11, 2000 (2000.10.
11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

[Title of the Invention] Carbonized material for building material and the like, and method for producing the same

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-combustible functional material, for example, a carbonized material suitable as a material for a building material, such as a heat insulating material, a sound insulating material, and a moisture absorbing material. It is possible to easily use raw materials from waste paper, waste materials, bark, and cellulosic fibrous materials such as rice husks and straw as agricultural by-products in a large amount of waste, which can be said as one symbol of a society that has become a raw material. It can be produced very inexpensively and efficiently, and can be used for heat insulating materials, soundproofing materials, moisture absorbing materials, etc. for building materials, and it can be considerably advantageous in workability. An object of the present invention is to provide a carbonized material for use and a novel production method therefor.

[0002]

2. Description of the Related Art As an environment that is rich in economy and culture is being prepared, a large amount of materials is consumed every day without distinction between corporate management and family life, and various waste generated in the process is Now, the handling is becoming an extremely large social problem from the viewpoint of natural environment conservation, not the problem of economic burden. In particular, looking at the handling of large volumes of waste paper, which is often referred to as a barometer in a high-economic society, newspapers and some magazines use recycled paper that uses recycled paper. Recycled paper itself is not only made of 100% recovered paper, but virgin pulp is added at a certain percentage and reused as a means of stabilizing quality. However, even with the cooperation of the industry actively using recycled paper, it is impossible to meet the requirements of the used paper market at all.

[0003] Such surplus waste paper that has no way of reuse or waste paper that is discarded without being collected is burned in an incinerator together with other combustible garbage and the like. It is believed that harmful dioxins are released into the atmosphere and destroys the natural environment, causing a large amount of social capital investment to build a high-performance incineration plant with less occurrence and a final landfill. In order to secure this, we will have to deal with various policy issues such as planning and planning for various difficulties. The problem of this disposal is that waste materials and wood chips generated in large quantities from waste paper, construction sites, sawmills, woodworking plants, timber landing piers, etc., and other cellulosic materials such as rice husks and straw from rice farmers etc. A similar problem is encountered with fibrous materials in general.

Techniques for processing and processing cellulosic fibrous materials by means other than incineration include, for example,
・ Japanese Patent Application Laid-Open No. Sho 62-15645 "Method for producing fibrous activated carbon"
(Toho Rayon), JP-A-4-231314, "Production method of activated carbon with high surface area" (Eucal Carbon Technology Co .: USA), JP-A-6-56416, "Production method of activated carbon" (Westvaco Co., Ltd.) : U.S.A., etc., which will be activated carbonized and used as a basic material in fields that require the excellent chemical treatment function of activated carbon, that is, deodorization function, filtration function, anion generation function, etc. Technology has been established for a long time.

However, in the case of activated carbon produced by these various activated carbonization techniques, the use of the activated carbon is related to a very special area, and high quality and performance are required as a material meeting the demand. In addition to the fact that the quality of the target raw material is limited and that considerable initial investment must be prepared for the maintenance of high-performance equipment, for example, the above-mentioned Toho rayon technology, In order to shorten the time required for the oxidation process, the oxidation process is divided into two parts, a preliminary oxidation treatment at 300 to 400 ° C. under an inert atmosphere having an oxygen content of 0.5 to 5%, and a steam and carbon dioxide gas atmosphere. Below, a two-stage oxidation treatment step of a main oxidation treatment in a high temperature range of 700 to 1000 ° C. is required. In the technology, a cellulose-based material is treated with an additive solution such as phosphoric acid, carbonized under an inert atmosphere at 450 to 1200 ° C., and further activated under an oxidizing atmosphere with steam or the like at 700 ° C. or more. And also
-Westvaco Co. As in the technology, for wood (lignocellulose), the treatment process is complicated and involves high operability, such as finely pulverizing and carbonizing them, and then molding the carbonized powder again. For example, waste paper and waste materials that are generated in large quantities every day and vary widely in quality are treated as cellulosic fibrous materials to be treated because of the quality and economics. Must also be made almost impossible.

On the other hand, instead of being used in such advanced fields, treatment by a traditional carbonization means for use as a fuel, soil improvement material, moisture proof material, heat insulation material, sound absorbing material, etc., that is, charcoal burning and charcoal (sumi) ). This charcoal burning technology burns wood materials at high temperature, and then
It is based on a production method in which oxygen is cut off and a steamed state is formed by a dehydration action at high temperature, and cellulose is decomposed and carbonized. This technology has not changed since ancient times.

However, the process of burning in a high temperature range,
After that, in the charcoal baking treatment, in which all of the processes of shutting off oxygen and incompletely burning are indispensable, a large amount of carbon dioxide and carbon monoxide are generated in any process, which directly leads to air pollution. And the fact that it is a completely unsuitable treatment means for carbonizing film-like or granular cellulosic fibrous materials such as waste paper and wood chips.

