JP2008121127A - Method for producing pulp - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing pulp, by which processes can be simplified and treatments of a waste liquid can be reduced. <P>SOLUTION: This method for producing the pulp comprises steps of charging wood chips 1 in a chemical liquid 3 containing at least a basic substance and an aluminum compound, adding and heating a silicon compound to the chemical liquid 3 to synthesize zeolite 4, when the wood chips 1 are digested, and thus producing the pulp to which the zeolite 4 is fixed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pulp production method for producing a pulp having zeolite fixed by using a cooking process of wood chips and having a cation exchange ability, an adsorption ability for adsorbing malodorous substances, and the like.

  In recent years, paper has been fixed with zeolite that has an ability to exchange cations such as silver ions and copper ions having antibacterial properties and cations in zeolite and adsorbs malodorous substances. There are papers with high functionality. Paper with this functionality can be used for antibacterial sheets by utilizing the antibacterial action of cations that are fixed by changing the cations supported on the zeolite to cations such as silver ions and copper ions. Harmful inorganic substance removal sheet using the ability to adsorb odorous substances such as volatile organic compounds, and to use it for filters for air purifiers or to fix heavy metal ions etc. with ion exchange capacity Used for etc. Thus, functional paper has antibacterial properties and adsorbability to adsorb odorous substances and volatile organic compounds by zeolite, and is superior to other papers.

  A method for producing a paper having this functionality is as follows. When making a pulp as described in Patent Document 1 below, the zeolite is added to the suspension of the pulp and the zeolite is added to the paper by an internal addition method. In addition to the method of fixing to zeolite, there is a method of fixing a zeolite such as that described in Patent Document 2 below to the pulp itself, and papermaking the pulp to which the zeolite has been fixed.

  When the zeolite is fixed to the pulp itself, after the cooking step of pulping the wood chips, the zeolite is synthesized and fixed to the pulp, and the zeolite is pulped through these two steps. To settle. Specifically, as shown in FIG. 11, the wood chip 22 is heated in a chemical solution 23 containing a basic substance such as sodium hydroxide and water in an autoclave 21 of a digester, and the wood chip 22 is heated. The lignin is dissolved, the pulp bound by the lignin is loosened, and cooking is performed in which each pulp is dispersed in one pulp 24. After cooking, the chemical solution 23 is treated as a waste solution. Next, in order to fix the zeolite 25 to the extracted pulp 24, for example, a chemical solution 26 containing a basic substance such as sodium hydroxide, an aluminum compound such as sodium aluminate, a silicon compound such as water glass, and water. The pulp 24 is charged into the slab and heated to synthesize the zeolite 25, and the zeolite 25 thus synthesized is fixed and fixed to the pulp 24. After the zeolite 25 is fixed on the pulp 24, the chemical liquid 26 is treated as a waste liquid. In this way, the pulp 24 in which the zeolite 25 is fixed is obtained.

  However, in such a manufacturing method of the pulp 24, the cooking step and the synthesis and fixing step of the zeolite 25 are completely separate steps, and the chemical solution 23 in the cooking step and the chemical solution 26 in the synthesis and fixing step of the zeolite 25 are water. Despite being common in that it contains a basic substance such as sodium oxide and water, the chemical solutions 23 and 26 used in the respective steps are treated as waste liquids, and therefore, there are two steps for discharging the waste liquid. There is a process, and the amount of chemicals to be used increases and costs increase. Moreover, in such a pulp manufacturing method, it is difficult to significantly improve production efficiency.

JP 2005-068597 A Japanese Patent No. 3317660

  Accordingly, the present invention simplifies the process, and can produce a pulp having zeolite fixed and adsorbing cation exchange capacity, malodorous substances, etc. without treating the chemical liquid as waste liquid during cooking. It aims at providing the manufacturing method of.

  The present invention, which achieves the above-mentioned object, adds the aluminum compound and silicon compound necessary for the synthesis of zeolite to the chemical solution for digesting wood chips, so that the cooking of wood chips, the synthesis of zeolite and the pulp with one chemical solution To produce a pulp with zeolite fixed.

  That is, the method for producing pulp according to the present invention is a method for producing a pulp in which zeolite is fixed. At the time of cooking wood chips, the wood chips are put into a chemical solution containing at least a basic substance and an aluminum compound. The method is characterized in that a silicon compound is added to a chemical solution and heated to synthesize zeolite to produce a pulp in which the zeolite is fixed. In this pulp manufacturing method, pulp having an anthracite fixed as zeolite can be manufactured.

  Further, the pulp production method according to the present invention is a method for producing a pulp in which zeolite is fixed, and after wood chips are put into a chemical solution containing at least a basic substance and an aluminum compound, the wood chips are digested. The method is characterized in that a silicon compound is added to a chemical solution and heated to synthesize zeolite to produce a pulp in which the zeolite is fixed. In this pulp production method, a pulp in which faujasite X-type or philipsite is fixed as zeolite can be produced.

  In the present invention, an aluminum compound is contained in the chemical solution, and wood chips are added to the chemical solution, and when the wood chips are digested, the silicon compound is added to the chemical solution and heated, whereby cooking, synthesis of zeolite and pulp are performed. Fixing at the same time. Thereby, in this invention, since a synthesis | combination and fixation of a zeolite and a zeolite can be performed by one process, without passing through a two step process, a process can be simplified and the chemical | medical solution at the time of cooking is used effectively. By doing so, waste liquid can be reduced. In the present invention, an analsim can be synthesized as a zeolite, and a pulp on which the analcyme is fixed can be produced.

