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WO2020137120A1 - Procédé de production de produit fibreux, produit fibreux et filtre - Google Patents

Procédé de production de produit fibreux, produit fibreux et filtre Download PDF

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Publication number
WO2020137120A1
WO2020137120A1 PCT/JP2019/041377 JP2019041377W WO2020137120A1 WO 2020137120 A1 WO2020137120 A1 WO 2020137120A1 JP 2019041377 W JP2019041377 W JP 2019041377W WO 2020137120 A1 WO2020137120 A1 WO 2020137120A1
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WO
WIPO (PCT)
Prior art keywords
layered double
double hydroxide
paper
fiber
product according
Prior art date
Application number
PCT/JP2019/041377
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English (en)
Japanese (ja)
Inventor
劉兆涛
大野睦浩
朝倉健夫
Original Assignee
日本国土開発株式会社
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Publication of WO2020137120A1 publication Critical patent/WO2020137120A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately

Definitions

  • the present invention relates to a method for manufacturing a textile product, a textile product, and a filter.
  • a fiber product such as paper containing a layered double hydroxide is desired for use as a wallpaper or the like having a function of adsorbing harmful substances.
  • an object of the present invention is to provide a fiber product in which layered double hydroxide or a functional material is hard to be desorbed, a fiber product in which a functional material is hard to be desorbed, a manufacturing method thereof, and a filter.
  • a first aspect of a method for producing a fiber product containing a layered double hydroxide is to mix an acidic solution containing at least one of divalent metal ions and trivalent metal ions with an alkaline solution in the presence of fibers. Then, it has a synthesis step of synthesizing the layered double hydroxide and a molding step of removing the water content of the mixed liquid generated in the synthesis step and molding.
  • a second aspect of the method for producing a fiber product containing a layered double hydroxide is to mix an acidic solution containing at least one of divalent metal ions and trivalent metal ions with an alkaline solution,
  • the method includes a synthesizing step of synthesizing a hydroxide, a mixing step of mixing fibers with the mixed solution generated in the synthesizing step, and a molding step of removing water from the mixed solution to perform molding.
  • FIG. 5A is a diagram showing a filter according to the fourth embodiment
  • FIG. 5B is a diagram showing a vertical cross section of the filter of FIG. 5A.
  • FIG. 7 is a table showing the results of experiments using the experimental apparatus of FIG. 6.
  • the paper product means a product formed by intertwining paper fibers, and includes thin flat paper, and columnar products used for filters and the like.
  • the fiber for paper means, for example, a natural fiber such as cellulose such as a plant fiber, a chemical fiber, a glass fiber or a metal fiber. Further, as the fiber for paper, other fibers can be used as long as they can be used for manufacturing paper.
  • FIG. 1 shows a flowchart of a method for manufacturing a paper product according to the first embodiment.
  • the method for manufacturing a paper product according to this embodiment mainly includes a synthesizing step S10 and a molding step S20.
  • Synthesis step S10 In the synthesis step S10, an acidic solution L1 containing a divalent metal ion and a trivalent metal ion in at least one of them and an alkaline solution L2 are mixed in the presence of paper or paper fibers to synthesize a layered double hydroxide. To do. Generally, it is preferable that both the divalent metal ion and the trivalent metal ion be contained in the acidic solution L1 side.
  • At least one of the acidic solution L1 and the alkaline solution L2 may contain the paper or the paper fiber and mix them. ..
  • the paper or the paper fibers may be contained in the alkaline solution L2
  • the paper or the paper fiber may be placed in a container or the like, and the acidic solution L1 and the alkaline solution L2 may be simultaneously supplied to the paper or the paper fiber.
  • this method is preferable when it is not desired to expose the paper or the paper fiber to the acidic solution L1 or the alkaline solution L2.
  • a liquid such as water may be added to the paper or the paper fiber, and the acidic solution L1 and the alkaline solution L2 may be supplied to this liquid.
  • the layered double hydroxide has a general formula of M 2+ 1-x M 3+ x (OH) 2 (A n- ) x/n ⁇ mH 2 O (where M 2+ is divalent).
  • Metal ions M 3+ is a trivalent metal ion
  • a n ⁇ is an n-valent anion, a non-stoichiometric compound represented by 0 ⁇ x ⁇ 1, m>0), and is called a hydrotalcite-like compound Sometimes.
  • Examples of the divalent metal ion (M 2+ ) include Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+. ..
  • Examples of the trivalent metal ion (M 3+ ) include Al 3+ , Fe 3+ , Cr 3+ , Mn 3+ and the like.