[0008] Further, disadvantageously, the charcoal produced by this traditional means has a solid structure in which the carbon chains in the composition are cut, and thus naturally has properties such as flexibility and elasticity. If you do not have it, therefore, if you intend to use it as a moisture proof material, a heat insulating material, a sound absorbing material, etc. on the uneven surface or curved surface of the building frame or equipment, etc., once crush the solid charcoal, Use by applying and bonding the carbon powder, kneading it in a binder such as resin, and re-molding, or mixing and adhering it to fibers etc. as appropriate, and molding it into a flexible material as a whole The disadvantage is that secondary processing is indispensable for use, and extra consideration and cost are required for measures against dust and coal generated in the secondary processing. Also comes with Therefore, so far, it has not been found that this traditional charcoal-based carbonization process has been applied and put to practical use as a technology for treating cellulosic fibrous bodies such as waste paper and waste materials generated in large quantities every day. .

In view of the above situation, the present invention has been effectively used only within a very limited range so far, and a considerable amount of the invention is incinerated or landfilled at a large cost. In addition to paying attention to the cellulosic fibrous body that has been sent to disposal, especially waste paper, it is also noted that carbon (that is, carbonized cellulose) has nonflammability with an oxygen index of 65 and high heat insulation. As a result of repeated trial and error, such as initiating development and research, and trying many trials and experiments, in order to pursue the possibility of application to building materials, etc. It is possible to efficiently carbonize the cellulosic fibrous body such as waste paper, etc., and to ensure that the carbonized material for building materials and the like having a new structure that maintains the flexibility of used paper, and the carbonized material for building materials etc. Sutra Which has led to the completion of the manufacturing process of new construction materials for carbide materials makes it possible to produce a manner.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The carbonized material for building materials and the like according to the present invention basically has the following structure. That is, cellulosic fibers impregnated with a phosphorus compound such as phosphoric acid, or an additive liquid comprising a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. Body at approximately 65 ° in an active atmosphere
The heat treatment is performed within a temperature range of about C to about 400 ° C., preferably about 80 ° C. to about 300 ° C., for a required time according to the concentration of the additive liquid, thereby suppressing generation of combustible gas due to heating or flame. This is a carbonized material for building materials and the like made of a carbonized material that promotes dehydration and carbonization while increasing the carbonization residue and at least reaching a weight reduction rate of just over 40%.

[0011] In the carbonized material for building materials and the like having the basic structure, the more preferable structure is a phosphorus compound such as phosphoric acid, or a phosphorus compound and any one of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. A cellulosic fiber sheet impregnated with either one or a mixture of two or more of them is placed in an active atmosphere at about 65 ° C. to 400 ° C., preferably about 80 ° C. Or within a temperature range of about 300 ° C.
A heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing the generation of flammable gas due to heating or flame, thereby increasing the amount of carbonized residue. By keeping the carbon chain in the middle of dehydration carbonization, and keeping the sheet body shape and flexibility as a carbonized material, it can be used alone or in combination with other materials to keep a single-layer or laminated structure It includes a sheet-like carbonized material for building materials and the like that can be handled as a material.

[0012] The carbonized material for building materials and the like having the desirable constitution may be a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. The cellulosic fiber sheet impregnated with the additive liquid is placed in an active atmosphere at about 65 ° C. to 400 ° C., preferably about 8 ° C.
Within a temperature range of about 0 ° C. to 300 ° C., heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing generation of flammable gas due to heating or flame, and carbonization residue is generated. And at least a weight loss of 4
By reaching a little over 0%, leaving the carbon chain in the middle of the dehydration carbonization of cellulose, and making it a carbonized material while maintaining the sheet body shape and flexibility, it can be used alone or in combination with other materials, It can be handled as a single-layer or laminated shape-retaining material, and can also be shown as a sheet-like carbonized material for building materials and the like, which is used as a non-combustible heat insulating material, a moisture absorbing material, a sound absorbing material, and a deodorizing material.

Further, the carbonized material for building materials and the like according to the above-mentioned basic structure and a desirable structure among them includes carbonized materials for building materials and the like which can be shown by the following structures, respectively. It is. Cellulose-based fiber sheet body impregnated with a phosphorus compound such as phosphoric acid, or an additive liquid comprising a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. At about 65 ° C. to 4 ° C. in an active atmosphere.
About 00 ° C, preferably about 80 ° C to 300 ° C
Within the temperature range of about, heat treatment for the required time according to the concentration of the additive liquid, promote dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame, increase carbonization residue, increase weight loss rate It reaches over 40%, leaving the carbon chain in the middle of the dehydration carbonization of cellulose, making it a carbonized material while maintaining the shape and flexibility of the sheet body, and then performing boric acid treatment for wood coating. This is a carbonized material for building materials or the like, which is also provided with a function of preventing insects such as termites.

