JP3742985B2 - Carbonized material for building materials, etc., and method for producing the same - Google Patents

Description

[0001]
OBJECT OF THE INVENTION
The present invention relates to a carbonized material suitable as a nonflammable functional material, for example, a heat insulating material for building materials, a soundproofing material, a hygroscopic material, and the like, and is a cellulosic fiber body, particularly one of an advanced society. Cellulosic fiber bodies such as waste paper in a large amount of waste that can be symbolized, waste wood, bark, and agricultural by-products such as rice husks and straws can be easily used as raw materials, and it is extremely inexpensive and efficient. Carbonized materials for building materials, etc. with a new structure, which can be used for heat insulating materials for building materials, soundproofing materials, hygroscopic materials, etc. A new manufacturing method for this purpose is to be provided.
[0002]
[Prior art]
Amid a rich environment both economically and culturally, a large amount of material is consumed every day regardless of corporate management and family life, and the various wastes generated in the process are now an economic burden. It is not a problem but its handling has become a very big social problem from the viewpoint of natural environment conservation.
In particular, looking at the handling of a large amount of used paper, which is said to be a barometer of advanced economic society, newspapers and some magazines currently use recycled paper using recovered paper, but that Recycled paper itself is not made of 100% recovered paper, but it is reused as a product that stabilizes quality by adding virgin pulp at some percentage. The current situation is that, even with the cooperation of the industry that actively uses recycled paper, the demand of the used paper market cannot be satisfied.
[0003]
Such surplus waste paper that cannot be reused or waste paper that is discarded without being collected is burned in an incinerator together with other combustible waste, etc., and harmful dioxins are produced by burning paper containing prohibited items. It is considered to be a major cause of the destruction of the natural environment as a result of being released into the atmosphere, and a large amount of social capital investment is required for the construction of a high-performance incineration plant that is less likely to occur, or a final landfill position is secured. For this reason, the government will be engulfed by policy issues such as planning for various difficulties and having to work on planning. This waste disposal problem is caused by other cellulosic materials, such as waste paper and wood waste generated in large quantities from waste paper, construction sites, sawmills, woodworking processing plants, timber landing wharfs, etc. It is a problem that the fiber body as a whole has as well.
[0004]
Examples of techniques for treating and processing cellulosic fiber bodies by means other than incineration disposal include, for example, Japanese Patent Application Laid-Open No. 62-15645, “Production Method of Fibrous Activated Carbon” (Toho Rayon), Japanese Patent Application Laid-Open No. Hei 4 No. 231314 “Method for producing high surface area activated carbon” (Eucer Carbon Technology Co .: USA), Japanese Patent Application Laid-Open No. 6-56416 “Method for producing activated carbon” (West Vaco Co .: USA), etc. Has been established for a long time as a basic material for fields that require the excellent chemical treatment function of activated carbon, that is, the deodorization function, filtration function, anion generation function, etc. .
[0005]
However, in the case of activated carbon produced by these various active carbonization technologies, its use is related to a very special field, and high quality and performance are required as a material that meets the demand, so it should be treated. In addition to the fact that the quality of raw materials is limited and a considerable initial investment is required for the development of high-performance equipment, for example, the Toho Rayon Technology mentioned above, the oxidation process In order to shorten the required time, the oxidation process is divided into two parts, a pre-oxidation treatment at 300 to 400 ° C. in an inert atmosphere with an oxygen content of 0.5 to 5%, a steam and carbon dioxide atmosphere, 700 It requires a two-step oxidation process called the main oxidation process in a high temperature range of ˜1000 ° C., or Yuker Carbon Technology Co. In the technology, the cellulose-based material is treated with an additive solution such as phosphoric acid, carbonized in an inert atmosphere of 450 to 1200 ° C., and further activated in an oxidizing atmosphere such as steam of 700 ° C. or higher. And Westvaco Co. Like technology, wood (lignocellulose) is targeted, they are finely pulverized and carbonized, and then the carbonized powder is molded again, both of which involve complicated processing steps and high operability. Therefore, it is economically and economically to treat waste paper and waste materials that occur in large quantities every day and have large variations in quality as cellulosic fibers to be treated. Is something that should be almost impossible.
[0006]
On the other hand, it is not used in such advanced fields, but is processed by traditional carbonization means for use as fuel, soil improvement materials, moisture-proof materials, heat insulating materials, sound absorbing materials, etc. A method is also conceivable. This charcoal burning technique is based on a manufacturing method in which wood materials and the like are burned at a high temperature, then oxygen is cut off and steamed by a dehydration action at a high temperature, and cellulose is decomposed and carbonized. It has not changed since ancient times.
