WO2016024047A1 - Procédé pour le traitement de la cellulose et solutions alcalines obtenues à partir du traitement de la cellulose - Google Patents

Procédé pour le traitement de la cellulose et solutions alcalines obtenues à partir du traitement de la cellulose Download PDF

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Publication number
WO2016024047A1
WO2016024047A1 PCT/FI2015/050527 FI2015050527W WO2016024047A1 WO 2016024047 A1 WO2016024047 A1 WO 2016024047A1 FI 2015050527 W FI2015050527 W FI 2015050527W WO 2016024047 A1 WO2016024047 A1 WO 2016024047A1
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Prior art keywords
cellulose
pulp
naoh
solution
hemicelluloses
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PCT/FI2015/050527
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English (en)
Inventor
Heikki Hassi
Panu Tikka
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Scitech-Service Oy
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Priority to CN201580043616.XA priority Critical patent/CN106687644B/zh
Publication of WO2016024047A1 publication Critical patent/WO2016024047A1/fr

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Classifications

    • 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
    • D21C11/0057—Oxidation of liquors, e.g. in order to reduce the losses of sulfur compounds, followed by evaporation or combustion if the liquor in question is a black liquor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • 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
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds

Definitions

  • the invention relates to a method for treating cellulose.
  • the invention also relates to a method of treating alkali solutions obtained from the treatment of cellulose.
  • the method is especially suitable for the treatment of cellulose and for the treatment of alkali solutions in the manufacture of regenerated cellu- lose-based products.
  • Regenerated fibres can be manufactured by a chemical process from natural raw materials consisting of large molecules, such as cellulose.
  • cellulose based regenerated fibres i.e. regenerated cellulose fibres
  • regenerated cellulose fibres include, for example, viscose fibres and other fibres whose manufacturing process comprises the intermediate step of xanthogenation of cellulose, for example modal.
  • the regenerated fibres can also be modified further, for example by chemical treatments. By the modification, it is possible to obtain, for example, special fibres with various functional properties, such as flame-retardant properties, electrical conductivity, or antimicrobicity.
  • modified regenerated fibres include, for example, cellulose based hybrid fibres, such as silicate-containing viscose fibres which are poorly inflammable or non- inflammable, i.e. so-called flame-retardant fibres.
  • the manufacturing process of viscose fibres requires the pre- treatment of the cellulose raw material (pulp), whereby the cellulose is chemically converted to alkali cellulose having a chemical composition typical of viscose fibre process.
  • cellulose raw material pulp
  • alkali cellulose having a chemical composition typical of viscose fibre process.
  • the alkali solution is sodium hydroxide solution in water at a concentration above 17%. This process produces spent liquor, which is excess alkali solution squeezed out of the cellulose.
  • Such solution is usually at least partly reused in making a new alkali solution for mercerization.
  • dissolving pulp is used as the cellulose raw material, which is then treated with the alkali solution to make alkali cellulose.
  • Dissolving pulp is made from wood by a special process which gives low yield pulp with a high alpha-cellulose content.
  • US-patent 2,859,210 (Seaman et al.) presents a method of producing alkali cellulose where the starting material is "low cost pulp". The starting material is first treated with a 10% NaOH-solution and subsequently pressed to squeeze out spent liquor containing hemicelluloses within the liquor. The material is then treated in a second step with an about 16% NaOH-solution, and subsequently pressed, whereafter the treated pulp is in the form of alkali cellulose ready for shredding and xanthogenation. Thus, the treatment involves also mercerization.
  • WO 2012/136878 Another method developed for high-hemicellulose fibre raw material, which is not dissolving pulp, such as for paper pulp, is presented in WO 2012/136878 (Carbatec Oy).
  • the pulp is also treated in two steps with NaOH solutions.
  • the concentration of the NaOH solution may be 8 to 25%, preferably 16 to 21 %, and in the second treatment step 8 to 25%, preferably 10 to 16%. It is advantageous that in the second step a lower effective sodium hydroxide concentration than in the first step is applied.
