WO2019004076A1 - Composition de réducteur de viscosité et procédé de concentration de liqueur noire - Google Patents

Composition de réducteur de viscosité et procédé de concentration de liqueur noire Download PDF

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Publication number
WO2019004076A1
WO2019004076A1 PCT/JP2018/023786 JP2018023786W WO2019004076A1 WO 2019004076 A1 WO2019004076 A1 WO 2019004076A1 JP 2018023786 W JP2018023786 W JP 2018023786W WO 2019004076 A1 WO2019004076 A1 WO 2019004076A1
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black liquor
concentration
radical scavenger
viscosity
present disclosure
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PCT/JP2018/023786
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English (en)
Japanese (ja)
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藤槻薫麗
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株式会社片山化学工業研究所
ナルコジャパン合同会社
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Publication of WO2019004076A1 publication Critical patent/WO2019004076A1/fr

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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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/10—Concentrating spent liquor by evaporation

Definitions

  • the present disclosure relates to a thickener composition for reducing the viscosity of black liquor in the black liquor concentration step of a chemical pulping process, and a black liquor concentration method.
  • FIG. 1 An example of the production flow of chemical pulp such as kraft pulp is shown in FIG.
  • lignocellulosic material chips 11 are stored in a chip silo 12, they are selected by a chip screen (not shown) and sent to a chip bin 13 and then chipped in a steaming vessel 14
  • the gas phase inside is replaced by water vapor.
  • a chip whose permeability is enhanced in the steaming vessel 14 is a solution containing sodium hydroxide or the like in the digester 16 after the penetration of the digestion liquid into the interior of the chip is promoted in the penetration column 15 by the introduction of the alkaline digestion liquid. Steamed together with Thereby, the pulp slurry in which the black liquor and the pulp in which the non-fiber component is dissolved is mixed is discharged.
  • the pulp slurry discharged from the digester 16 is washed in the black liquor washing tower 17 and then passed through the screen 18, the decker 19 and the unexposed and high concentration storage tower 20, and then introduced into the oxygen digester 21 where After ligninization is performed, it is transferred to a bleaching step (not shown).
  • black liquor is discharged in the black liquor washing tower 17, the screen 18, the decker 19 and the like.
  • the discharged black liquor is transferred to a black liquor concentration process.
  • the black liquor collected in the dilute black liquor tank (stock tank) 22 in the black liquor concentration step is concentrated by the evaporator 23.
  • energy recovery and chemical recovery are performed in the recovery boiler 24.
  • the recovered energy is sent to the turbine 25 and the medicine is transferred to the green liquor tank 26.
  • the transferred chemicals are regenerated into white liquor by causticizing treatment 27 or the like, and then are supplied as white liquor to the permeation tower 15 through the white liquor tank 28.
  • Patent Document 1 a viscosity reducer for black liquor
  • Patent Document 2 a black liquor concentration aid
  • a viscosity reducing agent capable of improving the flowability of concentrated black liquor from the viewpoint of further improving the concentration rate of black liquor (solids concentration of black liquor concentrate) and further improving the treatment efficiency and energy recovery rate
  • concentration rate of black liquor solids concentration of black liquor concentrate
  • the present disclosure provides, in one or more embodiments, a viscosity reducing composition capable of improving the flowability of concentrated black liquor, and a black liquor concentration method.
  • the present disclosure relates, in one aspect, to a viscosity reducing composition for reducing the viscosity of black liquor in a black liquor concentration process of a chemical pulping process, the viscosity reducing composition comprising a radical scavenger.
  • the present disclosure relates, in one aspect, to a method of concentrating black liquor comprising concentrating black liquor in a chemical pulping process in the presence of a radical scavenger.
  • a viscosity reducing composition capable of improving the flowability of concentrated black liquor, and a black liquor concentration method.
  • FIG. 1 is a flow chart showing an example of the flow of a chemical pulp production system.
  • FIG. 2 is a schematic diagram for demonstrating the measuring method of the distance of the black liquor used in the Example.
  • FIG. 3 is a graph showing an example of the result of the dynamic viscosity measurement performed in Experimental Example 2.
  • the present disclosure can suppress the decrease in fluidity (or increase in viscosity) of the black liquor concentrate obtained by concentrating the black liquor in the presence of a radical scavenger, and furthermore, the solid content of the black liquor during concentration Based on the finding that the concentration can be increased, preferably the concentration efficiency of black liquor can be improved.
  • chemical pulp refers to a pulp which is a chemical reaction and which is pulped by decomposing wood chips and / or separating lignin and the like (kraft pulp, sulfite pulp, alkali pulp). Etc.
  • black liquor refers to a black or brown liquid produced in a chemical pulping process.