[0007]
However, in the charcoal burning process in which both the process of burning in a high temperature region and the subsequent process of shutting off oxygen and incomplete combustion are indispensable, a large amount of carbon dioxide and carbon monoxide are generated in any process. In addition, it has the most troublesome problem today that directly leads to air pollution, and there is a fact that it is completely unsuitable for carbonization of film-like or granular cellulosic fibrous bodies such as waste paper and wood chips.
[0008]
To make matters worse, the charcoal produced by this traditional means has a solid structure in which the carbon chain in the composition is cut, so naturally it does not have properties such as flexibility and elasticity. Therefore, if it is intended to be used as a moisture-proof material, heat insulating material, sound absorbing material, etc. on an uneven surface or curved surface of a building frame, equipment, etc., once solid carbon is pulverized, the carbon powder Can be applied and bonded, kneaded into a binder such as resin, or remolded, or mixed and adhered to fibers as appropriate, and molded into a flexible product as a whole. In addition to this, secondary treatment processing is indispensable for use, and there are also the disadvantages that extra consideration and cost are required for countermeasures against dust coal generated in the secondary treatment processing step. Came from What so far, the carbonization of the traditional charcoal type is also applied as the processing technique used paper and waste materials such as cellulose fiber material to generate a large amount everyday, it is impossible to find the facts that have been put to practical use.
[0009]
In view of the circumstances as described above, the present invention has not been effectively used so far within a very limited range, and a considerable amount of it is used for incineration or landfill disposal at a large cost. Attention is also focused on the cellulosic fiber body that has been made, especially waste paper, and carbon (that is, carbonized cellulose) is also attracted to the non-flammability of oxygen index 65 and high thermal insulation, In order to pursue the possibility of application to building materials, etc. as a large-scale usage destination, we have quickly started development and research, and repeated trial and error such as trying many trial experiments, etc. As a result, waste paper with high flammability etc. Can be carbonized efficiently, and the carbonized material for building materials with a new structure that maintains the flexibility of used paper and the carbonized material for building materials can be reliably and economically used. Produce Which has led to the completion of the manufacturing process of new construction materials for carbide material that allows.
[0010]
[Structure of the invention]
The carbonized material for building materials and the like according to the present invention basically has the following configuration.
That is, a cellulosic fiber impregnated with an additive solution comprising either a phosphorous compound such as phosphoric acid or a phosphorous compound and any one or a mixture of sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof. The body is heated in an active atmosphere within a temperature range of about 65 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C. for a required time according to the concentration of the added solution, Or it is a carbonization material for building materials etc. which consists of the carbonization material which accelerated | stimulated dehydration and carbonization, increased the carbonization residue, suppressing the generation | occurrence | production of the combustible gas by a flame, and reached at least 40% of weight reduction rate.
[0011]
In the carbonization material for building materials and the like according to this basic structure, a more desirable structure includes a phosphorous compound such as phosphoric acid, a phosphorous compound and sulfuric acid, ammonium sulfate, boric acid, or a derivative thereof, or A cellulosic fiber sheet body impregnated with an additive liquid consisting of any of a mixture of two or more is about 65 ° C to 400 ° C, preferably about 80 ° C to 300 ° C in an active atmosphere. Heat treatment within the temperature range of about C and for the required time according to the concentration of the additive solution, while increasing the carbonization residue by promoting dehydration and carbonization while suppressing the generation of flammable gas by heating or flame, at least weight By reaching a reduction rate of slightly over 40%, leaving a carbon chain in the middle of dehydration carbonization of cellulose, and making it a carbonized material that maintains its sheet shape and flexibility And either combined with either alone or in other materials, a single layer or sheet-like building materials for carbide material was made to be handled as a shape retaining material of the laminated structure is included.
[0012]
The carbonized material for building materials and the like having such a desirable structure is composed of either a phosphorus compound such as phosphoric acid, or a mixture of the phosphorus compound and one or more of sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof. The cellulosic fiber sheet body impregnated with the additive solution is within a temperature range of about 65 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C. in an active atmosphere, and the concentration of the additive solution Heat treatment for the required time according to the conditions, dehydration and carbonization are promoted while suppressing the generation of flammable gas by heating or flame, carbonization residue is increased, and at least a weight reduction rate of 40% is reached. By leaving the carbon chain in the middle and making it a carbonized material that maintains the sheet shape and flexibility, it can be used alone or in combination with other materials to form a single layer. None allows handled as shape retaining material of the laminated structure, may also indicate incombustible insulation material and absorbent material, sound absorbing material, as a sheet-like building materials for carbide material was made to deodorizing material.
[0013]
Furthermore, the carbonization materials for building materials and the like which are based on the basic configuration described above and the desirable configurations therein include the carbonization materials for building materials and the like which can be shown by the following configurations.