  • Examples of the anion (A n- ) include ClO 4 - , CO 3 2- , HCO 3 - , PO 4 3- , SO 4 2- , SiO 4 4- , OH - , Cl - , NO 2 - , NO 3 -, etc.
  • the divalent metal ion (M 2+ ) and the trivalent metal ion (M 3+ ) included in the above general formula do not have to be one type, and may include a plurality of types.
  • Mg 2+ 1-x Al 3+ x (OH) 2 (A in which the divalent metal ion (M 2+ ) is Mg 2+ and the trivalent metal ion (M 3+ ) is Al 3+ n- ) x/n ⁇ mH 2 O (Mg-Al type), divalent metal ion (M 2+ ) is Mg 2+ , and trivalent metal ion (M 3+ ) is Fe 3+ Mg 2+ 1-x Fe 3+ x (OH) 2 (A n- ) x/n ⁇ mH 2 O (Mg-Fe type) and divalent metal ion (M 2+ ) are Fe 2+ Trivalent metal ion (M 3+ ) is Fe 3+ , Fe 2+ 1-x Al 3+ x (OH) 2 (A n- ) x/n ⁇ mH 2 O (Mg-Fe type) and divalent metal ion (M 2+ ) are Fe 2+ Trivalent metal ion (M 3
  • the layered double hydroxide according to the first embodiment is in the form of slurry or gel, and the crystallite size in the slurry or gel is preferably 20 nm or less, more preferably 10 nm or less. Is better.
  • the average crystallite size is preferably 10 nm or less.
  • the specific surface area of the layered double hydroxide according to the first exemplary embodiment is not particularly limited, but a larger value is preferable because the adsorption performance can be improved.
  • the layered double hydroxide can have, for example, a specific surface area by the BET method of 20 m 2 /g or more, preferably 30 m 2 /g or more, and more preferably 50 m 2 /g or more. And more preferably 70 m 2 /g or more.
  • the upper limit of the specific surface area is not particularly limited.
  • the specific surface area by the BET method can be determined, for example, by measuring a nitrogen adsorption/desorption isotherm using a specific surface area/pore distribution measuring device and creating BET-plot from the measurement result. For example, if the crystallite size of the layered double hydroxide is 20 nm or less, the specific surface area can be 20 m 2 /g or more.
  • Synthesis of the layered double hydroxide is performed by mixing an acidic solution L1 containing a divalent metal ion and a trivalent metal ion with an alkaline solution L2.
  • the layered double hydroxide synthesized here can have a larger specific surface area as the crystallite size is smaller. Therefore, it is preferable that the aging time after the synthesis is short, and that after the acidic solution L1 and the alkaline solution L2 are mixed, at least 120 minutes or less, preferably 60 minutes or less, and more preferably, neutralization is performed simultaneously with the mixing.
  • the aluminum source of aluminum ions is not limited to a specific substance as long as it can generate aluminum ions in water.
  • alumina, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminum nitrate, bauxite, an alumina production residue from bauxite, aluminum sludge and the like can be used.
  • these aluminum sources may be used alone or in combination of two or more kinds.
  • the magnesium ion source of magnesium ions is not limited to a specific substance as long as it can generate magnesium ions in water.
  • brucite, magnesium hydroxide, magnesite, a calcined product of magnesite, or the like can be used.
  • These magnesium sources may be used alone or in combination of two or more kinds.
  • the aluminum compound as the aluminum source and the magnesium compound as the magnesium source need not be completely dissolved as long as the aluminum ion and the magnesium ion are present in the acidic solution L1.
  • the acid contained in the acidic solution L1 is not particularly limited as long as it makes the aqueous solution acidic, and nitric acid or hydrochloric acid can be used, for example.
  • the alkali contained in the alkaline solution L2 is not particularly limited as long as it makes the aqueous solution alkaline, and for example, sodium hydroxide, calcium hydroxide or the like can be used. Further, sodium carbonate, potassium carbonate, ammonium carbonate, aqueous ammonia, sodium borate, potassium borate and the like can also be used. Any of these may be used alone or in combination of two or more.
  • a solution having a pH adjusted to 8 to 14 can be used, and a solution having a pH adjusted to 8 to 11 is preferably used.
  • the paper or the paper fiber may be added to either or both of the acidic solution L1 and the alkaline solution L2, or may be placed in a container for mixing the acidic solution L1 and the alkaline solution L2. good.