  • the black liquor produced in the kraft pulp manufacturing process is wood chip when the wood chip serving as a raw material is digested with chemicals such as sodium hydroxide and sodium sulfide (also referred to as white liquor). It is formed by dissolving a component other than the fiber (for example, lignin having a role of bonding fibers, a resin component, etc.) in a drug.
  • the black liquor contains an organic substance and a chemical used in a digestion step or the like such as sodium hydroxide or a reactive component thereof.
  • the organic matter includes, in one or more embodiments, lignin, carbohydrate derived from cellulose or hemicellulose, and the like.
  • the black liquor is drained in the washing step after digestion (such as the black liquor washing tower 17, the screen 18 and the decker 19 in the flow diagram of FIG. 1) in one or more embodiments.
  • the solid content concentration of the black liquor discharged from the black liquor washing tower 17 is 15% by weight to 25% by weight in one or more embodiments.
  • the "black liquor concentration step” includes concentrating the collected black liquor.
  • the black liquor concentration step may further include, in one or more embodiments, burning the obtained black liquor concentrate to recover energy, recovering a chemical of inorganic substance, and the like.
  • the black liquor concentration step includes, in one non-limiting embodiment, concentration by an evaporator 23 as shown in the flow chart of FIG. 1.
  • the present disclosure relates, in one aspect, to a thickener composition (a thickener composition of the present disclosure) for reducing the viscosity of black liquor in the black liquor concentration step of a chemical pulping process.
  • the viscosity reducing composition of the present disclosure contains a radical scavenger.
  • the viscosity reducing composition of the present disclosure in one or more embodiments, it is possible to suppress the decrease in the flowability of black liquor associated with concentration. According to the viscosity reducing composition of the present disclosure, in one or more embodiments, it is possible to suppress an increase in the viscosity of black liquor associated with concentration. According to the viscosity reducing composition of the present disclosure, the flowability of the black liquor concentrate can be improved in one or more embodiments. According to the viscosity reducing composition of the present disclosure, in one or more embodiments, the viscosity of the black liquor concentrate can be reduced.
  • the solid content concentration of black liquor at the time of concentration can be increased, and furthermore, the concentration efficiency of black liquor can be preferably improved.
  • the processing capacity associated with black liquor concentration can be improved.
  • the combustion efficiency when burning concentrated black liquor and recovering energy can be improved.
  • a reduction in the viscosity of the black liquor in the black liquor concentration step means to reduce or suppress an increase in the viscosity of the black liquor accompanying the black liquor concentration step.
  • the reduction of the viscosity of the black liquor in the black liquor concentration step may include, in one or more embodiments, suppressing the reduction in flowability of the black liquor in the black liquor concentration step.
  • the viscosity reducing composition of the present disclosure in one or more embodiments, contains a radical scavenger as a main component of the viscosity reducing component.
  • “containing the radical scavenger as the main component of the viscosity reducing component” means that the ratio of the radical scavenger in the viscosity reducing component contained in the viscosity reducing agent composition is 50 in one or more embodiments. 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, 95% by weight or more It is about 100% by weight.
  • the viscosity reducing component contained in the viscosity reducing composition in one or more embodiments, suppression of the flowability decrease of black liquor associated with concentration, suppression of viscosity increase of black liquor associated with concentration, There may be mentioned components capable of achieving at least one effect selected from the group consisting of the improvement of the flowability of the black liquor concentrate and the reduction of the viscosity of the black liquor concentrate.
  • the viscosity reducing composition of the present disclosure may, in one or more embodiments, contain substantially only the radical scavenger as a viscosity reducing component.
  • radical scavenger in one or more embodiments, a radical scavenger used as a polymerization inhibitor or a polymerization inhibitor can be used.
  • radical scavengers examples include, in one or more embodiments, nitrogen radical scavengers, aromatic radical scavengers, organic acid radical scavengers, catechin radical scavengers, and the like.
  • the radical scavenger is preferably a nitrogen-based radical scavenger or an aromatic radical scavenger, and more preferably a nitrogen-based radical scavenger, from the viewpoint of being able to further suppress the decrease in fluidity of the black liquor concentrate.
  • the nitrogen-based radical scavenger refers to a radical scavenger containing at least one nitrogen atom in one or more embodiments.
  • a nitrogen based radical scavenger in one or more embodiments, an amine based radical scavenger, a tetramethylpiperidine oxyl based radical scavenger, an aromatic nitro compound, a heterocyclic aromatic nitro compound, an aliphatic nitro compound, a nitroso Examples thereof include compounds, nitrogen free radical type compounds, N-oxide compounds, N-hydroxyl-imine compounds, acylamino-substituted aromatic compounds, and N-acyl-enamine compounds.
