JP2009120469A - Method for effective use of metakaolin in paper sludge ash and coal ash and device for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effective use of metakaolin in paper sludge ash and coal ash and a device for manufacturing the same. <P>SOLUTION: The method is for recycling metakaolin, which is a major component of ash and has been treated as an industrial waste, based on the principle of producing a whitened uniform composite material of metakaolin and an organic substance by washing metakaolin in PS ash and coal ash and adding a ferroelectric organic molecule. The composite material of metakaolin and an organic substance is used as a substitution to kaolin which is a natural stone used generally as a filler for paper making and a pigment for coating. By-products such as a deinking auxiliary agent, a dispersant, aluminum sulfate and an absorbent are possibly produced. Further, unslaked lime and aluminum sulfate are mixed to produce a composite of calcium oxide, aluminum oxide and calcium sulfate for manufacturing an environmentally friendly coated paper with excellent whiteness. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

PS boilers generated by burning paper sludge (hereinafter abbreviated as PS) generated from the pulp and paper industry production process, biomass boiler combustion ash (wood ash after combustion, ash of petroleum decolorizer, paper sludge ash) and coal boiler , Which is the main component of coal ash generated from coal, and a composite containing metal atoms in metakaolin as an industrial waste, we propose a method to effectively use it as a substitute for natural mineral resources.

Treatment of coal ash generated from PS incinerators, biomass boiler combustion ash (wood ash after combustion, ash of petroleum decolorizers, paper sludge ash) and coal boilers is a common issue in the industry, and technologies that make effective use are proposed Has been. In particular, coal contains 8 to 20% by weight of ash (12% by weight in general, although it varies depending on the production area), and the use of coal as a fuel causes the problem of the continued increase in combustion ash. Yes.

In the electrical industry, we have developed a method for processing coal ash from coal boilers that are discharged in large quantities into concrete aggregate (Patent Document 2) and a method for processing into synthetic stone that functions as roadbed material by hydrothermal action. ing.

University institutions have developed a technique for processing PS ash discharged from a PS incinerator into artificial zeolite (Patent Document 6) and apatite, and have developed a method of using it as an aggregate of the material.

In the paper industry, PS ash and coal ash are generated in large quantities during production, as in other industries. Even in the paper manufacturing industry, only a part is used for the application of the soil conditioner utilizing the above-mentioned roadbed material and porous characteristics (Patent Document 2).

Especially in the paper industry, it is highly useful as a substitute for natural white minerals that are consumed in large quantities, and methods for use as substitutes for natural white minerals (kaolin, clay, white carbon, calcium carbonate) have been studied. (Patent Document 5). However, foreign matters remained and sufficient whitening could not be achieved, so that it could not be used as a substitute for natural white minerals.

In the papermaking process, to improve surface smoothness and printing characteristics, a coating solution is applied to the surface of the paper base with a size press and a coating machine to improve the adsorption performance and improve the ink landing performance. There is a competition among paper manufacturers for the development of coating liquids that improve printing characteristics that speed ink drying. (Patent Document 8)

  The quality of kaolin blended in the coating solution varies depending on the production area, and those that have high whiteness and improved printing characteristics may be depleted in the future. In addition, although there is a technique for artificially producing kaolin, it requires a lot of energy and consumes fossil fuels to transport and process the raw materials. Therefore, the development of technology for processing raw materials by burning PS generated from the manufacturing process and using the generated PS ash as an alternative to high-quality kaolin at low cost with little energy has been underway.

Research at the basic chemistry level such as the development of highly functional materials has progressed, research on optical effects due to changes in the behavior of π electrons due to the addition of chemicals in organic and inorganic molecules has progressed, and the possibility of utilization methods due to chemical action on metakaolin appears. I came. (Patent Document 7)

Mineralogically, in the study of natural minerals, the differences in the molecular structure of each mineral have been clarified by the X-ray structural analysis of the characteristics and characteristics of each mineral. In particular, in the component ratio of coal ash, the ratio of silicon oxide to aluminum oxide is 2 to 3: 1 and it is revealed as a result of analysis that a complex corresponding to kaolin or kaolin is formed. It came to be inferred that it can be treated as metakaolin obtained by removing crystal water from kaolin.

Based on the latest technology in basic science and mineralogy, we have studied technology diversion to PS ash and coal ash-derived metakaolin, and have studied the technology that can obtain the whiteness equivalent to natural white minerals in the present invention.

In recent years, there is no paper stock with a cellulose content of 100%, natural white ash PS ash, metakaolin derived from coal ash has been used for fillers and pigments to improve cellulose substitute and opacity, improve paper stock quality It is expected to be used as a raw material for papermaking that has a function higher than that of white minerals.

Coal ash can be controlled to some extent depending on the combustion state of the coal boiler, and if it can be developed into porous particles by the gas ejected from the inside, particularly a uniform and whitened silicon oxide / aluminum oxide / organic compound composite , By blending into the paper base material as a filler for papermaking material, it has bulky properties and at the same time, blended as a pigment in the coating liquid to be coated with a size press or coat machine, adsorbs oily substances such as ink, In addition, since it has an early drying property, it has excellent material properties as a papermaking raw material.

In particular, it can be further processed from the whitened metakaolin / organic compound complex, and can be made into acid clay or activated silicate gel, silicon oxide, and blended with the paper base material to reduce cellulose and absorb carbon dioxide. In addition to contributing to the protection of forest resources, acid clay and activated silicate gel can also be used as a colorant for carbonless paper, and coloring is achieved by adsorbing the capsule paint contained in carbonless paper and pressure-sensitive paper during color development. To do. Improve the printing characteristics of paper products as well as the above-mentioned metakaolin / organic complex, and give coated paper excellent properties in terms of whiteness, glossiness, smoothness, ink acceptability and ink set drying properties. Can do.

In addition, after washing and whitening the main ingredients of PS ash and coal ash, it is processed into sodium silicate (water glass) and used as an auxiliary agent in the DIP process. The method used as a flocculant, acid clay, activated clay (active silicic acid gel amorphous) is used as an adsorbent for KP wastewater, and lignin in the waste liquid can be adsorbed and recovered to be used as an energy resource.
Japanese Patent Publication No. 5-163017 Japanese Patent Publication No. 10-280380 Japanese Patent Publication No. 10-102620 Japanese Patent Publication No. 2000-53412 Japanese Patent Publication 2001-39710 Japanese Patent Publication No. 2002-348114 Japanese Patent Publication No. 2004-196656 Japanese Patent Publication No. 2006-342433 Japanese Patent Publication No. 2007-190494 Japanese Patent Publication No. 2007-915815

The method for processing a metakaolin derived from a combustion apparatus has the following problems.

In the electric power industry, coal boilers are used, and a large amount of ash is generated with a large amount of coal combustion, and technology for effectively using metakaolin contained in ash has been developed. It is processed into soil improvement materials, roadbed materials, zeolites, and silica gels that make use of porous properties, but their use is limited and it is not the demand corresponding to the amount generated.

A general method for whitening metakaolin derived from a combustion apparatus is to contact the metal kaolin in a combustion apparatus with hydrogen ions, carbon monoxide, or carbon dioxide, and change the optical characteristics to whiten. A combustion process that makes efficient contact with hydrogen ions, carbon monoxide, or carbon dioxide gas is required, and a dedicated combustion device is required.Practical combustion devices that are already in widespread use in industry can be whitened. Because this is not possible, large-scale capital investment is required. Further, in order to use it as a papermaking raw material, at least a whiteness of JIS 80 ° or more is necessary, but the conventional method cannot stably produce a whiteness of JIS 80 ° or more.

There is a technology for whitening by coating the surface with metakaolin contained in ash generated from the combustion of sludge incinerators in the paper industry. To coat the surface to increase volume and whiteness, a surface coating agent is required, and to process the aggregate, it is necessary to use it as a raw material for quality control and breakage of the aggregate. Due to the impact, it has not been put into practical use due to cost and quality.

When metakaolin is heat-treated with caustic soda in the gray state derived from a general combustion device and processed into non-crystalline sodium silicate (water glass), the metal ions taken into the crystal due to the adsorption performance of metakaolin are impurities. And has an adverse effect. In addition, sodium silicate (water glass) and sulfuric acid are mixed, and the gel-like substance of the sodium sulfate / silicon oxide / aluminum oxide composite has a black impurity and cannot be used as a papermaking raw material.

The wastewater from the manufacturing process is coagulated and precipitated, and the generated PS is combusted. Recently, biomass resources and PS are co-fired, so the PS incinerator is a broad biomass incinerator, and there is a concern about environmental impact simply by disposing of biomass ash generated as a residue. By doing so, reducing the use of natural resources, making them recyclable resources, and considering the impact on the natural environment are also important social issues.

      Develop applications as substitutes for ores that use natural resources as a papermaking raw material, reduce the use of natural resources, consider the impact on the natural environment, and provide high quality to users who are the mission of the manufacturing industry In order to provide quality, it is required to make products with high added value.

Along with an increase in the use of waste paper, the amount of chemicals used to remove inks and adhesive foreign matter present in the DIP raw material has also increased. In order to increase the amount of sodium silicate (water glass) used as a deinking agent assistant and reduce the production cost, a method is required that can produce and use sodium silicate (water glass) at low cost.

The quality of DIP raw materials has been deteriorating due to the expansion of demand in China, and a large amount of inks and adhesive foreign matter has been included. Conventionally, colloidal silica has been used as an adsorbent, but the cost of chemicals is high, and a method for discharging inks and adhesive foreign substances out of the system at low cost is required. Since metakaolin, acid clay, and activated silicate gel have ion adsorption performance, it is desired to develop technology that can be used for the purpose of adsorbing inks and sticking foreign substances and separating them from raw materials.

  In the paper making process, substitute kaolin derived from metakaolin is added to the coating solution to improve surface smoothness and printing characteristics, and it is applied to the surface of the paper base with a size press and a coating machine, and coating using conventional kaolin. It is necessary to develop a coating solution that gives the paper base printing properties that improve the adsorption performance, improve the ink deposition performance, and increase the ink drying speed.

Aluminum sulfate components are used for flocculants in production processes or in wastewater treatment facilities. Substances that are likely to be generated as by-products in manufacturing facilities are required to reduce logistics costs and effectively use by-products by self-manufacturing in-house.

The paper industry has become a problem in terms of profitability due to an imbalance between production costs and product prices economically every time raw materials soar, and efforts to improve quality and reduce production costs are required. In particular, a plurality of chemicals are used, and reduction of transportation costs due to material balance has become a major issue by using resources effectively.

In order to achieve the above object, the present invention provides the following configurations. The configuration is shown in FIG.
(1) In the first aspect of the present invention, silicon oxide / aluminum oxide (Al ₂ O ₃ .2 to 3SiO ₂ .2H ₂ O) controls the combustion state in a PS incinerator and a coal boiler, and ash It is characterized by the property of porosity due to the gas ejected from the inner surface and the change to a crystal structure that does not contain crystallization water by heat of 600 ° C. or higher, and metakaolin (Al ₂ O ₃ .2-3SiO ₂ ). In addition, oil absorption of 30 to 45 before and after metakaolinization is 50 to 70, and when used as a raw material for papermaking, it exhibits excellent properties of inking, and as an adsorbent for organic substances It will be possible to demonstrate the function of.
It can be produced in the same manner after replacing lower kaolin containing a large amount of impurities with low general whiteness with metakaolin.

(2) A second aspect of the present invention is a particle size distribution in which metakaolin in the ash is generally centered on 30 μm, ash content of 5 μm or more is pulverized after classification, and 0.2-5 μm particle size after pulverization treatment. The specific gravity of the distribution is 1.55 to 1.6.