Cellulosic fiber sheet body impregnated with a phosphorous compound such as phosphoric acid, or an additive liquid composed of any one of phosphorous compounds and sulfuric acid, ammonium sulfate, boric acid, or a mixture thereof. In an active atmosphere within a temperature range of about 65 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C., for a required time according to the concentration of the additive solution, While suppressing the generation of flammable gas due to the flame, dehydration and carbonization are promoted to increase the carbonization residue, and the weight reduction rate reaches 40%, leaving the carbon chain in the middle of the dehydration carbonization of cellulose, and the sheet body shape and flexibility Charcoal for building materials that has been given a pest control function, such as termites, for wood coating by making it a carbonized material that maintains its properties and then treating with boric acid. Material is it.
[0014]
Cellulosic fiber bodies are the most representative ones such as used paper such as newspapers and magazines, and used corrugated paper, but other construction sites, lumber mills, woodworking factories, wood landing wharves, etc. It can also be applied to other cellulosic fibers in general, such as waste materials and wood chips generated in large quantities from rice farms, rice husks and straws from rice farmers, etc. As a raw material to be used for hygroscopic materials, etc., for example, paper made specially in a bulky structure such as a paper towel, roll paper toilet paper, etc. Of course, it is also intended to be used as it is or processed as appropriate, and the properties are also flat, sheet-like Special reasons that must be particularly restricted, such as those having a laminated structure, a block shape, a box or a cylinder, a granular or powdery shape, a straw shape, a rod shape, etc. However, it is intended for cellulosic fiber bodies of various types and properties.
[0015]
The additive liquid exerts an inhibitory effect on the generation of incombustible gas during pyrolysis of cellulose, concealing action due to vitrification, and generation of flammable gas due to chemical change (esterification). It must be capable of promoting the function of increasing the amount of carbonized residue, and either one or two of phosphorous compounds such as phosphoric acid, phosphorous compounds and sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof It shall consist of any of the above mixtures.
[0016]
The cellulosic fiber body impregnated with the additive solution is within a temperature range of about 65 ° C. to 400 ° C., preferably about 80 ° C. to 300 ° C., under an active atmosphere. By performing heat treatment only for the required time according to the concentration and reaching a weight reduction rate of more than 40%, the carbonization residue is increased and the predetermined carbonization ends, and carbon during the dehydration carbonization of cellulose in the material composition Carbonized material for building materials, etc. made of carbonized material with the chain remaining.
[0017]
Even at a predetermined heat treatment temperature within a temperature range of about 65 ° C. to 400 ° C., a material with a small amount of impregnation with the additive liquid becomes a hard carbonized material and is softer than a material with a large amount of impregnation. It makes a difference in sex. This is due to the difference in the residual ratio of the carbon chain of the polysaccharide in the treated cellulose as the amount of the additive solution increases, and as a result of decomposition to carbon alone due to the small amount of the additive solution impregnated, the flexibility, that is, Therefore, it can be said that the flexibility of the obtained carbonized material can be adjusted by controlling the amount of the additive liquid impregnated.
[0018]
Carbonization with flexibility remaining in this way is possible in the normal air after the test piece (charcoal) treated with cellulose in a normal inert gas atmosphere and the additive solution impregnation treatment. When comparing the X-ray diffraction data of the specimen of the present invention heated and carbonized with virgin pulp (Kim towel ... paper) as the raw material of each specimen, as shown in FIG. Pulp) is characterized by a 15 ° (2θ) broad peak and a peak around 23 °, whereas in the case of the specimen (charcoal), a weak broad peak of 20 ° to 30 °. In the case of the specimen of the present invention, although it appears only as (it is difficult to express as a peak), an apparent peak appears even if it does not become a peak as much as virgin pulp. Obtained by liquid impregnation treatment The carbonized material has some characteristics of the paper that is the raw material, and a part of the carbonized chain of cellulose remains in the carbonized material, which is considered to contribute to the flexibility remaining close to the raw material.
[0019]
On the other hand, the carbonized material for building materials of this invention has an oxygen index (oxygen index is the oxygen concentration necessary for combustion) of the chart (carbonized layer) of 65, and that of the raw material is 18 and is a flammable substance. Compared to other materials, the material has much higher incombustibility and heat insulation, and naturally it can be used as an incombustible material, and its chart has a large specific surface area and high adsorption power. Because it has a function as a moisture absorbent and deodorant, it can also be expected to adsorb gas, and since the chart contains a large amount of air and has high heat insulation performance, it has performance as an incombustible heat insulation material. At the same time, sound absorption characteristics are also obtained by the damping effect between the carbon fibers.
[0020]
[Related invention]
In relation to the carbonized material for building materials according to the present invention having the above-described configuration, the present invention includes a method for producing the carbonized material for building materials having the following configuration.