  • N, N′-di-sec-butyl-1,4-phenylenediamine PDA
  • N, N′-bis (1,4-dimethylpentyl) ) -1,4-phenylenediamine N- (1,4-dimethylpentyl) -N'-phenyl-1,4-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -1
  • 4-phenyldiamine N-phenyl-N'-isopropyl-1,4-phenylenediamine, N, N'-di-phenyl-1,4-phenylenediamine or N, N'-di-2-naphthyl-1
  • Phenylenediamine based radical scavengers such as 2,4-phenylenediamine, hydroxylamine based compounds such as N, N-diethylhydroxylamine (PDA), N, N′-bis (1,4-dimethyl
  • a tetramethylpiperidine oxyl-based radical scavenger in one or more embodiments, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-Hydroxy-TEMPO, H-TEMPO), 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO), 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-cyano-2,2,6,6 -Tetramethylpiperidine-1-oxyl, 4-benzoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4 -Oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl piperidine 1-oxyl, or bis - (2,2,6,6-tetramethylpiperidine-1-oxyl) - sebacate, and the like.
  • the aromatic nitro compound includes, in one or more embodiments, 3,5-dinitrobenzoic acid and the like.
  • Heterocyclic aromatic nitro compounds include, in one or more embodiments, 2-methyl-4-nitroimidazole and the like.
  • Aliphatic nitro compounds include, in one or more embodiments, tris (hydroxymethyl) nitromethane and the like.
  • the nitroso compound includes, in one or more embodiments, 1-nitroso-2-naphthol and the like.
  • the N-oxide compound includes, in one or more embodiments, imidazole-N-oxide, 1- (2-hydroxymethyl) piperazine-N-oxide, methylmorpholine-N-oxide and the like.
  • the N-hydroxyl-imine compound includes, in one or more embodiments, N-hydroxyphthalimide and the like.
  • Acylamino-substituted aromatic compounds include, in one or more embodiments, acetanilide or N-acetyl-5-methoxytryptamine and the like.
  • As a nitrogen free radical type compound the above-mentioned phenylenediamine type radical scavenger etc. are mentioned in one or more embodiments.
  • N-acyl-enamine compounds include, in one or more embodiments, uric acid and the like.
  • aromatic radical scavenger in one or more embodiments, hydroquinone, benzoquinone, methoquinone, ethylhydroquinone, propylhydroquinone, butylhydroquinone, pentylhydroquinone, hexylhydroquinone, tert-butylhydroquinone, hydroxyhydroquinone, naphthoquinone, phenol, 2-Methylphenol, 2-ethylphenol, 2-propylphenol, catechol, 4-tert-butylcatechol, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, resorcinol, homocatechol, p-cresol, 2 -Methoxyphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,6-dimethoxyphenol, 2-tert-butyl- -Methylphenol, 2,6-di-tert-butyl-4
  • nitrogen such as an amine radical scavenger, a tetramethylpiperidine oxy radical scavenger and a nitroso compound is preferable from the viewpoint of being able to further suppress a decrease in fluidity of the black liquor concentrate.
  • radical radical scavengers or aromatic radical scavengers and more preferred are amine radical scavengers and tetramethylpiperidine oxy radical scavengers.
  • radical scavenger 4-hydroxy-TEMPO, DEHA, 1-nitroso-2-naphthol and 4-tert-butyl catechol are preferable, and more preferably, from the viewpoint of being able to further suppress the decrease in fluidity of the black liquor concentrate.
  • 4-Hydroxy-TEMPO and DEHA are preferable, and more preferably, from the viewpoint of being able to further suppress the decrease in fluidity of the black liquor concentrate.
  • the radical scavenger is preferably a compound having a lower viscosity, and more preferably a nitrogen-based radical scavenger having a lower viscosity or an aromatic radical having a lower viscosity, since the decrease in fluidity of the black liquor concentrate can be further suppressed. It is a scavenger.
  • Lower viscosity nitrogen based radical scavengers include, in one or more embodiments, 4-Hydroxy-TEMPO, DEHA, and the like.
  • the viscosity reducing composition of the present disclosure may, in one or more embodiments, include one type of radical scavenger, or may include two or more types of radical scavengers in combination.
  • the content of the radical scavenger in the viscosity reducing composition of the present disclosure is 1 wt% or more, 5 wt% or more, or 10 wt% or more, or 90 wt% or less, 85 It is less than or equal to 70% by weight.
  • the viscosity reducing composition of the present disclosure may, in one or more embodiments, include a viscosity reducing component other than a radical scavenger.
  • the viscosity reducing component other than the radical scavenger include, in one or more embodiments, organic solvents, surfactants, and known black liquor viscosity reducing agents such as emulsions of amide wax and mineral oil.
