WO2009093615A1 - クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法 - Google Patents

クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法 Download PDF

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WO2009093615A1
WO2009093615A1 PCT/JP2009/050890 JP2009050890W WO2009093615A1 WO 2009093615 A1 WO2009093615 A1 WO 2009093615A1 JP 2009050890 W JP2009050890 W JP 2009050890W WO 2009093615 A1 WO2009093615 A1 WO 2009093615A1
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Prior art keywords
pulp
group
washing
general formula
kraft pulp
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PCT/JP2009/050890
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English (en)
French (fr)
Japanese (ja)
Inventor
Makoto Yamauchi
Sachiko Furuya
Takeo Shimoya
Masanori Nikaidoh
Yasufumi Noda
Hirotoshi Ushiyama
Michiko Koide
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Lion Corporation
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Priority to JP2009550536A priority Critical patent/JP5475469B2/ja
Priority to CN200980103194.5A priority patent/CN101939481B/zh
Priority to EP09703584A priority patent/EP2236665A4/en
Publication of WO2009093615A1 publication Critical patent/WO2009093615A1/ja

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
    • D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications

Definitions

  • the present invention relates to a kraft pulp cleaning agent and a method for producing kraft pulp using the cleaning agent.
  • Kraft pulp is generally produced through a cooking process in which wood chips are digested with a mixed solution of caustic soda and sodium sulfide, and a separation process in which black liquor containing lignin is separated from the pulp slurry produced in the cooking process.
  • an oxygen delignification reaction step in which oxygen is allowed to act under alkaline and high temperature pressurization is performed after the separation step for the purpose of reducing the drainage load.
  • unbleached pulp unbleached kraft pulp
  • this unbleached pulp is used for cardboard (boardboard), etc.
  • bleached to produce a bleached pulp with improved whiteness is used for fine paper.
  • Bleaching is performed by multistage bleaching (multistage bleaching).
  • multistage bleaching chlorine dioxide, hydrogen peroxide and the like are generally used as bleaching agents.
  • a method for increasing the bleaching efficiency a method of adding a bleaching assistant to the bleaching process has been proposed.
  • a polyhydric alcohol, a polyhydric phenol, or an alkylene oxide adduct thereof and an aliphatic monohydric alcohol are proposed.
  • Patent Document 1 A method using an etherified product as a bleaching assistant (see Patent Document 1), a method using a bleaching assistant comprising a combination of a specific water-soluble polymer and / or peroxide and a nonionic surfactant (Patent Document) 2)) and the like have been proposed.
  • Patent Document 2 a method using a bleaching assistant comprising a combination of a specific water-soluble polymer and / or peroxide and a nonionic surfactant
  • Patent Document 2 a method using a bleaching assistant comprising a combination of a specific water-soluble polymer and / or peroxide and a nonionic surfactant
  • Patent Document 3 a pulp washing method in which a polyoxyethylene alkylphenyl ether surfactant is added to various washing steps of a pulp production method, and a surfactant is added to the washing step after the cooking step.
  • a pulp cleaning method Patent Document 4 has been proposed.
  • the present invention can improve the washing efficiency of the pulp and the energy efficiency in the pulp production.
  • the pulp after the oxygen delignification reaction step A cleaning agent for kraft pulp that can improve whiteness, can reduce the amount of bleaching agent added, prevents foaming, and can reduce the amount of antifoaming agent used, and the cleaning agent It aims at providing the kraft pulp manufacturing method.
  • Means for solving the problems are as follows. That is, ⁇ 1> A cleaning agent used for cleaning the pulp raw material after decomposing the lignin component contained in the digested pulp raw material using oxygen, and the following general formulas (1), (2) and ( 3) a nonionic surfactant comprising at least one selected from the compounds represented by 3), which contains a nonionic surfactant having a lower cloud point than the washing temperature in washing the pulp raw material.
  • R 1 O- (PO) n -[(EO) m ⁇ (PO) k ] H...
  • R 1 represents either a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms.
  • n, m, and k represent the average number of added moles, n represents 0 to 10, and the sum of m and k is 1 to 100.
  • EO and PO represent an ethylene oxide unit and a propylene oxide unit, respectively, and the addition form of EO and PO in [(EO) m ⁇ (PO) k ] may be either random or block.
  • R 2 represents either a linear alkyl group having 10 to 20 carbon atoms or an alkenyl group.
  • AO represents at least one oxyalkylene group selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • y represents 1 to 10.
  • R 3 is a methyl group.
  • R 4 represents an alkyl group having 10 to 20 carbon atoms.
  • EO represents an ethylene oxide group.
  • x and z both represent the number of moles of ethylene oxide added, and the sum of x and z is 2 to 10.
  • a nonionic surfactant composed of at least one selected from the compounds represented by the following general formulas (1), (2) and (3): And since the nonionic surfactant with a cloud point lower than the washing temperature in the washing
  • the nonionic surfactant is a cleaning agent for kraft pulp according to the above ⁇ 1>, which has a cloud point of 55 ° C. or lower.
  • a kraft pulp manufacturing method comprising: a washing step for washing, wherein the washing step comprises at least one selected from the compounds represented by the general formulas (1), (2) and (3)
  • a method for producing kraft pulp comprising adding a detergent for kraft pulp containing an ionic surfactant and a nonionic surfactant having a lower cloud point than the washing temperature in the washing step.