That is, the cellulose fiber body is impregnated with an additive liquid comprising either a phosphorous compound such as phosphoric acid, or a phosphor compound and any one or a mixture of sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof. A cellulose fiber body impregnated with the additive solution in an active atmosphere, in a temperature range of about 65 ° C to 400 ° C, preferably about 80 ° C to 300 ° C, Heat treatment for the required time according to the concentration of the additive solution, while suppressing the generation of flammable gas by heating or flame, promoting dehydration and carbonization to increase the carbonization residue, the carbonization residue increases, at least weight reduction The process of stopping the heat treatment when the rate reaches over 40%, the building material etc. that has obtained the carbonized material leaving the carbon chain in the middle of dehydration carbonization of cellulose by the above process, etc. A method for producing a carbide material.
[0021]
According to a more desirable configuration, the cellulosic fiber body may be a phosphorous compound such as phosphoric acid, or a mixture of phosphorous compound and one or more of sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof. The step of impregnating the additive liquid composed of any of the above, and the cellulosic fiber body impregnated with the additive liquid in an active atmosphere at about 65 ° C to 400 ° C, preferably about 80 ° C to 300 ° C. A process of increasing the carbonized residue by promoting dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame, within a temperature range of The process of stopping the heat treatment at least when the weight loss rate reaches over 40%, and removing the residual additive liquid component as much as possible by washing the carbonized material with water The process of drying the carbonized material from which the remaining additive liquid component has been removed, and the above-described process, for building materials and the like having a configuration in which the carbonized material is left with the carbon chain in the middle of dehydration carbonization of cellulose remaining. It can be set as the manufacturing method of a carbonization raw material.
[0022]
In addition, in the manufacturing method of the carbonized material for building materials and the like of the present invention having the above-described configuration, as a pretreatment step of impregnating the cellulose-based fiber sheet body with an additive liquid, as in an old newspaper or an old magazine Infinite number of permeation holes that penetrate the thickness direction in the averaged arrangement as much as possible on the entire plane of the cellulosic fiber sheet that is laminated with a maximum of about 2 cm thickness of used waste paper and other paper materials The manufacturing method of the carbonization raw material for sheet-like building materials etc. which incorporated the process to carry out and obtained the carbonization sheet laminated body which maintained the flexibility with thick board form from laminated paper is included.
[0023]
The cellulosic fiber body is intended for cellulosic fiber bodies of various types and properties as described above in the carbonization materials for building materials and the like that form the basis of the present invention. Inhibits non-combustible gas generation during pyrolysis, concealing action due to vitrification, and generation of flammable gas due to chemical change (esterification), and promotes dehydration and carbonization of cellulose to increase the amount of carbonized residue It must be capable of increasing the function of phosphorous compounds such as phosphoric acid, or a mixture of phosphorous compounds and one or more of sulfuric acid, ammonium sulfate, boric acid, or derivatives thereof Any suitable means such as dipping, coating, or spraying is included as homogeneously as possible not only in the surface of the cellulosic fiber body but also in the thickness direction. Solution added to the entire cellulosic fibrous body is made to be impregnated strip by suitable means capable.
[0024]
In addition, this additive liquid impregnation step can be carried out collectively so that a plurality of sheets are laminated when the cellulosic fiber body as a target is a sheet body. In order to increase the penetration efficiency of the additive liquid and to achieve a homogeneous penetration state in the thickness direction, the thickness of the laminated cellulosic fiber sheet body is as average as possible over the entire plane. The pretreatment process should be performed after drilling innumerable penetration holes penetrating in the vertical direction before entering the additive liquid impregnation treatment process. Further, in the heat treatment process following the additive liquid impregnation treatment process, heating is performed. The temperature is homogeneously transmitted in a short time from the surface side of the cellulosic fiber sheet body made into a laminated shape to the back in the thickness direction, and uniform carbonization proceeds on the surface side and the back, Overall material quality To stabilize, it is desirable to a restricted limit of lamination thickness of about approximately 2 cm.
[0025]
Thus, the cellulosic fiber body in which the additive solution is uniformly impregnated is heat-treated in a wet state or once in a dry state.
Normal pyrolysis of cellulose starts at about 300 ° C., and the cellulose having the molecular structure shown in FIG. 2 is converted to repoglucosan (β-glucosan C6H10O5) in FIG. 3 by pyrolysis, and further combustible gas (furfuryl). Alcohol C5H6O2, furfural C5H4O2, methanol CH4O, ethanol C2H6O, acetaldehyde C2H6O, glyoxal C2H2O2, etc.).
[0026]
In the production method of the present invention, thermal decomposition that does not produce levoglucosan in the normal pyrolysis process of cellulose proceeds, thereby suppressing subsequent decomposition into combustible gas and increasing carbonization residue. .