  • the surfactant in one or more embodiments, nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants and the like can be mentioned.
  • organic solvents and surfactants are preferable in that synergetic effect with the radical scavenger in the viscosity reducing effect can be obtained.
  • the viscosity reducing composition of the present disclosure can be a long-term storage stability good one-component formulation suitable for addition to black liquor in the black liquor concentration step. It may contain an organic solvent, a surfactant and the like. Thus, in one or more embodiments, the viscosity reducing composition of the present disclosure may be a one-component formulation including a radical scavenger and at least one of an organic solvent and a surfactant.
  • Organic solvents include, in one or more embodiments, hydrophilic organic solvents.
  • hydrophilic organic solvent include glycol ether solvents, glycol solvents, alcohol solvents, amine / amide solvents and the like as one or more embodiments. These organic solvents may be used alone or in combination of two or more in one or more embodiments.
  • glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, in one or more embodiments.
  • a glycol ether solvent in one or more embodiments, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the like are preferable.
  • glycol solvent in one or more embodiments, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butyl propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, or tributylene glycol, etc. Can be mentioned.
  • alcohol solvents in one or more embodiments, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol, 1,4-butanediol, 1,5-pentanediol, benzyl alcohol Or 2-ethyl-1-hexanol and the like.
  • the organic solvent As the organic solvent, the dispersibility of the radical scavenger in black liquor is improved, and the radical scavenger can be contained at a high concentration in the viscosity reducing composition, and the storage stability of the viscosity reducing composition for a long period of time
  • glycol ether solvents, glycol solvents or amine / amide solvents are preferred.
  • glycol ether solvents with lower viscosity, glycol solvents or amine / amide solvents are preferable, and glycol ether solvents with lower viscosity are more preferable.
  • the lower viscosity glycol ether solvents include, in one or more embodiments, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.
  • the content of the organic solvent in the viscosity reducing composition of the present disclosure is 1 wt% or more, 5 wt% or more, or 10 wt% or more, or 60 wt% or less, 45 wt% % Or less or 40% by weight or less.
  • nonionic surfactants are preferred.
  • the nonionic surfactant include, in one or more embodiments, a compound in which an alkylene oxide is added to a linear or branched saturated or unsaturated alcohol having a hydrocarbon group having 6 to 22 carbon atoms, 6 carbon atoms
  • a compound obtained by adding an alkylene oxide to a linear or branched saturated or unsaturated amine having a hydrocarbon group of ⁇ 22 a compound obtained by adding an alkylene oxide to a fatty acid having 6 to 22 carbon atoms, 2 to 10 carbon atoms
  • a radical scavenger can be contained at a high concentration in the viscosity reducing composition, and the dispersibility of the radical trapping agent in the black liquor is improved, and the long term of the viscosity reducing composition is achieved.
  • a compound in which an alkylene oxide is added to a linear or branched saturated or unsaturated amine having a hydrocarbon group having 6 to 22 carbon atoms is preferable, and a compound having a lower viscosity is more preferable. It is.
  • the surfactant content in the viscosity reducing composition of the present disclosure is 1 wt% or more, 5 wt% or more, or 10 wt% or more, or 50 wt% or less, 45 It is less than or equal to 40% by weight.
  • the viscosity reducing composition of the present disclosure may, in one or more embodiments, include water.
  • the water include, in one or more embodiments, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like.
  • the water content in the viscosity reducing composition of the present disclosure is, in one or more embodiments, 5 wt% or more, 10 wt% or more, or 15 wt% or more, or 95 wt% or less, 90 wt% Or less than 85% by weight.
  • the viscosity reducing composition of the present disclosure is a one-component preparation including a radical scavenger and an organic solvent and / or a surfactant
  • 1 part by weight to 85 parts by weight of the radical scavenger The organic solvent and / or the surfactant may be contained in an amount of 0.1 parts by weight or more based on 1 part by weight of the radical scavenger, and the balance may be water or the organic solvent.
  • the viscosity reducing composition of the present disclosure if used to reduce the viscosity of black liquor in the black liquor concentration step of a chemical pulp manufacturing process such as kraft pulp, in one or more embodiments, the addition site thereof Is not particularly limited.
  • the addition site of the viscosity reducing composition of the present disclosure in one or more embodiments not particularly limited, the solid content concentration of black liquor from the point that the flowability improvement effect after black liquor concentration can be sufficiently obtained
  • the solid content concentration of the black liquor is 50% by weight or less in one or a plurality of embodiments from the point that the location of the black liquor concentrate is 70% by weight or less and the decrease in fluidity of the black liquor concentrate can be further suppressed.