(3) A third aspect of the present invention is a production method in which metakaolin, which is the main component of the combustion ash, is changed to a metakaolin / organic complex and whitened (washed and bleached). Metakaolin, the main component of combustion ash, has a molecular structure with a weak potential tetrahedron, or is a ferroelectric substance having a carboxyl group or a hydroxyl group, and a dipole-constituting organic substance group (of glycol, methanol, ethanol) Monohydric or polyhydric alcohols, acetone, acetamide, acetonitrile, citric acid, aldehyde compounds, potassium acetate, sodium bicarbonate, compounds with ketones and thiourea, urea, oxonium ions, formamide, hydrazine, chlorine dioxide or KP The residual bleaching component) is intercalated, and the dipole aligns the orientation of the π-electron arrangement that affects non-uniform optical properties. Although the organic molecular arrangement varies depending on the structure of the crystal structure and the conditions for intercalation, the optical properties change by shifting the interatomic distance of the crystal structure of the metakaolin / organic complex to 4Å, 8Å, 17Å, 22Å. Whitening (washing and bleaching) by changing to a uniform metakaolin / organic complex. As for the influence force of the ferroelectric substance, the temperature condition differs for each substance. These phenomena are caused by the fact that bipolar ferroelectrics intercalate in the crystal structure and cause a cooperative phenomenon in the solid. However, in the present invention, it is predicted that the bipolar ferroelectric in the metakaolin intercalates into the crystal structure, and the disordered inorganic ionic crystal polarization forms a domain by the phase transition. I was able to confirm that there was. Thiourea and urea are the types that generate dipoles below the critical temperature and cause a displacement type ferroelectric phase transition of polar π molecules. Molecular groups that have hydroxyl groups and carbonyl groups on the same π molecule, such as acetone and alcohols, and that form strong hydrogen bonds between the molecules two-dimensionally on the net cause a hydrogen bond chain type ferroelectric phase transition. Type. Polar π electrons can be arranged in concert by strong intermolecular hydrogen bonds. In either case, the ions taken into the inside are discharged, and the bipolar ferroelectric is intercalated to change the optical characteristics and create a uniform material structure.

(4) According to a fourth aspect of the present invention, in the third aspect, in the formation of the metakaolin / organic compound complex, the organic substance is ion-exchanged or interacted at a reaction temperature of 10 to 150 ° C. for 0.5 to 144 hours. By being calated, the discharged ions are separated by washing together with the metakaolin / organic compound complex.

(5) According to a fifth aspect of the present invention, the caustic soda reacts with silicon oxide by boiling the metakaolin / organic compound complex for 5 to 12 hours (100 to 220 ° C.) after the addition of caustic soda, and the amorphous structure substance silicic acid Soda (water glass) is produced. In addition, at this time, it is possible to select a method for producing an organic complex in which the organic component remains under heating conditions and a method for producing an inorganic complex in which the organic component is decomposed and the organic component is gas-separated at the boiling point or higher in the cooling process. It is characterized by.

(6) The sixth aspect of the present invention is that an amorphous inorganic composite (oxidation of sodium, silicon, aluminum) is performed by adding sulfuric acid or aluminum sulfate to the amorphous structural substance sodium silicate (water glass) of the fifth aspect. Products and sulfate gel materials) Amorphous, specific gravity 2 to 2.2 Whiteness JIS 90 ° or more is produced.

(7) According to a seventh aspect of the present invention, there is provided a yield improver that promotes electrical bonding between the amorphous inorganic composite (the oxide of sodium, silicon, aluminum and sulfate gel-like substance) of the sixth aspect and cellulose. The amorphous sodium sulfate / silicon oxide / aluminum oxide complex (gel-like substance) mixed with the papermaking raw material and entangled with cellulose constitutes the paper web, so that the light passing through the paper web from its unique particle structure The arrangement is characterized by irregular reflection.

(8) According to an eighth aspect of the present invention, an amorphous inorganic composite (sodium, silicon, silicon sulfate, sodium sulfate, and calcium carbonate) is added to the amorphous structural substance sodium silicate (water glass) of the fifth aspect. (Aluminum, calcium oxide and sulfate gel material) Amorphous, specific gravity 2 to 2.2 Whiteness JIS 90 ° or more is produced.

(9) The ninth aspect of the present invention is a yield improvement that promotes electrical bonding between the amorphous inorganic composite (sodium, silicon / aluminum / calcium oxide and sulfate gel-like substance) of the eighth aspect and cellulose. By mixing the agent with the papermaking raw material, the amorphous sodium sulfate / silicon oxide / aluminum oxide complex (gel-like substance) entangled with cellulose constitutes the paper web, and passes through the paper web from its unique particle structure. The arrangement is such that light is diffusely reflected.

(10) The tenth aspect of the present invention is used as a deinking aid for the DIP raw material after being processed into the amorphous structure substance sodium silicate (water glass) of the fifth aspect. Amorphous structure material (water glass) is characterized in that it disperses the free ink and prevents it from being separated from the cellulose and recombined.

(11) In the eleventh aspect of the present invention, after processing into the amorphous structure material sodium silicate (water glass) of the fifth aspect, lignin is added together with bleach and caustic soda in the DIP bleaching step and the TMP bleaching step. It is characterized by stabilizing the crystals in the reaction to form colorless and transparent crystals.

(12) In the twelfth aspect of the present invention, the metakaolin / organic complex of the fourth aspect is boiled (150 to 300 ° C.) in a hydrothermal action region for 2 hours to 2 months, thereby obtaining a plate-like or spherical shape. It is characterized by a uniform change to the crystal structure. However, when produced at less than 150 ° C., it is in the state of the metakaolin / organic complex of the fourth aspect, but can be used as it is as the metakaolin / organic complex. When used as a pigment for paper base coating in papermaking, crystals having a hexagonal plate structure are generally used. Depending on the crystal structure and features of the test, it can be used for fillers and pigments.

(13) A thirteenth aspect of the present invention is a yield improver used for promoting electrical bonding between the metakaolin / organic compound complex of the twelfth aspect and cellulose in the paper making process, as in the seventh aspect. Is mixed with a papermaking raw material to constitute a paper web, and the amount of cellulose used is reduced, and in the optical properties, the light passing from the surface of the paper web is blocked, and the opacity is improved by irregular reflection. Has characteristics.

(14) According to a fourteenth aspect of the present invention, the metakaolin / organic compound of the twelfth aspect is blended as a pigment in a coating solution for coating on the surface of a paper sheet in a papermaking process size press and a coating machine. Due to the electrical adsorption characteristics of the composite, the manufactured paper web is placed on a printing machine and has a large specific surface area and exhibits excellent properties when it comes into contact with ink.

(15) According to a fifteenth aspect of the present invention, the metakaolin / organic composite of the fourth aspect is boiled after adding sulfuric acid (95 to 105 ° C.) to elute the aluminum oxide stepwise into the reaction solution, Acid clay (aluminum silicate), which is an intermediate material that has been treated for 3 to 5 hours to elute 30 to 50% by weight of aluminum oxide. It is characterized by the formation of white clay (active silicate gel amorphous).

(16) According to a sixteenth aspect of the present invention, in the papermaking process, the acid clay or activated silicate gel according to the fifteenth aspect is used to increase the yield used for electrically bonding to cellulose as in the seventh aspect. By mixing the agent with the papermaking raw material to form the paper web, the amount of cellulose used is reduced, and in the optical properties, the light passing from the paper web surface is blocked, and the opacity is improved by irregular reflection. Use for.

(17) According to a seventeenth aspect of the present invention, the acidic clay or activated silicate gel of the fifteenth aspect is blended as a pigment in a coating solution for coating on the surface of a paper sheet in a papermaking process size press and a coating machine. Alternatively, due to the electrical adsorption characteristics of activated clay (activated silicic acid gel amorphous), the manufactured paper web is put on a printing machine and exhibits excellent properties when it comes into contact with ink. In addition, acidic clay or activated clay (active silicic acid gel amorphous) is used as a colorant in a coating solution for carbonless paper or pressure-sensitive paper. The color former capsule contained in the coating of carbonless paper and pressure sensitive paper breaks, and the acid clay or activated clay (active silicate gel amorphous) absorbs the color former, and the organic cation in the dye exchanges with the exchangeable inorganic cation. Then, an ionic complex is formed and coloration is exhibited. A color former (generally benzidine) is adsorbed on the surface or between layers by an ion exchange function, and the ferric oxide of the ash component obtains electrons to become ferric oxide, which is an organic amine-based color former (benzidine) ) Loses electrons and causes a resonance reaction to develop color.

(18) According to an eighteenth aspect of the present invention, an acid clay or activated clay (active silicic acid gel amorphous) according to the fifteenth aspect is produced, and the aluminum oxide component is eluted in a 30 to 100% by weight reaction solution. It becomes aluminum sulfate and is characterized by having an aggregation effect of aluminum sulfate. It is used for the purpose of coagulating and precipitating insoluble impurities contained in the washing filtrate of the third aspect, and can also be used as a coagulant in general waste water. Further, the amorphous inorganic composite of the sixth aspect (sodium, silicon, aluminum oxide and sulfate gel substance), the amorphous inorganic composite of the eighth aspect (sodium, silicon, aluminum, calcium oxide) And sulfate gel materials).

(19) The nineteenth aspect of the present invention is a composite of calcium oxide / aluminum oxide / calcium sulfate by mixing the aluminum sulfate and calcium hydroxide of the eighteenth aspect and controlling the concentration, temperature and reaction time. Precipitate body crystals. The calcium oxide / aluminum oxide / calcium sulfate complex generally has the characteristics of a calcium sulfoaluminate complex, has a particle size distribution of 0.3 to 2 μm, and has a needle-like crystal structure with a whiteness of JIS 95 ° or more, The specific gravity is 1.48.

(20) According to a twentieth aspect of the present invention, the calcium oxide / aluminum oxide / calcium sulfate composite according to the nineteenth aspect is blended as a pigment in a coating solution in a papermaking process, and is coated with a size press and a coating machine. As a result, it is possible to utilize the characteristics of whiteness JIS 95 ° or more as a pigment, and to give the paper base excellent properties in terms of glossiness, smoothness, ink acceptability and ink set drying properties. is there.

(21) The twenty-first aspect of the present invention is the amorphous inorganic composite of the sixth aspect (sodium, silicon, aluminum oxide and sulfate gel-like substance), the amorphous inorganic composite of the eighth aspect ( Sodium, silicon, aluminum, calcium oxide and sulfate gel material), 15th aspect of acid clay or activated clay (active silicic acid gel amorphous) is mixed with the raw material before DIP dust removal process or before KP screening process. It is characterized in that after it is electrically adsorbed and condensed on an adhesive foreign matter / pitch, which is an organic substance in the raw material, it is easily discharged out of the system in a dust removal step as a large foreign matter.

(22) The twenty-second aspect of the present invention is an acidic clay or activated clay (active silicic acid gel) having a large specific surface area, among the substances produced by the processing methods of the metakaolin / organic complex of the fourth, twelfth and fifteenth aspects. Amorphous) is preferred, but it has organic ion adsorption performance and can be used as an adsorbent for a processing apparatus that adsorbs lignin in KP wastewater. After concentration by adsorption of organic ions in the processing equipment, from the wavelength range of ultraviolet light to infrared light in which the functional group of one or more kinds of component molecules is in an electronically excited state by an acidic substance and volatile organic matter generator Acidic substances (carbon dioxide, hydrogen sulfide, hydrogen, oxygen, sulfur dioxide) and volatile organic substances from the liquid containing the adsorbent that adsorbs the organic ions by irradiating the selected one or more wavelengths of electromagnetic waves It is characterized by producing and separating (organic substances derived from methane, ethane, methanol, ethanol, other lignin components). At the same time, the adsorbent is also regenerated.

(23) A twenty-third aspect of the present invention is a group of organic substances washed with sulfuric acid or ferroelectric materials (glycol, methanol, ethanol monovalent or polyhydric alcohols, acetone, acetamide, acetonitrile, citric acid, aldehyde compound, acetic acid A compound having potassium, sodium hydrogen carbonate, ketone and thiourea, urea, oxonium ion, formamide, hydrazine, chlorine dioxide or KP bleached wastewater residual bleaching component) are intercalated and can be regenerated as the adsorbent.

(24) The twenty-fourth aspect of the present invention is characterized in that in the twenty-second aspect, the separated acidic substance and volatile organic substance are burned with heavy oil and a recovery boiler to recover energy.

(25) A twenty-fifth aspect of the present invention is a metakaolin-organic compound complex obtained by quantitatively blending the metakaolin / organic compound complex of the fourth and twelfth aspects and quicklime or calcium carbonate and intercalating while utilizing the characteristics of the organic compound. A calcium oxide / aluminum oxide / silicon oxide composite can be produced. As a substitute for the metakaolin / organic complex, a calcium oxide / aluminum oxide / silicon oxide complex can be used.