  • R 1 O- (PO) n -[(EO) m ⁇ (PO) k ] H...
  • R 1 represents either a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms.
  • n, m, and k represent the average number of added moles, n represents 0 to 10, and the sum of m and k is 1 to 100.
  • EO and PO represent an ethylene oxide unit and a propylene oxide unit, respectively, and the addition form of EO and PO in [(EO) m ⁇ (PO) k ] may be either random or block.
  • R 2 represents either a linear alkyl group having 10 to 20 carbon atoms or an alkenyl group.
  • AO represents at least one oxyalkylene group selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • y represents 1 to 10.
  • R 3 is a methyl group.
  • R 4 represents an alkyl group having 10 to 20 carbon atoms.
  • EO represents an ethylene oxide group.
  • x and z both represent the number of moles of ethylene oxide added, and the sum of x and z is 2 to 10.
  • the pulp raw material is cooked in the cooking step.
  • the oxygen delignification reaction step the lignin component contained in the digested pulp raw material is decomposed using oxygen.
  • the nonionic surfactant is at least one selected from the compounds represented by the general formulas (1), (2) and (3), and is based on the washing temperature in the washing step.
  • a detergent for kraft pulp containing a nonionic surfactant having a low cloud point is added, and the pulp raw material is washed following the oxygen delignification reaction step. As a result, the cleaning efficiency of the pulp is improved.
  • the nonionic surfactant is a method for producing kraft pulp according to any one of ⁇ 3> to ⁇ 4>, wherein a cloud point is 55 ° C. or lower.
  • the conventional problems can be solved, the object can be achieved, and the pulp washing efficiency and the energy efficiency in pulp production can be improved.
  • Kraft pulp washing that can improve the whiteness of the pulp after the oxygen delignification reaction step, thus reducing the amount of bleach added, preventing foaming and reducing the amount of antifoam added And a kraft pulp manufacturing method using the cleaning agent.
  • FIG. 1 is a schematic view for explaining an example of the method for producing kraft pulp of the present invention.
  • FIG. 2 is a schematic view for explaining another example of the method for producing kraft pulp of the present invention.
  • FIG. 3 is a schematic view for explaining the washing machines A and B in FIG.
  • the cleaning agent for kraft pulp of the present invention is used to clean the pulp raw material after decomposing the lignin component contained in the digested pulp raw material with oxygen, and at least a specific nonionic surfactant is used. And other components as necessary.
  • the nonionic surfactant used in the present invention is a nonionic surfactant consisting of at least one selected from the compounds represented by the general formulas (1), (2) and (3). And as long as it contains the nonionic surfactant whose cloud point is lower than the washing temperature in the washing
  • the nonionic surfactant preferably has a cloud point of 10 ° C. or more lower than the washing temperature, and the washing temperature is usually 65 ° C. to 90 ° C.
  • the cloud point of the nonionic surfactant is preferably 55 ° C. or lower.
  • the nonionic surfactant when the washing temperature is above the cloud point of the nonionic surfactant, the nonionic surfactant cannot form micelles. In this case, the surface activity is hardly exhibited and the nonionic surfactant component is dispersed in white in the wash water in the form of oil droplets.
  • the present invention is characterized in that a nonionic surfactant is used above its cloud point, that is, at a temperature at which it does not function as a natural surfactant.
  • the cloud point is a property peculiar to a nonionic surfactant and refers to a temperature at which an aqueous solution becomes cloudy when the temperature of the aqueous solution of the nonionic surfactant is increased.
  • nonionic surfactants hydrate due to hydrogen bonds between hydrophilic groups and water molecules, but at temperatures above the cloud point, the hydrogen bonds with water are broken and the degree of hydration decreases. It is a phenomenon.
  • it is set as the value measured as follows. (Method for measuring cloud point of nonionic surfactant) After preparing a 2% by weight nonionic surfactant aqueous solution at 25 ° C., 80 g of the nonionic surfactant aqueous solution was weighed in a transparent glass container having a capacity of 100 ml equipped with a thermometer and a stirring rod, Gently raise the temperature while stirring at.
  • the solution When the aqueous solution starts to become cloudy, the solution is taken out from the hot bath at a temperature 3 to 5 ° C. and allowed to cool. Even when a 2% by weight nonionic surfactant aqueous solution was already prepared at 25 ° C., it was allowed to stand in a constant temperature water bath at 25 ° C. for 1 hour for a transparent glass container having a capacity of 100 ml as described above. After confirming by visual inspection, if cloudiness is still confirmed, the cloud point is set to 25 ° C. or lower.
  • the nonionic surfactant needs to have a certain hydrophobic group in the molecule other than having a cloud point lower than the washing temperature in washing the pulp raw material, and the hydrophobic group has a carbon number as the hydrophobic group.
  • Alkylene oxide (EO / PO) adducts of higher alcohols having 10 to 20 linear or branched aliphatic hydrocarbon groups, alkylene oxide (EO / PO) adducts of fatty acid alkyl esters, alkylene oxides of aliphatic amines ( EO) adducts can be used.
  • R 1 O- (PO) n -[(EO) m ⁇ (PO) k ] H...
  • R 1 represents either a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms.