  • a black liquor stock tank upstream of the concentration process (for example, stock tank 22 in the flow chart of FIG. 1), or The inlet of the evaporator (for example, the evaporator 23 in the flow chart of FIG. 1) or an intermediate tank may be mentioned.
  • a black liquor washing tower e.g., a black liquor washing tower in which the discharged black liquor is washed in a chemical pulp production process upstream of the black liquor concentration process. Black liquor washing tower 17 in the flow diagram of FIG.
  • a screen for screening black liquor washed in the washing tower (eg, screen 18 in the flow diagram of FIG. 1), and washing concentration of the black liquor that has been screened (E.g., the decker 19 in the flow diagram of FIG. 1).
  • the addition site of the viscosity reducing composition of the present disclosure may be before or after the upstream side of the black liquor concentration step (for example, the digestion step) in one or more embodiments.
  • the process on the upstream side of the black liquor concentration process includes, in one or more embodiments, a chemical pulp production process, a white liquor tank, a white liquor preparation process, and the like.
  • the viscosity reducing composition of the present disclosure can also be used, in one or more embodiments, as a flow improver to improve the flowability of black liquor in the black liquor concentration process of chemical pulp manufacturing processes such as kraft pulp. . Therefore, in another aspect, the present disclosure is a flow improver for improving the flowability of black liquor in the black liquor concentration process of a chemical pulp manufacturing process such as kraft pulp, which contains a radical scavenger It relates to a quality improver.
  • the viscosity reducing composition of the present disclosure can also be used, in one or more embodiments, as a black liquor concentration aid for use in the black liquor concentration process of a chemical pulp manufacturing process such as kraft pulp. Accordingly, the present disclosure relates, in another aspect, to a black liquor concentration aid for use in a black liquor concentration step of a chemical pulp production process such as kraft pulp, wherein the black liquor concentration aid contains a radical scavenger. .
  • the present disclosure relates, in one aspect, to a method of concentrating black liquor in a chemical pulping process such as kraft pulp (black liquor concentration method of the present disclosure).
  • the black liquor concentration method of the present disclosure involves concentrating black liquor in a chemical pulping process in the presence of a radical scavenger.
  • a radical scavenger as described above, the viscosity reducing agent composition of the present disclosure may be used.
  • the black liquor concentration method of the present disclosure in one or more embodiments, it is possible to suppress the decrease in the flowability of black liquor associated with the concentration. According to the black liquor concentration method of the present disclosure, in one or more embodiments, it is possible to suppress an increase in the viscosity of black liquor accompanying concentration. According to the black liquor concentration method of the present disclosure, the flowability of the black liquor concentrate can be improved in one or more embodiments. According to the black liquor concentration method of the present disclosure, in one or more embodiments, the viscosity of the black liquor concentrate can be reduced. According to the black liquor concentration method of the present disclosure, in one or more embodiments, the solid content concentration of black liquor at the time of concentration can be increased, and furthermore, the concentration efficiency of black liquor can be preferably improved. According to the black liquor concentration method of the present disclosure, in one or more embodiments, the throughput associated with black liquor concentration can be improved. According to the black liquor concentration method of the present disclosure, the combustion efficiency of concentrated black liquor can be improved in one or more embodiments.
  • the black liquor concentration method of the present disclosure comprises adding a radical scavenger to the black liquor produced in the chemical pulping process.
  • the black liquor concentration method of the present disclosure in one or more embodiments, comprises adding the thickener composition of the present disclosure to the black liquor produced in the chemical pulping process.
  • the addition amount of the radical scavenger can be appropriately adjusted according to the solid content concentration of the black liquor in one or more embodiments.
  • the concentration of the radical scavenger is, in one or more embodiments, 0.0005% to 3% by weight based on the solid content of the black liquor. From the viewpoint of further improving the concentration rate of black liquor, 0.001 wt% or more, 0.01 wt% or more, 0.02 wt% or more, 0.03 wt% or more, 0.04 wt% or more, or 0. 5% by weight or more, and 2% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, 0.2% by weight or less from the same viewpoint It is 0.1% by weight or less.
  • the radical scavenger in a point where the solid content concentration of the black liquor is 70% by weight or less, from the viewpoint that the flowability improvement effect after black liquor concentration can be sufficiently obtained.
  • adding to a place where the solid content concentration of the black liquor is 50% by weight or less Preferably, it is added to a portion which is more preferably 30% by weight or less, even more preferably a portion which is 20% or less.
  • a black liquor stock tank for example, the stock tank 22 of the flow chart of FIG.
  • a black liquor washing tower for example, the flow chart of FIG. 1 in which the discharged black liquor is washed in the kraft pulp production process upstream of the black liquor concentration process.