The most typical cellulosic fibrous materials are used paper such as newspapers and magazines, and used corrugated paper, and the like. Other examples include building sites, sawmills, woodworking plants, and the like. Other cellulosic fibrous materials, such as waste materials and wood chips generated in large quantities from timber landing wharves and rice husks and straw from rice farmers, can also be targeted. As raw materials to be used for materials, sound absorption, hygroscopic materials, etc., for example, those made specially in a bulky structure such as paper towels, and those with roll structure toilet paper with roll structure Of course, those provided for other applications as they are, or those which are appropriately processed, etc., are of course also intended to be of interest. , Sheets, laminated structures, blocks, boxes or cylinders, granules or powders, straws, rods, etc. It is intended for cellulosic fibrous bodies of various types and properties for no particular reason.

The additive liquid exerts an effect of suppressing any of generation of incombustible gas at the time of thermal decomposition of cellulose, masking action by vitrification, and generation of combustible gas due to chemical change (esterification), and dehydration of cellulose. Must be able to fulfill the function of promoting carbonization and increasing the amount of carbonized residue, and a phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
It shall consist of either ammonium sulfate, boric acid, or a mixture of any one or more of these derivatives.

[0016] The cellulosic fibrous body impregnated with the above-mentioned additive solution is subjected to a temperature of approximately 65 ° C to 400 ° C under an active atmosphere.
Heat treatment within a temperature range of about 80 ° C. to about 300 ° C. for a required time according to the concentration of the additive solution to achieve a weight reduction rate of more than 40%, thereby obtaining a carbonized residue. Is increased and the predetermined carbonization is terminated, and the carbonized material for building materials and the like is formed from a carbonized material with the carbon chain remaining in the middle of the dehydration carbonization of cellulose in the material composition.

Even at a predetermined heat treatment temperature within a temperature range of about 65 ° C. to 400 ° C., when the impregnated amount of the additive liquid is small, the carbonized material is harder than that of the impregnated amount. This causes a difference in flexibility. This is due to the difference in the residual ratio of the carbon chains of the polysaccharide in the treated cellulose with the amount of the additive liquid, and the small amount of the additive liquid impregnated, as a result of decomposition into simple carbon, its flexibility, that is, It is considered that the flexibility is lost. Therefore, it can be said that the flexibility of the obtained carbonized material can be adjusted by controlling the amount of the impregnated liquid.

The reason why carbonization with the flexibility remaining is possible is that the specimen (charcoal) treated with cellulose in a normal inert gas atmosphere and the liquid impregnated with an additive solution are used. A specimen of the present invention heated and carbonized in air,
Fig. 1 shows a comparison of X-ray diffraction data with virgin pulp (Kim towel ... paper) as a raw material of each specimen.
As shown in Fig. 1, ordinary paper (virgin pulp)
It is characterized by a broad peak of 2 ° and a peak near 23 °, whereas the specimen (charcoal) has a weak broad peak of 20 ° to 30 ° (expressed as peak). In the case of the test specimen of the present invention, although the peak does not become as high as that of virgin pulp, a clear peak appears, so that it is impregnated with the additive liquid. In the carbonized material obtained, a part of the carbonized chain of cellulose remains in the carbonized material, while slightly retaining the characteristics of paper as the raw material, and this is considered to contribute to the flexibility remaining close to the raw material.

On the other hand, in the carbonized material for building materials and the like according to the present invention, the chart (carbonized layer) has an oxygen index (oxygen index: oxygen concentration required for combustion) of 65, and that of the raw material is 18
In comparison to being a flammable substance, it is a material with much higher non-combustibility and high heat insulation, and naturally it can be used as a non-combustible material, and its chart has a large specific surface area In addition, since it has a high adsorptive power, it can also function as a moisture absorbent and deodorant, it can also be expected to adsorb gas, and the chart contains a large amount of air and has high insulation performance, so it is non-combustible insulation In addition to having the performance as a material, sound absorbing characteristics can be obtained by the damping effect between carbon fibers.

[0020]

[Related Invention] The present invention relates to a carbonized material for a building material or the like of the present invention having the above-described structure as a gist. The present invention includes a method for producing a carbonized material for a building material or the like having the following structure. I have. That is, a cellulose compound, a phosphorus compound such as phosphoric acid, a phosphorus compound and sulfuric acid, ammonium sulfate, boric acid,
Or a step of impregnating an additive liquid consisting of any one or a mixture of two or more of the derivatives thereof, the cellulosic fibrous body impregnated with the additive liquid is subjected to approximately 65 ° C. in an active atmosphere. The heat treatment is performed within a temperature range of about C to about 400 ° C., preferably about 80 ° C. to about 300 ° C., for a required time according to the concentration of the additive liquid, thereby suppressing generation of combustible gas due to heating or flame. While dehydrating,
The step of promoting carbonization to increase the carbonization residue, the step of increasing the carbonization residue, and stopping the heat treatment when the weight reduction rate reaches at least over 40%. This is a method for producing a carbonized material for a building material or the like in which a carbonized material is obtained while leaving a carbon chain.