  • an acidic solution L1 containing aluminum ions and magnesium ions and an alkaline solution L2 containing alkali are mixed at a predetermined ratio.
  • a layered double hydroxide is produced.
  • the mixing can be performed by adding the acidic solution L1 to the alkaline solution L2 all at once, or by dropping the acidic solution L1 into the alkaline solution L2, but other methods may be used.
  • a method of stopping the aging there is a method of lowering the pH of the mixed solution to a value at which the crystal growth of the layered double hydroxide stops after the mixing of the acidic solution L1 and the alkaline solution L2 is completed.
  • the pH should be 9 or less.
  • aging can be stopped by diluting with water within 120 minutes, preferably within 60 minutes, and more preferably simultaneously with mixing after the completion of mixing the acidic solution L1 and the alkaline solution L2.
  • the iron ion source is not limited to a specific substance as long as it can generate iron ions in water.
  • iron chloride or the like can be used.
  • these iron sources may be used alone or in combination of two or more kinds.
  • the magnesium ion source of magnesium ions is not limited to a specific substance as long as it can generate magnesium ions in water.
  • brucite, magnesium hydroxide, magnesite, a calcined product of magnesite, or the like can be used.
  • These magnesium sources may be used alone or in combination of two or more kinds.
  • the iron compound as the iron source and the magnesium compound as the magnesium source need not be completely dissolved as long as the iron ion and the magnesium ion are present in the acidic solution L1.
  • the acid contained in the acidic solution L1 is not particularly limited as long as it makes the aqueous solution acidic, and nitric acid or hydrochloric acid can be used, for example.
  • the alkali contained in the alkaline solution L2 is not particularly limited as long as it makes the aqueous solution alkaline, and for example, sodium hydroxide, calcium hydroxide or the like can be used. Further, sodium carbonate, potassium carbonate, ammonium carbonate, aqueous ammonia, sodium borate, potassium borate and the like can also be used. Any of these may be used alone or in combination of two or more.
  • a solution having a pH adjusted to 8 to 14 can be used, and a solution having a pH adjusted to 8 to 11 is preferably used.
  • the paper or the paper fiber may be added to either or both of the acidic solution L1 and the alkaline solution L2, or may be placed in a container for mixing the acidic solution L1 and the alkaline solution L2. good.
  • an acidic solution L1 containing iron ions and magnesium ions and an alkaline solution L2 containing alkali are mixed at a predetermined ratio.
  • a layered double hydroxide is produced.
  • the mixing can be performed by adding the acidic solution L1 to the alkaline solution L2 all at once, or by dropping the acidic solution L1 into the alkaline solution L2, but other methods may be used.
  • a method of stopping the aging there is a method of lowering the pH of the mixed solution to a value at which the crystal growth of the layered double hydroxide stops after the mixing of the acidic solution L1 and the alkaline solution L2 is completed.
  • the pH should be 9 or less.
  • aging can be stopped by diluting with water within 120 minutes, preferably within 60 minutes, and more preferably simultaneously with mixing after the completion of mixing the acidic solution L1 and the alkaline solution L2.
  • the acidic solution L1 side contains iron ions and magnesium ions
  • the acidic solution L1 side contains iron ions and the alkaline solution L2 side contains magnesium ions. It is also possible to contain the above, or to contain magnesium ions on the acidic solution L1 side and iron ions on the alkaline solution L2 side, or to contain both iron ions and magnesium ions on the alkaline solution L2 side. is there.
  • the layered double hydroxide immediately after being neutralized as described above is in the form of slurry or gel.
  • This slurry-like or gel-like layered double hydroxide may be used as it is in the molding step S20 described later.
  • the molding step S20 is a step of removing the water content of the mixed liquid generated in the synthesis step S10 and molding the mixture into a desired shape.
  • the water content of the mixed liquid may be removed until the mixture of paper or paper fibers and the composite layered double hydroxide is formed into a desired shape.
  • water is removed by applying pressure to a paper or a mixture of paper fibers and a layered double hydroxide until the water content becomes 70% or less, preferably 65% or less, more preferably 60% or less.
  • compression separation using a filter press, suction filtration, centrifugal separation, or the like may be used.
  • the pressure applied when removing water is not limited, but may be, for example, 0.7 MPa or more and 4 MPa or less, preferably 0.9 MPa or more and 3 MPa or less. This is because if the pressure applied at the time of removing water is less than the lower limit value described above, the water content of the mixed liquid is not sufficiently removed, and if it exceeds the upper limit value described above, water may leak from the sealing member such as packing.