  • alkali solutions that have been used for the mercerization of cellulose raw material have the drawback that they contain hemicelluloses dissolved from the raw material, and if such solutions are circulated for making fresh batches of alkali solutions, the hemicelluloses will gradually accumulate in these solutions.
  • the high content of hemicelluloses in solutions used for mercerization are known to have detrimental effect on the later stages of viscose process, especially in the form of increased consumption of carbon disulphide in the xanthogenation step. Discarding the spent liquors after the treatment of the cellulose raw material would be one choice, but it will cause environmental problems and increase the costs of chemicals.
  • US 4342600 suggests the addition of substances causing cross-linkage or blocking of active groups of hemicelluloses in the circulated alkali solutions.
  • US 3988198 suggests heat-treatent of spent effluents from the cold caustic extraction of cellulosic pulps to cause thermal degradation of hemicelluloses. The heat treatment takes place at a temperature of 140 - 240°C, preferably 175 - 200°C for a sufficient time (30 min - 3h) to decrease the hemicellulose content in the spent effluent so that it can be reused without risk of deposition of hemicelluloses on the fibers.
  • the heat-treated effluents are suitable for use in cooking, bleaching and caustic extraction of pulps.
  • the present invention combines the maximum hemicellulose removal from the feedstock cellulose pulp and the destruction of it in the spent lye solution in view of re-using and recirculating the lye.
  • the feedstock cellulose-based raw material
  • cellulose pulp which has been manufactured by a chemical pulping method of the original plant raw material (wood or non-wood material) to raise its cellulose content.
  • the cellulose pulp grade can be characterized by the pulping method by which it has been prepared.
  • Hardwood based kraft and partial prehydrolyzed kraft pulps show best hemicellulose removal at about 5 % NaOH concentration, as do also non- wood based soda and kraft pulps, whereas softwood based kraft pulps show best hemicellulose removal at about 10 % NaOH concentration.
  • Sulfite pulps made by Na or Mg based bisulfite pulping can be best be treated by standard mercerization lye typically at about 17% NaOH, thus without any dilution of the standard lye.
  • the method according to the invention comprises
  • this raw-material specific alkali solution can then be recirculated to treatment of new batch of the pulp grade after oxidation of hemicelluloses.
  • the samples of the pulp grade are preferably taken from the same batch of the pulp grade which will be used in the large-scale operation.
  • preliminary testing means conducting a test series with different NaOH solutions for samples of that pulp grade
  • a large-scale operation means an industrial scale operation for a large batch of the pulp grade by treating it with the NaOH solution for manufacturing purposes, that is, making products with the alkali-treated pulp grade as raw material.
  • the concentration of the NaOH solution for the large-scale treatment is not necessarily selected among the concentrations of the test solutions, but the concentration can be between two concentrations or outside the range of concentrations, as a result of interpolation of extrapolation for example.
  • concentration of NaOH is preferably selected in view of the optimum hemicelluloses removal, other selection criteria can also be used, that is, if the concentration is enough for causing the removal of the hemicellulose to a degree which is sufficient for the manufacturing purposes and especially if the hemicellulose reduction is still more efficient than that obtainable with standard mercerization solution with a higher (17% - 18%) NaOH concentration.
  • a raw material specific alkali solution can be used for treating the cellulose-based raw material (pulp) to optimise the process with respect to hemicellulose removal and consumption of alkali solution.
  • the variables can be the starting material (softwood, hardwood, non-wood, and even single plant species within these groups) and the chemical pulping method used for the starting material for making a particular pulp grade. All pulp grades obtained as a result of any combination of these variables can be used in the method. Possible variations between different production batches within the same pulp grade can be eliminated by frequent testing. Further, a new method for making the hemicellulose containing spent alkali solutions reusable is provided.
  • Hemicelluloses in the alkali solution are oxidized in the treatment of spent alkali solutions.
  • the oxidation of polymeric hemicelluloses causes the degradation of the polymeric structure and formation of hydroxy acids.
  • the process which can be called “degradative oxide- tion”, is simple to perform and requires only oxygen and possible oxidation catalyst to accelerate the reaction, without the use of excessive temperatures or complicated separation equipment such as ultrafiltration equipment.