(26) In a twenty-sixth aspect of the present invention, an organic compound [sodium silicate organic complex, which decomposes an organic component and does not separate gases while the intercalated state of the metakaolin / organic complex is maintained under heating conditions. Sodium, silicon, aluminum oxide organic composite, sodium, silicon, aluminum, calcium oxide organic composite, acid clay (aluminum silicate) organic complex, activated clay (active silicate gel) organic complex, calcium oxide -Aluminum oxide-calcium sulfate organic composite, aluminum sulfate organic composite]. In addition, organic complex [sodium silicate organic complex or oxide organic complex of sodium, silicon, aluminum or oxide organic complex of sodium, silicon, aluminum, calcium or acid clay (aluminum silicate) organic complex or activated clay [Active Silicate Gel] Organic Complex or Calcium Oxide / Aluminum Oxide / Calcium Sulfate Organic Complex or Aluminum Sulfate Organic Complex] exhibits the same properties as the inorganic complex of the fifth, eighth, fifteenth, and nineteenth aspects. It is characterized by that.
In the following, sodium silicate or sodium, silicon, aluminum oxide or sodium, silicon, aluminum, calcium oxide, aluminum silicate, activated silicate gel or calcium oxide / aluminum oxide / calcium sulfate / aluminum sulfate Organic complex [Sodium silicate organic complex or sodium, silicon, aluminum oxide organic complex or sodium, silicon, aluminum, calcium oxide organic complex or acidic clay (aluminum silicate) organic complex or activated clay (active Silica gel) organic composite or calcium oxide / aluminum oxide / calcium sulfate organic composite or aluminum sulfate organic composite] can be used.

(27) A twenty-seventh aspect of the present invention is the fifth, eighth, fifteenth, or nineteenth aspect. Organic complex in which organic components intercalated in metakaolin remain [sodium silicate organic complex or oxidation of sodium, silicon, aluminum Organic composites or oxide organic composites of sodium, silicon, aluminum, calcium or acidic clay (aluminum silicate) organic composites or activated clay (active silicate gel) organic composites or calcium oxide / aluminum oxide / calcium sulfate The organic composite or the aluminum sulfate organic composite] can be used in the same applications as the inorganic composite of the fifth, eighth, fifteenth, and nineteenth aspects.

(28) According to a twenty-eighth aspect of the present invention, the metakaolin / organic compound complex subjected to the hydrothermal action of the eighteenth and nineteenth aspects is fertilized, and a method utilizing the turbidity of 0.02 to 3.5 μm or less. A production method characterized by separating particles and obtaining a clay material.

(29) In a twenty-ninth aspect of the present invention, a cationic polymer polymer is used in the papermaking pretreatment step for particles of 0.02 to 3.5 μm or less of the metakaolin complex (organic complex or inorganic complex) of the twenty-eighth aspect. Alternatively, a filler (calcium carbonate, kaolin or metakaolin-organic compound complex of the present invention [sodium silicate] is used by blending with cationic starch or a cationic polymer polymer and a cationic starch blended in a proportion of 0 to 100% by weight. Organic complex or sodium, silicon, aluminum oxide organic complex or sodium, silicon, aluminum, calcium oxide organic complex or acidic clay (aluminum silicate) organic complex or activated clay (active silicate gel amorphous) organic Complex or calcium oxide / aluminum oxide / calcium sulfate The arm organic complex or aluminum sulfate organic complex], characterized in that for fixing to the cellulose fibers.

(30) In the thirtieth aspect of the present invention, in the KP cooking step, particles having a metakaolin complex (organic complex or inorganic complex) of 0.028 to 3.5 μm or less according to the twenty-eighth aspect are used as a cooking aid (catalyst). In addition to the digester with the cooking liquor, when the cooking solution penetrates into the wood chips and separates the lignin components, the separated lignin is actively captured, and the chemical reaction contact area between the cooking liquor and the wood chips is increased. Promotes cellulose extraction. At this time, in the digester, regardless of whether it is a single tower type or a double tower type, the inlet, middle, end and cooking temperature of the kettle, the cooking pressure, and the method of adding the cooking liquid can be selected under conditions suitable for the cooking method. It can be added as a cooking aid (catalyst) suitable for each cooking method. Compared to cellulose extraction by cooking without adding the usual metakaolin complex (organic complex or inorganic complex), the digestibility is improved and the degradation of cellulose by cooking liquid or the discharge of knot koji can be suppressed. This is characterized in that the yield is improved and as a result, the cellulose is torn and the tensile strength is increased.

(31) In a thirty-first aspect of the present invention, the metakaolin complex (organic complex or inorganic complex) of 0.028 to 3.5 μm or less is used as the raw material before the dust removal equipment in the DIP step in the twenty-eighth aspect. Adds a complex (organic complex or inorganic complex), adsorbs the adhering foreign matter in the raw material due to the ion adsorption performance of the metakaolin complex (organic complex or inorganic complex), and removes the adhering foreign matter together with the adhering foreign matter with a dust removal device. It is characterized by being discharged.

In one aspect of the present invention, the combustion state of a PS incinerator or coal boiler is optimized, and the crystal structure of the generated ash (wood ash after combustion, ash of petroleum decolorizer, paper sludge ash and coal ash) is effectively utilized. Change to the most suitable porous particles. A uniform metakaolin / organic compound complex is formed by slurrying metakaolin, adding pulverization and an organic compound. The metakaolin-organic compound complex is whitened (washed and bleached) due to the change in optical properties, and can be effectively used in a wide variety of ways. In the past, depending on landfill treatment as waste, it was limited to some limited effective use methods, so the impact of the increasing waste is on the environment such as permanent storage management of waste, landfill disposal site and transportation costs On the other hand, the company was heavily pressed into the management of the company every year in terms of economics and the situation was worried in the future.
Natural white minerals that are used as raw materials for papermaking in the paper industry are limited, and the quality varies from production area to production, and it is highly significant that metakaolin / organic composites can be used more functionally with stable quality as a substitute for natural ore. .

As a papermaking raw material, when it is used as a filler mixed with cellulose in a paper web, it can contribute to the improvement of opacity, the function as a back-through prevention agent, and the volume of natural resources cellulose to reduce carbon dioxide.

When used as a raw material as a pigment for a coating liquid to be applied to the surface of a paper base to improve printing properties, an inexpensive metakaolin / organic composite according to the present invention or an acid clay or activated clay is undercoated, and calcium oxide is oxidized. Adopting a double coating method that top coats a product / aluminum oxide / calcium sulfate composite, it is possible to produce environment-friendly high-whiteness coated paper of higher quality than conventional coated paper. Environment-friendly high-whiteness coated paper has excellent properties in terms of whiteness, gloss, smoothness, ink acceptability and ink set drying.

Acid clay or activated silicate gel is used as a colorant in a coating solution for carbonless paper or pressure sensitive paper. The color former capsule contained in the coating of carbonless paper and pressure-sensitive paper is broken, the acid clay or activated silicate gel absorbs the color former, the organic cation in the dye is exchanged with the exchangeable inorganic cation, and the ionic complex is formed. Generates, shows color and exhibits excellent material performance.

Amorphous sodium silicate (water glass) produced by boiling a metakaolin / organic complex with caustic soda is currently purchased and used. As the circulation system of DIP raw materials has been built year by year and its value is increasing, the use of the amorphous structure material sodium silicate (water glass) as a deinking aid has been increasing. The non-crystalline structural substance sodium silicate (water glass) is useful for dispersing the free ink, separating it from the cellulose and preventing it from recombining.

Waste liquid generated by sulfuric acid treatment of metakaolin / organic compound is also used as paper sulfate coagulant as aluminum sulfate and at the same time non-crystalline inorganic complex (sodium, silicon, aluminum, calcium oxide and sulfate gel) Used as raw material chemicals for processing.

Metakaolin / organic compound (plate-like crystal, spherical crystal) as it is or heated in the hydrothermal action region to adjust the crystal structure and acid-treated acid clay, activated clay, amorphous inorganic complex (sodium, (Silicon, aluminum, calcium oxide and sulfate gel-like substances) have ion adsorption performance and can be used as a coagulant for adsorption of lignin in KP wastewater and removal of deinking agent and sticking foreign matter in DIP process. it can. In particular, acid clay and activated clay are suitable.

Disposal of PS ash and coal ash, reduction of landfill operation and maintenance costs, and self-manufacturing of alternative chemicals using natural ore based on metakaolin / organic composites have a synergistic effect and are not limited to the paper industry It also has a great economic effect on the electrical industry.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the configuration diagram of FIG. 1, a portion surrounded by a thick line schematically shows an embodiment in which the present invention is combined with each step of the paper industry. The present invention is intended for a silicon oxide / aluminum oxide composite having a layered molecular structure, and the molecular bond state is limited to those in which the basic molecular configuration takes a specific structure depending on how the apexes of the tetrahedral structure are shared is not. A silicon oxide / aluminum oxide composite that is combusted to 600 ° C. or higher in a combustion furnace such as a biomass incinerator or a coal boiler and metaboliteized by discharging crystal water is suitable. Kaolin, white carbon, clay, talc, bentonite used in papermaking raw materials are burned and collected by PS boilers, recovered from the manufacturing process, coal-derived fly ash, bottom ash The present invention is applicable to silicon oxide / aluminum oxide having a layered molecular structure to which the present invention can be applied. Since PS ash is recycled, the ingredients are omitted. Component of a typical coal ash is directed to gravel Aosumi, nitrous gravel Aosumi, _anthracite, SiO 2: 40 to 70 _{wt%, Al} 2 O 3: _{17~32 wt%, Fe} 2 O 3: _2~20 wt%, CaO: 0.1 to 16 wt%, MgO: 0.4~2.1 _wt%, SO 3: _{0.3~6.5 wt%,} Na 2 O: _0.1~2.7 wt %, Cl: less than 0.02% by weight, F: less than 0.01% by weight. Since Australian lignite is not suitable for the present invention, the ingredients are omitted. As can be seen from the data, coal ash has a silica to aluminum oxide ratio of 2-3: 1, and about 65 to 95% by weight of the total ash is composed of a silicate / aluminum oxide composite. Show. The weight component ratio (SiO ₂ + Al ₂ O ₃ ) / (Fe ₂ O ₃ + CaO + MgO) is called the acidity, and the acidity can be used as an indicator of the ash properties. The coal-derived ash that is advantageous to the present invention is controlled by the ratio of SiO ₂ / Al ₂ O ₃ and the acidity, and is used according to the application. Hereinafter, the ash components are collectively referred to as metakaolin, and the present invention is applied to metakaolin as a main component.

      Metakaolin burned to 600 ° C. or higher can be obtained from a PS boiler (biomass boiler) 101 or a coal boiler 104. For example, the combustion ash is separated and discharged from the combustion gas or exhaust gas at the lower part of the PS boiler (biomass boiler) 101 from the combustion gas or exhaust gas at the lower part of the dust collector after the dust collection by the screw conveyor or rotary feeder. It is stored in the PS storage silo 103 at a location separated by a jet packer car and a tank truck via the storage silo 102. Similarly, the coal boiler 104 is discharged from the furnace bottom and the dust collector, and is stored in the coal ash storage tank 106 via the coal ash storage tank 105 by the transfer device.

  Metakaolin is sent from the PS storage silo 103 or the coal ash storage tank 106 to the dissolution tank 108 previously filled with a fixed amount of water by a constant supply device (metalling screw, rotary feeder). The melting tank structure is a general tank shape, and a cylindrical plate diagram 23 or an inclined bottom diagram 24 is used. When charging with a flexible container, use a pot-shaped tank and provide a worker's fall prevention fence. A chelating agent 107 (capable of using sodium silicate in step 300B-305 in FIG. 7 as a chelating agent) that collects the filtrate or fresh water and metal ions that have been clarified in a cleaning device 114 and a concentrating device 129, which will be described later, at a constant ratio by weight Dissolve to a concentration of 0 to 80% by weight. At this time, the dust collector for the dissolution tank 108 is operated, and the recovered ash is recovered into the dissolution tank 108. After completion of acceptance, the mixture is stirred for a certain period of time with the stirrer of the dissolution tank 108, and when the mixture is homogenized, it is fed to the foreign matter screen 109. Remove foreign matter of 500 μm or more out of the system. There are screens of vibrating screen type, rotary blade self-cleaning screen type, and inclined screen type. In any case, a slit screen, a hole screen, or a mesh screen can be selected. In general, the vibrating sieve type is suitable. The target particle size distribution of metakaolin of 40 μm or less (generally 10 μm or less, which is generally used as a papermaking raw material) is pulverized by a pulverizer 111. The grinder 111 uses a commercially available device (FIG. 15) and selects glass beads 3 having a diameter of 0.5 to 3 mm and ceramic beads 3 made of zirconia suitable for metakaolin treatment while entering from the nozzle 1 and exiting the nozzle 4. Then, the mixture is filled in the pulverizer 111, and the ceramic or metal stirring rotor 2 having a shape characteristic is rotated in combination with multiple stages, and the particles are sandwiched between the beads 3 and used. The bead 3 does not flow out from the nozzles 1 and 4, and even if the beads 3 flow out, they are classified by the classifier 112, mixed into the slurry liquid, and do not flow. The particle size is controlled by adjusting the processing amount per unit and adjusting the residence time in the pulverizer 111.