As a more desirable structure, a cellulose compound is added to a phosphorus compound such as phosphoric acid or a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof. A step of impregnating the additive liquid composed of any one of the mixtures with the cellulose-based fibrous body impregnated with the additive liquid in an active atmosphere at about 65
The heat treatment is performed for a required time according to the concentration of the additive liquid within a temperature range of about 400 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C., thereby suppressing generation of flammable gas due to heating or flame. A step of promoting dehydration and carbonization to increase the amount of carbonized residue; a step of increasing the amount of carbonized residue and stopping the heat treatment when the weight reduction rate reaches at least over 40%; A step of removing or removing as much as possible the additive liquid component, a step of drying the carbonized material from which the residual additive liquid component has been removed, and by the above steps, to obtain a carbonized material while leaving the carbon chain in the middle of dehydration and carbonization of cellulose. A method for producing a carbonized material for a building material or the like having the above configuration as a gist.

In the method for producing a carbonized material for building materials and the like according to the present invention having the above-described structure, an old newspaper or an old newspaper is used as a pretreatment step of a step of impregnating a cellulosic fiber sheet body with an additive liquid. A myriad of perforations that penetrate through the thickness direction of the cellulosic fibrous sheet body, which is made up of laminated paper and other paper materials such as magazines, with a thickness of up to about 2 cm, in an averaged arrangement over the entire plane. And a method for producing a sheet-like carbonized material for building materials and the like, which is obtained by incorporating a step of perforating a laminated sheet to obtain a carbonized sheet laminate in a thick plate shape while maintaining flexibility.

As described above, the cellulosic fibrous body is intended to cover various types and properties of the cellulosic fibrous body as described above in the carbonized material for building materials and the like, which is the basis of the present invention. In addition, it exerts an inhibitory effect on the generation of non-combustible gas during the thermal decomposition of cellulose, the masking effect by vitrification, and the generation of flammable gas due to chemical change (esterification), and promotes the dehydration and carbonization of cellulose to promote carbonization. It must be able to perform the function of increasing the amount of the residue, and a phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
Ammonium sulfate, boric acid, or a mixture thereof with any one or more of the derivatives thereof, and may be formed by any appropriate means, such as dipping, coating or spraying, and the like. The additive liquid is impregnated into the entire cellulosic fibrous body by an appropriate means capable of impregnating the inside of the thickness direction as uniformly as possible.

In the case where the target cellulosic fibrous body is a sheet body, the additional liquid impregnating step can be performed collectively so that a plurality of sheets are laminated. At that time, in order to increase the permeation efficiency of the additive liquid and to realize a homogeneous permeation state inside the thickness direction, the entire plane of the laminated cellulose fiber sheet was averaged as much as possible. The pretreatment step of forming an infinite number of perforation holes penetrating in the thickness direction in the arrangement should be performed before the addition liquid impregnation processing step, and further, the heat treatment step following the addition liquid impregnation processing step In, the heating temperature is uniformly transmitted within a short time from the surface side of the laminated cellulosic fiber sheet body to the depth direction in the laminated state, and uniform carbonization is realized on both the surface side and the depth. Progress, elementary To allow the overall quality stabilized, it is desirable to a restricted limit of lamination thickness of about approximately 2 cm.

The cellulosic fibrous body thus uniformly impregnated with the additive liquid is heated as it is in a wet state or once in a dry state. Normal thermal decomposition of cellulose starts at about 300 ° C., and the cellulose having the molecular structure shown in FIG. 2 is converted into repoglucosan (β-glucosan C6H10O5) in FIG.
Combustible gas (furfuryl alcohol C5H6O
2, furfural C5H4O2, methanol CH
4O, ethanol C2H6O, acetaldehyde C
2H6O, glyoxal C2H2O2, etc.).

In the production method of the present invention, the pyrolysis that does not generate levoglucosan in the usual pyrolysis process of cellulose proceeds, thereby suppressing the subsequent decomposition into combustible gas and increasing the carbonization residue. Things. Therefore, in the heating step of the present invention, the target cellulosic fibrous body requires the above-described additive liquid impregnating step in advance, and does not generate levoglucosan even during the thermal decomposition of cellulose. Efficient esterification reaction by acid such as phosphoric acid and decompose cellulose into hemicellulose and decompose to polysaccharide phosphate ester without decomposing cellulose. This is to perform carbonization.

This heating step must be continued at least until the weight reduction rate reaches a little over 40%, which is a standard for confirming that the carbonization has progressed to a predetermined degree in the above-mentioned process. In the heat treatment, dehydration and carbonization are promoted while suppressing generation of combustible gas due to heating or flame.