  Further, in the present invention, the chemical solution contains an aluminum compound, the wood chips are poured into the chemical solution, the wood chips are digested, and then the chemical solution used for cooking is used as it is without being used as a waste solution. By adding the compound and heating, the zeolite can be synthesized and fixed to the pulp with the chemical solution after cooking. Thereby, in this invention, since a synthesis | combination and a synthesis | combination and fixation of a zeolite can be performed by one process, without passing through a two-step process, a process can be simplified and the chemical | medical solution after cooking is used effectively. By doing so, waste liquid can be reduced. In the present invention, faujasite X-type or philipsite can be synthesized as zeolite, and faujasite X-type or philipsite can be fixed to the pulp.

  Hereinafter, the manufacturing method of the pulp to which this invention is applied is demonstrated in detail. This pulp production method is a method of producing a pulp in which zeolite is fixed by compounding zeolite having a cation exchange ability and a malodorous substance adsorption ability with the pulp. In this pulp manufacturing method, in the cooking process of wood chips, the synthesis of zeolite and the zeolite and pulp are combined and fixed to the pulp, so that the cooking process and the synthesis and fixing process of zeolite performed separately. Can be performed in one step.

  Wood chips used as the raw material for pulp include conifers such as pine, fir, tsuga, spruce, larch, radiatapine, broadleaf trees such as eucalyptus, poplar, beech, maple and hippopotamus, as well as kenaf, mitsumata, kouzo, ganpi, mulberry , Manila hemp, reed, bamboo, bagasse and the like.

The zeolite compounded with the pulp and fixed to the pulp is a crystalline aluminosilicate, and the main chemical composition is SiO ₂ , Al ₂ O ₃ , Na ₂ O, H ₂ O, or the like. Examples of the zeolite include high silica zeolite such as ZSM-5, faujasite X-type, A-type zeolite, philipsite, and anal sime. These zeolites have the ability to adsorb malodorous substances, cation exchange ability, molecular sieving ability, catalytic action and the like. Adsorption ability adsorbs malodorous substances such as acetaldehyde contained in exhaust gas, etc., and volatile organic compounds (VOC) such as formaldehyde contained in adhesives and paints, etc., in the pores formed in the zeolite. It is ability. The molecular sieving ability is the ability to select molecules using the pores formed in the zeolite. This molecular sieving ability depends on the pore diameter because it uses pores. Cation exchange capacity exchanges adsorbed cations with cations such as silver ions and copper ions to neutralize the permanent negative charge generated by isomorphous substitution of silicon ions in the zeolite structure with aluminum ions. With the ability to do so, it is possible to fix various cations on the zeolite. Further, due to this cation exchange capacity, zeolite has a selectivity called an ion sieving effect. This ion sieving effect mainly depends on the pore size, and zeolite having a smaller pore size has a larger ion sieving effect.

  For example, among the zeolites, analthym has a large pore diameter of about 0.22 nm and has a large ion sieving effect as compared with other zeolites because the pore diameter is small. Since anal thyme has this ion sieving ability, it has a cation exchange ability, and it is considered that cations such as sodium ions and cations such as silver ions in the anal sime are exchanged. In addition, since the anal thyme has a small pore diameter, the adsorption capacity for adsorbing malodorous substances such as VOC is inferior to other zeolites.

  The faujasite X type has a large pore diameter among zeolites, and the maximum pore diameter is about 0.74 nm. Thus, the faujasite X type uses large pores, and therefore has an excellent adsorbing ability for adsorbing malodorous substances such as VOC. Therefore, the faujasite X type has a higher adsorption effect than other zeolites having a small pore diameter.

  Philipsite has a maximum pore size of about 0.44 nm, which is smaller than that of faujasite X type, but it has a bad odor than an anthracite with a maximum pore size of about 0.22 nm. Has the ability to adsorb substances.

  Such zeolite-fixed pulp can be used for filters for air purifiers by utilizing the adsorbing ability of malodorous substances of the fixed zeolite, or by using the ion exchange capacity for silver ions and copper ions. It is carried and used for harmful inorganic substance removal sheets and antibacterial sheets.

In order to synthesize zeolite, silicon compounds, aluminum compounds, basic substances, water, and the like are required in order to generate SiO ₂ , Al ₂ O ₃ , Na ₂ O, H ₂ O and the like having main chemical compositions.

  Examples of the silicon compound include water glass, colloidal silica, paper sludge (papermaking residue), sodium metasilicate, potassium metasilicate, potassium orthosilicate, silica sol, and the like.

  Examples of the aluminum compound include sodium aluminate, potassium aluminate, aluminum sulfate, aluminum chloride, and aluminum nitrate.

  Examples of the basic substance include sodium hydroxide and potassium hydroxide.

  In such a method for producing a pulp on which zeolite has been fixed, in the step of cooking wood chips, cooking of wood chips, synthesis of zeolite, and composite of zeolite and pulp are performed to fix zeolite to pulp.