The metakaolin having a particle size distribution optimized by the pulverizer 111 is classified by the classifier 112.
Use a general classifier. As the classifier, a vibration sieve type, a centrifugal type or the like is used. In the vibration sieve type, the screen mesh can be appropriately replaced depending on the application and quality control can be performed. The centrifugal separator type is a type that classifies by centrifugal force, and generally a vibrating sieve is preferable. Particles with a diameter outside the setting rejected by the classifier 112 are returned to the front of the pulverizer 111 and pulverized again. The passed one is received in the sorting tank 113, and the elution component in the slurry liquid is separated to the filtrate side by the washing machine 114. The ions eluted by the metakaolin slurry liquid are replaced with the clarified filtrate or fresh water of the cleaning device 114 and the concentration device 129, diluted to 0 to 65% by weight at the outlet of the cleaning device, and received into the storage tank 115. The cleaning machine can be selected from a disk thickener type, a drum thickener type, a film filter type, a wire press type, and a rotary filter type. Concentrators include disc thicker type, drum thicker type, film filter type, wire (belt) press type, rotary filter type, centrifuge type, screw press type, slaker type, and sedimentation tank type as well as the washing machine. In the case of a washing machine, the solid content of the slurry liquid is once scraped off with a filter cloth, and replaced with washing water and diluted and washed. The concentrator concentrates only water through the filter cloth or removes the solid content of the slurry liquid on the filter cloth and separates the solid content. Also, water is mechanically discharged from the filter cloth, and the slurry solid content is concentrated by scraping with a screw and a drag conveyor. There is also a type in which the concentrated slurry solids are extracted from the lower part of the sedimentation tank. In particular, any type can be selected here, but a disk thickener type and a wire (belt) press type with a small installation space are suitable.

Thereafter, the solution is fed to an in-line mixer 116, and an appropriate amount (0.1 to 1.2 with respect to the weight ratio of metakaolin of 1 to 1.2) of the washing bleach 117 [having a molecular structure with a weak potential tetrahedron, or carbosil Organic substance group that is a ferroelectric substance having a hydroxyl group or a hydroxyl group and that constitutes a dipole (glycol, methanol, ethanol monovalent or polyhydric alcohols, acetone, acetamide, acetonitrile, citric acid, aldehyde compound, potassium acetate, hydrogen carbonate Compound having sodium and ketone and thiourea, urea, oxonium ion, formamide, hydrazine, aqueous chlorine dioxide solution or KP bleach wastewater residual bleaching component)] at 25-90 ° C., and stored in the stabilization tank 118 for 3-10 hours . At this time, sufficient reaction time is taken, the bipolar ferroelectric intercalates into the crystal structure, drives out metal ions, etc., and at the same time aligns the orientation of the π-electron that affects the uniform optical characteristics, changing the optical characteristics And whitening (washing and bleaching) the metakaolin by forming a uniform metakaolin-organic compound complex. As an example, the addition amount is in a weight ratio with respect to metakaolin 1, 0.2 to 1 in the case of thiourea, 0.1 to 0.8 in the case of urea, 0.1 to 0.73 in the case of acetone. Since the influence force exerted by the substance varies depending on the temperature condition and the state of metakaolin for each substance, the effective chemicals, addition amount, and reaction time are actually determined by a table test. Recently, an in-line mixer is used in which the stator fluid is divided and uniformly mixed in a plurality of stages. As a mixer, there is a type in which a paddle is attached to a rotor for rotation and stirring, and a stirring method in a tank. A fluid separation type using a stator in a general mixer is suitable.

The whitened metakaolin / organic complex is applied to a washing machine 119 having a single or a plurality of washing steps, and the washing liquid and the reaction liquid are replaced 1 to 3 times to wash impurities. The filtrate separated by the washing machine 119 is sequentially used in the countercurrent flow in the previous washing step. The filtrate from the washing machine 119 is sent to the washing filtrate tank 120 and used as dilution water at the outlet of the all-process washing machine 114. The slurry liquid from the washing machine 119 is dropped into a small tank (stand pipe), transferred to the in-line mixer 121, and mixed with 15 to 45% dilute sulfuric acid. Dilute sulfuric acid is washed away by the washing machine 123, and the filtrate is sent to the filtrate tank 124 and circulated and used in the washing machine 123, and a part thereof is used for adjusting the pH of the clarification tank 125. After the impurities are settled and separated in the clarification tank 125, they are sent to the dissolution tank 108 and used for dissolution. In the clarification tank 125, aluminum sulfate 204 used as a flocculant and caustic soda 127 for pH adjustment are mixed, the SS component is settled and separated, and impurities are released out of shape. The clarification tank uses a general-purpose tank such as a sedimentation tank or a high-speed sedimentation tank. The sediment settled at the bottom of the sedimentation tank is pumped out and discharged out of the system. The supernatant is collected as a filtrate.

The washed metakaolin / organic composite is stored in the white metakaolin tank 128. Depending on the conditions for use in the next step, caustic soda is added as necessary to adjust the pH. The whitened metakaolin / organic compound complex is concentrated as a chemical raw material that can be used by the concentrator 129, converted into powder by the dryer 130, and then stored in the silo 131. Further, the concentration can be adjusted and the slurry liquid can be used effectively. The main applications are the filler 801 in the papermaking process pretreatment 132, the coating liquid pigments 902, 1002, and 1016 in the coating preparation, and the ion adsorbent 506 for KP wastewater treatment (the next steps 212 and 213 are more preferable). .

  As an example, an acid clay and activated clay processing method will be described with reference to FIG. 4 processing step 200A (acid treatment). The whitened metakaolin / organic compound complex is transferred from the raw material storage tank 136 to the in-line mixer 201, and 15 to 45 wt% sulfuric acid is added to the metakaolin / organic compound complex by 2 to 3 times, and the reactor 202 is charged. The reactor 202 uses a structure that can be heated from room temperature to 300 ° C. at a rate of 0.5 to 3 ° C./min. Steam or electricity is used as a heating energy source of the reactor, and the whitened metakaolin / organic compound complex The slurry is heated indirectly. FIG. 16 shows a pressure vessel of a type using steam. The header 5-a and the body portion 5-b are all jacket type, and heat source steam is put into the jacket portion. FIG. 17 uses electricity as a heat source. An electric resistance coil is provided in each of the reactor header 5-a and the trunk portion 5-b, and is heated by the amount of current supplied. In FIGS. 6 and 7, the periphery is surrounded by a heat insulating agent to avoid heat dissipation loss. In the case of FIG. 16, saturated steam at a set temperature is discharged from the nozzle 9 by a steam trap or a temperature control valve, the drain is transferred to a drain tank, and flushed to produce dryers 130, 214, 319, 412. It is recovered and used in the process. One or a plurality of reactors are installed, and charging, manufacturing, cooling, and discharging processes are used while shifting the phase of the circulation cycle. The production conditions vary depending on the origin of the metakaolin / organic complex to be effectively used, but when reacting as an adsorbent / coagulant, the reaction time is 95 to 140 ° C. and the reaction time is 3 to 5 hours. At this time, acid clay is generated. Furthermore, when the reaction is carried out with a reaction time of 6 to 12 hours as a whole, activated clay (activated silicate gel) is produced.

    After the reaction, the reactor 202 is slowly cooled, acid clay, activated clay, and aluminum oxide eluted and enhanced adsorption performance are sent from the reactor 202 to the separator 203 and washed by the washer 205. . Separation apparatuses include a disc thicker type, a drum thicker type, a film filter type, a wire (belt) press type, a rotary filter type, a centrifuge type, a screw press type, a slaker type, an inclined screen type, and a sedimentation tank type. Here, a method of separating the solid content from the sedimentation tank type and the supernatant separated and separated by an inclined screen is preferable. Solids are extracted from the lower part of the settling tank and transferred to the washing machine 205. The supernatant liquid of the separation device is transferred to the aluminum sulfate tank 204 and used as a reaction liquid with sodium silicate in the clarification tank 125, the flocculant, and the in-line mixer 310. Moreover, it uses for the reaction liquid with calcium hydroxide with the in-line mixer 405. The liquid washed and separated by the washing machine 205 is used as a diluent at the pump suction port at the outlet of the raw material storage tank 136. The surplus liquid is transferred to the filtrate tank 124 and the clarification tank 125. The acid clay and the activated clay slurry are washed with water by the washing machine 205, diluted at the washing machine outlet, adjusted to an appropriate concentration of 5 to 80% by weight, and received in the storage tank 207. A pulverizer 208 pulverizes the particle size distribution as necessary (generally, a particle size of 0.2 μm to 10 μm) or an amorphous gel until it is uniformly dispersed. After pulverization, the vibration sieve mesh of the classifier 209 is selected and classified according to the application. The rejected product is returned to the pulverizer again for quality control. After classification, the concentrate is concentrated by the concentrator 210 and stored in the acid clay storage tank 212 and the activated clay storage tank 213 or transported to the dryer 214, and after drying, stored in the powder silo 215 and commercialized. The filtrate of the washing machine 205 and the concentrator 210 is used in the filtrate tank as the clarification tank 125 and the raw material storage tank 136 dilution water in the previous step after recovery. Acid clay and activated clay can be used for the paper making process 132 filler 801, coating pigments 902, 1002, and 1016, carbonless paper, pressure sensitive paper colorant 135, and KP wastewater treatment facility adsorbent 506.

  A processing method for adjusting the crystal structure of the metakaolin / organic composite by the processing step 200B will be described. The main equipment is the same as the processing step 200A in FIG. Step 200B in FIG. 5 transfers the whitened metakaolin / organic compound complex from the raw material storage tank 136 to the inline mixer 201, and the inline mixer 201 does not add sulfuric acid, but with 2 to 3 volumes of water relative to the metakaolin / organic compound complex. Dilute and fill reactor 202 to cause hydrothermal action. A reactor having the same structure as in step 200A is used, and the whitened metakaolin / organic compound slurry is indirectly heated. Although it varies depending on the origin of the metakaolin to be effectively used, when the reaction is carried out as a papermaking process filler or a coating paper coating liquid pigment, the reaction time is in the range of 100 to 300 ° C. for 2 hours to 2 months. In particular, within 5 hours at 150 to 180 ° C. is preferable from the viewpoint of production cost.

After the reaction, the reactor 202 is slowly cooled at an optimal temperature gradient to prepare a plate-like or spherical crystal structure suitable for the papermaking process filler and the coating paper coating liquid pigment. The reaction solution is sent from the reactor to the separation device 203. The metakaolin / organic compound complex is concentrated to 5 to 80% by weight of the solid content in the separator 203 and washed with the filtrate 211 of the concentrator 210 in the washer 205. The concentration after washing is 5 to 80% by weight, is received in the storage tank 207, transferred to a pulverizer, and the particle size is adjusted by pulverization. The separator filtrate and the washer filtrate are transferred to the filtrate tank 206 or the filtrate tank 211. The filtrate is used as dilution water in the raw material storage tank 136 outlet pump suction port. A suitable particle size is a particle size distribution range of 0.02 to 5 μm for fillers and 0.2 to 10 μm for pigments. Grind until a final slurry with a particle size distribution suitable for the product. Since the explanation is the same for the classifier 209 and later, a description thereof will be omitted.