  • the oxidation products of the hemicellulose can be left in the alkali solution treated.
  • the oxidation produces harmless hydroxy acids, such as isosaccha- rinic acid, as the result of degradation of the hemicelluloses to monomers.
  • the alkali solution where at least part of the hemicelluloses are degraded and oxidized to hydroxy acids can be used in the dissolution of cellulose xanthogenate, to avoid or considerably reduce the harmful effects of hemicelluloses in the ageing of viscose and in the following process steps.
  • the oxidation products of hemicellulose do not consume oxygen during the ageing of viscose.
  • the hemicelluloses can be oxidized partly to a level where their residual content is no more harmful or has considerably decreased effect.
  • the processing conditions of the alkali solution temperature, oxygen feed, catalyst, reaction time
  • the removal of hemicelluloses can be complete or nearly complete.
  • the alkali solution can be reused as such in the same process ore elsewhere.
  • alkali solution that has been in contact with a cellulose raw material containing hemicelluloses, "spent liquor", or "spent lye" usually a filtrate from the treatment of pulp, is subjected to oxidative treatment.
  • the sodium hydroxide concentration in water can vary according to the original NaOH concentration and the treatment process, and the types of hemicelluloses and their concentration is dependent on the original cellulose raw material from which they are removed to the alkali solution.
  • Oxygen source and possible catalyst is added to the alkali solution, and the oxidation is allowed to proceed in selected reaction conditions to a desired conversion degree.
  • Air can be used as oxygen source. Air can be dissolved in the alkali solution prior to the process to a suitable level, or the solution can be aerated during the process.
  • the temperature can be about 50°C
  • the reaction time can be 10 - 30 h
  • cobalt can be used as catalyst, to mention one example.
  • the oxidation products of the hemicellulose can be left in the alkaline solution, which can be reused without a need to separate them.
  • All kinds of pulp will be suitable as raw material, be it sulphite pulp, kraft pulp, partially prehydrolyzed pulp, hardwood pulp, softwood pulp, and the optimal circum- stances of hemicelluloses reduction can be determined for all of them, especially in terms of the concentration of the aqueous NaOH solution, which is used for the treatment of the pulp in question. Further, the hemicelluloses dissolved from the pulp to the NaOH solution can be effectively removed form the alkaline filtrate obrtained after the treatment.
  • the treatment of the starting material by NaOH in the first step is adjusted according to the wood species that is the raw material of the pulp and the method by which the pulp is made, following the principle as explained below.
  • the raw material that is treated with the alkali solution can be a cellulose raw material which is atypical of the viscose process. It can be TCF (totally chlorine free) pulp and/or ECF (elemental chlorine free) pulp made for paper making or for other non-dissolving conversion processes. It can also be partially (mildly) prehydrolyzed kraft pulps, which are markedly more economical to produce compared to fully prehydrolyzed highly purified dissolving pulps.
  • This cellulose raw material is usually wood-based. It can also be made of straw, sugar cane bagasse, or other annual plants or other non-wood plants.
  • Such an atypical raw material is characterized by a high hemicellulose content, expressed in alkali resistance R18, which is typically ⁇ 93% and advantageously ⁇ 90%.
  • R18 value refers to the part (%) of pulp not dissolved in an 18% NaOH solution at +20°C.
  • the alkali solution from the treatment of this cellulose raw material has usually a high hemicellulose content and it is well-suitable for the removal of hemicelluloses by oxidation.
  • the alkali solution from which the hemicel- luloses are removed at least partly can be used for the dissolution of the cellulose xanthogenate which is prepared from this cellulose raw material after the alkali solution treatment.
  • the viscose is introduced in an acidic regeneration bath where it is made into fibres or other products of regenerated cellulose, such as films or granules.
  • Cellulose-based hybrid fibres, especially cellulose/silica hybrid fibres having flame-retarding properties can also be made in an analogical manner, where waterglass is added to the viscose before it is introduced into the acidic regeneration bath.
  • the state of the art mercerization NaOH solutions are not optimal in view of removing hemicelluloses in a first NaOH treatment of the feedstock hemi-containing cellulose.
  • the optimal NaOH concentration depends on the wood species and process history of the cellulose pulp in question. Hardwood based kraft and partial prehydrolyzed kraft pulps show best hemicellulose removal at about 5 % NaOH concentration, whereas softwood based kraft pulps show best hemicellulose removal at about 10 % NaOH concentration.