  • the dehydrated mixture can be formed into a desired shape, for example, a columnar shape used for a filter or the like to form a paper product.
  • the product molded in the molding step S20 can be used as it is as a paper product, as shown by a broken line frame in FIG. 1, a drying step S30 for drying the paper product is performed after the molding step S20. Is also good.
  • paper-making may be performed using a solution of paper or fiber for paper containing layered double hydroxide. Specifically, when the mixed solution is spread on the net or the paper scraps, the water content passes through the nets or the paper scraps and drops, while the layered double hydroxide and the paper or the paper fiber remain on the nets or the paper scraps. By removing water from this and drying it in the drying step S30, a sheet-shaped paper can be manufactured. Well-known methods may be used as specific means for removing paper, removing water, and drying.
  • the paper product of the first embodiment will be described.
  • the layered double hydroxide grows from the surface of the paper fiber. Therefore, there is an effect that it is difficult for the layered double hydroxide powder to be detached from the paper.
  • the relative amount of the layered double hydroxide is reduced by the addition of the binder, and the layered double hydroxide is covered by the binder.
  • the surface area of the hydroxide is reduced and the adsorption ability of the paper product is reduced, in the first embodiment, since the binder is not used, the amount of the layered double hydroxide contained in the paper can be increased and the layered double hydroxide can be contained. The surface area of the double hydroxide can be increased. Thereby, the adsorption performance can be sufficiently exhibited.
  • the specific surface area of the layered double hydroxide contained in the paper product of the first embodiment is not particularly limited, but a larger value is preferable because the adsorption performance can be improved.
  • the layered double hydroxide can have, for example, a specific surface area by BET method of 20 m 2 /g or more, preferably 30 m 2 /g or more, and more preferably 50 m 2 /g or more. It is preferable that it is 70 m 2 /g or more.
  • the upper limit of the specific surface area is not particularly limited.
  • the specific surface area by the BET method can be determined, for example, by measuring a nitrogen adsorption/desorption isotherm using a specific surface area/pore distribution measuring device and creating BET-plot from the measurement result. For example, if the crystallite size of the layered double hydroxide is 20 nm or less, the specific surface area can be 20 m 2 /g or more.
  • a columnar filter see the filter 10 in FIG. 3 and the filter 30 in FIG. 5A
  • sheet-shaped paper used as wallpaper, or the like can be used.
  • Example 1 Paper product of the first embodiment (forming step after synthesis on paper fiber)
  • magnesium chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • aluminum chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • an acidic solution L1 magnesium chloride hexahydrate
  • sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • the acidic solution L1, the alkaline solution L2, and the fiber for paper (30 g) were mixed, and further, a sufficient amount of distilled water was rapidly mixed into the mixed solution in a short time. Then, the solution was used to make paper and dried at 100° C. for 10 hours to produce paper.
  • Example 2 ⁇ Paper product of the first embodiment of the invention (molding process after synthesis on paper)
  • magnesium chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • aluminum chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • an acidic solution L1 is dissolved in distilled water to prepare an acidic solution L1.
  • sodium hydroxide is dissolved in distilled water to prepare an alkaline solution L2.
  • the acidic solution L1 and the alkaline solution L2 were mixed with paper (30 g), and further, a sufficient amount of distilled water was rapidly mixed with the mixed solution in a short time. Then, the paper was taken out from the solution and dried at 100° C. for 10 hours to manufacture the paper.
  • the paper product of the second embodiment means a product formed by entwining paper fibers, and includes thin flat-formed paper and columnar products used for filters and the like.
  • the fiber for paper means, for example, plant fiber, chemical fiber, glass fiber, metal fiber or the like. Further, as the fiber for paper, other fibers can be used as long as they can be used for manufacturing paper.
  • the paper product of the second embodiment contains a functional material.
  • the functional material means a material having one or more specific functions such as an adsorption function and a catalyst function. Examples of such a functional material include zeolite, activated carbon, schwertmannite, zirconium, and cerium. Also, a photocatalyst such as titanium oxide may be used. Further, the functional material may be a layered double hydroxide prepared separately instead of the layered double hydroxide synthesized in the synthesis step described later. The functional material may be one kind of material or a mixture of plural kinds.
  • FIG. 2 shows a flowchart of a method for manufacturing a paper product according to the second embodiment.
  • the method for manufacturing a paper product according to the second embodiment mainly includes a synthesizing step S110 and a molding step S120.