  • n, m, and k represent the average number of added moles, n represents 0 to 10, and the sum of m and k is 1 to 100.
  • EO and PO represent an ethylene oxide unit and a propylene oxide unit, respectively, and the addition form of EO and PO in [(EO) m ⁇ (PO) k ] may be either random or block.
  • the carbon number of R 1 is not particularly limited as long as it is 10 to 20, and is appropriately selected depending on the purpose. Although it can be selected, it is preferably 12 to 18 in that the whiteness improvement effect and the handling property at low temperatures can be more compatible. When the number of carbon atoms is less than 10, the affinity with the colored component is lowered, and the whiteness improvement effect may be lowered. On the other hand, when the number of carbon atoms exceeds 20, the melting point becomes too high, handling properties at low temperatures may be impaired, and the affinity with colored components may be reduced and the whiteness improvement effect may be reduced. is there. Moreover, since the higher fatty acid used as a raw material hardly exists in nature, it is economically disadvantageous.
  • the higher alcohol that forms the alcohol residue represented by R 1 O is not particularly limited and may be appropriately selected depending on the intended purpose. Even a synthetic alcohol having a branch has a linear distribution. It may be a natural alcohol having, for example, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol, nonadecyl alcohol, eicosyl alcohol, Etc. Among these, lauryl alcohol, tridecyl alcohol, cetyl alcohol, and stearyl alcohol are preferable because they can achieve both an effect of improving whiteness and handling at low temperatures. Moreover, as a higher alcohol, the mixture of the said alcohol can also be used.
  • the number of moles n of propylene oxide added directly to the higher alcohol residue R 1 O is not particularly limited as long as it is 0 to 10, and can be appropriately selected according to the purpose. 6 is preferred.
  • the total number of carbon atoms of R 1 and propylene oxide added directly to the higher alcohol that is, the lower limit value of the carbon number of the (R 1 O— (PO) n —) moiety in the general formula (1)
  • the carbon number of the (R 1 O— (PO) n —) moiety in the general formula (1) is less than the lower limit (less than 10), the hydrophobicity necessary for affinity with the colored component is insufficient. The whiteness improvement effect may be reduced.
  • the upper limit of the carbon number of the (R 1 O— (PO) n —) moiety in the general formula (1) is not particularly limited as long as it is 50 or less, and may be appropriately selected according to the purpose. However, 45 or less is preferable, and 40 or less is more preferable.
  • the carbon number of the (R 1 O— (PO) n —) moiety in the general formula (1) exceeds the upper limit (50), the melting point becomes too high and handling at low temperatures may be impaired. is there.
  • the sum of m and k in the general formula (1) is not particularly limited as long as it is 1 to 100, and can be appropriately selected according to the purpose. However, the whiteness improvement effect can be further improved. In this respect, 2 to 80 is preferable, and 5 to 60 is more preferable.
  • the sum of m and k is less than 1, the interaction with the colored component becomes weak, and the whiteness improvement effect may be reduced.
  • the sum of m and k exceeds 100, the penetration rate into the fiber is slowed, the whiteness improving effect is lowered, and at the same time, the production cost is increased, which may be economically disadvantageous.
  • the number of carbons of the higher alcohol that forms the alcohol residue such as the nonionic surfactant of the general formula (1) having a cloud point lower than the washing temperature, or (R 1 O— (PO) n —)
  • the number of moles added is determined according to the number of carbons in the portion. For example, when the number of carbon atoms in the (R 1 O— (PO) n —) moiety is the same, the smaller the added mole number of EO, the lower the cloud point, and the same added EO number of EO ( As the number of carbon atoms in the R 1 O— (PO) n —) portion increases, the cloud point decreases.
  • the carbon number of the (R 1 O— (PO) n —) moiety in the general formula (1) and the added mole number of EO in the (— [(EO) m ⁇ (PO) k ] H) moiety are the same. If there is, the cloud point can be lowered as the added mole number of PO in the-[(EO) m ⁇ (PO) k ] H) portion increases.
  • the number of carbons of the higher alcohol forming the alcohol residue such that the nonionic surfactant in the general formula (1) has a cloud point lower than the washing temperature in accordance with the washing temperature The number of added moles m and k of EO and PO is determined according to the number of carbon atoms in the R 1 O— (PO) n —) moiety.
  • polyoxyethylene (4EO) decyl ether polyoxyethylene (5EO) decyl ether, polyoxyethylene (6EO) decyl ether, poly Oxyethylene (7EO) decyl ether, polyoxyethylene (8EO) decyl ether, polyoxyethylene (5EO) secondary alkyl (C12-14) ether, polyoxyethylene (7EO) secondary alkyl (C12- 14) Ether, polyoxyethylene (8EO) secondary alkyl (C12-14) ether, polyoxyethylene (9EO) secondary alkyl (C12-14) ether, polyoxyethylene (3EO) isotridecyl ether, poly Oxyethylene (5EO) isotridecyl ether, poly Xylethylene (7EO) isotridecyl ether, polyoxyethylene (9EO) isotridecyl ether, polyoxyethylene (3EO) lauryl ether, polyoxyethylene (4EO) lauryl ether, polyoxyethylene (5EO)
  • Neugen XL-40 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Neugen XL-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Daiichi Kogyo Seiyaku Co., Ltd. no Igen XL-70, Daiichi Kogyo Seiyaku Co., Ltd.