Therefore, in the heating process of the present invention, the subject cellulose-based fiber body requires the above-described additive solution impregnation step in advance, and the strong dehydration action of phosphoric acid and sulfuric acid so as not to produce levoglucosan even during the thermal decomposition of cellulose. By causing esterification reaction with acids such as phosphoric acid and decomposing cellulose into hemicellulose phosphates without rapidly decomposing cellulose, the production of tar and flammable gas is efficiently suppressed. Carbonization is performed.
[0027]
This heating step must be continued at least until reaching a weight reduction rate of slightly over 40%, which is a guideline for confirming that carbonization has progressed to a predetermined degree in the above-described process. Then, dehydration and carbonization are promoted while suppressing generation of combustible gas by heating or flame.
[0028]
FIG. 4 shows the dehydration reaction from the esterification of cellulose with phosphoric acid, the position of dehydration, and the resulting structure.
Then, the dehydration reaction from esterification is carried out as follows. The hemicellulose of FIG. 4-1 is esterified by phosphoric acid treatment as shown in FIG. 4-2, and then the cellulose is dehydrated when the phosphoric acid is separated again by continuous heat treatment. Will be disassembled.
As described above, cellulose is prevented from becoming levoglucosan by a dehydration reaction such as phosphoric acid. As a result, generation of combustible gas is suppressed, and efficient dehydration carbonization is performed without accompanying a flame. It has been confirmed that this reaction can be realized even at a low temperature of 300 ° C. or less, which is said to cause thermal decomposition of cellulose.
[0029]
As shown in FIG. 5, when the phosphoric acid is added to the cellulose and the endothermic reaction of the cellulose during heating is measured by thermal analysis (DTA), the endothermic peak of the cellulose decreases as the amount of phosphoric acid increases. It is known that the dehydration reaction of cellulose occurs in preference to the production of repoglucosan and the like. Further, when a phosphoric acid compound is added to the cellulose and heated, as shown in FIG. 6, the rate of heat generation decreases with an increase in the amount of phosphorus added, so that the cellulose is burned slowly and an oxidation reaction without a flame. It turns out that it will move to.
[0030]
FIGS. 7 to 9 show the weight loss due to the phosphoric acid treatment concentration on the cellulose and the heating temperature by a constant temperature dryer, 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 untreated cellulose (Kim towel white) is 72 hours after the weight change within 1 hour which seems to be adhering water. However, no change in weight is observed (a slight change is moisture absorption until measurement). However, in the case of heat treatment by phosphoric acid impregnation of the present invention, the weight loss increases with the treatment concentration of phosphoric acid.
[0031]
Therefore, even at 100 ° C, which is lower than the normal cellulose decomposition temperature (250 ° C), a sufficient dehydration reaction occurs depending on the concentration of phosphoric acid. It has been confirmed that carbonization occurs even after the temperature of 65 ° C.
[0032]
Further, as shown in FIGS. 8 and 11, in a dryer set at 150 ° C., remarkable dehydration carbonization occurs at 100 ° C. or higher, and a large weight reduction is observed even in a low concentration phosphoric acid treated product. Although the weight loss within the time is 23% to 40%, the untreated product of the additive solution shows almost no change in weight after the initial weight loss within 1 hour. That is, although cellulose does not decompose at 150 ° C., it can be seen that dehydration carbonization occurs by heat treatment after impregnation with the additive solution.
[0033]
At 200 ° C., as shown in FIG. 9 and FIG. 12, dehydration carbonization action appears remarkably, and the weight change within one hour is the largest. Is getting bigger.
In addition, the cellulose not treated with the additive solution also started to decompose after 24 hours, and after 72 hours, the weight decreased to the same level as that of the additive-impregnated treated product. The surface of the product was close to brown, and the tar content was observed, but the additive-impregnated product was black and no surface change was observed after 1 hour, but the amount of additive-impregnated treatment was small (1.1% P) was a carbonized sheet that was harder and less flexible than the one with a large amount of additive liquid impregnation.
[0034]
This is considered to be due to the fact that the flexibility due to the remaining carbon chain of the polysaccharide is lost by the cellulose impregnation liquid impregnation treatment, as a result of decomposition to carbon alone according to the small amount of the additive liquid impregnation treatment. From this fact, it can be seen that the flexibility of the carbonized material can be adjusted by changing the amount of the additive liquid impregnation treatment.
And from the X-ray diffraction data result (FIG. 1) of the specimen treated with cellulose in a normal inert gas atmosphere, the specimen according to the present invention, and virgin pulp (Kim towel ... paper) as a raw material, the additive solution The fact that the carbonized material of the present invention that has been impregnated and heat-treated remains part of the carbonized chain of cellulose in the carbonized sheet, leaving a little of the characteristics of the paper, as described above.