A processing method for adjusting the crystal structure of the metakaolin / organic composite by the processing step 200C will be described. The main equipment is the same as the processing steps 200A and 200B in FIG. Step 200C in FIG. 27 transfers the whitened metakaolin / organic compound complex from the raw material storage tank 136 to the inline mixer 201, and the inline mixer 201 does not add sulfuric acid, but with 2 to 3 volumes of water relative to the metakaolin / organic compound complex. Dilute and fill reactor 202 to cause hydrothermal action. A reactor having the same structure as that in steps 200A and 200B is used, and the whitened metakaolin / organic compound slurry is indirectly heated. It depends on the origin of the metakaolin used effectively, but it is Celsius when it is used as a clay material (metakaolin / organic complex or metakaolin / inorganic complex) or KP cooking aid (catalyst) used in the papermaking process yield agent. In the range of 100 to 300 ° C., the reaction time is heated for 2 hours to 2 months. In particular, within 5 hours at 150 to 180 ° C. is preferable from the viewpoint of production cost.
In Step 200C of FIG. 27, the manufacturing method can be applied even if the organic substance is replaced with a metakaolin inorganic substance that does not intercalate.

After the reaction, the reactor 202 is slowly cooled at an optimal temperature gradient, and clay materials (metakaolin / organic complex or metakaolin / inorganic complex) used as a papermaking process yield agent, DIP pitch control agent, KP cooking aid Prepare a plate-like or spherical crystal structure suitable for (catalyst) applications. The reaction solution is sent from the reactor to the separation device 203. The metakaolin / organic complex is separated into solid turbid particles and settled particles by the separation device 203, the settled material is concentrated to 5 to 80% by weight, temporarily stored in the residue tank 217, and then pulverizer 218. Is pulverized to a particle size distribution of 0.02 to 3.5 μm and transferred to a raw material storage tank. Supernatant water suspended in the separation device 203 is transferred to the water fertilizer device 220 and separated from the filtrate and the suspended matter. At this time, the time for sedimentation can be shortened by adding a flocculant. The settled turbid substance is 5 to 80% by weight, received in the storage tank 222, transferred to a pulverizer, and the particle size is adjusted by pulverization. The water fertilizer filtrate and the concentrator filtrate are transferred to the filtrate tank 221 or the filtrate tank 226. The filtrate is used as dilution water in the raw material storage tank 136 outlet pump suction port. In the case of clay materials (metakaolin / organic composites or metakaolin / inorganic composites) used as a papermaking process yield agent, 0.02 to 3.5 μm or less, even in the case of DIP pitch control agents and KP cooking aids (catalysts) Similarly, a particle size distribution range of 0.02 to 3.5 μm is a suitable particle size. Grind until a final slurry with a particle size distribution suitable for the product. The clay material finished after the classifier 224 is transferred to the yield improving agent in the paper making process 132, removed to the adhesive foreign matter in the DIP process 600, the pitch control in the KP process 700, and the cooking aid (catalyst) and used.

For example, in FIG. 6 Calcium organic compound complex (reactant with intercalate complex) step 300A, the metakaolin / organic compound complex is transferred from the raw material tank 136 to the inline mixer 301, and the inline mixer 301 converts the quick lime or calcium carbonate to metakaolin. -Addition of 0.15 to 0.2 g for quick lime and 0.27 to 0.35 g for calcium carbonate to 1 g weight of organic complex (when organic substances are urea and thiourea). It is diluted with water and charged into the reactor 302 to produce a calcium oxide / aluminum oxide / silicon oxide composite having a whiteness of 80 ° or more from the metakaolin / organic composite. Heat reaction is performed at 60 to 210 ° C. for 1 to 5 hours.

Foreign substances and unreacted residues are classified by the residue separator 304, and the calcium oxide / aluminum oxide / silicon oxide composite is transferred to the calcium organic compound composite tank 324. As the residue separator and classifier, a vibrating sieve type, a centrifugal type, or the like is used. In the vibration sieve type, the screen mesh can be appropriately replaced depending on the application and quality control can be performed. The centrifugal separator type is a type that classifies by centrifugal force, and generally a vibrating sieve is preferable. Particles with a diameter outside the setting rejected by the classifier 312 are returned to the front of the pulverizer 311 and pulverized again. The passed one is received in the stock tank 313, and the unreacted liquid component in the slurry liquid is separated to the filtrate side by the washing machine 314. Since the pH adjustment tank and the subsequent steps are the same as the step of preparing the particle crystals of the metakaolin / organic complex in step 200B in FIG.

  As an example, FIG. 7 Sodium silicate / sodium sulfate (calcium) organic composite (gel-like substance) FIG. 6 Step 300B (alkali treatment) to silicon soda (water glass) and amorphous silicon oxide / aluminum oxide composite A method of processing will be described. The whitened metakaolin / organic composite is added in an in-line mixer 301 in an amount of 5 to 50% by weight caustic soda to the metakaolin / organic composite in a volume of 2 to 3 times, and charged into a reactor 303 that causes hydrothermal action. The reactor 303 has the same structure and function as those shown in FIGS. Although it varies depending on the origin of the metakaolin-organic compound complex to be effectively used, when the reaction is performed as an amorphous substance sodium silicate (water glass), the reaction time is heated in the range of 100 to 190 ° C. for 3 to 12 hours.

  After the reaction, the reactor 303 is slowly cooled, and silicon soda (water glass) and the reaction solution that have changed to an amorphous structure are sent from the reactor 303 to the water glass tank 305 via the residue separator 304. The generated silicon soda (water glass) is once stored in the water glass tank 305 and then supplied to each process by a transfer pump for each application. The feature of sodium silicate is that it has the effect of precipitating divalent cations that impair the peptization effect as silicate. In addition, it has a feature of masking the surface of a divalent cation, and a feature that a silicate ion or colloidal silicic acid is adsorbed on the particles to form a protective colloid that makes the entire surface negative. Taking advantage of these characteristics, it is used as a deinking aid 307 in the DIP process 600, and the DIP raw material is made alkaline, and is mixed with caustic soda in the used paper charging process and added to the charging device. In addition, in the deinking process, a constant ratio is added together with caustic soda and deinking agent in the kneader before the soaking device, and ink with positive electrification is used to prevent reattachment to cellulose for the purpose of removing free ink. . In the DIP bleaching step 308 and the TMP bleaching step 309, sodium silicate is added as a stabilizer together with caustic soda and a bleaching agent. Sodium silicate acts as a stabilizer when the lignin is crystallized colorless. In addition, silicon soda (water glass) can be used as a dispersant 306 that generally suppresses an increase in viscosity at the time of blending 50% by weight or more of pigment for coating liquid in paper making process coating preparation. It is possible to improve the fluidity of a coating liquid that exhibits high viscosity because of high pigment content. When the silicon oxide / aluminum oxide / organic composite and calcium oxide / aluminum oxide / calcium sulfate composite are blended, the viscosity becomes particularly high. It can be used as the dispersant 306.

Amorphous silicon soda (water glass) 305 is used as a paper filler / pigment, and is mixed with sulfuric acid 122, aluminum sulfate 204 or a filtrate 206 of sulfuric acid-treated reaction liquid in an in-line mixer 310 to produce an amorphous inorganic composite. (Sodium, silicon / aluminum oxide and sulfate gel substance) are formed. When sulfuric acid 122 is added, 1.34 to 2.38 sulfuric acid is added to 1 g of sodium silicate weight, and in the case of aluminum sulfate 204 and waste acid 206, aluminum sulfate 1.58 to 2.38 is added to sodium silicate weight 1. Add 8g. The produced amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) is pulverized by the pulverizer 311 until it is uniformly dispersed. Unreacted and residue are classified, and rejected is discharged out of the system. The slurry classified by the classifier 312 is received in the stock tank 313 and then transferred to the washing machine 314 and washed with the filtrate 318. The pH of the slurry solution after washing is adjusted with caustic soda in the pH adjusting tank 316. After pH adjustment, it is stored in an amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) tank 319 by a concentrator 317 or sent to a dryer 322 by a conveyor, and after drying, a powder silo 323 Is stored. The filtrate separated by the concentrator 317 is collected in the filtrate tank 318 and used as a washing liquid for the preceding washing machine 314.

  At this time, when derived from PS, the calcium and titanium dioxide components contained in PS further form a composite with the amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance). The papermaking process 132 can be used for fillers 801 and pigments 902, 1002, and 1016 for coated paper coating solutions.

    Amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) 319 stored in tank 319 is stored as an amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) 319. In order to add as a filler 801 in the papermaking process 132 pretreatment, the flow sheet of FIG. 12 passes through a vibrating screen for foreign matter classification, is temporarily stored in the storage tank 802, and is then transferred to a service tank 803 having a small capacity. . In general, the feed pump (807) for transferring the raw material from the service tank 803 to the head box 806 in the paper machine pretreatment process is mixed immediately before 810, but the addition position is determined by the correlation with the yield agent.

When an amorphous inorganic composite (sodium, silicon, aluminum, calcium oxide and sulfate gel-like substance) 319 is added in order to remove the sticking foreign matter in the DIP raw material in FIG. 10 is added in front of the dust removing device 612 in the DIP process 600 in FIG. 10, and is condensed due to the organic ion adsorption performance. The dust removing device 612 makes it easy to reject flocs that have grown greatly.

Even when an amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) 319 is used as a pitch control agent in the KP process 700 of FIG. 11, after the KP exposure process, before the fine-selection process dust remover 715 The flocs that have been grown and condensed due to the organic ion adsorption performance, and which have grown large, are rejected by the dust remover.

Amorphous structured silicon soda (water glass) 305 is used as a paper filler / pigment, so it is mixed with sulfuric acid 122, aluminum sulfate 204 or filtrate 206 of sulfuric acid-treated reaction liquid, calcium carbonate and in-line mixer 310 to produce amorphous An inorganic complex (sodium, silicon, aluminum, calcium oxide and sulfate gel-like substance) is formed. When sulfuric acid 122 is added, 1.34 to 2.38 g of sulfuric acid, 0.93 to 1.64 g of calcium carbonate or 0.52 to 0.92 g of quicklime are added to sodium silicate weight 1, aluminum sulfate 204 and waste acid In the case of 206, with respect to sodium silicate weight 1, 1.58 to 2.8 g of aluminum sulfate, 0.93 to 1.64 g of calcium carbonate, or 0.52 to 0.92 g of quicklime are added. The formed amorphous inorganic composite (sodium, silicon, aluminum, calcium oxide and sulfate gel-like substance) is pulverized by the pulverizer 311 until it is uniformly dispersed. Since it is the same manufacturing process and effect as the amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance), the amorphous inorganic composite (sodium, silicon, aluminum, calcium oxide and sulfuric acid) The handling of (salt gel material) can be read as an inorganic composite (sodium, silicon, aluminum oxide and sulfate gel material).

Amorphous inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) as in the case of using metakaolin / organic composite 218 and acidic clay 212 or activated silicate gel 213 as filler 801 in papermaking process 132 Since 319 is handled, the description is omitted.

As an example, a method for producing a calcium oxide / aluminum oxide / calcium sulfate composite according to step 400 in FIG. 6 will be described. Quick lime having a particle size distribution suitable for the reaction is transferred from the silo 402 to the dissolution tank 403, and after stirring and dissolving, the slurry is stored in the charcoal storage tank 404. When calcium carbonate is used, it is transferred from the calcium carbonate silo 402 to the dissolution tank 403. When the slurry liquid and the waste liquid 206 or aluminum sulfate 204 of the reaction solution obtained by subjecting the metakaolin / organic compound 136 to sulfuric acid treatment with the in-line mixer 405 to be quick lime 402, the weight of quick lime is 1 g, and the waste liquid 206 or aluminum sulfate 204 is 1.14 to In the case of calcium carbonate 401 in the case of calcium carbonate 401, 0.88 to 1.71 g of waste liquid 206 or aluminum sulfate 204 is mixed with respect to 1 g of calcium carbonate, and in an indirect heat exchange crystal precipitation tank 406, The calcium oxide / aluminum oxide / calcium sulfate complex is precipitated while controlling the concentration of 5 to 80% by weight, the temperature of 10 to 90 ° C., and the residence time of 1 to 3 hours. The structure of the indirect heat exchange crystal precipitation tank has a dispersion plate inside the jacket. The inner diameter is determined according to the processing amount based on the residence time. The jacket is preferably divided into several parts and is given a temperature gradient along the flow. As for the temperature, let warm water pass through the jacket and set the warm water temperature according to the internal temperature. The calcium oxide / aluminum oxide / calcium sulfate complex is adjusted to an appropriate concentration of 5 to 80% by weight and pulverized to a required particle size distribution (generally, a particle size of 0.2 μm to 5 μm) with a pulverizer 408. . After pulverization, a classifier 409 vibrating sieve mesh is selected, and the classified and rejected particles are returned to the pulverizer 408 again for quality control. After concentrating with the concentrator 410, it is stored in the storage tank 412 or sent to the dryer 413 by a conveyor and stored in the powder silo 414. The filtrate separated by the concentrator 410 is collected in the filtrate tank 411 and used as dilution water in the previous dissolution tank 403 after recovery. Further, when stored in the storage tank 412, when the concentration becomes 60% by weight or more, the viscosity becomes high and the fluidity is lowered. Therefore, the dispersant (water glass) 306 is used in order to suppress the viscosity at a concentration necessary for the coating liquid. Is added to blending tanks 902, 1002, 1016 for preparing a papermaking process 133 size press or coating machine coating process 134 coating liquid. The silicon oxide / aluminum oxide / organic composite compounded in blending tanks 902, 1002, and 1016 generally produces a coating solution at 60 to 80% by weight as a pigment.