  • Synthesis step S110 In the synthesis step S110, an acidic solution L1 containing a divalent metal ion and a trivalent metal ion in at least one of them and an alkaline solution L2 are mixed in the presence of paper or paper fibers to synthesize a layered double hydroxide. To do. Generally, it is preferable that both the divalent metal ion and the trivalent metal ion be contained in the acidic solution L1 side.
  • the method of mixing the acidic solution L1 and the alkaline solution L2 in the presence of paper or paper fibers is the same as that of the first embodiment, and therefore the description thereof will be omitted.
  • the layered double hydroxide, the acidic solution L1 and the alkaline solution L2 in the present embodiment are also the same as those in the first embodiment, and therefore the description thereof will be omitted.
  • the forming step S120 is a step of removing the water content of the mixed liquid generated in the synthesizing step S110 in the presence of the functional material to form a desired shape.
  • the water content of the mixed liquid may be removed until the mixture of paper or paper fibers, a functional material, and the synthesized layered double hydroxide is hard enough to be molded into a desired shape.
  • water is removed from a mixture of paper or paper fibers, a functional material, and a layered double hydroxide by applying pressure until the water content is 70% or less, preferably 65% or less, and more preferably 60% or less. To do.
  • the dehydrated mixture can be formed into a desired shape, for example, a columnar shape used for a filter or the like to form a paper product.
  • the product molded in the molding process S120 can be used as it is as a paper product, as shown by a broken line frame in FIG. 2, a drying process S130 for drying the paper product is performed after the molding process S120. Is also good.
  • a paper plow (making up) is performed using a solution of paper or a fiber for paper containing a layered double hydroxide and a functional material.
  • a solution of paper or a fiber for paper containing a layered double hydroxide and a functional material Just go. Specifically, when the mixed solution is spread on the net or the paper scraps, the water drops through the nets or the paper scraps, while the layered double hydroxide, the functional material, the paper or the paper fibers are placed on the nets or the paper sandals. Remain.
  • a sheet of paper can be manufactured.
  • Well-known methods may be used as specific means for removing paper, removing water, and drying.
  • the functional material may be mixed at least before the layered double hydroxide synthesized in the synthesis step S110 is dried, for example, may be mixed after the layered double hydroxide is synthesized, or may be mixed before the synthesis. You may do it.
  • the functional material When mixing after the synthesis of the layered double hydroxide, the functional material may be mixed with the mixed liquid generated in the synthesis step S110, and then the water may be removed before molding.
  • the functional material When mixing the layered double hydroxide before synthesis, it is sufficient to mix the functional material in at least one of the acidic solution L1 and the alkaline solution L2.
  • the functional material may be contained in the alkaline solution L2, and if it is not desired to be exposed to the alkaline solution L2, it may be contained in the acidic solution L1.
  • the functional material may be placed in a container or the like, and the acidic solution L1 and the alkaline solution L2 may be simultaneously supplied to the functional material.
  • this method is preferable when it is not desired to expose the functional material to the acidic solution L1 or the alkaline solution L2.
  • a liquid such as water may be added to the functional material, and the acidic solution L1 and the alkaline solution L2 may be supplied to this liquid.
  • the paper product of the second embodiment will be described.
  • the paper product of the second embodiment is a product in which paper or paper fibers and a functional material are bound by a layered double hydroxide. Therefore, there is an effect that it is difficult for the layered double hydroxide and the powder of the functional material to be detached from the paper. Further, since the layered double hydroxide is used instead of the binder, it is possible to manufacture a paper product having the function of the layered double hydroxide in addition to the function of the functional material. When a layered double hydroxide is used as the functional material, the relative amount of the layered double hydroxide contained in the paper can be increased because the binder is not present, and the surface area of the layered double hydroxide can be increased by the binder. Since there is no problem that the value becomes small, the adsorption performance can be sufficiently exhibited.
  • the specific surface area of the layered double hydroxide or functional material contained in the paper product of the second embodiment is not particularly limited, but the larger the specific surface area, the more the adsorption performance can be improved. preferable.
  • the layered double hydroxide and the functional material may, for example, BET specific surface area of which is equivalent to or exceeds the 20 m 2 / g, preferably better not less than 30 m 2 / g, more preferably 50 m 2 /G or more, and more preferably 70 m 2 /g or more.
  • the upper limit of the specific surface area is not particularly limited.
  • the specific surface area by the BET method can be determined, for example, by measuring a nitrogen adsorption/desorption isotherm using a specific surface area/pore distribution measuring device and creating BET-plot from the measurement result. For example, if the crystallite size of the layered double hydroxide or the functional material is 20 nm or less, the specific surface area can be 20 m 2 /g or more.