FIG. 4 shows the dehydration reaction from the esterification of cellulose with phosphoric acid, the dehydration position, and the resulting structure.
In the dehydration reaction from the esterification, the hemicellulose in FIG. 4-1 is esterified by phosphoric acid treatment as shown in FIG. Will be decomposed. As described above, cellulose is prevented from becoming levoglucosan by the dehydration reaction of phosphoric acid or the like, so that generation of combustible gas is suppressed, and efficient dehydration and carbonization is performed without involving a flame. It has been confirmed that this reaction can be realized even at a low temperature of 300 ° C. or lower, which is generally said to cause thermal decomposition of cellulose.

When phosphoric acid was added to cellulose and the endothermic reaction of the cellulose during heating was measured by suggestive thermal analysis (DTA), as shown in FIG. 5, as the amount of added phosphoric acid increased, the endothermicity of the cellulose increased. It is known that the peak shifts to a lower temperature side, and from this fact, it is clear that the dehydration reaction of cellulose occurs in preference to the production of lepoglucosan and the like. Further, when a phosphoric acid compound is added to cellulose and heated, as shown in FIG. 6, the rate of heat generation decreases as the amount of phosphorus added increases, so that the combustion of cellulose is performed slowly and the oxidation reaction without a flame is performed. It turns out that it shifts to.

FIG. 7 to FIG. 9 show the weight loss due to the phosphoric acid treatment concentration of the cellulose and the heating temperature by the constant temperature drier, and FIGS. 10 to 12 show the reduction rate. As can be seen from FIGS. 7 and 10, in the dryer set at 100 ° C., the weight change of the cellulose not treated with phosphoric acid (Kim towel white) is 72 hours after the weight change within 1 hour, which is considered to be the attached moisture. No change in weight was observed (a slight change was slight moisture absorption until measurement). However, in the case of the heat treatment by phosphoric acid impregnation of the present invention, the weight loss increases with the treatment concentration of phosphoric acid.

Therefore, even at 100 ° C., which is lower than the normal decomposition temperature of cellulose (250 ° C.), a sufficient dehydration reaction occurs depending on the concentration of phosphoric acid. It has been confirmed that carbonization occurs even after 65 ° C., which is the ammonia desorption temperature.

As shown in FIG. 8 and FIG.
In a dryer set at 50 ° C., remarkable dehydration carbonization occurs at 100 ° C. or higher, and a large weight loss is observed even in a low-concentration phosphoric acid-treated product.
% To 40%, but 1% for untreated products
After the initial weight loss within hours, there is almost no change in weight. That is, it is understood that cellulose is not normally decomposed at 150 ° C., but dehydration carbonization is caused by the heat treatment after the impregnation of the additive liquid.

At 200 ° C., as shown in FIGS. 9 and 12, the dehydration carbonization effect is remarkable, and the weight change within one hour is the largest, and the weight change thereafter is small with a small amount of the impregnation treatment with the additive liquid. Cellulose is larger. Also, the cellulose untreated with the additive liquid began to decompose after 24 hours, and after 72 hours, the weight was reduced to the same level as that of the treated article impregnated with the additive liquid. The surface of the product was almost brown and adhesion of tar was observed.
No change in the surface after time was observed, but a small amount of the impregnated solution (1.1% P) resulted in a hard and inflexible carbonized sheet as compared with a large amount of the impregnated solution. .

It is thought that the flexibility due to the residual carbon chains of the polysaccharide disappeared by the impregnation of the cellulose with the additive liquid as a result of the decomposition of the carbon into a simple substance in accordance with the small amount of the impregnation with the additive liquid. Can be From this fact,
It can be seen that the flexibility of the carbonized material can be adjusted by changing the amount of the impregnated liquid. From the results of X-ray diffraction data (FIG. 1) of the specimen treated with cellulose in a normal inert gas atmosphere and the specimen according to the present invention and virgin pulp (kim towel paper) as a raw material, the additive liquid was obtained. The fact that the carbonized material of the present invention, which has been impregnated and heat-treated, causes a part of the carbonized chain of cellulose to remain in the carbonized sheet and slightly retains the characteristics of paper is as described above.

[0035]

Example 1 Cellulose fibrous material such as paper and cotton was impregnated with an additive solution containing phosphoric acid as a main component, and then subjected to approximately 65 ° C.
To about 400 ° C., preferably about 80 ° C. to 3
Heat treatment is carried out within a temperature range of about 00 ° C., and the heat treatment is continued until the weight reduction rate, which is a measure of the progress of carbonization, reaches a little over 40%.
Sublimation or the like of phosphoric acid due to treatment such as neutralization suppresses removal and action of the residual additive solution, and produces a flexible carbonized sheet or carbonized felt at low cost.

[0036]

Embodiment 2 This embodiment shows a typical embodiment in which a cellulosic fibrous body is once defibrated and then formed into a board by appropriate means and carbonized.
A more specific description will be added according to the process diagram shown in FIG. First, in the defibration process, waste paper and rice straw, etc., which have been transported as raw materials, are subdivided by known means such as shredders and crushers, and in the case of books and magazines, clasps such as staples are crushed and mixed. In addition to the above, there is a possibility that foreign matter may enter the recovery stage. Therefore, a process of removing such foreign matter such as metal and stone by air classification or a magnetic separator should be performed in parallel. The defibrating means may be any known one such as a wet type, a semi-dry type, and a dry type.