  • Black liquor washing tower black liquor washing tower 17) a screen for screening the black liquor washed in the washing tower (for example, screen 18 of the flow chart of FIG.
  • the radical scavenger may or may not be added before or after the digestion step, which is the step upstream of the black liquor concentration step.
  • the upstream process of the black liquor concentration process includes, in one or more embodiments, a chemical pulp production process upstream of the black liquor concentration process, a white liquor tank, a white liquor preparation process, and the like.
  • the black liquor concentration method of the present disclosure adds an alkali agent to the black liquor in addition to the radical scavenger in one or more embodiments, from the viewpoint of further suppressing the decrease in fluidity of the black liquor concentrate. May be included.
  • alkali agent examples include sodium hydroxide, potassium hydroxide, sodium carbonate and the like as one or more embodiments.
  • a white liquor may be used as an alkaline agent in one or more embodiments.
  • the black liquor concentration method of the present disclosure includes, in one or more embodiments, an organic solvent, a surfactant, an amide-based wax, and a mineral oil in addition to the above-mentioned agents, as long as the effects of the present disclosure are not impaired.
  • the method may include the addition of a known black liquor thickener such as an emulsion, an antifoamer such as silicone, a pitch controller, a scale controller such as a polyvalent carboxylic acid chelating agent, and the like.
  • the organic solvent and surfactant are as described above.
  • the amount of the organic solvent added can be appropriately adjusted according to the solid content concentration of the black liquor, the concentration of the radical scavenger, and the like in one or more embodiments.
  • the concentration of the organic solvent is, in one or more embodiments, 0.0005% to 3% by weight based on the solid content of the black liquor. From the viewpoint of further improving the concentration rate of black liquor, 0.001 wt% or more, 0.01 wt% or more, 0.02 wt% or more, 0.03 wt% or more, 0.04 wt% or more, or 0.
  • the blending ratio of the organic solvent to the radical scavenger is, in one or more embodiments, 100: 1 to 1: 5, preferably 4: 1 to 1: 2.
  • the solid concentration of the black liquor after concentration is 70 wt% or more, 75 wt% or more, 76 wt% or more, 77 wt% or more, 78 wt%
  • the black liquor can be concentrated to 79% by weight or more or 80% by weight or more.
  • the solid content concentration of black liquor can be determined by measuring the water content with an infrared moisture meter in one or more embodiments.
  • the black liquor concentration method of the present disclosure in one or more embodiments, can further improve the reduction or suppression effect of the increase in viscosity of the black liquor accompanying the black liquor concentration step in combination with the viscosity reducing effect of the radical scavenger.
  • the method may further include adding at least one of an organic solvent and a surfactant.
  • the organic solvent and surfactant may be added as a mixture with the radical scavenger, or may be added separately from the radical scavenger, and the viscosity reducing effect of the radical scavenger and It is preferable to add it in combination with a radical scavenger, from the viewpoint of obtaining a synergetic effect of
  • the present disclosure is a method of producing a viscosity reducing composition comprising the radical scavenger and at least one of an organic solvent and a surfactant (the production method of the present disclosure), which comprises: Mixing at least one of a solvent and a surfactant. According to the manufacturing method of the present disclosure, in one or more embodiments, it is possible to manufacture a viscosity reducing agent composition containing a radical scavenger at a high concentration.
  • a viscosity reducing agent composition of a one-component formulation suitable for addition to black liquor in the black liquor concentration step and excellent in storage stability for a long period is manufactured. can do.
  • the effect of reducing or suppressing the increase in the viscosity of the black liquor accompanying the black liquor concentration step is further improved. It is possible to produce a viscosity reducing agent composition capable of obtaining a synergetic effect with the viscosity reducing effect of the scavenger.
  • the manufacturing method of this indication can be conveniently used for manufacture of the viscosity reducing agent composition containing the radical scavenger with low solubility in water, and the oil-soluble radical scavenger in one or several embodiment.
  • a one-part aqueous preparation containing a higher concentration of radical scavenger by mixing with an organic solvent and a surfactant can be done.
  • mixing with an organic solvent and a surfactant makes it possible to obtain a one-component preparation having good dispersibility in black liquor.
  • the manufacturing method of the present disclosure includes, in one or more embodiments, blending at least 0.1 parts by weight or more of the organic solvent and the surfactant with respect to 1 part by weight of the radical scavenger. In one or more embodiments, the production method of the present disclosure adds water as the balance as needed, and mixes the radical scavenger, at least one of the organic solvent and the surfactant, and water. May be included.