  • Neugen XL-80 Lion Co., Ltd. Leo Coal SC-50, Lion Co., Ltd. Leo Coal SC-70, Lion Co., Ltd. Leo Coal SC-80, Lion Co., Ltd.
  • Leo Coal SC-90 Lion Co., Ltd. Leo Coal TD-30, Lion Co., Ltd. Leo Coal TD-50, Lion Co., Ltd. Leo Coal TD-70, Lion Co., Ltd. Leo Coal TD-90 Manufactured by Lion Corporation, Leox CC-30, Lion Corporation Leox CC-40, Lion Corporation Leox CC-50, Lion Corporation Leox CC-60, Lion Corporation Leox CC-70, Nippon Emulsion Corporation EMALEX102, Nippon Emulsion Corporation EMALEX103, Japan Emulsion Corporation Examples include EMALEX 105 manufactured by Nippon Emulsion Co., Ltd., EMALEX 107 manufactured by Nippon Emulsion Co., Ltd., EMALEX 602 manufactured by Japan Emulsion Co., Ltd., EMALEX 603 manufactured by Japan Emulsion Co., Ltd., EMALEX 606 manufactured by Japan Emulsion Co., Ltd.
  • polyoxyethylene (7EO) polyoxypropylene (3PO) isotridecyl ether polyoxyethylene (20EO) poly Oxypropylene (7PO) isotridecyl ether, polyoxyethylene (2EO) polyoxypropylene (1PO) isotridecyl ether, polyoxyethylene (3EO) polyoxypropylene (1PO) isotridecyl ether, polyoxyethylene (5EO) Polyoxypropylene (1PO) isotridecyl ether, polyoxyethylene (9EO) polyoxypropylene (2PO) isotridecyl ether, polyoxyethylene (5EO) polyoxypropylene (3.5PO) secondary alkyl (C12-14) )ether Polyoxyethylene (7EO) polyoxypropylene (4.5PO) secondary alkyl (C12-14) ether, polyoxyethylene (7EO) polyoxypropylene (8.5PO) secondary alkyl (C12-14) ether, And polyoxyethylene (9EO) polyoxypropylene (4.5PO) secondary alkyl (C12-14) ether, poly
  • Lionol TD-730 manufactured by Lion Corporation, Lionol TD-2007 manufactured by Lion Corporation, Lionol TDL-20 manufactured by Lion Corporation, Lionol Corporation manufactured by Lion Corporation. TDL-30, Lion Corp. Lionol TDL-50, Lion Corp. Lionol TDM-90, Lion Corp. Lionol L-535, Lion Corp. Lionol L-745, Lion Corp. Lionol L-785, Lion For example, Lionol L-950 manufactured by KK
  • the cloud point of the compound represented by the general formula (1) needs to be lower than the washing temperature, and in order to obtain a sufficient effect, the cloud point needs to be 10 ° C. or more lower than the washing temperature. is there. When the cloud point is higher than the washing temperature, it becomes difficult to separate the colored substance (lignin degradation product) and the pulp to be washed with the washing hot water.
  • R 2 represents either a linear alkyl group having 10 to 20 carbon atoms or an alkenyl group.
  • AO represents at least one oxyalkylene group selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • y represents 1 to 10.
  • R 3 is a methyl group.
  • (R 2 —CO—) is a fatty acid ester residue.
  • the number of carbon atoms of the fatty acid ester residue is not particularly limited as long as it is 10 to 20, and can be appropriately selected according to the purpose, but is preferably 12 to 18. When the number of carbon atoms is less than 10, the affinity with the colored component is lowered, and the whiteness improvement effect may be lowered. On the other hand, when the number of carbon atoms exceeds 20, the melting point becomes too high, and handling properties at low temperatures may be impaired.
  • the fatty acid ester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, and methyl oleate. Can be mentioned.
  • the number of added moles y of the polyoxyalkylene group in the general formula (2) is not particularly limited as long as it is 1 to 10, and can be appropriately selected according to the purpose, depending on the alkyl chain length of the fatty acid ester. Thus, it is determined to have a cloud point lower than the washing temperature.
  • the polyoxyalkylene group is a polyoxyethylene group
  • R 2 is a lauric acid ester
  • y is 1 to 9
  • R 2 is In the case of oleate, y is 1-10.
  • R 4 represents an alkyl group having 10 to 20 carbon atoms.
  • EO represents an ethylene oxide group.
  • x and z both represent the number of moles of ethylene oxide added, and the sum of x and z is 2 to 10.
  • R 4 in the general formula (3) is not particularly limited as long as it is an alkyl group having 10 to 20 carbon atoms, and can be appropriately selected according to the purpose, but is preferably 12 to 18.
  • the number of carbon atoms is less than 10, the affinity with the colored component is lowered, and the whiteness improvement effect may be lowered.
  • the number of carbon atoms exceeds 20, the melting point becomes too high, and handling properties at low temperatures may be impaired.
  • the added mole number x + z of the polyoxyethylene group in the general formula (3) is not particularly limited as long as it is 1 to 10, and can be appropriately selected according to the purpose. According to the alkyl chain length, X + z is determined to have a cloud point below the washing temperature.