  • a columnar filter see the filter 10 in FIG. 3 and the filter 30 in FIG. 5A
  • sheet-shaped paper used as wallpaper, or the like can be used.
  • Example 1 Paper product of the second embodiment (layered double hydroxide)
  • magnesium chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • aluminum chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • an acidic solution L1 is dissolved in distilled water to prepare an acidic solution L1.
  • sodium hydroxide is dissolved in distilled water to prepare an alkaline solution L2.
  • the acidic solution L1, the alkaline solution L2, and the fiber for paper (30 g) were mixed, and further, a sufficient amount of distilled water was rapidly mixed into the mixed solution in a short time.
  • layered double hydroxide (22 g) as Functional Material 1 was further added to the mixed solution and mixed.
  • the solution was used to make paper and dried at 100° C. for 10 hours to produce paper.
  • Example 2 ⁇ Paper product (zeolite) of the second embodiment
  • magnesium chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • aluminum chloride hexahydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • alkaline solution L2 prepared an alkaline solution L2.
  • the acidic solution L1, the alkaline solution L2, and the fiber for paper (30 g) were mixed, and further, a sufficient amount of distilled water was rapidly mixed into the mixed solution in a short time.
  • zeolite (22 g) as the functional material 2 was added to the mixed solution and mixed.
  • the solution was used to make paper and dried at 100° C. for 10 hours to produce paper.
  • Example 3 Paper products of the present invention (activated carbon) First, magnesium chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and aluminum chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in distilled water to prepare an acidic solution L1. Further, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in distilled water to prepare an alkaline solution L2. Next, the acidic solution L1, the alkaline solution L2, and the fiber for paper (30 g) were mixed, and further, a sufficient amount of distilled water was rapidly mixed into the mixed solution in a short time. Then, activated carbon (22 g) was further added as the functional material 3 to the mixed solution and mixed. Finally, the solution was used to make paper and dried at 100° C. for 10 hours to produce paper.
  • activated carbon 22 g
  • the layered double hydroxide was used as the functional material 1
  • the zeolite was used as the functional material 2
  • the activated carbon was used as the functional material 3.
  • the powder synthesized as follows was used. First, magnesium chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and aluminum chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in distilled water to prepare an acidic solution. Further, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in distilled water to prepare an alkaline solution.
  • the acidic solution and the alkaline solution were mixed, and further, a sufficient amount of distilled water was quickly mixed with the mixed solution without time. Then, the solution was filtered, and the obtained filtered product was dried at 100° C. for 10 hours to produce a powdery layered double hydroxide.
  • zeolite of the functional material 2 one manufactured by Wako Pure Chemical Industries, Ltd. (code No. 268-01522) was used.
  • the activated carbon of the functional material 3 one manufactured by Wako Pure Chemical Industries, Ltd. (code No.034-18051) was used.
  • the acidic solution L1 and the alkaline solution L2 containing divalent metal ions and trivalent metal ions in at least one of them are used for paper or paper.
  • the acid solution L1 and the alkaline solution L2 may be mixed to synthesize a layered double hydroxide, and then paper or paper fibers may be mixed with the mixed solution after synthesis (the mixing step is performed). ..
  • the powdery layered double hydroxide is mixed with the paper or the fiber for paper to perform paper making (raising). Compared with, there is an effect that the layered double hydroxide is hard to be detached from the paper.
  • the functional material may be mixed before mixing the paper or the fiber for paper, or the functional material may be mixed after mixing the paper or the fiber for paper.
  • Modification 2 In the molding steps S20 and S120 of the first and second embodiments, it is possible to remove water from the mixed liquid, wash (wash with water), and then mold. By this washing, NaCl produced when synthesizing the layered double hydroxide from the acidic solution L1 and the alkaline solution L2 can be removed from the paper. At this time, since the NaCl attached to the layered double hydroxide is also removed, the anion exchange function of the layered double hydroxide is improved, and arsenic, fluorine, boron, selenium, hexavalent chromium, nitrite noise, Adsorption performance of adsorbing other anionic harmful substances can be improved. Since NaCL also functions as a binder for binding fibers for paper, for example, even if the paper product contains NaCl, there is no problem. If NaCl is used as the binder, washing should not be performed. ..