  • the present disclosure may relate to one or more of the following: [1] A viscosity reducing agent composition for reducing viscosity of black liquor in a black liquor concentration process of chemical pulp manufacturing process, which contains a radical scavenger. [2] The viscosity reducing composition according to [1], wherein the radical scavenger is at least one of a nitrogen-based radical scavenger and an aromatic radical scavenger. [3] A black liquor concentration aid, which is a black liquor concentration aid for use in a black liquor concentration process of a chemical pulp production process, containing a radical scavenger. [4] A method of concentrating black liquor by concentrating black liquor in the chemical pulping process in the presence of a radical scavenger. [5] The method for concentrating black liquor according to [4], which comprises adding a radical scavenger to the black liquor produced in the chemical pulping step.
  • Example 1 The viscosity of the black liquor concentrate obtained by concentrating the dilute black liquor to a water content of 25% was evaluated.
  • Diluted black liquor solids concentration 18.6% by weight, inorganic matter 43.3% by weight, organic matter 56.8% by weight discharged from the black liquor washing tower of softwood kraft pulp of the kraft pulp manufacturing plant with chemicals shown in Table 1 below) % By weight
  • the concentration of each drug added was 0.01% by weight based on the solid content of the dilute black liquor.
  • the solid concentration (water content) of the sample was determined by measuring the weight of the solid after heating the sample to evaporate all the water.
  • the viscosity reduction was evaluated by the movement distance of the sample (black liquor after concentration).
  • the moving distance is as follows: After heating the obtained sample to 105 ° C. in a state in which the water does not evaporate (state in which the water content does not change), the centrifuge tube containing the sample is inclined to 90 ° to measure the distance of the flowing black liquor It asked by doing.
  • the moving distance of the black liquor starts from the liquid level with the centrifuge pipe standing vertically (arrow X in Fig. 2), and from the start point X, the tip of the black liquor that flows when the centrifuge pipe is inclined 90 degrees It was obtained by measuring the distance (Z in FIG. 2) to (arrow Y in FIG. 2).
  • Table 1 The results are shown in Table 1 below.
  • the movement distance is represented as a relative value where the movement distance of no addition (Comparative Example 1) is 100.
  • Examples 1 to 4 using the radical scavenger had a longer moving distance than Comparative Examples 1 and 2, and the flowability of the black liquor concentrate decreased due to the concentration of the black liquor ( Viscosity increase) can be suppressed.
  • Example 5 As Example 5, the measurement of the dynamic viscosity in the concentrated black liquor (solid content concentration 80 weight%) which added DEHA was performed. A dilute black liquor (solids concentration 17.9% by weight, inorganic matter 34.3% by weight, organic matter 65.7%) discharged from a black liquor washing tower of softwood kraft pulp in a kraft pulp manufacturing plant in a 100 ml beaker with DEHA The sample was prepared by heating with a heating wire heater to evaporate water after adding and mixing (weight%).
  • the water content of each sample is measured using an infrared moisture meter (FD-230 manufactured by Kett Science Laboratory Co., Ltd.) at a weight fluctuation rate of 0.10 at 105 ° C.
  • the water content was measured as% when it became constant at 2.5% for 2.5%, and the water content was adjusted to 20% by performing addition of water etc. as needed, and used as a measurement sample.
  • DEHA was added so that it might become 0.01 weight% with respect to solid content concentration.
  • the viscosity at a shear rate of 0.1 rpm of a concentrated black liquor (black liquor solid content concentration 80% by weight, Example 5) to which DEHA was added was about 100 Pa ⁇ s, and diethanolamine was added. It could be reduced to about 1/3 of the viscosity of Comparative Example 3 and a blank (black liquid solid concentration 80% by weight). Moreover, the viscosity was comparable with the viscosity of the blank whose solid content concentration is 75 weight%.
  • Example 3 The viscosity of the black liquor concentrate obtained by concentrating the dilute black liquor to a water content of 20% was evaluated.
  • 4-Hydroxy-TEMPO or DEHA having a concentration shown in Table 2 below and a dilute black liquor discharged from the black liquor washing tower of hardwood kraft pulp of the kraft pulp manufacturing plant used in Experimental Example 2 were mixed.
  • the sample was then boiled to evaporate the water while stirring using a heating wire heater. Thereafter, the water content of each sample was measured using an infrared moisture meter (FD-230, manufactured by Kett Science Laboratory Co., Ltd.).
  • the movement distance is represented as a relative value where the movement distance of no addition (Comparative Example 3) is 100.
  • Example 6 to which 4-Hydroxy-TEMPO or DEHA was added was longer than the migration distance of no addition (Comparative Example 3) at any concentration, and the black liquor solid content concentration was 80 wt. Even in the case of concentration to%, it was possible to suppress the decrease in fluidity (increase in viscosity) of the concentrated black liquor accompanying the concentration of the black liquor.