As the additive solution, a commercially available phosphoric acid solution, for example, a plating additive solution, or a fertilizer such as ammonium sulfate or phosphorous phosphorus can be used for economic reasons. What is necessary is just to select and employ | adopt suitably according to the usage purpose etc. of the carbonized material after a process. In addition, the use of inexpensive boric acid or borax is also effective for termite control, etc., and is sent to these additive liquid impregnation steps.

The additive solution used in this step may be a commercially available phosphoric acid solution such as a plating additive solution, ammonium sulfate,
It is also possible to use a fertilizer such as phosphorus phosphorus, and what kind of solution to which phosphoric acid is to be used may be appropriately selected and used depending on the purpose of use of the carbonized material after the treatment.
Use of inexpensive boric acid or borax is also effective for termite control, and the use of a mixture thereof is also effective.

The additive liquid treatment may be performed by a method such as spray coating or immersion, or by mixing the additive liquid powder and the defibrated fibers in a dry state, then blending them with steam, and further performing preheating. In the case of the wet method, a method of mixing a foaming agent, a foaming agent, and the like to collide with air may be considered. There is also a method in which dust scattering prevention and addition liquid impregnation are simultaneously performed by spraying with an aqueous solution or the like at the time of defibration in the opened defibration step.

The cellulosic fibrous body that has been subjected to the additive liquid impregnating treatment in this way continues to the heating step. This step is
In order to dehydrate and carbonize the treated cellulosic fibrous body, it is preferable to perform the drying in a dry state as much as possible, which leads to a loss of heating energy. In particular, in the case of a heat treatment in a low temperature range such as 65 to 100 ° C., this drying step is performed. Is a mandatory condition. If the heat source for the heat treatment is ammonium sulfate, a mixture of phosphorus and ammonium, or sulfuric acid, carbonization occurs from a low temperature range of around 65 ° C. Therefore, it is easy to use waste heat in addition to electricity, gas, petroleum, etc. In this case, since the reaction occurs slowly, it is possible to obtain a material which is in the process of decomposing cellulose, and to apply it to fertilizers and the like. In addition, even if it is directly heated by a flame, carbonization is performed while controlling the flammable gas by the effect of the additive liquid, so that there is less fear of fire. (If the concentration of the additive solution is low or the mixture does not contain a sulfate group, there is a risk of ignition at high temperatures, so that sufficient care must be taken in the formulation of the additive solution.)

The processing time required for this heating step depends on the concentration of the additive solution (1.5 to 15%) and the heating temperature (65 to 400 ° C.).
According to the correlation with C), it must be carried out continuously until the weight phenomenon rate reaches at least a little over 40%. If the heat source of the heat treatment is ammonium sulfate, a mixture of phosphorus and sulfuric acid, and carbonization occurs from 65 ° C,
In addition to electricity, gas, petroleum, etc., waste heat can be used,
In the heat treatment in the low temperature range, the reaction occurs slowly, so that the material can be used during the decomposition of cellulose,
Application to fertilizer and others is possible. In addition, even if it is directly heated by a flame, carbonization is performed while suppressing the flammable gas by the effect of the additive liquid, so that there is less fear of fire. (If the concentration of the additive solution is low or the mixture does not contain a sulfate group, there is a risk of ignition at high temperatures, so that sufficient care must be taken in the formulation.)

[0042]

Example 3 Waste paper fiber and inorganic fiber such as rock wool are mixed and molded, impregnated with the additive liquid used in Example 3, and then heated with a hot air dryer at 180 ° C. (heating at a high frequency is also possible). Yes) and carbonized to form a board with high shape retention strength and flexibility.

[0043]

The carbonizing material for construction and the like of the present invention and the method for producing the same according to the present invention, which are constituted as described above, pay attention to the thermal decomposition mechanism of cellulose, and can suppress the generation of combustible gas by chemicals and carbonize it. It is based on the knowledge that it is possible to impregnate the cellulosic fibrous body with an additive liquid containing phosphoric acid as a main component, and until the weight loss rate reaches a little over 40%, which is a measure for confirming the completion of carbonization. Heat treatment to promote dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame, so that it is in high-temperature air (in an inert gas atmosphere and does not shut off oxygen)
Does not generate levoglucosan (tar component), so that no flammable gas is generated and dehydration carbonization does not involve a flame (reduces the risk of fire). Therefore, air pollution may occur during the manufacturing process. It has no major features, and it has the major features of preventing the occurrence of fire, ensuring the safety of work, and efficiently generating carbon.