  • the compound represented by the general formula (3) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • polyoxyethylene EO addition number: 2 to 10
  • oleylamine manufactured by Lion Corporation
  • polyoxyethylene EO addition number: 2 to 10
  • C12-14 amine manufactured by Lion Corporation, Esomin C / 12, O / 15
  • the dosage form of the cleaning agent for kraft pulp of the present invention is not particularly limited as long as it is a liquid, and can be appropriately selected according to the purpose. Even if a nonionic surfactant is added directly, Or may be diluted with water and added.
  • the detergent for kraft pulp of the present invention is not particularly limited as long as it contains the nonionic surfactant, and can be appropriately selected according to the purpose, but the handling property can be further improved. It is preferable to contain water at the point which can do. When water is contained, it depends on the number of moles added such as ethylene oxide, but it may gel in the region where the water content is approximately 30% to 70% by mass. It is preferable to do.
  • the water content is preferably 1% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass.
  • the amount of the cleaning agent for kraft pulp of the present invention is not particularly limited and can be appropriately selected depending on the purpose.
  • the compound represented by the general formulas (1) to (3) 0.003 mass% to 10 mass% is preferable, 0.005 mass% to 1 mass% is more preferable, and 0.01 to 0.1 mass% is still more preferable. If the amount used is less than 0.003% by mass, the desired whiteness improvement effect may not be obtained. If the amount used exceeds 10% by mass, the foaming property is increased or the whiteness is commensurate with the amount added. The improvement effect may not be recognized, and it may be economically disadvantageous.
  • the whiteness of the pulp can be improved.
  • the kraft pulp manufacturing method includes a bleaching step
  • the whiteness of the pulp before bleaching is improved, and chlorine dioxide.
  • the amount used can be reduced, foaming can be prevented, and the amount of antifoaming agent added can be reduced.
  • the reason why this effect is obtained is not clear, but by using a nonionic surfactant having a cloud point lower than the washing temperature in the washing step, a colored substance on the pulp surface is added to the active agent layer phase-separated by the cloud point.
  • Solubilized and repeated washing and dewatering of the pulp in a multi-stage washing process removes colored substances on the pulp surface, improves whiteness, and contributes to a reduction in the amount of chemicals used in the bleaching process . Therefore, the nonionic surfactant is required to have not only a cloud point but also an appropriate hydrophobic chain in the structure.
  • the method for producing kraft pulp of the present invention includes at least a cooking step, an oxygen delignification reaction step, and a washing step, and further includes other steps appropriately selected as necessary.
  • the nonionic surfactant is at least one selected from the compounds represented by the general formulas (1), (2) and (3), and is based on the washing temperature in the washing step.
  • a detergent for kraft pulp containing a nonionic surfactant having a low cloud point is added.
  • the nonionic surfactant preferably has a cloud point of 10 ° C. or more lower than the washing temperature, and the washing temperature is usually 65 ° C. to 90 ° C.
  • the cloud point of the nonionic surfactant is preferably 55 ° C. or lower.
  • the cooking step is a step of cooking the pulp raw material.
  • a pulp raw material wood chip
  • non-fiber parts such as lignin component, fatty acid sodium salt, and rosin acid sodium salt in the pulp raw material are present. Dissolved. After the alkali cooking, it is separated into pulp slurry and black liquor and washed.
  • the oxygen delignification reaction step is a step of decomposing the lignin component contained in the digested pulp raw material using oxygen, that is, a step of decomposing a lignin component that could not be removed in the cooking step.
  • the oxygen delignification method in which oxygen is allowed to act under alkaline and high-temperature pressurization was developed and is now widely used. If 40% to 50% of the lignin remaining in the pulp after the cooking process is decomposed by carrying out the oxygen delignification reaction, it is only possible to reduce the amount of chlorine-based bleaching chemicals used in the subsequent stage.
  • the wastewater generated in the oxygen delignification reaction step can be circulated to the cooking step, so that chemicals and energy can be recovered and the wastewater load can be reduced.
  • the washing step is a step of washing the pulp raw material after the oxygen delignification reaction step, that is, a step of removing lignin decomposition products and colored components generated by the oxygen delignification reaction by washing.
  • the washing process is performed between the oxygen delignification reaction process and the bleaching process.
  • the washing of the pulp raw material is performed, for example, by adding washing water to the pulp slurry (pulp concentration is about 10% by mass) sent from the cooking step to make a slurry having a pulp concentration of about 1% by mass. Is called.
  • the washing step is generally performed by a countercurrent multi-stage washing method.
  • the counter-flow multi-stage cleaning method is a method of cleaning by connecting two to five cleaning machines in series.
  • Wash water collected by the last-stage washing machine is used as washing water by the previous-stage washing machine
  • further washing water used by the previous-stage washing machine is collected and used as washing water for the previous-stage washing machine.
  • the temperature of the pulp slurry introduced into the washing machine that is, the washing temperature is usually 65 ° C. to 90 ° C., which is the temperature of the pulp slurry in the vat of the washing machine.
  • the washing step is preferably a multi-stage washing step in which a plurality of these washing machines are combined.
  • the cleaning step for adding the kraft pulp cleaning agent is followed by a multi-stage cleaning step having at least one rinsing cleaning step, more preferably two or more rinsing cleaning steps. Is desirable.
  • the washing machine is used alone, the added kraft pulp detergent may not be sufficiently removed, and the whiteness may not be sufficiently improved due to redeposition of coloring components.