Wood chip cooking is a process performed to remove lignin from wood chips. That is, the cooking removes lignin from the bound fibers bound by lignin, loosens the bound fibers, promotes pulping into individual fibers, and obtains pulp. A general cooking chemical used for cooking includes a basic substance and water. In cooking, wood chips are impregnated with cooking chemicals and heated, the lignin is eluted with basic substances and water contained in the cooking chemicals, and the lignin is extracted to extract the fiber. The binding is loosened and pulped. Examples of the cooking method include alkali cooking using sodium hydroxide, kraft cooking performed with a chemical solution using sodium hydroxide and sodium sulfide, and the like. Thus, a basic substance such as sodium hydroxide is required for cooking the wood chips. For this reason, among the above-mentioned zeolites, high silica zeolite such as ZSM-5 has a small molar ratio of Na ₂ O and SiO ₂ (Na ₂ O / SiO ₂ ), that is, the proportion of basic substances is small. It is not suitable for a production method using a cooking process. On the other hand, faujasite X-type, A-type zeolite, philipsite, anal sime, etc. use a cooking process because Na ₂ O / SiO ₂ is large, that is, the ratio of basic substances for pulping is sufficient. Suitable for manufacturing methods.

  The synthesis of zeolite is performed by a method called hydrothermal synthesis. Hydrothermal synthesis uses hydrothermal reaction to perform synthesis by reacting substances such as aluminum compounds, basic substances, silicon compounds, water at a high temperature of 100 ° C. or higher. Is a reaction involving water at high temperature and high pressure.

  As described above, cooking of wood chips and synthesis of zeolite are common in that heating is required and that a basic substance and water are used. Therefore, in the cooking process, if an aluminum compound or silicon compound necessary for the synthesis of the zeolite is added to the chemical solution containing basic substance or water and heated, the zeolite is synthesized, the zeolite and pulp are combined, and the zeolite is pulped. Can be fixed.

  Specifically, a method for producing pulp in which an anthracite is fixed as zeolite is performed as follows.

  First, the air in the wood chip 1 shown in FIG. 1 is deaerated.

  Next, as shown in FIG. 1, the autoclave 2 is used in the digester, and sodium aluminate is used as an aluminum compound necessary for the synthesis of, for example, an anthracite 4 and the basicity necessary for the synthesis and pulping of the anthracim 4. A chemical solution 3 consisting of sodium hydroxide and water is added as a substance.

  Next, the wood chip 1 is put into the chemical solution 3 and left for 12 hours or more, for example, about 24 hours, so that the chemical solution 3 penetrates the wood chip 1.

  Next, after adding, for example, water glass as a silicon compound necessary for synthesizing the analthim 4 to the chemical solution 3 containing the wood chip 1 with stirring, the temperature is 160 ° C. to 200 ° C., for example, 170 ° C. for 1 hour. The pulp 5 in which the anusymme 4 is fixed is obtained by heating and cooking the wood chip 1, synthesizing the analthum 4, combining the analthum 4 and the pulp 5, and fixing the analthum 4 to the pulp 5. Is obtained. Both the cooking of the wood chip 1 and the synthesis of the analthim 4 can be performed at a temperature of 160 ° C. to 200 ° C., for example, about 170 ° C. Thereby, in the manufacturing method of this pulp 5, cooking of the wood chip | tip 1 and the synthesis | combination of the anal sime 4 and fixation to the pulp 5 can be performed simultaneously.

  In the above-described method for producing the pulp 5 to which the analthim 4 is fixed, the aluminum compound and the silicon compound necessary for the synthesis of the analthim 4 are not simultaneously added to the chemical solution 3, and the wood chip 1 is added to the chemical solution 3 containing the aluminum compound. After the chemical solution 3 is infiltrated into the wood chip 1 and the silicon compound is added to synthesize the analthime 4, the aluminum compound penetrates into the pulp 5. The analthim 4 can be fixed on the surface.

  In addition, in the method for producing the pulp 5 to which the analthim 4 is fixed, when an aluminum compound and a silicon compound necessary for the synthesis of the analthim 4 are added to the chemical solution 3 at the same time, the analthim 4 is synthesized outside the pulp 5 or on the surface. As a result, the analsim 4 is not fixed to the pulp 5, and the analsim 4 and the pulp 5 are separated. In the manufacturing method of the pulp 5 to which the anal thyme 4 is fixed, an aluminum compound is contained in the chemical solution 3, the wood chip 1 is introduced into the chemical solution 3, the aluminum compound is permeated into the wood chip 1, and then the silicon compound is added. By adding to the chemical solution 3 and digesting and synthesizing the anal sym 4, it is possible to prevent the anal sym 4 from being synthesized inside and on the surface of the pulp 5, and the anal sym 4 and the pulp 5 can be prevented from being separated. Can be fixed.

  Here, when the wood chip 1 is digested, if the wood chip 1 is too small, the amount of pulping is small and the chemicals are wasted. If the wood chip 1 is too much, the anal sym 4 does not settle on the pulp 5, so It is preferable that the weight ratio of the liquid to the liquid is [chemical solution 3 added with a silicon compound (liquid)] / woodchip 1 (solid) = 3 to 100.

Further, to synthesize analcime 4, chemical 3 to the silicon compound is added to be used in order to fix the pulp 5, the molar ratio of SiO ₂ and _Al 2 _{O 3} is _{SiO 2 / Al 2 O 3 =} 2.5~ 4, preferably SiO ₂ / Al ₂ O ₃ = 3, the molar ratio of Na ₂ O and SiO ₂ is Na ₂ O / SiO ₂ = 1 to 1.5, and H ₂ O and Na ₂ O Silicon compound such as aluminum compound such as sodium aluminate, basic substance such as sodium hydroxide, amount of water, and water glass to be added so that the molar ratio of H ₂ O / Na ₂ O = 30 to 150 Adjust the amount.