[0035]
[Example 1]
A cellulosic fiber body such as paper or cotton is impregnated with an additive liquid containing phosphoric acid as a main component, and a temperature range of about 65 ° C to 400 ° C, preferably about 80 ° C to 300 ° C. Heat treatment until the weight loss rate, which is a standard for confirming the degree of carbonization, reaches 40% or more, and then the remaining phosphoric acid is washed with water or neutralized as necessary. The sublimation of phosphoric acid and the like suppress the removal and action of the residual additive solution, and produce a flexible carbonized sheet and carbonized felt at low cost.
[0036]
[Example 2]
This example shows a typical example in which a cellulosic fiber body is defibrated once and then carbonized in a board shape by appropriate means. According to the process diagram shown in FIG. We will add specific explanations.
First, as a defibration process, waste paper and rice straw that have been transported as raw materials are subdivided by known means such as shredders and crushers, and in the case of books and magazines, staples such as staples are crushed and mixed. In addition, since foreign matter may be mixed in at the recovery stage, the process of removing foreign matter such as metals and stones by air classification or magnetic separation should be performed in parallel.
It should be noted that the defibrating means may be any of known methods such as wet, semi-dry, and dry methods.
[0037]
As the additive liquid, commercially available phosphoric acid liquid, for example, plating additive liquid, fertilizer such as ammonium sulfate, phosphoric acid, and the like can be used for economical reasons. What is necessary is just to make it select and employ | adopt suitably according to the intended purpose etc. of the carbonized material after a process. In addition, the combination of inexpensive boric acid and borax is also effective for controlling white ants, etc., and is sent to these additive liquid impregnation processes.
[0038]
As the additive solution used in this process, commercially available phosphoric acid solutions such as plating additive solutions and fertilizers such as ammonium sulfate and phosphorous acid can be used for economic reasons, and any phosphoric acid binding solution is used. Whether or not to do so may be appropriately selected and adopted depending on the purpose of use of the carbonized material after the treatment. In addition, the combined use of inexpensive boric acid or borax is effective for controlling white ants, and the use of these admixtures is also effective.
[0039]
In addition to spray coating and dipping, the additive solution treatment can be performed by mixing the additive solution powder and the defibrated fiber in a dry manner, then mixing them with steam and further preheating, or in a wet process. A method of mixing air with a foaming agent, a foaming agent, etc., and confronting air is also conceivable. There is also a method of performing dust scattering prevention and additive liquid impregnation treatment by an aqueous solution spray or the like at the same time during the defibration in the defibrating process.
[0040]
The cellulosic fiber body that has been subjected to the additive liquid impregnation treatment is then continued to the heating step. In this process, in order to dehydrate and carbonize the treated cellulosic fiber body, it is preferable to perform it in a dry state as much as possible, resulting in a loss of heating energy, and particularly in a low temperature region such as 65 to 100 ° C. Then, this drying step is an essential condition. The heat source for heat treatment is carbonization from a low temperature around 65 ° C when ammonium sulfate, phosphorous mixture or sulfuric acid is used, so it is easy to use waste heat in addition to electricity, gas, oil, etc. In this case, since the reaction occurs slowly, it is possible to obtain materials during the decomposition of cellulose, and it can be applied to fertilizers and the like. Moreover, even if heated directly by a flame, the carbonization is performed while controlling the combustible gas due to the additive liquid effect, so that there is less fear of fire. (In the case where the concentration of the additive solution is low, or in the case of a formulation containing no sulfate group, there is a risk of ignition at a high temperature. Therefore, sufficient care must be taken in the formulation of the additive solution.)
[0041]
The processing time required for this heating process is continued until the weight phenomenon rate reaches at least about 40%, depending on the correlation between the concentration of the additive solution (1.5 to 15%) and the heating temperature (65 to 400 ° C.). Must be implemented. The heat source for heat treatment is the use of ammonium sulfate, phosphoric acid mixture or sulfuric acid, which causes carbonization from 65 ° C. In addition to electricity, gas, oil, etc., waste heat can be used, and heat treatment in a low temperature range. In this case, since the reaction takes place slowly, it becomes possible to use materials during the decomposition of cellulose, and it can be applied to fertilizers and others. Further, even when heated directly by a flame, carbonization is performed while suppressing the flammable gas due to the additive liquid effect, so that there is less concern about fire. (In the case where the concentration of the additive solution is low, or in the case of a formulation containing no sulfate group, there is a possibility of ignition at a high temperature, so that sufficient care is required for the formulation.)
[0042]
[Example 3]
Waste paper fibers and inorganic fibers such as rock wool are mixed and molded, impregnated with the additive solution used in Example 3 above, then heated in a hot air dryer at 180 ° C (high-frequency heating is also possible) and carbonized. And molding a board with high shape retention strength and flexibility.