  • Sulfite pulps made by Na or Mg based bisulfite pulping can be best treated by standard mercerization lye typically at 17-18% NaOH, thus without any dilution of the lye.
  • the concentration of the NaOH solution is selected according to the pulp type to be treated, and the pulp is then treated with the NaOH solution having the selected concentration in the first treatment for removing hemicelluloses from the pulp.
  • the second treatment of the pulp with an alkaline solution takes place in a NaOH concentration of at least 16 %, preferably 17-18%, to obtain alkali cellulose.
  • Feedstock cellulose pulp Eucalyptus kraft paper pulp (hardwood based kraft pulp)
  • Paper grade Eucalyptus paper pulp was used in this experiment.
  • the pulp contained 18,4 g hemicelluloses per 100 g pulp.
  • 200 g air dry pulp sheet was shredded in small pieces and stirred 15 min in 5 I of NaOH solution of certain controlled concentration at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min. The pressed out lye and the pulp cake were collected and analyzed.
  • the best hemicellulose removal was achieved by using 5 % NaOH solution.
  • the achieved residual hemicellulose content 3,4 % is technically on useful level and corresponds to the hemicellulose level of conventional merceriza- tion of standard dissolving pulp.
  • the second NaOH treatment, mercerization, further dissolved some hemicellulose and the final alkali cellulose hemicellulose content was 3,1 %.
  • Feedstock cellulose pulp Birch kraft paper pulp (hardwood based kraft pulp)
  • Paper grade birch kraft pulp was used in this experiment.
  • the feedstock pulp contained 25,0 g hemicelluloses per 100 g pulp.
  • 100 g air dry pulp sheet was shredded in small pieces and stirred 15 min in 2,5 I of NaOH solution of certain controlled concentration at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min. The pressed out lye and the pulp cake were collected and analyzed.
  • the feedstock pulp contained 16,8 g hemicelluloses per 100 g pulp.
  • 100 g air dry pulp sheet was shredded in small pieces and stirred 15 min in 2,5 I of NaOH solution of certain controlled concentration at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min. The pressed out lye and the pulp cake were collected and analyzed.
  • the obtained pulp cake was stirred in 2,5 I of 18 weight-% NaOH solution 15 min at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min.
  • the pressed out lye and the pulp cake were collected and analyzed.
  • the best hemicellulose removal was achieved by using 5 % NaOH solution.
  • the achieved residual hemicellulose content 2,8 % is technically on an useful level and corresponds to the hemicellulose level of conventional merceri- zation of standard dissolving pulp.
  • the second NaOH treatment, merceri- zation, further dissolved some hemicellulose and the final alkalicellulose hemicellulose content was 1 ,1 %.
  • Example 4 Feedstock cellulose pulp: Softwood kraft paper pulp Paper grade Softwood kraft pulp was used in this experiment.
  • the feedstock pulp contained 17,1 g hemicelluloses in 100 g pulp.
  • 100 g air dry pulp sheet was shredded in small pieces and stirred 15 min in 2,5 I of NaOH solution of certain controlled concentration at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min. The pressed out lye and the pulp cake were collected and analyzed.
  • the obtained pulp cake was stirred in 2,5 I of 18 weight-% NaOH solution 15 min at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min.
  • the pressed out lye and the pulp cake were collected and analyzed.
  • the best hemicellulose removal was achieved by using 10 % NaOH solution.
  • the achieved residual hemicellulose content 10,1 % is technically not quite on an useful level.
  • the second NaOH treatment, mercerization, further dissolved some hemicellulose and the final alkalicellulose hemicellulose content was 8,0 %, significantly lower than the feedstock pulp, may be on useful level.
  • Feedstock cellulose pulp Softwood Mg Bisulfite pulp
  • Paper grade Softwood Mg Bisulfite pulp was used in this experiment.
  • the feedstock pulp contained 17,1 g hemicelluloses in 100 g pulp.
  • 100 g air dry pulp sheet was shredded in small pieces and stirred 15 min in 2,5 I of NaOH solution of 18 weight-% concentration at 22 °C temperature.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min.
  • the pressed out lye and the pulp cake were collected and analyzed.
  • the obtained alkaline pulp slurry was pressed in hydraulic press with 18 bar pressure for 15 min.
  • the pressed out lye and the pulp cake were collected and analyzed.
  • the very good hemicellulose removal was achieved by using the same NaOH solution than is the case in the second mercerization stage, 18 % NaOH solution.