In the chemical solution 3 to which the silicon compound is added, by setting the SiO ₂ / Al ₂ O ₃ to 2.5 to 4, it is possible to synthesize the analthime 4 and fix the analthime 4 to the pulp 5. it can. Further, the chemical 3 silicon compound is _added, the Na ₂ O / SiO 2 and _1-1.5, the H ₂ O / Na 2 O by such a 30 to 150, in the wood chips 1 Lignin can be extracted to make wood chip 1 into pulp 5.

  In the manufacturing method of the pulp 5 to which the anal sym 4 is fixed as described above, the synthesis of the anal sym 4 and the aluminum compound necessary for the synthesis of the anal sym 4 in the autoclave 2 of the digester in which the wood chip 1 is cooked in the cooking process of the wood chip 1. In addition, a chemical solution 3 composed of a basic substance necessary for pulping and water is contained, and after the wood chip 1 is immersed in the chemical solution 3 for a while, water glass necessary for the synthesis of the analthim 4 at the time of cooking is used. By adding and heating the silicon compound, cooking of the wood chip 1, synthesis of the analthim 4, and the composite of the analthum 4 and the pulp 5 can be performed simultaneously with the fixing of the analthim 4 to the pulp 5. Thereby, in the manufacturing method of the pulp 5 to which the anal sym 4 is fixed, the cooking process and the fixing process for synthesizing the anal sym 4 and combining the anal sym 4 and the pulp 5 to fix the anal sym 4 to the pulp 5 are separated. In the cooking step, the cooking of the wood chip 1, the synthesis of the analthum 4, and the composite of the analthim 4 and the pulp 5 can be performed simultaneously with the fixing of the analthim 4 to the pulp 5. Since the process can be simplified and the operation of treating the waste liquid can be omitted, the pulp 5 in which the analthym 4 is fixed with one chemical liquid 3 can be efficiently produced. In the method for producing the pulp 5 to which the anal sym 4 is fixed, cooking with one chemical solution 3 and synthesis and fixing of the anal sym 4 can be performed, so that the amount of chemicals can be reduced as compared with the case of performing in two stages. And cost can be reduced.

  In addition, in the method for producing the pulp 5 to which the analthim 4 is fixed, there is no need to change the chemicals constituting the chemical solution 3 in the cooking step, the synthesis of the analthim 4 and the fixing step to the pulp 5, and one chemical solution is required. 3, the pulp 5 to which the analthym 4 is fixed can be produced. In addition, in the method of manufacturing the pulp 5 to which the anal sym 4 is fixed, the synthesis of the anal sim 4 and the fixing to the pulp 5 are performed simultaneously with the digestion, so that the heating is performed once, and the cooking time and the synthesis time are the cooking process and the anal sim. The amount of heat required for cooking and the synthesis and fixing of the anal thyme 4 can be reduced and saved because it is shorter or no different than when the 4 combining and fixing steps are performed separately.

  Moreover, in the manufacturing method of the pulp 5 to which the anal sime 4 is fixed, the wood chip 1 is immersed in the chemical solution 3 containing the aluminum compound for a while, and the chemical solution 3 is preliminarily permeated into the wood chip 1. Becomes easy to fix to the pulp 5, and the analthim 4 can be fixed to the pulp 5 without using a binder. Thereby, in the manufacturing method of the pulp 5 to which the anal sym 4 is fixed, the anal sym 4 can be fixed to the pulp 5 without using a binder. A sieving effect and an ability to adsorb malodorous substances can be exhibited.

  In addition, the pulp 5 to which the analthym 4 obtained as described above is fixed can produce a functional paper utilizing the ion exchange ability of the analthym 4 through a paper making process. As functional paper, using the ion exchange ability of Analcym 4, the cations in Analcym 4 are exchanged with cations such as silver ions and copper ions, and the antibacterial activity of cations such as silver ions exchanged and supported Examples thereof include an antibacterial sheet utilizing action and a harmful inorganic substance removing sheet.

  Next, the manufacturing method of the pulp in which the faujasite X type is fixed will be described. In addition, when producing pulp with fixed faujasite X type, synthesis of faujasite X type becomes difficult if the temperature condition is 160 ° C. or higher. The faujasite X-type synthesis performed at a lower temperature cannot be performed simultaneously. Therefore, when synthesizing the faujasite X type, the silicon compound is not put into the chemical solution containing the aluminum compound at the first stage of the cooking process as in the above-described Analthim 4, but the first stage of the cooking process is used. In the stage, after cooking for about 1 to 2 hours without adding a silicon compound, the temperature of the chemical solution is lowered to a temperature lower than 160 ° C., for example, 60 ° C. to 130 ° C., and the silicon compound is added while stirring. Perform faujasite X-type synthesis.

  Specifically, first, the air in the wood chip 11 shown in FIG.

  Next, the autoclave 12 is used in the digester, and sodium aluminate is used as an aluminum compound necessary for the synthesis of the faujasite X type 16 in the autoclave 12 and is necessary for the synthesis of the faujasite X type 16 and the cooking of the wood chip 11. A chemical solution 13 consisting of sodium hydroxide and water is added as a basic substance.