[0043]
[Function and effect]
The knowledge that the carbonization material for construction, etc. of the present invention having the structure as described above, and the method for producing the same, pay attention to the thermal decomposition mechanism of cellulose, can suppress the generation of flammable gas by chemicals, and can be carbonized. In addition, the cellulose fiber body is impregnated with an additive solution containing phosphoric acid as a main component, and heat treatment is performed until the weight reduction rate reaches 40% or more, which is a guideline for confirming that carbonization is completed. In order to promote dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame, levoglucosan (tar component) even in high-temperature air (in an inert gas atmosphere or without oxygen blocking) ) Does not generate flammable gas, does not cause flame in dehydration carbonization (the risk of fire is reduced), and thus causes air pollution in the manufacturing process Re or no, also possible to prevent the occurrence of a fire, it is possible to ensure the safety of operations, and has a great feature that it is possible to efficiently produce carbon.
[0044]
In addition, the concentration of phosphoric acid impregnated into the cellulosic fiber body is hardly carbonized at 1% or less, and when it exceeds 20%, the temperature control is very delicate in obtaining a flexible carbonized material. Therefore, the concentration is 1 to 20%, preferably 1.5 to 15% or more, and the heating temperature is also practical 65 to 400 ° C, preferably about 80 to 300 ° C. Since heat treatment is performed in the temperature zone, it is possible to leave a carbon chain in the carbonized material, and it is possible to realize a flexible carbonized material, including a heat insulating material, a sound absorbing material, an underfloor moisture absorbing material, Even in the production of building materials such as fireproof coatings, powder scattering from carbonized materials is almost eliminated, the workability is extremely improved, efficient production is possible, and inexpensive chemicals (such as ammonium sulfate and phosphorous acid) are added. Etc. is fertilizer And is capable of manufacturing with a simple heating device, and has the excellent effect of being able to provide highly functional building materials etc. at a relatively low cost. It can be expected.
[0045]
Further, in the present invention, so far, the cellulose-based fibrous body which is buried in the waste as a waste or has an effective processing method that can only be incinerated, that is, used paper such as newspapers and magazines. Various cellulosic fibers such as used and used corrugated paper, waste materials and wood chips generated in large quantities from construction sites, sawmills, woodworking plants, timber landing wharves, rice husks and straws from rice farmers, etc. Can be used as an effective waste treatment means.
In particular, in the case of the carbonization material for building materials and the like shown as an example representing the present invention and the example of the manufacturing method thereof, these characteristics can be surely achieved and should be extremely practical. it can.
[0046]
As described above, the carbonized material for building materials and the like, which has a novel structure of the present invention, and the method for producing the carbonized material are capable of achieving the intended purpose in general, and are disposed of in large quantities, such as waste paper, generated day and night. It is highly evaluated as an effective means of utilizing cellulosic fibrous materials as a product, and it also gains sufficient trust from the related departments as a means for easily and reliably processing these wastes without the generation of harmful by-products such as dioxins. As a result, it is expected to be widely adopted and disseminated.
[Brief description of the drawings]
FIG. 1 is a comparison graph in which composition analysis is performed by X-ray diffraction for three types of raw material cellulose (virgin pulp), phosphoric acid-treated charcoal and charcoal heat-treated in a normal inert atmosphere.
FIG. 2 is a structural formula of cellulose.
FIG. 3 is a structural formula of a flammable gas produced by pyrolysis of levoglucosan (tar content) produced by normal pyrolysis of cellulose.
FIG. 4 is a structural formula of 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 dehydration action from esterification with phosphoric acid.
FIG. 5 is a graph comparing changes in endothermic heat due to differences in concentration in differential thermal analysis (endothermic, exothermic measurement) data during heating of cellulose treated with phosphoric acid.
FIG. 6 is a graph showing a change in heat generation rate during combustion of cellulose (cotton) treated with a phosphoric acid compound.
FIG. 7 is a graph showing changes in weight at a heating temperature of 100 ° C. due to differences in the phosphoric acid treatment concentration of cellulose.
FIG. 8 is a graph showing changes in weight at a heating temperature of 150 ° C. due to differences in the phosphoric acid treatment concentration of cellulose.
FIG. 9 is a graph showing changes in weight at a heating temperature of 200 ° C. due to differences in the phosphoric acid treatment concentration of cellulose.
FIG. 10 is a graph showing the weight change rate at a heating temperature of 100 ° C. depending on the difference in the phosphoric acid treatment concentration of cellulose.
FIG. 11 is a graph showing the weight change rate at a heating temperature of 150 ° C. depending on the difference in the phosphoric acid treatment concentration of cellulose.
FIG. 12 is a graph showing the weight change rate at a heating temperature of 200 ° C. due to the difference in the phosphoric acid treatment concentration of cellulose.