  • the achieved residual hemicellulose content 3,7 % is techni- cally on an useful level and corresponds to the hemicellulose level of conventional mercerization of standard dissolving pulp.
  • the second NaOH treatment, mercerization, further dissolved some hemicellulose and the final alkalicellulose hemicellulose content was 3,0 %.
  • the removal of hemicelluloses from the spent alkali solutions obtained from the treatment of the above-mentioned pulp grades or any other pulp grades is explained in more detail.
  • alkali solutions from the treatment of a cellulose raw material where the hemicelluloses are in the form that is soluble to cold ( ⁇ 50°C, especially ⁇ 30°C) alkali solution can be treated with the oxidative degradation method.
  • the filtrate lye from the 1 st NaOH treatment in Example 3 was taken as the starting material for removal of dissolved hemicelluloses.
  • a very low catalytic amount of cobalt salt was added as an oxidation catalyst.
  • the cobalt ion concentration in the treatment was 0,36 ppm, i.e. 0,36 mg Co/I.
  • the lye was kept in a glass in a 55°C water bath for 28 hours, conditions typical for industrial lye intermediate storage tanks. Air for oxidation was introduced by two methods: (1 ) keeping the glass open to atmosphere and (2) pumping a small air flow and bubbling it to the lye. The following results were obtained:
  • the best hemicellulose removal result is obtained by using air bubbling to the lye tank.
  • At least 30 wt-%, preferably at least 50 wt-% of the hemicellulose in the hemicellulose alkaline solution can be removed by oxidative degradation.
  • the oxidation and consequently the removal of hemicellulose can be enhanced by active introduction of oxygen (for example oxygen contained in air) into the hemicellulose alkaline solution.
  • oxygen for example oxygen contained in air
  • the reaction conditions can be optimized, for example through supply of air to the hemicellulose alkaline solution.
  • metal ions as cobalt can be used as catalyst, such as transition metal ions.
  • suitable metals are Co, Mn, Fe, Cu and Cr.
  • a suitable dose is 0.1 - 10 ppm (mg/l alkaline solution).
  • the preferable dose is 0.2 - 1 mg Co/I.
  • the invention can be used in pulp industry in removing hemicelluloses from pulps by using optimum concentration of alkali (concentration of NaOH solution).
  • concentration of NaOH solution concentration of NaOH solution
  • the invention can be used in all processes where hemicelluloses are removed from pulp by treatment with alkali solutions (alkali extraction) to make dissolving pulp or other pulp grades.
  • the invention can be used for removing hemicelluloses in spent alkaline liquors (hemicellulose alkaline solutions) from the above-mentioned processes to make reusable alkaline liquors which can be again used for removing hemicelluloses, or which can be used in other processes.
  • the reusable alkaline liquors are used especially in such processes where the liquors will be in contact with cellulose or cellulose derivatives, which can be in fibrous form or in soluble form.
  • the reusable liquors are especially used in processes where they are in contact with pulp or used in manufacturing regenerated cellulose-based products, such as viscose.
  • the treated, that is, oxidized spent alkaline liquor (alkaline solution) is used in the same process that produced it.
  • the spent alkaline liquor that is made reusable by oxidation can be used several times to remove hemicellulose from the same pulp grade for which it was initially made specific by the NaOH concentration, for example by choosing the concentration as explained above.
  • the invention can be used in all processes which involve the dissolution of cellulose or cellulose derivative in an aqueous alkali solution and later precipitation in a precipitation or regeneration bath.
  • Other possible processes for making regenerated cellulose-based products where the alkali solution used for the dissolution can be treated according to the invention include thus for example cellulose carbamate process and a so-called Celsol or Biocelsol- processes, where cellulose or cellulose derivative is dissolved in sodium hydroxide solution.
  • cellulose carbamate process the cellulose derivative is dissolved in aqueous sodium hydroxide solution and the solution is introduced into an acid precipitation bath to form cellulose carbamate filaments or other products, which can be later hydrolysed to regenerated cellulose fibers.
  • the Celsol/Biocelsol processes involve the enzymatic pretreatment of cellu- lose and its dissolution into aqueous sodium hydroxide, and the solution is introduced, after a possible freezing and melting step, into an acid precipitation bath to form cellulose filaments or other products.
  • the invention is not restricted to the embodiment examples above, but it may vary within the scope of the claims.
  • the invention is suitable for all cellulose- based raw-materials that contain hemicelluloses, also those typically used in viscose process (dissolving pulp).