  • a multi-stage cleaning machine having two or more stages and add the cleaning agent for kraft pulp to the first-stage cleaning machine immediately after the oxygen delignification reaction step.
  • the addition position of the detergent for kraft pulp in the washing machine is not particularly limited as long as it is a place where it can be uniformly mixed with the pulp slurry after the oxygen delignification reaction step before being processed in the washing machine, depending on the purpose.
  • the suction port of the pump for feeding the pulp slurry to the washing machine, the inlet of the dilution water for adjusting the concentration of the pulp slurry, the suction port of the dilution water feeding pump, etc. are suitable. is there.
  • the kraft pulp cleaning agent does not sufficiently diffuse into the pulp slurry and exhibits a sufficient effect. It may not be done.
  • the cleaning agent for kraft pulp is added to the shower used in the washer, there is a possibility of causing foaming trouble.
  • the addition of the cleaning agent for kraft pulp of the present invention to the washer is preferably a washer immediately after the oxygen delignification reaction step.
  • the oxygen delignification reaction step in a washing step having a counter-current type two-stage vacuum drum type washing machine, it is preferable to add to the pulp slurry fed to the first stage washing machine.
  • the bleaching step is a step of bleaching the pulp after the washing step, and an oxidizing agent such as chlorine, hypochlorite, chlorine dioxide, ozone, or hydrogen peroxide is used.
  • an oxidizing agent such as chlorine, hypochlorite, chlorine dioxide, ozone, or hydrogen peroxide.
  • ECF Exponal Chlorine Free
  • the pulp slurry 1 is first charged into the oxygen delignification reaction tower 2 to obtain the pulp slurry 3 after the oxygen delignification reaction.
  • the pulp slurry 3 after this oxygen delignification reaction is No. 1 Repulper 4 No. 1 was transferred to the washer. Washed with 1 shower water 6 of washer.
  • This No. Pulp (exit pulp sheet) 9 washed with 1 washer was 2 Repulper 10 No. 2 was transferred to the washer. Washed with 2 washer shower water 12.
  • This No. Pulp (exit pulp sheet) 15 washed with two washers is transferred to a screen.
  • the 1-washer filtrate 7 is no. No. 1 washer filtrate tank 8 and no. Used as No.
  • the 2 washer filtrate 13 was No. It was transferred to the filtrate tank 14 of 2 washer.
  • the position for adding the detergent for kraft pulp can be uniformly mixed and supplied to the inlet of the first stage washing machine (pulp after the oxygen delignification reaction). It is preferable to add to the slurry 3, No. 1 repulper 4 or No. 1 repulper dilution water 5).
  • the kraft pulp manufacturing method of the present invention includes, for example, a cooking step, an oxygen delignification reaction step performed by an O 2 TW (oxygen delignification reaction tower) shown in FIG. It includes a washing process performed by a washer (washing machines A and B in FIG. 2) and a multi-stage bleaching process.
  • FIG. 3 is a schematic view for explaining the washing machines A and B in FIG.
  • the kraft pulp cleaning agent of the present invention is preferably added to the supply pipe for the filtrate for dilution (a) and pulp (b) in the cleaning machine schematic diagram of FIG. When added to the vat (c) or shower washing (d), mixing may be insufficient and the effect may not be sufficiently obtained, and foaming may occur in the washing machine.
  • the washing efficiency of the pulp can be improved.
  • the whiteness of the pulp after the oxygen delignification reaction step is improved. Therefore, the amount of bleaching agent added can be reduced, foaming can be prevented, and the amount of antifoaming agent added can be reduced.
  • the kraft pulp manufacturing method does not include the bleaching step, and thus does not have the effect of reducing the amount of chlorine used.
  • the cleaning efficiency is increased, it is used to obtain the same cleaning effect.
  • the amount of hot water to be used can be reduced and the amount of hot water to be used can be reduced, the amount of black liquor generated can be suppressed, and the load on the recovery boiler can be reduced.
  • the amount of pulp that can be treated with the same amount of hot water can be increased, and productivity can be improved.
  • Examples 1 to 10 and Comparative Examples 1 to 7 1 of the multistage filter washing process after the oxygen delignification reaction process of the cellulose pulp manufacturing apparatus comprising the cooking process, the oxygen delignification reaction process, the multistage filter washing process, and the multistage bleaching process with chlorine dioxide and hydrogen peroxide.
  • Hardwood cellulose pulp before the multistage bleaching process was collected from the washer at the stage. Next, 5.6 g as a dry weight of the collected cellulose pulp was weighed into a 500 mL beaker, 65 ° C. warm water was added so that the pulp concentration was 1% by mass, and then EO of various higher alcohols shown in Table 1.
  • a kraft pulp cleaning agent comprising a PO adduct
  • 10% by weight sodium hydroxide is added to the pulp to a solid content of 4% by weight.
  • the pulp slurry was prepared by stirring for 10 minutes while maintaining the temperature.
  • the prepared pulp slurry was immediately subjected to suction filtration using a Kiriyama funnel (diameter: 95 mm) to make paper.
  • the pulp slurry was divided so as to have a basis weight of 250 g / m 2 to prepare a total of three evaluation sheets.
  • the paper for evaluation was pressed and then dried by ventilation for about 24 hours to obtain a sample for measuring whiteness.