  Next, the wood chip 11 is put into the chemical solution 13 and left for 12 hours or more, for example, about 24 hours, so that the chemical solution 13 penetrates the wood chip 11.

  Next, the chemical solution 13 containing the wood chip 11 is heated at a temperature of 160 ° C. to 200 ° C. for 1 hour or more, for example, 160 ° C. or more for about 2 hours, and the wood chip 11 is digested to produce pulp 14. The chemical solution 13 is also used in the next synthesis of the faujasite X type 16 without making it a waste solution.

  Next, the temperature of the chemical solution 13 is lowered to about 60 ° C. to 130 ° C., and for example, water glass 15 is added as a silicon compound necessary for the synthesis of the faujasite X-type 16 to the chemical solution 13 containing the pulp 14 while stirring. The faujasite X-type 16 is synthesized for 1 hour or more, for example, about 3 hours, the synthesized faujasite X-type 16 and the pulp 14 are combined, and the faujasite X-type 16 is fixed to the pulp 14 Thus, the pulp 14 having the faujasite X type 16 fixed thereon is obtained. In this production method, in addition to the faujasite X type 16, it is also possible to synthesize A-type zeolite and Philipsite and fix them on the pulp.

  In the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed, the aluminum compound and the silicon compound necessary for the synthesis of the faujasite X type 16 are not simultaneously added to the chemical solution 13, but the aluminum compound is contained. The wood chip 11 is poured into the liquid chemical 13, the chemical liquid 13 is infiltrated into the wood chip 11, and then a silicon compound is added to synthesize the faujasite X-type 16. Can penetrate the pulp 14 inside or on the surface of the pulp 14.

  Moreover, in the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed as described above, when the aluminum compound and the silicon compound necessary for the synthesis of the faujasite X type 16 are added to the chemical solution 13 at the same time, the pulp 14 The faujasite X-type 16 is synthesized outside the interior and the surface, the faujasite X-type 16 is not fixed to the pulp 14, and the pulp 14 and the faujasite X-type 16 are separated. In the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed, the aluminum compound is contained in the chemical solution 13, the wood chip 11 is introduced into the chemical solution 13, and the aluminum compound is infiltrated into the wood chip 11. When the faujasite X type 16 is synthesized, the faujasite X type 16 is synthesized on the inside or the surface of the pulp 14 by adding a silicon compound to the chemical solution 13. Can be prevented from being separated, and the faujasite X-type 16 can be synthesized inside or on the surface of the pulp 14 to fix the faujasite X-type 16 to the pulp 14.

When fixing the faujasite X type 16 to the pulp 14, the chemical solution 13 to which the silicon compound is added is under the same conditions as in the case of the analthime 4, and the molar ratio of SiO ₂ to Al ₂ O ₃ is SiO ₂ / Al ₂ O ₃ = 2.5~4, and the preferably _{SiO 2 / Al 2 O 3 =} 3, Na 2 O and molar ratio of SiO ₂ is _Na 2 _O / SiO 2 = _1~1.5 next , such that the molar ratio of _{H 2} O and Na ₂ O is _{H 2 O / Na 2 O =} 30~150, aluminum compounds, basic substance, the amount of water, and the silicon compound of water glass to be added Adjust the amount. The amount of the wood chip 11 when the wood chip 11 is digested is also the same as that in the case of the anal sime 4, and [chemical solution 13 (liquid) to which a silicon compound is added] / wood chip 11 (solid) = 3 to 100 It is preferable that

  In the manufacturing method of the pulp 14 to which the faujasite X-type 16 is fixed as described above, after the wood chip 11 is digested in the cooking process of digesting the wood chip 11, the chemical solution 13 in the autoclave 12 is treated as a waste liquid. Without using the chemical solution 13 as it is, water glass 15 necessary for the synthesis of the faujasite X type 16 is added to the chemical solution 13 and heated to synthesize the faujasite X type 16 and the faujasite X type 16 and pulp. 14 is combined and fixed to the pulp 14, so that cooking, synthesis of the faujasite X-type 16 and fixing to the pulp 14 can be performed in the cooking process, and thus the process is simplified. In addition, since the work of treating the waste liquid can be omitted, the pulp 14 can be manufactured efficiently. Further, in the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed, the cooking, the synthesis of the faujasite X type 16 and the fixing to the pulp 14 can be performed with one chemical solution 13. The amount of chemicals can be reduced and the cost can be reduced as compared with the case of performing in two steps.

  Further, in the method for producing the pulp 14 to which the faujasite X type 16 is fixed, the wood chip 11 is immersed for a while in the chemical solution 13 containing the aluminum compound, and the chemical solution 13 is infiltrated into the wood chip 11 in advance. When a faujasite X type 16 is synthesized by adding a compound, the synthesized faujasite X type 16 is easily fixed on the pulp 14, and the faujasite X type 16 is fixed on the pulp 14 without using a binder. Can be made. Thereby, in the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed, the faujasite X type 16 can be fixed to the pulp 14 without using a binder. 16 is not covered with a binder, and the foul sight substance adsorption ability of faujasite X type 16 can be expressed.