  • the layered double hydroxide was couple
  • the hydroxide may be combined to produce a nonwoven product. For example, after the acidic solution L1 and the alkaline solution L2 are mixed in the presence of the non-woven fabric fiber to synthesize a layered double hydroxide, or the acidic solution L1 and the alkaline solution L2 are mixed to synthesize a layered double hydroxide. Alternatively, it is possible to mix fibers for a non-woven fabric with the mixed solution.
  • the water may be removed from the mixed solution generated when the layered double hydroxide is synthesized, and the molding may be performed.
  • the wet nonwoven fabric is formed.
  • the present invention is not limited to this, and the dry non-woven fabric may be manufactured using the non-woven fabric fibers (short fibers or long fibers) to which the layered double hydroxide or the functional material is bound after removing the water content.
  • a layered double hydroxide may be bonded to a fiber material obtained by mixing fibers for paper and fibers for non-woven fabric to produce a fiber product (hybrid product).
  • FIG. 3 shows an example in which the paper product of the second embodiment is used as the filter 10 of the filtering device 100 that filters water.
  • the filtering device 100 includes a housing 12, a filter 10 provided in the housing 12, support members 14A and 14B provided above and below the filter 10, a water supply pipe 16A, and a drain pipe 16B.
  • the weight ratio of the paper fiber to the layered double hydroxide synthesized in the synthesis step S110 is 3:1, and the powdery layered double hydroxide used as the functional material and the synthesis step S110. It is assumed that the total weight of the layered double hydroxide synthesized in (1) accounts for 60% of the entire filter 10.
  • the weight of the entire filter 10 is 400 g.
  • the filter 10 is formed in a substantially columnar shape, and a hollow portion 20 is provided at the center of the filter 10 from the upper end toward the lower end.
  • the material ratio of the filter 10 is not limited to the above.
  • the weight of the layered double hydroxide contained in the filter 10 can be 0.25 to 4 times, preferably 1 to 3 times the weight of the paper fiber.
  • the weight of the layered double hydroxide When the weight of the layered double hydroxide is less than 0.25 times the weight of the paper fiber, the adsorption of harmful substances becomes insufficient. Further, if the weight of the layered double hydroxide exceeds 3 times or 4 times the weight of the paper fiber, the water permeability of the filter 10 becomes insufficient. For this reason, it is preferable to determine the ratio of the material of the filter 10 in consideration of hardness, water absorption, water permeability, filtration performance, etc. of the filter 10.
  • the support members 14A and 14B are substantially disc-shaped members formed of a material such as plastic or rubber.
  • a through hole 22 is formed in the center of the support member 14A, and the through hole 22 is in communication with the hollow portion 20 of the filter 10.
  • the water supply pipe 16A is provided, for example, in the vicinity of the lower end of the housing 12 and is a pipe for introducing water before filtration into the housing 12.
  • the drain pipe 16B is connected to the support member 14A and is a pipe for taking out the water filtered by the filter 10 to the outside.
  • the water supply pipe 16A may supply water into the housing 12 from above the housing 12.
  • a pipe having a double structure may be provided in the upper part of the housing 12, and an outer pipe line of the double pipe structure may be used as the water supply pipe 16A and an inner pipe line may be used as the drain pipe 16B.
  • the water taken into the housing 12 from the water supply pipe 16A is filtered by permeating the filter 10 from the outside to the inside, and the filtered water is discharged through the hollow portion 20 and the through hole 22 to the drain pipe 16B. It is designed to be discharged from the outside.
  • FIG. 4 shows the result of measuring the boron concentration of the water discharged from the drainage pipe 16B using ICP emission spectroscopy.
  • the boron concentration of the water (stock solution) supplied from the water supply pipe 16A to the filtration device 100 was 98.15 mg/L.
  • the filter 10 of the third embodiment has , For at least 13 hours, it has been found to have suitable capacity as a filter.
  • FIG. 5A is a diagram showing a filter 30 according to the fourth embodiment.
  • the filter 30 is shaped like a cylinder.
  • FIG. 5B shows a state in which the filter 30 is vertically sectioned.
  • the filter 30 includes a powdery layered double hydroxide 32 as a functional material, and a paper product 34 that wraps the layered double hydroxide 32. That is, in the filter 30, the internal space of the paper product 34 is filled with the layered double hydroxide 32 as a functional material.
  • the weight ratio of the paper fiber and the layered double hydroxide synthesized in the synthesis step S10 is 3:1. Further, the total weight of the powdery layered double hydroxide 32 used as the functional material and the layered double hydroxide synthesized in the synthesis step S10 accounts for 70% of the entire filter 10, and the weight thereof is It is 65 g. That is, the paper fiber of the paper product 34 is about 27.9 g, and the layered double hydroxide synthesized in the synthesis step S110 is about 9.3 g.
