Classifications

• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/35—Polyalkenes, e.g. polystyrene
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
  • D21H17/375—Poly(meth)acrylamide
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
  • D21H17/45—Nitrogen-containing groups

Definitions

• the present invention relates to a method for manufacturing paper and paperboard. More specifically, the present invention relates to a technique for improving the quality of wastewater discharged from a paper manufacturing process using starch.
• starch is used as a paper strength enhancer, surface strength enhancer, or interlayer adhesive to maintain paper strength and printing suitability.
• the ratio of used paper used in the production of paper has increased, but many of the used paper, such as used paper coating layer and corrugated used paper paste, contains starch.
• papermaking process water contains a large amount of starch, but when microorganisms such as bacteria grow using these starches as nutrients, "slime” is found on the walls of the pipes and tanks and on the filter. A biofilm called is formed.
• This “slime” is a viscous gelatinous film formed on the surface of solid water, including both living and non-living materials, and causes slime damage such as reduced productivity and paper quality deterioration in the papermaking process. It is known.
• the microorganisms contained in the slime are bacteria that have a high ability to produce amylase, which is an amylolytic enzyme. For this reason, when the slime is formed, the amylase released from the paper making process water hydrolyzes the starch adhering to the pulp fibers and the insoluble starch particles dispersed in the water to produce glucose. Furthermore, organic acids such as formic acid, lactic acid, acetic acid and butyric acid are produced.
• Glucose and organic acids are difficult to remove because of their low molecular weight, which increases the drainage load.
• starch added for the purpose of improving paper strength and printing suitability disappears from the pulp slurry due to the action of amylase, which necessitates the addition of starch, spraying or coating, resulting in reduced manufacturing costs. It will also lead to an increase.
• a slime control agent that suppresses the formation of slime is used in the paper manufacturing process (see, for example, Patent Documents 1 to 4).
• a paper manufacturing method is also proposed in which amylase activity is measured at a predetermined location in the manufacturing process and a slime control agent is added based on the measured value. (See Patent Document 5). According to the paper manufacturing method described in Patent Document 5, it is possible to prevent deterioration of the quality of the paper using starch due to slime failure.
• Patent Document 6 a technique for preventing slime failure in the paper making process by adding a predetermined amount of a water-soluble cationic polymer and a cationic surfactant has also been proposed (see Patent Document 6). From the viewpoint of reducing the amount of starch used, a technique has also been proposed in which a cationic polymer is used as a fixing agent for an anionic sizing agent in place of or in combination with cationized starch (see Patent Document 7).
• the main object of the present invention is to provide a method for producing paper that can reduce the load on the waste water and that can obtain paper and paperboard of a certain quality.
• the method for producing paper according to the present invention includes a step of adding a slime control agent to papermaking process water containing starch, and a step of adding a polymer having a cationic functional group to the papermaking process water,
• the polymer having a cationic functional group is a polymer of a monomer alone represented by the following chemical formula (1) or a copolymer of a monomer represented by the following chemical formula (1) and acrylamide or styrene, and represented by the following chemical formula (1 ) Selected from the group consisting of monomers containing 20 to 100 mol% of monomer units derived from the monomer represented by formula (II), polymers having diallyldimethylammonium halide units, polymers having polyethyleneimine and epichlorohydrin units.
• An intrinsic viscosity ( ⁇ ) in a 1N saline solution at 25 ° C. of at least one polymer is 0.0 To use what is ⁇ 5dl / g.
• R 1 in the chemical formula (1) is a hydrogen atom or a methyl group
• R 2 and R 3 are each an alkyl group having 1 to 4 carbon atoms
• R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or benzyl A group
• Y is O or NH
• n is 2 to 5
• Z ⁇ is a halogen ion, a sulfate ion, a phosphate ion, a borate ion or an organic acid anion.
• the “paper” produced in the present invention includes paperboard.
• the slime control agent since a slime control agent and a specific polymer having a cationic functional group are added to the papermaking process water, the slime control agent suppresses the growth of the slime, and the starch during the papermaking process by the polymer. Is adsorbed and fixed in the papermaking raw material.
• the slime control agent may be added to the raw slurry.
• the amylase activity or redox potential of the papermaking process water is measured, and the slime control agent can be additionally added based on the measurement result.
• the mixture of an oxidizing agent and ammonium salt can be used, for example.
• the polymer having a cationic functional group may be added, for example, so that the solid content concentration in the papermaking process water is 0.1 to 100 mg / L.
• the slime control agent and the specific polymer having a cationic functional group are added to the papermaking process water, it is possible to suppress the deterioration of paper quality and reduce the load on the waste water.
• disassembly suppression processes and adsorption processes is not specifically limited, Which may be performed first and may be performed simultaneously.