  Further, the pulp 14 to which the faujasite X-type 16 obtained as described above is fixed can be used to produce a functional paper using the ion exchange ability of the faujasite X-type 16 through a papermaking process. . As functional paper, using the ion exchange ability of faujasite X type 16, cations in faujasite X type 16 are exchanged with cations such as silver ions and copper ions, and are exchanged and supported. Examples include antibacterial sheets that use the antibacterial action of cations such as silver ions and copper ions, and harmful inorganic substance removal sheets. Further, the pulp 14 to which the faujasite X type 16 is fixed can also produce a functional paper utilizing the foul odor substance adsorbing ability of the faujasite X type 16. Examples of the functional paper include a filter for an air purifier that utilizes the foul odor substance adsorption capacity of the faujasite X type 16.

  In addition, the manufacturing method of the pulp 14 to which the faujasite X type 16 is fixed as described above can also manufacture a pulp to which a philipsite is fixed as zeolite. Phillipsite is synthesized by increasing the water content in the chemical solution compared to the case of synthesizing faujasite X type 16. That is, when manufacturing pulp with Philipsite fixed, the water content in the chemical solution is 1.3 to 2 times the water content in the chemical solution 13 of the faujasite X type 16. To the extent.

  Even in a pulp to which a philipsite produced by the same method as that of the pulp 14 to which the faujasite X type 16 is fixed is fixed, the philipsite is fixed to the pulp without using a binder. Pulp with fixed phillipsite removes antibacterial sheets and harmful inorganic substances by utilizing the antibacterial action of cations such as silver ions and copper ions exchanged with cations in philipsite due to the cation exchange capacity of philipsite Used for sheets and the like. In addition, the pulp on which the philipsite is fixed is also used for a filter for an air purifier or the like that uses the adsorption capacity of the malodorous substance of the philipsite.

  Examples of pulp to which the present invention is applied will be described below. The present invention is not limited to these examples.

<Example 1>
In Example 1, cooking was performed in an autoclave (effective capacity: 3 L, normal pressure: 0.49 MPa to 0.98 MPa, maximum specification temperature: 200 ° C.) (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Water glass (Silica No. 3 manufactured by Mitsuwa Chemical Industry Co., Ltd.) is used for the silicon compound, sodium aluminate (Kishida Chemical Co., Ltd.) is used for the aluminum compound, and sodium hydroxide is used for the basic substance. (Special grade manufactured by Kanto Chemical Co., Inc.) was used. The chemical solution to which water glass is added is SiO ₂ / Al ₂ O ₃ (molar ratio) = 3, Na ₂ O / SiO ₂ (molar ratio) = 1.2, H ₂ O / Na ₂ O (molar ratio) = In order to obtain 40, 100 g of sodium aluminate, 129 g of sodium hydroxide, 1343 g of water, and 384 g of water glass to be added were used. Raditapine was used for the wood chip, and 50 g was used. The weight ratio of the chemical solution to which the water glass was added and the wood chip was as follows: chemical solution to which the water glass was added / wood chip = (sodium aluminate 100 g + sodium hydroxide 129 g + water 1343 g + water glass 384 g) / wood chip 50 g = 1957/50 = 39.

  First, before infiltrating a chemical | medical solution to a wood chip | tip, in order to deaerate the air which exists in a wood chip | tip, water was made to osmose | permeate a wood chip | tip, and it put in the suction filtration bell, and evacuated. When the deaeration is finished, 100 g of sodium aluminate, 129 g of sodium hydroxide, and 1343 g of water are mixed to prepare a chemical solution. The wood chips are immersed in the chemical solution, and the chemical solution is infiltrated into the wood chips. The penetration time is 24 hours. Next, after 24 hours, while stirring in an autoclave, 384 g of water glass was added little by little, and after fully dispersed, cooking, synthesis of zeolite and synthesis of zeolite and pulp were combined into pulp. Was fixed. The cooking time was 90 minutes and the cooking temperature was 170 ° C.

<Example 2>
In Example 2, after degassing of the wood chips, the wood chips were immersed in a chemical solution in which 100 g of sodium aluminate, 129 g of sodium hydroxide, and 1343 g of water were mixed for 24 hours. The chemical solution was infiltrated, and then digested by heating in an autoclave at 170 ° C. for 2 hours. While stirring after cooking, 384 g of water glass was added. After sufficiently stirring and mixing the water glass throughout, the zeolite was synthesized at 100 ° C. for 3 hours, and the zeolite and the pulp were combined and fixed to the pulp. In addition, the conditions of the chemical solution with water glass added, SiO ₂ / Al ₂ O ₃ = 3, Na ₂ O / SiO ₂ = 1.2, H ₂ O / Na ₂ O = 40, the chemical solution with water glass added / Wood chips = 39, etc. were performed in the same manner as in Example 1.

<Example 3>
In Example 3, when cooking, 100 g of sodium aluminate, 129 g of sodium hydroxide, and 1343 g of water were mixed to prepare a chemical solution, and after cooking as in Example 2, When adding 384 g of water glass, 500 ml of water was further added, and the conditions of the chemical solution to which water glass and water were added were SiO ₂ / Al ₂ O ₃ = 3, Na ₂ O / SiO ₂ = 1.2, H _2. O / Na ₂ O = 53 so that the weight ratio of water glass and water-added chemical solution to wood chips is water glass and water-added chemical solution / wood chips = (sodium aluminate 100 g + sodium hydroxide 129 g + 1843 g of water + 384 g of water glass) / wood chip 50 g = 2456/50 = 49, except that the synthesis of zeolite and fixation to pulp were performed. It was carried out in the same manner as.

  In Examples 1 to 3 as described above, wood chips could be pulped. Here, being able to be pulped means that there is no binding fiber after cooking, and each fiber (pulp) is dispersed.