  • concentration of the added drug was as low as 0.001% by weight, the moving distance was longer compared to the non-added Comparative Example 3, and the decrease in fluidity could be suppressed.
  • by setting the addition concentration to 0.01% by weight or more, it was possible to significantly suppress the decrease in fluidity as compared with the non-addition comparative example.
  • the viscosity reducing agent composition was prepared by mixing with water such that the total content of the radical scavenger and the organic solvent was 30% by weight.
  • the viscosity reducing agent composition is used as a drug, and the additive concentration of the radical scavenger and the organic solvent is added to the black liquor so that the concentration of the solid content of the black liquor is 0.01% by weight (the concentration of the solid content).
  • the viscosity of the black liquor concentrate was evaluated in the same manner as in Experimental Example 3 except for the above (Example 7).
  • 4-Hydroxy-TEMPO or DEHA was used as a radical scavenger.
  • Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or diethylene glycol monobutyl ether was used as the organic solvent.
  • the same evaluation was performed using 4-Hydroxy-TEMPO alone, DEHA alone or an organic solvent alone.
  • Example 7 in which the radical scavenger and the organic solvent were used in combination, although the addition concentration of the radical scavenger to the black liquor was small compared to the control of the radical scavenger alone, the control of the radical scavenger alone Showed the same suppression effect.
  • the concentrated black liquor obtained by using the radical scavenger and the organic solvent in combination is an effect exceeding that obtained by adding the suppressing effect obtained when the radical scavenger and the organic solvent are each used alone, and is a clear synergistic effect It can be said.

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Abstract

La présente invention concerne une composition de réducteur de viscosité et un procédé de concentration de liqueur noire, avec lesquels la fluidité de la liqueur noire concentrée peut être améliorée. L'objectif de la composition de réducteur de viscosité est de réduire la viscosité de la liqueur noire lors d'une étape de concentration de liqueur noire d'une étape de production de pâte à papier chimique, et la composition de réducteur de viscosité contient un piégeur de radicaux. L'invention concerne également un procédé de concentration de liqueur noire, dans lequel la liqueur noire d'une étape de production de pâte à papier chimique est concentrée en présence d'un piégeur de radicaux.
PCT/JP2018/023786 2017-06-30 2018-06-22 Composition de réducteur de viscosité et procédé de concentration de liqueur noire WO2019004076A1 (fr)

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JPS618396A (ja) * 1984-06-22 1986-01-16 大日本印刷株式会社 転写絵付シ−トおよびその製造方法
GB2237751A (en) * 1989-11-03 1991-05-15 Ahlstroem Oy Method of decreasing black liquor viscosity
US5900112A (en) * 1995-04-03 1999-05-04 North Carolina State University Method of reducing the viscosity of a black liquor using thiocyanate salt
JP2007070624A (ja) * 2005-08-12 2007-03-22 Tohpe Corp ビーズ状熱可塑性重合体粒子、該粒子の製造方法および該粒子を含む熱可塑性樹脂組成物
WO2017048163A1 (fr) * 2015-09-16 2017-03-23 Sca Forest Products Ab Procédé continu de production d'huile biologique à partir d'une liqueur noire épuisée

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JPS59228094A (ja) * 1983-06-09 1984-12-21 栗田工業株式会社 黒液の粘度低下剤
FI75615C (fi) * 1985-11-29 1991-08-26 Ahlstroem Oy Foerfarande foer saenkning av svartlutens viskositet.
JP2009179917A (ja) 2008-01-31 2009-08-13 Lion Corp 黒液濃縮方法および黒液濃縮助剤
CN101876153B (zh) 2010-04-01 2012-06-13 湖南泰格林纸集团有限责任公司 硫酸盐木浆黑液喷雾干燥工艺
JP6007081B2 (ja) 2011-12-20 2016-10-12 花王株式会社 リグニン分解物の製造方法
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Publication number Priority date Publication date Assignee Title
JPS618396A (ja) * 1984-06-22 1986-01-16 大日本印刷株式会社 転写絵付シ−トおよびその製造方法
GB2237751A (en) * 1989-11-03 1991-05-15 Ahlstroem Oy Method of decreasing black liquor viscosity
US5900112A (en) * 1995-04-03 1999-05-04 North Carolina State University Method of reducing the viscosity of a black liquor using thiocyanate salt
JP2007070624A (ja) * 2005-08-12 2007-03-22 Tohpe Corp ビーズ状熱可塑性重合体粒子、該粒子の製造方法および該粒子を含む熱可塑性樹脂組成物
WO2017048163A1 (fr) * 2015-09-16 2017-03-23 Sca Forest Products Ab Procédé continu de production d'huile biologique à partir d'une liqueur noire épuisée

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