  • Comparative Example 1 when Comparative Example 1 was not added with a cleaning agent, Comparative Example 6 was compared with Comparative Example 7 when Nonylphenol EO12 molar adduct (Lion Corporation's Liponox NC120) was used as a cleaning agent. Indicates a case where sodium dodecylbenzenesulfonate (Lypon LS-250, manufactured by Lion Corporation), which is an anionic surfactant, is used as a cleaning agent. In Table 1, compounds 1 to 6 were synthesized according to the following Production Examples 1 and 2.
  • propylene oxide manufactured by Asahi Glass Co., Ltd.
  • 46.4 g (0.8 mol) of propylene oxide (PO) was gradually added so as to maintain 115 ⁇ 5 ° C. and 0.1 to 0.3 MPa (gauge pressure).
  • aging was performed for 2 hours, and then unreacted PO was removed under reduced pressure.
  • Compound 5 and Compound 6 shown in Table 1 were synthesized in the same manner as in Production Example 2 so as to have a predetermined added mole number.
  • the compound 6 it supplied to the propylene oxide adduct of stearyl alcohol separately in steps of ethylene oxide and propylene oxide, and added, and it was set as the block adduct.
  • Example 11 the detergent synthesized in the following Production Example 3 was used.
  • (Production Example 3) It is obtained by calcining alumina hydroxide / magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kyoward 300) having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O for 3 hours at 750 ° C. in a nitrogen stream. A calcined alumina / magnesium hydroxide was obtained.
  • the cleaning agent for kraft pulp of Example 12 is manufactured by Lion Corporation, which is an ethylene oxide adduct (average number of moles added: 2 moles) of an aliphatic primary amine derived from coconut oil fatty acid corresponding to the general formula (3). Esomine C / 12 was used.
  • ⁇ Measurement of whiteness> Using a spectral color / whiteness meter PF-10 (manufactured by Nippon Denshoku Industries Co., Ltd.), the whiteness at three locations was measured for each produced evaluation sheet, and the average value of the three sheets was determined. Among the evaluation results in the table, the whiteness becomes better as the value becomes larger.
  • the whiteness improvement effect ( ⁇ whiteness) was determined from the difference from the whiteness when no nonionic surfactant as a detergent for kraft pulp was added (Comparative Example 1). If the whiteness improvement effect is 1.5% or more under these experimental conditions, it will contribute to the chlorine dioxide reduction effect.
  • Example 13 In a kraft pulp factory (coniferous kraft pulp production 350 tons / day), after the cooking process, the enzyme delignification reaction process, and the enzyme delignification reaction process, and the enzyme delignification reaction process, three vacuum drum washers (first stage: No. 1 washer, A kraft pulp manufacturing method including a washing step for washing pulp using a second stage: No. 2 washer and a third stage: No. 3 washer and a bleaching step was performed as follows. No. of vacuum drum washer The nonionic surfactant used in Example 8 was added to a pulp concentration adjusting filtrate introduced into one washer (bat temperature (washing temperature): 80 ° C.) so as to be 300 ppm with respect to the pulp. Next, no.
  • the washed pulp discharged from the 3 washer was collected, and the whiteness was measured as follows. As a result, the pulp was improved by 1.0% compared to when no nonionic surfactant (detergent) was added. . Moreover, when the amount of chlorine dioxide used in the bleaching step was measured as follows, it was possible to reduce it by 11.0%.
  • ⁇ Whiteness> An evaluation sheet with a basis weight of 250 g / m 2 was prepared using a TAPPI paper machine, and the whiteness was measured according to JIS P8148. The difference ( ⁇ ) from the whiteness when no nonionic surfactant (cleaning agent) was added was used as an evaluation index. Normally, the amount of chlorine dioxide added in the bleaching step of chemical pulp is adjusted by continuously sensing the whiteness of the pulp in the slurry, so if the whiteness improvement effect is 0.5% or more, chlorine dioxide. This will contribute to the reduction effect.
  • the reduction rate of the amount of chlorine dioxide used was calculated by (chlorine dioxide addition amount without addition of cleaning agent-chlorine dioxide addition amount with addition of cleaning agent) / chlorine dioxide addition amount without addition of cleaning agent) ⁇ 100 .
  • the horizontal axis represents the kappa number (KN number) indicating the degree of delignification after the enzyme delignification reaction
  • the vertical axis represents Create a graph with the amount of chlorine dioxide added to obtain the target whiteness of the final pulp after bleaching, and when the delignification degree after the oxygen delignification reaction is the same KN number from this graph
  • the amount of addition of chlorine dioxide was read to determine the amount of addition. This was performed in each case of no addition and addition of a cleaning agent, and the reduction rate of the chlorine dioxide was calculated.
  • the kappa number was measured according to JIS P8211.
  • Example 14 In a kraft pulp manufacturing plant (hardwood kraft pulp production amount of 1050 tons / day), after a cooking process, an enzyme delignification reaction process, and an enzyme delignification reaction process, a vacuum drum washer, a drum-type pressure washer, and press washing A kraft pulp manufacturing method including a washing step of washing using a machine and a bleaching step was performed as follows. 300 ppm of the nonionic surfactant used in Example 8 on the suction side of the filtrate feed pump for adjusting the pulp concentration introduced into the vacuum drum washer (bat temperature (washing temperature): 83 ° C.). It added so that it might become.