FIG. 13 is a production process diagram of a typical embodiment for carbonizing a board made of cellulosic fibrous material once defibrated.

Claims (7)

  Cellulose-based fiber sheet body impregnated with an additive solution comprising either a phosphorous compound such as phosphoric acid or a phosphoric compound and any one or a mixture of two or more of sulfuric acid, ammonium sulfate, boric acid or derivatives thereof Is heated in an active atmosphere within a temperature range of 80 ° C. to 300 ° C. for a required time according to the concentration of the additive solution, and dehydration and carbonization are promoted while suppressing generation of flammable gas due to heating or flame. By increasing the carbonization residue, at least reaching a weight reduction rate of over 40%, leaving the carbon chain in the middle of dehydration carbonization of cellulose, and making the carbonized material while maintaining the sheet body shape and flexibility alone, Or in combination with other materials, it can be handled as a shape-retaining material with a single layer or laminated structure, and becomes a non-combustible heat insulating material, moisture absorbing material, sound absorbing material, and deodorizing material. Sheet building materials for carbide material, characterized in that the.   Cellulose-based fiber sheet body impregnated with an additive solution comprising either a phosphorous compound such as phosphoric acid or a phosphoric compound and any one or a mixture of two or more of sulfuric acid, ammonium sulfate, boric acid or derivatives thereof Is heated in an active atmosphere within a temperature range of 80 ° C. to 300 ° C. for a required time according to the concentration of the additive solution, and promotes dehydration and carbonization while suppressing the generation of flammable gas due to heating or flame. The carbonization residue is increased and at least a weight reduction rate of 40% is reached. The carbon chain in the middle of dehydration carbonization of cellulose is left as a carbonized material while maintaining the shape and flexibility of the sheet, and boric acid treatment is performed. A carbonized material for building materials, etc., which is provided with a pest-preventing function such as termites for covering wood.   The cellulosic fiber body is a cellulosic fiber sheet-like body having a special structure such as paperboard, paper towel, cardboard, etc., and is made of a carbonized material as it is with a special structure before processing. Carbonized materials for building materials, etc. as described.   Carbonization for building materials or the like according to any one of claims 1 and 2, wherein the cellulosic fiber body is a plant waste such as rice husk, straw, bark, etc., and is made into a carbonized material in the form before treatment. Material.   Cellulosic fiber body is impregnated with an additive solution consisting of either a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound and sulfuric acid, ammonium sulfate, boric acid, or one or more of their derivatives. A step of heating, the cellulose fiber body impregnated with the additive solution in an active atmosphere within a temperature range of 80 ° C. to 300 ° C. for a required time according to the concentration of the additive solution, and combustible by heating or flame The process of increasing the carbonization residue by promoting dehydration and carbonization while suppressing the generation of reactive gases, the process of stopping the heat treatment when the carbonization residue increases, and at least when the weight reduction rate reaches over 40%, the carbonized material The step of removing residual additive liquid components by washing with water or removing as much as possible, the step of drying the carbonized material from which the residual additive liquid component has been removed, Method of manufacturing in which characterized in that to obtain a carbonized material while leaving a carbon chain, according to claim 1, 3 or 4 building materials for carbide material according to any one.   Cellulosic fiber body is impregnated with an additive solution consisting of either a phosphorus compound such as phosphoric acid, or a mixture of a phosphorus compound and sulfuric acid, ammonium sulfate, boric acid, or one or more of their derivatives. A step of heating the cellulosic fiber body impregnated with the additive solution in an active atmosphere within a temperature range of 80 ° C. to 300 ° C. for a required time according to the concentration of the additive solution, and flammable by heating or flame The process of increasing the carbonization residue by promoting dehydration and carbonization while suppressing the generation of reactive gas, the process of stopping the heat treatment when the carbonization residue increases, and at least when the weight reduction rate reaches over 40%, the carbonized material Washing with water to remove or remove as much as possible the residual additive liquid component, drying the carbonized material from which the residual additive liquid component has been removed, subjecting the resulting carbonized material to boric acid treatment, The above process is characterized in that to obtain a carbonized material while leaving a carbon chain of dehydration carbonization middle of cellulose, claims 2 to 4 or construction materials for carbide materials method according. Old paper and other paper materials such as old newspapers and old magazines are penetrated in the thickness direction in an averaged arrangement as much as possible over the entire plane of the cellulosic fiber sheet that is laminated up to a maximum thickness of about 2 cm. A carbonized sheet laminate in which the step of drilling innumerable permeation holes is incorporated before the step of impregnating the cellulose-based fiber sheet with the additive liquid, and is a thick plate from the laminated paper and maintains flexibility. The method for producing a carbonized material for a sheet-like building material or the like according to any one of claims 5 and 6 , characterized in that:

Images