When the concentration of phosphoric acid impregnated in the cellulosic fibrous body is less than 1%, carbonization hardly proceeds, and when the concentration exceeds 20%, a flexible carbonized material is obtained. Very subtle and impractical,
Therefore, the concentration is 1 to 20%, desirably 1.5 to 15
% Or more, and the heating temperature is practically 65 to 40.
Since the heat treatment is performed at a temperature range of 0 ° C., preferably around 80 to 300 ° C., a carbon chain can be left in the carbonized material, and a flexible carbonized material can be realized. In the case of manufacturing materials such as heat insulating materials, sound absorbing materials, underfloor moisture absorbing materials, and fire-resistant coating materials, powder scattering from carbonized materials is almost eliminated, workability is extremely improved, and efficient manufacturing is enabled. In addition, the use of inexpensive chemicals (ammonium sulfate and phosphorus ammonium are sold as fertilizers) as additive liquids, and also enables production with a simple heating device, and the use of high-performance building materials An excellent effect that it can be provided at a considerably low price can be expected.

Also, in the present invention,
Cellulosic fibrous materials that are buried as waste or incinerated or otherwise treated in an enormous amount, such as waste paper such as newspapers and magazines and used corrugated paper, or construction sites and Sawmill, woodworking shop,
It can be used as an effective waste disposal means because it can cover various cellulosic fibrous materials in general, such as waste materials and wood chips generated in large quantities from timber landing wharves and rice husks and straw from rice farmers. It has the advantage of being able to. In particular, in the case of the carbonized material for building material and the like and the method of manufacturing the material shown as a representative example of the present invention, it is necessary to ensure that these characteristics can be achieved and make it extremely practical. it can.

As described above, the carbonized material for building materials and the like having the novel structure of the present invention and the method for producing the same are intended to be able to achieve the intended purpose in general. In addition to being highly evaluated as an effective utilization means of cellulosic fibrous materials as wastes, as a means that can easily and reliably treat those wastes without generating harmful by-products such as dioxins, sufficient It is expected that it will gain trust and will be adopted and spread widely.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a comparison graph showing composition analysis of three types of raw material, cellulose (virgin pulp), charcoal treated by phosphoric acid, and charcoal heated in a normal inert atmosphere by X-ray diffraction.

FIG. 2 is a structural formula of cellulose.

FIG. 3 is a structural formula of a flammable gas generated by pyrolysis of levoglucosan (tar component), which is generated by ordinary pyrolysis of cellulose.

FIG. 4 is a structural formula of a phosphoric acid dehydration reaction of cellulose.

FIG. 4-1 is a structural formula showing a change due to dehydration of cellulose.

FIG. 4-2 is a structural formula illustrating a dehydrating action from esterification by phosphoric acid.

FIG. 5 is a graph comparing the change in heat absorption and heat generation due to the difference in concentration with the data of differential thermal analysis (measurement of heat absorption and heat generation) during heating of cellulose treated with phosphoric acid.

FIG. 6 is a graph showing a change in heat generation rate when burning cellulose (cotton) treated with a phosphate compound.

FIG. 7 is a graph showing a change in weight at a heating temperature of 100 ° C. due to a difference in the concentration of a phosphoric acid treatment of cellulose.

FIG. 8 is a graph showing a change in weight at a heating temperature of 150 ° C. depending on a difference in the phosphoric acid treatment concentration of cellulose.

FIG. 9 is a graph showing a change in weight at a heating temperature of 200 ° C. due to a difference in the concentration of phosphoric acid treatment of cellulose.

FIG. 10 is a graph showing a weight change rate at a heating temperature of 100 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 11 is a graph showing a weight change rate at a heating temperature of 150 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 12 is a graph showing a weight change rate at a heating temperature of 200 ° C. depending on a difference in a phosphoric acid treatment concentration of cellulose.

FIG. 13 is a manufacturing process diagram of a typical example of carbonizing a board made of a cellulosic fibrous body once defibrated.

Claims (9)