  • the material ratio of the filter 30 is not limited to the above.
  • the weight of the layered double hydroxide contained in the filter 30 can be 0.25 to 4 times, preferably 1 to 3 times the weight of the paper fiber. In this case, it is preferable to determine the material ratio of the filter 30 in consideration of hardness, water absorption, filtration performance, etc. of the filter 30.
  • the filter 30 is provided in the funnel 40, water (stock solution) is put into the funnel 40 from above, the water filtered by the filter 30 is received by the beaker 50, and the arsenic concentration of the filtered water is measured by ICP. It measured using the optical emission spectroscopy. The result is shown in FIG.
  • 16 L of water (stock solution) is filtered three times without changing the filter 30.
  • the arsenic concentration of the first stock solution was 422.6 ppb
  • the arsenic concentration of the second stock solution was 476.3 ppb
  • the arsenic concentration of the third stock solution was 430.1 ppb. there were.
  • it took a total of 73 hours to filter a total of 48 L of water (stock solution) but it was found that even if the filter 30 was used for 72 hours, the arsenic removal capacity did not deteriorate so much. It was also found that it is possible to produce water that satisfies the drinking water standard from water that contains a large amount of arsenic by adjusting the size and configuration of the filter.
  • paper products and non-woven fabric products described in the first and second embodiments and the modified examples can be used as products other than filters.
  • the paper products and non-woven fabric products described in the first and second embodiments and the modified examples can be used as products other than filters.
  • it can be used as wallpaper, adsorption mats that absorb harmful substances that exude from contaminated soil when laid under contaminated soil, pet sheets, sweatside pads, drip sheets laid on food trays, etc. Can also be used.
  • the layered double hydroxide has flame retardancy, it can be expected to suppress the fire when it is used in the above-mentioned wallpaper even when a fire occurs.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Afin de fournir un produit fibreux à partir duquel un hydroxyde double lamellaire qui ne peut se détacher facilement et son procédé de production, l'invention comprend une étape de synthèse (S10) consistant à mélanger, en présence de fibres, une solution acide (L1) et une solution alcaline (L2), dont au moins l'une contient un ion métallique divalent et un ion métallique trivalent, pour synthétiser un hydroxyde double lamellaire, et une étape de moulage (S20) consistant à éliminer l'humidité dans la solution mixte générée lors de l'étape de synthèse et à effectuer le moulage.
PCT/JP2019/041377 2018-12-27 2019-10-21 Procédé de production de produit fibreux, produit fibreux et filtre WO2020137120A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007538173A (ja) * 2004-05-18 2007-12-27 アクゾ ノーベル エヌ．ブイ． ハイドロタルサイトを含む板紙
JP2013241713A (ja) * 2012-05-22 2013-12-05 Shinshu Univ シルク複合ナノファイバー及びその製造方法
WO2018030521A1 (fr) * 2016-08-10 2018-02-15 日本製紙株式会社 Corps composite d'hydrotalcite et de fibre
WO2018124192A1 (fr) * 2016-12-27 2018-07-05 日本国土開発株式会社 Corps moulé en hydroxyde double lamellaire et procédé de fabrication de celui
WO2018180699A1 (fr) * 2017-03-31 2018-10-04 日本製紙株式会社 Procédé de fabrication d'une feuille de fibres composites à particules inorganiques
WO2019087694A1 (fr) * 2017-10-31 2019-05-09 日本製紙株式会社 Fibres composites d'oxyde de titane et leur procédé de production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007538173A (ja) * 2004-05-18 2007-12-27 アクゾ ノーベル エヌ．ブイ． ハイドロタルサイトを含む板紙
JP2013241713A (ja) * 2012-05-22 2013-12-05 Shinshu Univ シルク複合ナノファイバー及びその製造方法
WO2018030521A1 (fr) * 2016-08-10 2018-02-15 日本製紙株式会社 Corps composite d'hydrotalcite et de fibre
WO2018124192A1 (fr) * 2016-12-27 2018-07-05 日本国土開発株式会社 Corps moulé en hydroxyde double lamellaire et procédé de fabrication de celui
WO2018180699A1 (fr) * 2017-03-31 2018-10-04 日本製紙株式会社 Procédé de fabrication d'une feuille de fibres composites à particules inorganiques
WO2019087694A1 (fr) * 2017-10-31 2019-05-09 日本製紙株式会社 Fibres composites d'oxyde de titane et leur procédé de production

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