The completed coating solution passes through the in-line filters 905, 1005, 1019, 1010, 1025 and the defoamers 906, 1006, 1020, 1011, 1026 after the service transfer, and then the coating devices 907, 1007, 1021, 1012, 1026. And is applied to the web. At this time, a coating liquid containing a pigment mainly composed of a silicon oxide / aluminum oxide / organic composite was applied to the undercoat, and after drying, a calcium oxide / aluminum oxide / calcium sulfate composite was again formed. By applying the blended coating liquid to the double coating, eco-friendly high whiteness coated paper having high quality and high functionality is produced. As for the equipment to apply the coating liquid to the paper plate, use a base paper machine size press for the undercoat on the front and back, and a coat machine coater for the top coat on the front and back, or 2 coaters for undercoat and top coat on the front and back. A coat machine having a stage is used.

  As an example, FIG. 9KP wastewater treatment organic ion adsorption treatment process 500 will be described. The drainage discharged from the pulp manufacturing process contains pulp fibers, and the pulp fibers are collected in the KP manufacturing process by the pulp fiber recovery device 502. The structural example of a pulp fiber collection | recovery apparatus is shown in FIG. 21, FIG. Waste water after the pulp fiber recovery device 502 is sent to the adsorption tower 506 by a pump in the drain pit 503. The adsorption tower of FIG. 18 is preferably a multi-tower type, and a variety of adsorption tower configurations can be selected, but it is considered that three or more towers are desirable from the amount of KP wastewater. When using in parallel, use the same number of towers in each process in the cycle of adsorption, regeneration and adsorbent charging. When using adsorption towers in series, one tower is regenerated and each tower is run countercurrently from the one with the longest usage time. By passing through the tower immediately after regeneration, the organic components in the wastewater can be adsorbed to a predetermined amount and discharged.

The four tower type of the adsorption tower 506 will be described as an example. The drainage is filled with metakaolin / organic composites 131 and 215, acid clay 212 or activated clay (activated silicic acid gel amorphous) 213 in three towers 1 to 4. The KP drainage flows from the tower having a long operation time and finally passes through the tower immediately after the regeneration. The tower exit organic ion concentration immediately after regeneration (conductivity measured by a conductivity meter) is measured, and when the concentration rises to the set concentration, the tower having a long operation time is transferred to the regeneration cycle. Next, the operation is continued with the tower having the long operating time as the first tower and the third tower (the final tower) immediately after the regeneration as the first tower. The adsorbent is extracted from the tower that has been operating for a long time, and when the replacement is completed, the system is put on standby. When the organic component concentration at the outlet of the adsorption tower reaches the set value again, the adsorption tower is switched and regeneration is repeated. The concentrated tower is switched to a regeneration tower for use with a certain conductivity.

The adsorbent that adsorbs organic ions is sent to the recovery tank 511. Ultraviolet light (100 to 400 nm), visible light, which is transferred from the recovery tank liquid level to a degassing reactor 512 at a height of 10.3 m or more and makes the functional group of one or more component molecules electronically excited. (400 to 700 nm), a combination of electromagnetic waves having one or a plurality of wavelengths selected from the wavelength range of infrared light (0.7 to 10.6 μm), and the inside of the deaeration reactor 512 is evacuated. To 665 Pa to atmospheric pressure, hydrolyze organic ions at 10 to 90 ° C., and from the adsorbent (metakaolin / organic complex 131, 215, acidic clay 212 or activated silicate gel 213) to acidic substances (carbon dioxide, hydrogen sulfide, Hydrogen and oxygen, sulfur dioxide) and volatile organics (methane, ethane, methanol, ethanol and other lignin-derived organic materials) are produced and separated. Since the degassed gas may be condensed during the ventilation of the boiler, the drained organic compound is cooled in the heat exchanger 514 and recovered in the organic compound recovery tank 515 and burned in the recovery boiler or heavy oil boiler. Further, the degassed gas after cooling is heated or sent as it is to a recovery boiler or heavy oil boiler, and is supplied as combustion gas from a blow-in port equipped with a back-fire valve. The adsorbent regenerated in the degassing reactor 512 is sent to the regeneration tank 513, and the leg piping of the degassing reactor is sealed below the liquid level of the regeneration tank 513.

Compound having sulfuric acid or ferroelectric organic substance group (glycol, methanol, ethanol monovalent or polyhydric alcohol, acetone, acetamide, acetonitrile, citric acid, aldehyde compound, potassium acetate, sodium hydrogen carbonate, ketone in the regeneration tank 513 And thiourea, urea, oxonium ion, formamide, hydrazine, chlorine dioxide aqueous solution or KP bleach wastewater residual bleaching component) solution as an auxiliary, and regenerated at 0-90 ° C for 0.5-10 hours Complete. The gas generated by the addition of the auxiliary agent is sucked into the degassing reactor 512. When the deaeration blower is stopped, the odor blower is used as a substitute, and the odor gas is always collected from the recovery tank 511, the deaeration reactor 512, the regeneration tank 513, and the organic compound recovery tank 515, and burned in the boiler. To. In the event of a power failure, vent pipes and odor detectors will be installed to prevent gas from accumulating in each tank.

Examples of producing a metakaolin / organic composite from metakaolin, which is a feature of the present invention, are shown below, but the present invention is not limited to these examples. For reagents, we selected chemicals that could be tested at home and tested them as representative examples.
In addition, the manufacturing method of each medicine and paper sheet shown in the claims is limited to the production based on the metakaolin / organic compound complex, and the manufacturing method of each drug and paper sheet after the production of the metakaolin / organic compound complex is disclosed. Shown in patent. The relationship with the inorganic composite shown in the published patent is shown in FIG.

<Test method 1>
Metakaolin test conditions Sample 1: Burn 10g of coated paper, put the collected ash into a crucible, and recover the remaining inorganic material in the ash completely burned at 600 ° C or higher, and add it to the metakaolinized ash component in the inorganic material. Apply the invention. 2.5 g of ash was generated.
The burned coated paper is the same as the burned paper sludge.
The whiteness of ash was JIS 80 ° or more compared with the standard coated paper, and the hue changed to gray, so that it could not be used as a raw material for papermaking as it was.
Sample 2: Combustion of 10 g of coal, the collected ash is further put in a crucible, and the remaining ash is completely burned at 600 ° C. or more, and the remaining ash is recovered. The present invention is applied to the metakaolinized ash component in the mineral. 1.5 g of ash was generated.
The whiteness of ash was JIS 80 ° or more compared with the standard coated paper, and the hue changed to gray, so that it could not be used as a raw material for papermaking as it was.
Reagent: a distilled water (commercially available)
b to d ferroelectric reagents
b Urea (commercially available) Uses colorless crystals with a purity of 99% by weight or more in a 16.7% by weight aqueous solution with distilled water.
Made by Taiyo Pharmaceutical Co., Ltd.
c Ethanol (commercially available) A colorless liquid with a purity of 99.5% by weight or more
Manufactured by Kenei Pharmaceutical Co., Ltd.
d Glycerin + ethanol mixture (commercially available) Colorless liquid Liquid toothpaste
Kao Co., Ltd. 1) Metakaolin / Organic Complex Production Test Compare the ash whose whiteness is lower than JIS80 ° with the whiteness standard coated paper and kaolin raw material, and evaluate whether the whiteness is equal to or higher than a certain standard. .
<Test>
Reagents a, b, c, and d1.5 g were added at 23 ° C. (normal temperature) to 0.2 g of each of sample 1PS ash and sample 2 coal ash.
<Test results>
Compared with the sample 1PS ash and sample 2 coal ash before addition of reagent, coated paper (reference paper), and kaolin raw material, the gray color before addition of reagent is changed to white that is equal to or better than coated paper (reference paper) and kaolin raw material (natural stone). changed. Moreover, as a result of burning the sample which became a metakaolin-organic compound complex again at a temperature of 600 ° C. in a crucible, the organic component was changed to become brownish ash. Again, whiteness was restored by adding reagents ad. It is necessary to pay attention to drying, which indicates that the components and crystal structure of the metakaolin / organic complex change when heated more than necessary. It can be used as a substitute for whitened natural ore by volatilizing water at a temperature at which quality can be maintained.
2) Confirmation test of ink adsorption performance (deinking) of metakaolin / organic compound composite Sample 1PS ash and sample 2 coal ash metakaolin / organic compound 1.5g were prepared again and placed in an aqueous ink solution at 23 ° C (room temperature). , Stirred and left for 1 hour.
<Test results>
The coloring component was adsorbed, and the metakaolin / organic complex was precipitated at the bottom of the solution, and it was confirmed that the solution was clarified as compared with the aqueous ink solution to which the metakaolin / organic complex was not added.
3) Confirmation of crystal structure of metakaolin / organic complex.
3) Under 1.5-a hydrothermal conditions, 1.5 g of the metakaolin / organic compound complex is heated at 120 ° C. for 1 hour to confirm the crystal structure.
Strictly speaking, the solvent was changed from water to salad oil, the metakaolin / organic complex was included, and the test was heated at 120 ° C. for 1 hour to confirm the change in crystal structure.
3) Under 1.5-b hydrothermal condition, 1.5 g of the metakaolin / organic compound complex is heated at 200 ° C. for 1 hour to confirm the crystal structure.
Strictly speaking, the solvent was changed from water to salad oil, the metakaolin / organic complex was included, and the test was heated at 200 ° C. for 1 hour to confirm the change in crystal structure.
<Test results>
3) Under the condition -a, the metakaolin / organic compound complex was atomized and uniformly dispersed in the solvent and floated as compared to before the test. When observed with a microscope, the crystal structure in a spherical shape increases.
3) Under the condition of -b, compared to before the test, the metakaolin-organic compound complex is aggregated to form a flat crystal and form a small lump. When observed with a microscope, the plate-like crystal structure increases.
4) Sodium silicate production test by alkali boiling of PS ash, coal ash metakaolin / organic complex.
-> Urea water was intercalated into 92 g of coal ash, 50 g of caustic soda and 140 g of water were continuously boiled at 100 ° C., and it was confirmed that sodium silicate could be produced while replenishing evaporated water with hot water.
Moreover, it has confirmed that it can manufacture also from acid clay and activated clay.
5) Mixing sulfuric acid with a solution of sodium silicate (+ aluminum hydroxide), production test of amorphous sodium sulfate / silicon oxide / aluminum oxide composite (gel) → 174 g of sodium silicate (+ aluminum hydroxide) ( Dilution water was mixed with 76 g of sulfuric acid (concentration: 45 wt%) and adjusted to 1000 mL, and the reaction was confirmed.
It was confirmed that an amorphous sodium sulfate / silicon oxide / aluminum oxide composite (gel) was formed.
6) Production test of calcium oxide / aluminum oxide / calcium sulfate complex using waste liquid after treatment with metakaolin / organic complex sulfuric acid.
→ 900 g of waste liquid and 30 g of quicklime were mixed, heated once, gradually cooled, and allowed to stand. When the pH of the waste liquid was measured, it was confirmed that a calcium oxide / aluminum oxide / calcium sulfate complex was formed because the pH was between 7 and 10.
7) Coating liquid production and coating test (whiteness JIS 80 degrees)
In the papermaking process, the calcium oxide / aluminum oxide / silicon oxide organic compound composite is blended with 80% by weight and 10% by weight of heavy calcium so that the coating liquid pigment accounts for 90% by weight of the total liquid weight. prepared, also, in addition to oxidized starch 10 wt% of a pigment coating solution is blended into the coating liquid, in both the paper web surface, by coating the 12-15 g / m ^2, glossy surface Iron Was compared with a coated paper having a whiteness of JIS 80 degrees.
<Test results>
Coated paper equivalent to the reference paper was made using metakaolin / organic composite as a raw material.
8) Adsorbent test of lignin containing acid clay and activated clay 8) -a Mixing and stirring metakaolin in an aqueous solution prepared by boiling wood chips and eluting lignin, and comparing the state change with the mixture not mixed. The adsorption effect was confirmed.
<Test results>
When the acid clay and the activated clay are not mixed, the aqueous solution remains colored black, but when the acid clay and the activated clay are mixed, the solution is separated into a colorless layer and a black layer, and the supernatant liquid is clarified. It was confirmed. Moreover, it has been confirmed that acidic clay and activated clay function as adsorbents.
9) Calcium oxide / aluminum oxide / silicon oxide composite production test metakaolin / organic compound composite (prepared with a urea and b thiourea intercalated) 1.5 g 0.3g of quicklime and 0.27g of quicklime for sample b, put into a crucible, dissolve in 3ml of water, and then heat at 60-95 ° C to form a calcium oxide / aluminum oxide / silicon oxide composite Confirmed to be purified. The whiteness of the produced calcium oxide / aluminum oxide / silicon oxide composite is compared with the reference sample to confirm the whiteness.
<Test results>
It was confirmed that a calcium oxide / aluminum oxide / silicon oxide composite having a whiteness of 80 ° or more (estimated to be about 95 °) was produced from each of the sample a and the material b.
10) Yield test of calcium carbonate by pulp hand-pulling test 550 Canadian standard freeness soft wood craft pulp 0.04g is blended with 0.16mg cationized starch and 0.16mg clay material, and 6mg calcium carbonate In a state of being mixed and diluted with water to 1000 mL, a pulp sheet was prepared by hand-making, and placed for 5 minutes, and the calcium carbonate yield remaining in the pulp was confirmed.
<Test results>
It was confirmed that calcium carbonate remained in the 75% by weight pulp sheet and had a yield effect.
<Summary>
As a result of the test, the organic substance which is a ferroelectric substance was added to PS and metakaolin in coal ash, and it was able to be whitened. Published Patent Documents 5, 8, and 10 also show that it can be used as a substitute for white minerals particularly important for the paper industry.
As a high-quality, functional raw material, manufacturing costs can be reduced and new environmentally friendly products can be manufactured.