In Examples 1 to 3, there was no pulp bound after cooking, and each piece of pulp was made into one pulp. In Examples 1 to 3, Na ₂ O / SiO ₂ in the chemical solution to which water glass was added was 1.2, Na ₂ O / SiO ₂ was in the range of 2.5 to 3, and H _{Since 2} O / Na ₂ O is 40 or 53 and H ₂ O / Na ₂ O is in the range of 30 to 150, the amount of sodium hydroxide and water required for pulping is appropriate. It could be pulped.

In addition, in the manufacturing method of the pulp shown in Example 1, the conditions of the chemical | medical solution for pulping a wood chip were further examined. The chemical solution to which the examined water glass was added is SiO ₂ / Al ₂ O ₃ , Na ₂ O / SiO ₂ , H ₂ O / Na ₂ O, SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O / SiO ₂ = 0.4, H ₂ O / Na ₂ O = 40 (sample 1), SiO ₂ / Al ₂ O ₃ = 2; Na ₂ O / SiO ₂ = 1, H ₂ O / Na ₂ O = 17.5 (sample 2). Samples 1 and 2 were prepared by adjusting the amounts of sodium aluminate, sodium hydroxide, and water, respectively, and water glass (No. 3) was added when cooking and synthesizing zeolite. An attempt was made to produce a pulp in which zeolite was fixed by the same method.

In sample 1, Na ₂ O / SiO ₂ is 0.4, and the amount of basic substances necessary for pulping is small, so that many pulps are bound after cooking, and lignin extraction is not performed normally, and pulping is performed. I could not. In sample 2, H ₂ O / Na ₂ O was 17.5, and the amount of water required for pulping was small. Therefore, in this case as well, lignin extraction was not performed normally, and pulping could not be performed.

  Next, for Examples 1 to 3 that could be pulped, the obtained pulp was observed with a low vacuum scanning electron microscope (JSM-5510LV, manufactured by JEOL Ltd.). FIG. 3 shows an observation view of the pulp of Example 1 with a low vacuum scanning electron microscope, FIG. 4 shows an observation view of the pulp of Example 2, and FIG. 5 shows an observation view of the pulp of Example 3. In Example 1, it can be seen from FIG. 3 that the zeolite 32 is fixed on the pulp 31. In Example 2, it can be seen from FIG. 4 that the zeolite 34 is fixed to the pulp 33. In Example 3, it can be seen from FIG. 5 that the zeolite 36 is fixed on the pulp 35.

  Next, the synthetic substances fixed on the pulps of Examples 1 to 3 were evaluated. In the evaluation method, the waste liquid produced after cooking in the autoclave cannot be fixed to the pulps 31, 33, and 35, and the remaining synthetic substances are filtered out and the X-ray diffractometer (RINT2000 manufactured by Rigaku Corporation) is used. ) Was used to evaluate synthetic substances. FIG. 6 shows the evaluation results of the synthetic material of Example 1 using the X-ray diffractometer, FIG. 7 shows the evaluation results of Example 2, and FIG. 8 shows the evaluation results of Example 3. 6 to 8, the horizontal axis indicates the diffraction angle (2θ) (°), and the vertical axis indicates the diffraction intensity (cps). In the synthetic substance evaluation test, the synthetic substance remaining in the waste liquid was evaluated by measuring the peak of cellulose, which accounts for a large percentage of the zeolite-fixed pulp when X-ray diffraction was performed on the zeolite-fixed pulp. This is because the peak of zeolite is not clear. In the evaluation test by X-ray diffraction, which zeolite was produced by synthesis was evaluated, and the effect of the pulp on which the zeolite was fixed was confirmed by silver ion exchange and acetaldehyde adsorption as follows.

  As shown in FIG. 6, in Example 1, in the X-ray diffraction spectrum, diffraction peaks appear near diffraction angles (2θ) of 16 °, 26 °, and 30 °. You can see that Thereby, in Example 1, it can confirm that the anal sime was fixed to the pulp from the result shown in FIG.3 and FIG.6.

  As shown in FIG. 7, in Example 2, in the X-ray diffraction spectrum, the diffraction angle (2θ) is around 6 °, around 10 °, around 12 °, around 24 °, around 27 °, and around 30 °. Since peaks appear at around 34 °, it can be seen that the faujasite X type is synthesized. Thereby, in Example 2, it can confirm that the faujasite X type was fixed to the pulp from the result shown in FIG.4 and FIG.7.

  As shown in FIG. 8, in Example 3, the X-ray diffraction spectrum has peaks at diffraction angles (2θ) of around 12 °, around 18 °, around 22 °, around 28 °, and around 33 °. From the fact that it appears, it can be seen that Philipsite is synthesized. Thus, in Example 3, it can be confirmed from the results shown in FIG. 5 and FIG.

  From the above, as shown in Example 1, a method of synthesizing an anthracite at the same time as cooking in the cooking process, and after cooking in the cooking process as in Examples 2 and 3, the silicon compound is added to form It can be seen that the zeolite-fixed pulp can be obtained by either the jasite X type or the method of synthesizing the philippite.