• a slime control agent is added to the papermaking process water, and, for example, starch adsorbed on pulp fibers and starch dispersed in the papermaking process are decomposed by microbial amylase contained in the slime. Suppress. Thereby, it is possible to prevent the growth of slime and to suppress the decomposition of starch by amylase.
• the slime control agent used in this step is not particularly limited as long as it does not decompose starch, and can be appropriately selected from known compounds.
• Specific examples thereof include bromoamide compounds such as 2,2-dibromo-3-nitrilopropionamide and n-bromoacetamide, 1,2-bis (bromoacetoxy) ethane and 1,4-bis (bromoacetoxy).
• Bromoacetate compounds such as -2-butene, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or metal salts thereof, and 4,5-dichloro Isothiazolone compounds such as -2-octyl-4-isothiazolin-3-one, bromonitroalcohol compounds such as 2-bromo-2-nitro-1,3-propanediol and 2,2-dibromo-2-nitroethanol and esters thereof 4,5-dichloro-1,2-dithiolane-3-one, 3,3,4,4-tetrachlorothe Cyclic sulfur compounds such as lahydrothiophene-1,1-dioxide, methylenebisthiocyanate, 5-chloro-2,4,6-trifluoroisophthalonitrile, orthophthalaldehyde, dichloroglyoxime, 5,5-dimethylhydantoin, And hydantoin compounds such
• an inorganic slime control agent includes a mixture of an oxidizing agent and an ammonium salt, and a compound that generates hypochlorous acid or hypobromite.
• the oxidizing agent used here is not particularly limited, but a chlorine-based oxidizing agent is preferable, and sodium hypochlorite is more preferable.
• the ammonium salt is not particularly limited, and ammonium halides such as ammonium bromide, ammonium sulfate and ammonium nitrate can be used, and ammonium bromide is particularly preferably used.
• the addition position of the slime control agent is not particularly limited, and a place where slime growth is likely to occur or a place where slime tends to grow can be appropriately selected and added.
• at least raw material slurries such as waste paper raw materials and process waste paper (those with added or coated starch that could not be shipped as products) contain a slime control agent. It is desirable to make it.
• the slime control agent when the slime control agent is added to the raw slurry, if the effect cannot be maintained until the subsequent step, the slime control agent may be added as appropriate based on, for example, the water quality measurement result of the papermaking process. Furthermore, for example, when the water used in the papermaking process is reused to dilute the raw materials, etc., even if a slime control agent is added in the production process, the slime control agent is added again to the diluted water as necessary. It may be added. Thereby, the growth suppression effect of slime can be further enhanced.
• the slime control agent can also be added continuously, but intermittently as needed while controlling the quality of the papermaking process water such as amylase activity or ORP (Oxidation-reduction Potential). It is desirable to add to.
• the addition amount and the number of additions of the slime control agent are not particularly limited, but for example, the addition amount per one is 2 to 50 mg / L, and the addition number is 1 to 48 times / day.
• the addition amount and the number of additions of the slime control agent can be appropriately set based on the water quality measurement results of papermaking process water such as amylase activity or ORP.
• the amylase activity of the papermaking process water collected throughout the production process is monitored periodically, preferably continuously, What is necessary is just to increase the addition amount of a slime control agent, when a measured value exceeds the predetermined threshold value.
• the threshold value in that case is not specifically limited, For example, it can be set to 0.002CU / g.
• the growth of the slime is monitored by measuring the ORP of the papermaking process water periodically, preferably continuously.
• the amount of the slime control agent added may be increased.
• a slime control agent may be added so as to maintain the ORP value of the papermaking process water under a positive aerobic condition, and the starch degradation by microorganisms promoted under the anaerobic condition may be suppressed.
• OPR oxygen species
• the starch dispersed in the papermaking process is adsorbed by a polymer having a cationic functional group added to the papermaking process water, and fixed to the paper raw material. Thereby, the amount of starch which transfers to waste water can be reduced.
• the polymer having a cationic functional group is (a) a polymer of a monomer represented by the following chemical formula (2), or a polymer of this monomer and acrylamide or styrene. 2) containing 20 to 100 mol% of monomer units derived from the monomer represented by (2), (b) a polymer having diallyldimethylammonium halide units, (c) polyethyleneimine, and (d) epichlorohydrin units. And at least one polymer selected from the group consisting of polymers having an intrinsic viscosity ( ⁇ ) in 1N saline at 25 ° C. of 0.05 to 5 dl / g.
• R 1 is a hydrogen atom or a methyl group
• R 2 and R 3 are each an alkyl group having 1 to 4 carbon atoms
• R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a benzyl group.
• Y is O or NH
• n is 2 to 5
• Z is a halogen ion, a sulfate ion, a phosphate ion, a borate ion or an organic acid anion.