<Calculation conditions>
Coal combustion produces 12 wt% ash. The shortage will be supplemented by the power company.
We estimate the economic effects when using conventional kaolin formula, calcium oxide / aluminum oxide / calcium sulfate complex, and metakaolin / organic complex as coated liquid pigment.
Example) If the energy consumed for production per ton of coated paper in the paper industry is 2,830 × 10 ⁶ kCal / t, generally 17.8 × 10 ⁶ kCal / t is covered by a coal boiler. The amount of coal used is 2,871 kg / t (6,200 kCal / kg). At this time, the amount of generated coal ash is about 345 kg / t, which is about 12% by weight of the amount of coal used. Generally, 10 to 30% by weight of the coated paper is obtained by drying the coating liquid, and 65% by weight is used for the coating liquid when metakaolin / organic compound complex and kaolin are used after being changed. Coal ash suitable for the pigment may be used effectively. Significantly reduce the amount of buried coal ash and reduce the use of natural stone. As a result, the transportation of natural stone from foreign countries is reduced, which can contribute to the reduction of carbon dioxide.
<Result>
When the chemical processing cost is estimated, it is expected that the final product sales price can be reduced by 5 to 8% by transferring 65% by weight of the metakaolin / organic compound mixture to the coating liquid. In addition, the calcium oxide / aluminum oxide / calcium sulfate composite is applied by double coating, and the calcium oxide / aluminum oxide / calcium sulfate composite is mixed in an amount of 15 to 30% by weight. When 50% by weight is blended, it is expected that cost reduction of 3 to 6% of the final product selling price will be possible.

It is a block diagram which shows one Example of the system which applied this invention to the conventional industrial waste (coal ash and PS ash) and used effectively. It is a table | surface which shows the contrast of the utilization method as an inorganic composite of the conventional industrial waste (coal ash and PS ash) and the utilization method as an organic substance composite to which this invention is applied. It is a schematic block diagram of one Example of the system which applies this invention to the coal ash and PS ash which generate | occur | produced through the combustion apparatus, and adds the ferroelectric after washing | cleaning. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram of one Example of the system which applies this invention to a metakaolin-organic substance complex, and manufactures acid clay and activated clay (active silicic acid gel). It is a schematic block diagram of one Example of the equipment which applies this invention to a metakaolin and organic substance composite, and arranges a crystal structure. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram of one Example of the system which applies the present invention to a metakaolin / organic composite, and manufactures a reaction material of a composite obtained by intercalating an organic substance with metakaolin, calcium carbonate, and quicklime. 1 is a schematic configuration diagram of an embodiment of a system for manufacturing a sodium silicate / inorganic composite (gel-like substance) by applying the present invention to a metakaolin / organic composite. FIG. It is a schematic block diagram of one Example of the system which applies this invention to a metakaolin and organic substance composite, and manufactures a calcium oxide, aluminum oxide, and calcium sulfate composite. It is a schematic block diagram of one Example of the system which applies this invention to KP waste_water | drain, uses the substance which shows the organic ion adsorption property derived from a metakaolin and organic substance complex, and processes KP waste_water | drain. It is a schematic block diagram of one Example of the system which applies this invention to a DIP process, and uses the sodium silicate derived from a metakaolin-organic substance complex and the substance which shows a coagulation property. It is a schematic block diagram of one Example of the system which applies this invention to a KP process and uses the substance which shows the coagulation property derived from a metakaolin organic substance composite_body | complex. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram of one Example of the system which applies this invention to a papermaking process pre-processing, and adds the filler derived from a metakaolin organic substance composite_body | complex. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram of one Example of the system which applies this invention to a papermaking process size press, and undercoats the coating liquid containing the pigment derived from a metakaolin and organic substance complex. It is a schematic block diagram of one Example of the system which applies the present invention to a coat dispensing / coat machine coating process and undercoats or topcoats a coating liquid containing a pigment derived from a metakaolin / organic compound complex. It is a schematic block diagram which shows the principle and structure of the common grinder which can be used for this invention. It is the schematic which shows the structure of the general heating reactor (steam type) which can be used for this invention. It is the schematic which shows the structure of the general heating reactor (electric type) which can be used for this invention. It is the schematic which shows the structure of the packed tower packed with the general absorbent which can be used for this invention. It is the schematic which shows the structure of the photoreactive type acidic substance and volatile organic substance generator (dispersion plate use type) which can be used for this invention. It is the schematic which shows the structure of the photoreactive type acidic substance and volatile organic substance generator (top plate dispersion type) which can be used for this invention. It is the schematic which shows the structure of one Example (sand filter filtration raw material collection | recovery reiki type) of the fiber collection | recovery apparatus which can be used for this invention. It is the schematic which shows the structure of one Example (sand filter filtration screw extract type) of the fiber collection | recovery apparatus which can be used for this invention. It is the schematic which shows the structure of one Example (flat bottom type) of the dissolution tank which can be used for this invention. It is the schematic which shows the structure of one Example (inclined bottom type) of the dissolution tank which can be used for this invention. It is the schematic which shows the structure of one Example (pot type) of the dissolution tank which can be used for this invention. It is the schematic which shows the structure of one Example (disk type | mold) of the washing machine / concentrator which can be used for this invention. It is a schematic block diagram of one Example of the equipment which applies this invention to a metakaolin organic substance composite body, arranges a crystal structure, and fertilizes and manufactures the clay substance below a fixed particle.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw material inlet 2 Rotor 3 Bead (0.5-3 mm) Glass beads or zirconia 4 Raw material outlet 5-a Reactor cap 5-b Reactor body 6 Heating steam inlet 7 Raw material inlet 8 Raw material outlet 9 Heating steam drain or Condensation, leakage drain outlet 10 Electric heater coil 11 KP drain inlet / regenerated adsorbent input gas discharge / adsorbent discharge inlet 12 Adsorbent 13 KP drain outlet 14 Regenerated adsorber inlet 15 Adsorbent outlet 16 Multi-laser irradiation Device 17 Degassing reactor 17-a Dispersion plate
17-b Exhaust port 17-c Regenerated adsorbent outlet 17-d Weir plate 20 Absorbent inlet 30 Reaction liquid 40 Acidic substance / Volatile organic substance 50 Drainage receiving head tank 51 Raw material reject rake
52 Sand filter inlet raw material screen 53 Sand filter filter agent 54 Sand filter clogging reverse device 55 Filtration waste water discharge port hand control valve 56 Filtration waste water discharge port 57 Collected material reject chute 58 Waste water reject tank 59 Raw material collection tank 60 KP waste water adsorption Processing facility transfer pump 61 Return to KP manufacturing process 62 KP wastewater adsorption processing facility transfer pump 70 Raw material inlet 71 Body 71-a Flat bottom plate 71-b Inclined bottom
72 Discharge nozzle 73 Dust collector bag filter 74 Dust collector blower 75 Agitator 80 Raw material inlet 81 Pressurizing / air supply nozzle 82 Concentrated raw material 83 Filtrate discharge port 84 Dewatering sector 85 Collected raw material receiving chute 86 Washer / concentrator hood

Claims (35)