  Next, the exchangeability of silver ions was evaluated for the pulp on which the zeolites of Examples 1 to 3 were fixed. Weigh each 1g of the zeolite-fixed pulp of Examples 1 to 3 and add 30ml of 100ppm silver ion solution, let stand for 15 minutes, and then filter, and determine the concentration of silver ions in the solution after filtration. It was measured with an atomic absorption spectrophotometer (SAS 7500, manufactured by Seiko Instruments Inc.). The measurement results are as shown in FIG. In FIG. 9, the horizontal axis indicates the time (minutes) in which the pulp having zeolite fixed in the silver ion solution is allowed to stand, and the vertical axis indicates the silver ion concentration (ppm) in the solution after filtration. In addition, Blank shown in FIG. 9 evaluated the exchange property of the silver ion of the pulp obtained only by cooking, without synthesizing and fixing a zeolite.

  As shown in FIG. 9, in Examples 1 to 3, the concentration of silver ions in the solution was almost 0 ppm, and the silver ions in the solution were almost gone. It can be seen that the cation and silver ion in the Site X type and Philip site are exchanged. Thereby, in the pulp of Example 1- Example 3, it turns out that the exchange property of a silver ion is excellent by an anal symme, a faujasite X type, and a Philip sight.

  Next, Example 1 to Example 3 were evaluated for acetaldehyde adsorptivity. Using the pulp to which the zeolite obtained in Examples 1 to 3 is fixed, paper having a thickness of 0.265 mm in Example 1, 0.275 mm in Example 2, and 0.353 mm in Example 3 is made. Each piece was cut to a size of 5 cm × 5 cm, and paper was placed in a 200 cc stainless steel reaction vessel having a quartz cover, and acetaldehyde was injected with a microsyringe to 50 ppm. The acetaldehyde concentration of the solution in the stainless steel reaction vessel was quantified with a gas chromatograph (GC-390B, manufactured by GL Science Co., Ltd.). The measurement results are shown in FIG.

  From the results shown in FIG. 10, in Example 1 in which the analthym was fixed to the pulp, the acetaldehyde concentration was not significantly changed, and no acetaldehyde was adsorbed. This is due to the small pores of the analcime fixed on the pulp of Example 1.

  In Example 2 in which the faujasite X type was fixed to the pulp, the acetaldehyde concentration was 0 ppm 25 minutes after the injection, indicating that the acetaldehyde adsorptivity is excellent. In Example 2, since the faujasite X-type pores fixed on the pulp were large, a large amount of acetaldehyde could be adsorbed. Thereby, in Example 2, it turns out that not only the exchange property of silver ion is excellent, but also the adsorptivity of acetaldehyde is also excellent.

  In Example 3 in which the philipsite was fixed on the pulp, the acetaldehyde concentration was slightly reduced, indicating that the acetaldehyde adsorbability is better than that of the analthime of Example 1.

  From the above results, as in Example 1, when digesting wood chips, by adding a silicon compound to a chemical solution containing sodium aluminate simultaneously with cooking, an anthracite with excellent silver ion exchangeability is fixed. It can be seen that the finished pulp can be produced. Further, as in Example 2 and Example 3, after the cooking in the cooking process, the faujasite X type and the lip site having excellent silver ion exchange and acetaldehyde adsorption properties are fixed by adding a silicon compound. It can be seen that the finished pulp can be produced.

  In addition, from the above results, zeolite with higher functionality than analcite such as faujasite X type and Philip sight by adding silicon compound to chemical solution containing aluminum compound after cooking during cooking process of wood chips It can be seen that can be fixed.

It is a figure explaining the method to manufacture the pulp to which the anal sime to which this invention was applied was fixed. It is a figure explaining the method to manufacture the pulp to which the faujasite X type to which this invention was applied was fixed. It is a figure showing the low vacuum scanning electron micrograph of the pulp in which the anal sime was fixed. It is a figure showing the low vacuum scanning electron micrograph of the pulp in which the faujasite X type was fixed. It is a figure showing the low vacuum scanning electron micrograph of the pulp in which the philipsite was fixed. It is a figure which shows the X-ray-diffraction result of the pulp of Example 1. It is a figure which shows the X-ray-diffraction result of the pulp of Example 2. It is a figure which shows the X-ray-diffraction result of the pulp of Example 3. It is a figure which shows the result of the silver ion exchange property of the pulp of Example 1- Example 3. It is a figure which shows the result of the adsorptivity of the acetaldehyde of the pulp of Example 1- Example 3. It is a figure explaining the conventional manufacturing method of the pulp in which the zeolite was fixed.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Wood chip, 2 Autoclave, 3 Chemical liquid, 4 Anal thyme, 5 Pulp, 11 Wood chip, 12 Autoclave, 13 Chemical liquid, 14 Pulp, 15 Water glass, 16 Faujasite X type

Claims (4)

In a method for producing a zeolite-fixed pulp,
Pulp in which wood chips are put into a chemical solution containing at least a basic substance and an aluminum compound, and during the cooking of the wood chips, a silicon compound is added to the chemical solution and heated to synthesize zeolite and the zeolite is fixed. A method for producing pulp, characterized in that   The method for producing pulp according to claim 1, wherein the zeolite is an anthracite. In a method for producing a zeolite-fixed pulp,
Wood chips were put into a chemical solution containing at least a basic substance and an aluminum compound, and after digesting the wood chips, a silicon compound was added to the chemical solution and heated to synthesize zeolite and the zeolite was fixed. A method for producing pulp, comprising producing pulp.   4. The method for producing pulp according to claim 3, wherein the zeolite is faujasite X-type or philipsite.

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