  • Example 13 the whiteness of the washed pulp collected from the press washer was improved by 1.1% compared to when no nonionic surfactant (detergent) was added, The amount of chlorine dioxide used in the bleaching process was reduced by 5.2%.
  • Example 15 In a kraft pulp factory (coniferous kraft pulp production 300 tons / day), after the cooking process, enzyme delignification reaction process, and enzyme delignification reaction process, two vacuum drum type washers (first stage: No1 washer, second A kraft pulp manufacturing method including a washing step for washing pulp using a No. 2 washer and a bleaching step was performed as follows. No. of vacuum drum washer The nonionic surfactant used in Example 8 was 300 ppm with respect to the pulp on the suction side of the filtrate feed pump for adjusting the pulp concentration introduced into one washer (bat temperature (washing temperature): 80 ° C.). It added so that it might become. Next, in the same manner as in Example 13, the vacuum drum washer No. The whiteness of the washed pulp collected from 2 washers is improved by 1.0% compared to when no nonionic surfactant (detergent) is added, and the amount of chlorine dioxide used in the bleaching process is 12.0%. Reduced.
  • Example 16 In a kraft pulp manufacturing plant (coniferous kraft pulp production 300 tons / day), a drum displacer (pressure type multi-stage washer: DD washer) was used after the cooking, enzyme delignification reaction, and enzyme delignification reaction steps. Then, a kraft pulp manufacturing method including a washing step for washing the pulp in two stages and a bleaching step was carried out as follows. The nonionic surfactant used in Example 8 was added to the pulp introduced into the DD washer (pulp temperature (washing temperature): 80 ° C.) so as to be 300 ppm based on the pulp.
  • DD washer pulse temperature (washing temperature): 80 ° C.
  • Example 13 the whiteness of the washed pulp collected from the DD washer outlet is improved by 0.5% compared to when no nonionic surfactant (detergent) was added, The amount of chlorine dioxide used in the bleaching process was reduced by 5.0%.
  • the cleaning agent for kraft pulp of the present invention can be suitably used as a cleaning agent used for cleaning kraft pulp used for producing, for example, high-quality paper and cardboard.

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PCT/JP2009/050890 2008-01-22 2009-01-21 クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法 WO2009093615A1 (ja)

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JP2011026713A (ja) * 2009-07-21 2011-02-10 Lion Corp クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法
JP2014500898A (ja) * 2010-11-11 2014-01-16 イーコラブ インコーポレイティド 瓶用クリーニングおよびラベル除去のための方法
JP2014240378A (ja) * 2013-05-11 2014-12-25 松本油脂製薬株式会社 アルキレンオキサイド付加物およびその用途
RU2636306C2 (ru) * 2012-04-18 2017-11-21 ДжиПи СЕЛЛЬЮЛОУС ГМБХ Использование поверхностно-активного вещества для обработки пульпы и улучшение введения крафт-пульпы в волокно для получения вискозы и других вторичных волокнистых продуктов
WO2020230351A1 (ja) * 2019-05-15 2020-11-19 株式会社片山化学工業研究所 パルプの洗浄

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US9512237B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Method for inhibiting the growth of microbes with a modified cellulose fiber
US9511167B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Modified cellulose from chemical kraft fiber and methods of making and using the same
US9512563B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Surface treated modified cellulose from chemical kraft fiber and methods of making and using same
KR101739949B1 (ko) 2009-05-28 2017-05-25 게페 첼루로제 게엠베하 화학적 크래프트 섬유로부터의 변형된 셀룰로즈 및 이들을 제조 및 사용하는 방법
US10174455B2 (en) 2013-03-15 2019-01-08 Gp Cellulose Gmbh Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same
CN104088184B (zh) * 2014-06-26 2017-01-11 孔慧 一种洗浆助剂及其制浆工艺方法
DE102017200430A1 (de) * 2017-01-12 2018-07-12 CHT Germany GmbH Ablagerungsverhinderung in der Zellstoff-Herstellung nach dem Sulfatverfahren (Kraft-Aufschluss)
JP7400394B2 (ja) * 2019-11-25 2023-12-19 セイコーエプソン株式会社 解繊方法および繊維体成形方法
JP6908097B2 (ja) * 2019-12-03 2021-07-21 栗田工業株式会社 パルプシートの製造方法及びパルプスラリー用脱水向上剤
KR102426912B1 (ko) * 2020-04-20 2022-07-28 박용철 친환경 습강지의 제조방법

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JP2011026713A (ja) * 2009-07-21 2011-02-10 Lion Corp クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法
JP2014500898A (ja) * 2010-11-11 2014-01-16 イーコラブ インコーポレイティド 瓶用クリーニングおよびラベル除去のための方法
RU2636306C2 (ru) * 2012-04-18 2017-11-21 ДжиПи СЕЛЛЬЮЛОУС ГМБХ Использование поверхностно-активного вещества для обработки пульпы и улучшение введения крафт-пульпы в волокно для получения вискозы и других вторичных волокнистых продуктов
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WO2020230351A1 (ja) * 2019-05-15 2020-11-19 株式会社片山化学工業研究所 パルプの洗浄

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EP2236665A1 (en) 2010-10-06
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