Paper sludge burned in a sludge incinerator and silicon oxide / aluminum oxide composite contained in coal fuel for boilers change to a crystal structure that does not contain crystal water due to the combustion environment of 600 degrees Celsius or higher, and contain crystal water A weight ratio of 0.1 to 0.1 wt% of a silicon oxide / aluminum oxide composite (generally a particle having a particle size distribution centered on a diameter of 30 μm and represented by the chemical formula Al ₂ O ₃ .2-3SiO ₂ , hereinafter referred to as metakaolin). A group of organic substances that are ferroelectrics at a ratio of ~ 1.2 (glycol, methanol, monovalent or polyhydric alcohols of ethanol, acetone, acetamide, acetonitrile, citric acid, aldehyde compounds, potassium acetate, sodium bicarbonate, ketone Compounds and thiourea, urea, oxonium ion, formamide, hydrazine, chlorine dioxide Alternatively, a method for producing a metakaolin-organic compound composite in which KP bleached wastewater residual bleaching component) is intercalated and uniformly whitened. The metakaolin-organic compound complex is prepared by using a commercially available pulverizer (wet or dry) media with a diameter of 0.5 to 3 mm and a classifier, and having a particle diameter of 40 μm or less and a whiteness of 50 ° or more. Production method.     A method for producing an amorphous structural material sodium silicate (water glass), in which the metakaolin / organic complex is boiled with caustic soda (100 to 220 ° C.). Sulfuric acid or aluminum sulfate is added to the above-mentioned non-crystalline structural material sodium silicate (water glass), and an inorganic composite having a specific gravity of 2 to 2.2 whiteness JIS 90 ° or more (sodium, silicon, aluminum oxide and sulfate gel) Substance). A method for producing a paper base, wherein the inorganic composite (sodium, silicon, aluminum oxide and sulfate gel-like substance) is blended in a papermaking raw material in an amount of 1 to 30% by weight. Sulfuric acid, aluminum sulfate, or calcium carbonate is added to the amorphous structural material sodium silicate (water glass) of claim 3, and an inorganic composite (sodium, silicon, aluminum, calcium of specific gravity 2 to 2.2 whiteness JIS 90 ° or more) (Oxide and sulfate gel substance). A method for producing a paper base, wherein the inorganic composite (sodium, silicon, aluminum, calcium oxide and sulfate gel-like substance) is blended in a papermaking raw material in an amount of 1 to 30% by weight. 3. A method for producing a DIP raw material in which an amorphous structural material sodium silicate (water glass) is used as a deinking aid in a DIP charging step and a deinking step. The slurry solution of the metakaolin / organic complex of claim 2 is boiled in a hydrothermal action region (90 to 300 ° C.) for 2 hours to 2 months, particle size distribution 0.02 to 5 μm, specific gravity 1.55 to 1.6. A method for producing a plate-like or spherical crystal structure substance having a whiteness of JIS 80 ° or more. A method for producing a paper web, wherein 1 to 30% by weight of the metakaolin / organic composite after the hydrothermal action is added to a pulp raw material in a papermaking process. The metakaolin / organic compound complex of claim 9 is blended in a paper making process in an amount of 10 to 90 wt%, commercially available kaolin in an amount of 0 to 80 wt% and heavy calcium in an amount of 0 to 10 wt%. In addition to the pigment for coating liquid, the coating liquid contains 10-30% by weight of binder (oxidized starch, latex) and preservatives, dusting inhibitors, and dyes. The whiteness of JIS80 ° or more is applied by coating each grade in the range of 12g / m ² or less, 12-15g / m ² , 15-20g / m ² How to make a paper web. The metakaolin / organic compound complex of claim 2 is boiled after adding sulfuric acid in an amount of 15 to 45% by weight (90 to 105 ° C.), and aluminum oxide is eluted stepwise into the reaction solution and treated for 3 to 5 hours to oxidize aluminum. Acidic clay (aluminum silicate), which is an intermediate substance from which 30 to 50% by weight of the product is eluted, is treated for 6 to 12 hours to dissolve most of the aluminum oxide, and the activated clay (active silicate gel amorphous) due to the collapse of the structure Production method. A method for producing a paper web, wherein the acid clay or activated clay (active silicate gel amorphous) is blended in a pulp raw material in an amount of 0 to 30% by weight in a papermaking process. The acidic clay or activated clay (active silicate gel amorphous) according to claim 12 is blended in an amount of 10 to 90% by weight, commercially available kaolin in an amount of 0 to 80% by weight, and heavy calcium in an amount of 0 to 10% by weight. Manufactured to occupy 50 to 90% by weight of the total weight, and in addition to the coating liquid pigment, 10 to 30% by weight of binder (oxidized starch, latex) and preservatives, dusting inhibitors and dyes were blended. formulated in the coating liquid, the size in both by press and coating machine to the web surface 12 g / ^{m 2} or less, 12-15 g / ^m 2, the whiteness of coating for each grade in the range of 15 to 20 g / ^{m 2} A method for producing a paper sheet of JIS 80 ° or more. A method for producing a flocculant mainly composed of aluminum sulfate, wherein the aluminum sulfate component eluted in the waste liquid after acid treatment according to claim 12 is stored and the SS component in the filtrate and waste liquid is used for coagulation precipitation.
The aluminum sulfate component in the waste liquid is reacted with calcium hydroxide to produce a calcium oxide / aluminum oxide / calcium sulfate complex (characterized by calcium sulfoaluminate complex, having a particle size distribution of 0.
3-2 μm, needle crystal structure, whiteness JIS 95 ° or more, specific gravity 1.48). In the paper making process, the calcium oxide / aluminum oxide / calcium sulfate composite is blended in an amount of 10 to 90% by weight, commercially available kaolin in an amount of 0 to 80% by weight, and heavy calcium in an amount of 0 to 10% by weight. In addition to the pigment for coating liquid, 10-30% by weight of binder (oxidized starch, latex) and preservatives, dusting inhibitors, and dyes. formulated into compounded coating liquid, size press and 12 g / ^{m 2} or less on both sides to the web surface at coating machine, 12-15 g / ^m 2, was applied for each grade in the range of 15 to 20 g / ^{m 2} How to make a paper web. An undercoating solution comprising the metakaolin / organic composite of claim 2 and 9 mixed therein, and 0 to 90% by weight of the calcium oxide / aluminum oxide / calcium sulfate composite of claim 16 and the metakaolin / organic composite 0 to 90% by weight, 0 to 80% by weight of commercially available kaolin and 0 to 10% by weight of heavy calcium are produced so that the coating pigment occupies 50 to 90% by weight of the total liquid weight, In addition to the coating liquid pigment, 10-30% by weight binder (oxidized starch, latex) and preservatives, dusting inhibitors, and dyes are blended into the coating liquid, and the coating liquid is undercoated with a size press and a coating machine. coat, and total coating amount of the top coat to the web surface (both sides) 12 g / ^{m 2} or less, 12-15 g / ^m 2, brightness JIS80 ° coated for each grade in the range of 15 to 20 g / ^{m 2} The web of the method of manufacturing the above. The acidic clay of claim 12, activated clay (active silicic acid gel amorphous) or the inorganic composite of claim 4 (sodium, silicon, aluminum oxide and sulfate gel), the inorganic composite of claim 6 (sodium) , Silicon, aluminum, calcium oxide and sulfate gel-like substances) are used in place of the metakaolin-organic compound composite of claim 18 to produce undercoat and topcoat coating solutions. and, size press and the total coating amount of the undercoat and top coat at the coat machine to the web surface (both sides) 12g / ^{m 2} or less, 12~15g / ^m 2, of 15~20g / ^{m 2} range A method for producing a paper sheet having a whiteness of JIS 80 ° or more applied for each grade. The undercoat and topcoat coating solutions of claim 19 are recombined, and the total amount of undercoat and topcoat applied to the surface of the paper (both sides) is 12 g / m ² or less by a size press and a coat machine, A method for producing a paper sheet having a whiteness of 80 ° or more applied for each grade in the range of 12 to 15 g / m ² and 15 to ²⁰ g / m ² . The acidic clay or activated clay (active silicic acid gel amorphous) according to claim 12 has organic ion adsorption performance, and therefore adsorbs lignin in the KP wastewater, and functional groups of one or more kinds of component molecules as electrons. By irradiating an electromagnetic wave having one or a plurality of wavelengths selected from a wavelength range of ultraviolet light to infrared light in a state of mechanical excitation, the acid clay or activated clay (adsorbed silicate gel amorphous) adsorbing the lignin is adsorbed. Having a step of generating and separating acidic substances (carbon dioxide, hydrogen sulfide, hydrogen, oxygen, sulfur dioxide) and volatile organic substances (organic substances derived from methane, ethane, methanol, ethanol and other lignin components) from the liquid containing Characteristic KP wastewater treatment equipment. From the liquid containing acid clay or activated clay (active silicic acid gel amorphous) in the preceding paragraph, derived from acidic substances (carbon dioxide, hydrogen sulfide, hydrogen, oxygen, sulfur dioxide) and volatile organic substances (methane, ethane, methanol, ethanol and other lignin components) The organic clay is separated from the acid clay or activated silicic acid gel after separation into sulfuric acid or organic compounds (glycol, methanol, ethanol monovalent or polyhydric alcohols, acetone, acetamide, acetonitrile, citric acid, aldehyde compounds, acetic acid. Intercalate potassium, sodium bicarbonate, ketone compounds and thiourea, urea, oxonium ions, formamide, hydrazine, chlorine dioxide or KP bleached wastewater bleaching components), acid clay or activated clay (active silicic acid gel amorphous) ) Wastewater treatment equipment to be recycled. The acidic substances (carbon dioxide, hydrogen sulfide, hydrogen, oxygen, sulfur dioxide) and volatile organic substances (organic substances derived from methane, ethane, methanol, ethanol, and other lignin components) of claim 21 and 22 are burned in heavy oil and a recovery boiler. Wastewater treatment equipment. A method for producing a metakaolin / organic compound complex according to claim 1, 2 or 22, wherein the ion exchange or intercalation reaction with a ferroelectric is carried out at 10 to 150 ° C. 3. A process according to claim 1, wherein the ion exchange or intercalation reaction with a ferroelectric is carried out for 0.5 to 144 hours, especially 3 to 36 hours. The metakaolin-organic compound complex of claim 2 or 9 and quick lime or calcium carbonate are quantitatively blended, and the particle size of the metakaolin-organic compound complex intercalated with the organic compound is calcium oxide / aluminum oxide / silicon oxide organic compound complex Distribution 0.3 to 10 μm Specific gravity 1.55 to 3 Whiteness JIS80 ° or more production method of the substance. A method for producing a paper web, wherein the calcium oxide / aluminum oxide / silicon oxide organic compound complex of the preceding paragraph is blended in a pulp raw material in an amount of 1 to 30% by weight in a papermaking process. The calcium oxide / aluminum oxide / silicon oxide organic compound composite according to claim 26 or 27 is blended with 10 to 90 wt%, commercially available kaolin with 0 to 80 wt% and heavy calcium with 0 to 10 wt% in the paper making process. And the coating liquid pigment accounts for 50 to 90% by weight of the total liquid weight, and in addition to the coating liquid pigment, 10 to 30% by weight of binder (oxidized starch, latex) and a preservative, Anti-dusting agent and dye are blended in the coating solution, and the size is in the range of 12g / m ² or less, 12-15g / m ² , 15-20g / m ² A method for producing a paper sheet having a whiteness of JIS 80 ° or more to be applied every time. An undercoat and topcoat coating solution is produced using a calcium oxide / aluminum oxide / silicon oxide organic compound complex instead of the metakaolin / organic compound complex of claims 11, 18, and 20. Size press and the total coating amount of the undercoat and top coat at the coat machine to the web surface (both sides) 12g / ^{m 2} or less, 12~15g / ^m 2, grade in the range of 15~20g / ^{m 2} A method for producing a paper sheet having a whiteness of JIS 80 ° or more applied every time.   An organic component intercalated in metakaolin remains in the product of claim 3, 4, 6, 12, and the resulting organic compound complex [sodium silicate organic complex or sodium, silicon, aluminum oxide organic complex or sodium , Silicon, aluminum, calcium oxide organic complex or acidic clay (aluminum silicate) organic complex or activated clay (active silicate gel amorphous) organic complex or calcium oxide, aluminum oxide, calcium sulfate organic complex or Manufacturing method of aluminum sulfate organic composite]. A method of using the organic complex as a substitute for an inorganic complex in claim 5, 7, 10, 11, 13, 14, 15, 17, 18, 19, 20, 27, 28, 29. 10. A silicon oxide / aluminum oxide inorganic composite obtained by hydrofertilizing the silicon oxide / aluminum oxide inorganic composite and organic composite according to claim 2 and 9 and separating the turbid particles together with the supernatant water. And a method for producing particles of an organic composite clay material having a particle size of 0.02 to 3.5 μm or less. By using the clay material of the previous item in the pre-processing step of papermaking, a cationic polymer, a cationized starch, or a mixture of a cationic polymer and a cationized starch in a proportion of 0 to 100% by weight, Calcium carbonate, kaolin or metakaolin / organic complex organic complex of the present invention [sodium silicate organic complex or sodium, silicon, aluminum oxide organic complex or sodium, silicon, aluminum, calcium oxide organic complex or acidic Clay clay (aluminum silicate) organic complex or activated clay (active silicate gel amorphous) organic complex or calcium oxide / aluminum oxide / calcium sulfate organic complex / aluminum sulfate organic complex] Silica used for purpose Method of manufacturing an oxide-aluminum oxide inorganic complexes and organic complexes clay material. A silicon oxide / aluminum oxide inorganic composite and organic composite clay material of claim _2, 9, 32, 33 in a KP cooking step (Na ₂ S 25-70 g / liter, NaOH 40-70 g / liter, cooking aid) Digestive agent (catalyst comprised of dilute agent, diluted black liquor or Na ₂ S25-30 g / liter, Na ₂ S ₃ 0.5-35 g / liter, NaOH 40-70 g / liter, cooking aid, diluted black liquor) ), And a method for producing a silicon oxide / aluminum oxide inorganic composite and an organic composite clay material that promotes cellulose extraction from wood chips under the same cooking conditions with H factor. The inorganic composite of claim 4 (sodium, silicon, aluminum oxide and sulfate gel) or the inorganic composite of claim 6 (sodium, silicon, aluminum, calcium oxide and sulfate gel) The acid clay or activated clay (active silicate gel amorphous) according to claim 12 or the silicon oxide / aluminum oxide inorganic complex and organic complex clay material according to claim 32 before the DIP selection / dust removal process and before the KP selection process. A method for producing a DIP raw material or a KP raw material, which is mixed with a raw material and uses a coagulation action to remove adhesive foreign matter and pitch from the raw material.

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