• the intrinsic viscosity ( ⁇ ) specified here is a value calculated by measuring the flow time using a Cannon Fenceke viscometer and using the Huggins equation and the Mead-Fuoss equation from the measured value. is there.
• the content of monomer units derived from the monomer represented by the chemical formula (2) which is a copolymer of the monomer represented by the chemical formula (2) and acrylamide or styrene
• the monomer is less than 20 mol%, a sufficient adsorption effect on the pulp fiber cannot be obtained.
• the amount of the drug used increases, leading to a decrease in operability such as drainage and deterioration of formation.
• the monomer unit derived from the monomer represented by the chemical formula (2) The content of 20 mol% or more is used.
• the addition position of the polymer having a cationic functional group is not particularly limited, and can be appropriately set according to the purpose. However, it is desirable that the polymer is continuously added to a place where a lot of starch is contained. For example, when reducing the drainage load, it is desirable to add in the white water recovery process discharged from the papermaking process, and when aiming at improving paper strength, it is desirable to add to the raw material line of the papermaking process.
• the amount of the polymer having a cationic functional group can be appropriately set according to the starch concentration in the papermaking process water and the properties of the raw material, but the polymer concentration in the papermaking process water is 0.1 to 100 mg / L as a solid concentration.
• the solid content concentration is preferably 0.5 to 50 mg / L.
• a sulfuric acid band for example, a sulfuric acid band, a sizing agent, a paper strength enhancer, a yield / drainage improver, and the like. May be added.
• a slime control agent and a specific polymer having a cationic functional group are added to the papermaking process water, so that only the growth of the slurry is suppressed.
• the amount of starch flowing into the waste water can be reduced.
• COD of waste water can be kept low.
• starch in the papermaking process water can remain in the paper raw material, so that it is possible to reduce the amount of additional starch and paper strength enhancer added. It becomes. As a result, a paper product with the same strength can be produced with a smaller amount of starch than in the past.
• the starch adsorptivity evaluation uses this pulp slurry as it is, and in the other evaluation tests, the pulp slurry 15L with a solid content concentration of 2% by mass added with 2% by mass starch aqueous solution, A pulp slurry for testing was obtained. At that time, a special grade reagent manufactured by Kishida Chemical Co., Ltd. was used as the starch. The degree of anionization of this starch as measured by the colloidal equivalent was ⁇ 0.15 meq / g, which was slightly anionic. The starch was dissolved by heating with a hot plate stirrer to prepare a 2% by weight starch aqueous solution.
• a hand-made paper having a basis weight of 120 g / m 2 was prepared from the above-described test pulp slurry in accordance with the method defined in JIS P 8029.
• amylase activity of the filtrate was measured using a commercially available amylase measurement kit (manufactured by Megazyme® International® Ireland). Furthermore, the measurement of COD (Mn) was performed in accordance with the measurement method at 100 ° C. defined in JIS K 0102, using the supernatant of papermaking process water.
• Hand-made paper 1.0 g was immersed in 50 ml of pure water, and this was left to stand in a warm bath at 90 ° C. for 30 minutes, and the starch contained in the paper was extracted with hot water. And the starch concentration in water was computed according to the method mentioned above, and this was made into the starch concentration in paper. Moreover, evaluation of the strength of paper measured the bursting strength based on the method prescribed
• a slime control agent having a molar ratio of ammonium sulfate and sodium hypochlorite of 1: 1 at a molar ratio of 1000 mg / L was prepared.
• polymer A (DAM / St) is dimethylaminoethyl methacrylate / styrene
• polymer B (DAM / AAM) is dimethylaminoethyl methacrylate / acrylamide
• polymer C (Poly-DADMAC) is polydiallyldimethylammonium chloride
• Polymer D (EMA / Epi) is dimethylamine / epichlorohydrin
• Polymer E (PEI) is polyethyleneimine
• Polymer F (DAA / AAm) is dimethylaminoethyl acrylate / acrylamide
• Polymer G (DAM) is dimethylaminoethyl methacrylate
• Polymer H (AA / AAm) is acrylic acid / acrylamide.
• COD reduction rate shown in the above Table 3 is a value obtained by the following mathematical formula (1).
• Examples 1 to 10 using polymers A to E were superior in starch adsorption effect and COD reduction effect compared to Comparative Examples 1 to 6 using polymers F to H.
• Examples 11 and 12 in which a slime control agent was added to suppress starch degradation by amylase derived from microorganisms, further adsorbed starch with a cationic polymer, and fixed on handmade paper, Compared with Comparative Examples 7 to 10 in which either the control agent or the polymer having a cationic functional group was not added, the amount of starch and COD in water could be greatly reduced. Further, the handmade papers obtained in Examples 11 and 12 had a higher starch content and higher strength than the handmade papers obtained in Comparative Examples 7 to 10.

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• 2010
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