[Claims] 1. A phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
A cellulosic fibrous body impregnated with an additive liquid consisting of either one of ammonium sulfate, boric acid, or a derivative thereof, or a mixture of two or more thereof, is subjected to approximately 65 ° C. to 400 ° C. in an active atmosphere. C, preferably within a temperature range of about 80 ° C. to 300 ° C.,
Heat treatment for the required time according to the concentration of the additive liquid, and promote dehydration and carbonization while suppressing generation of flammable gas due to heating or flame, increase carbonization residue, and increase carbonization residue to at least a weight reduction rate of more than 40%. A carbonized material for building materials, etc., characterized in that it is used as a material. 2. A phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
A cellulosic fiber sheet impregnated with an additive liquid consisting of any one of ammonium sulfate, boric acid or a derivative thereof, or a mixture of two or more thereof, is subjected to an active atmosphere at about 65 ° C. to 400 ° C. ° C, desirably within a temperature range of about 80 ° C to 300 ° C, and heat-treats for a required time according to the concentration of the additive liquid, and dehydrates while suppressing generation of flammable gas due to heating or flame. Promote carbonization to increase carbonization residue, at least a weight reduction rate of just over 40%, leave carbon chains in the middle of dehydration carbonization of cellulose, and maintain a carbonized material while maintaining the shape and flexibility of the sheet. A sheet-like material characterized in that it can be handled as a single-layer or laminated shape-retaining material by itself or in combination with other materials. For building materials such as carbide material. 3. A phosphorus compound such as phosphoric acid or a phosphorus compound and sulfuric acid;
A cellulosic fiber sheet impregnated with an additive liquid consisting of any one of ammonium sulfate, boric acid or a derivative thereof, or a mixture of two or more thereof, is subjected to an active atmosphere at about 65 ° C. to 400 ° C. ° C, desirably within a temperature range of about 80 ° C to 300 ° C, and heat-treats for a required time according to the concentration of the additive liquid, and dehydrates while suppressing generation of flammable gas due to heating or flame. Promote carbonization to increase carbonization residue, at least a weight reduction rate of just over 40%, leave carbon chains in the middle of dehydration carbonization of cellulose, and maintain a carbonized material while maintaining the shape and flexibility of the sheet. By itself or combined with other materials, it can be handled as a single-layer or laminated shape-retaining material, non-combustible insulation and moisture absorbing material, sound absorbing material, Sheet building materials for carbide material, characterized in that as a Nioizai. 4. A phosphorus compound such as phosphoric acid, or a phosphorus compound and sulfuric acid,
A cellulosic fiber sheet impregnated with an additive liquid consisting of any one of ammonium sulfate, boric acid or a derivative thereof, or a mixture of two or more thereof, is subjected to an active atmosphere at about 65 ° C. to 400 ° C. ° C, desirably within a temperature range of about 80 ° C to 300 ° C, and heat-treats for a required time according to the concentration of the additive liquid, and dehydrates while suppressing generation of flammable gas due to heating or flame. Carbonization is promoted to increase the carbonization residue, at least a weight reduction rate of more than 40% is reached, and the carbon chain in the middle of the dehydration carbonization of cellulose is left as a carbonized material while maintaining the sheet shape and flexibility. The building material according to any one of claims 1 to 3, wherein the material is subjected to boric acid treatment so as to have a function of preventing insects such as termites for covering wood. Carbide material. 5. The cellulosic fibrous body is a cellulosic fibrous sheet having a special structure such as paperboard, paper towel, corrugated cardboard, etc., and is made into a carbonized material with the special structure before treatment. 5. The carbonized material for building materials or the like according to any one of 1 to 4 above. 6. The method according to claim 1, wherein the cellulosic fibrous body is a plant waste such as rice husk, straw, bark, etc., and is made into a carbonized material in the form before treatment. Carbonized materials for building materials. 7. An addition of a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, and derivatives thereof to a cellulosic fibrous body. Step of impregnating the liquid, and adding the cellulosic fibrous body impregnated with the additive liquid in an active atmosphere at about 65 ° C. to 400 ° C., preferably about 8 ° C.
Within a temperature range of about 0 ° C. to 300 ° C., heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing generation of flammable gas due to heating or flame, and carbonization residue is generated. The step of increasing the amount of carbonization, the step of increasing the amount of carbonized residue, and stopping the heat treatment when the weight loss rate reaches at least over 40%; The method for producing a carbonized material for building materials according to any one of claims 1 to 6, wherein a carbonized material is obtained. 8. Addition to a cellulosic fibrous body comprising a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound with one or more of sulfuric acid, ammonium sulfate, boric acid, or a derivative thereof. Step of impregnating the liquid, and adding the cellulosic fibrous body impregnated with the additive liquid to about 65 ° C. to 400 ° C., preferably about 8
Within a temperature range of about 0 ° C. to 300 ° C., heat treatment is performed for a required time according to the concentration of the additive liquid, and dehydration and carbonization are promoted while suppressing generation of flammable gas due to heating or flame, and carbonization residue is generated. A step of increasing the amount of carbonized residue, a step of stopping the heat treatment when the weight reduction rate reaches at least 40% or more, a step of washing the carbonized material with water to remove residual additive liquid components or remove as much as possible, A step of drying the carbonized material from which the residual additive liquid component has been removed, by the above steps, a carbonized material having a carbon chain remaining during the dehydration and carbonization of cellulose is obtained. 6. The method for producing a carbonized material for building materials or the like according to any one of 6. 9. Thickness of waste paper and other paper materials such as old newspapers and old magazines is arranged as evenly as possible over the entire plane of a cellulosic fibrous sheet body laminated up to a thickness of about 2 cm. The step of forming an infinite number of perforation holes penetrating in the vertical direction is incorporated before the step of impregnating the cellulosic fibrous sheet body with the additive liquid, and while maintaining the flexibility in the form of a thick plate from the laminated paper. The method for producing a sheet-like carbonized material for a building material or the like according to claim 7, wherein the carbonized sheet laminate of (1) is obtained.