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Abstract

Dans un procédé pour le traitement de matière première à base de cellulose, des hémicelluloses dans la matière première sont d'abord dissoutes dans une solution alcaline spécifique de la matière première. La solution alcaline d'hémicelluloses obtenue est oxydée pour dégrader les hémicelluloses, et la solution alcaline oxydée est ré-utilisée dans le même procédé ou dans un autre procédé.
PCT/FI2015/050527 2014-08-14 2015-08-14 Procédé pour le traitement de la cellulose et solutions alcalines obtenues à partir du traitement de la cellulose WO2016024047A1 (fr)

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CN201580043616.XA CN106687644B (zh) 2014-08-14 2015-08-14 用于处理纤维素的方法和自处理纤维素得到的碱溶液

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FI20145722A FI125891B (en) 2014-08-14 2014-08-14 Process for the treatment of cellulose and alkali solutions obtained from the treatment of cellulose
FI20145722 2014-08-14

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US10793984B2 (en) 2016-08-04 2020-10-06 Pvh Corporation Non-iron fabrics and garments, and a method of finishing the same
JP2021527754A (ja) * 2018-06-11 2021-10-14 ザ ユニバーシティー オブ クイーンズランド セルロースナノ繊維を含む材料

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US3652386A (en) * 1968-10-29 1972-03-28 Mo Och Domsjoe Ab Process for treating cellulosic materials with alkali and oxygen in the presence of complex magnesium salts
US3843473A (en) * 1971-08-23 1974-10-22 Mo Och Domsjoe Ab Impregnation of cellulosic pulp under superatmospheric pressure with waste alkaline oxygan gas bleaching liquor followed by oxygen-alkali bleaching
US3935022A (en) * 1973-07-23 1976-01-27 Hannes Sihtola Method for the removal of hemicellulose from hemicellulose-containing caustic liquors
US5595628A (en) * 1992-05-05 1997-01-21 Grant S.A. Production of pulp by the soda-anthraquinone process (SAP) with recovery of the cooking chemicals
US20140054506A1 (en) * 2011-02-28 2014-02-27 Aalto University Foundation Method of Recovering Chemicals

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Publication number Priority date Publication date Assignee Title
US3652386A (en) * 1968-10-29 1972-03-28 Mo Och Domsjoe Ab Process for treating cellulosic materials with alkali and oxygen in the presence of complex magnesium salts
US3843473A (en) * 1971-08-23 1974-10-22 Mo Och Domsjoe Ab Impregnation of cellulosic pulp under superatmospheric pressure with waste alkaline oxygan gas bleaching liquor followed by oxygen-alkali bleaching
US3935022A (en) * 1973-07-23 1976-01-27 Hannes Sihtola Method for the removal of hemicellulose from hemicellulose-containing caustic liquors
US5595628A (en) * 1992-05-05 1997-01-21 Grant S.A. Production of pulp by the soda-anthraquinone process (SAP) with recovery of the cooking chemicals
US20140054506A1 (en) * 2011-02-28 2014-02-27 Aalto University Foundation Method of Recovering Chemicals

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* Cited by examiner, † Cited by third party
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US10793984B2 (en) 2016-08-04 2020-10-06 Pvh Corporation Non-iron fabrics and garments, and a method of finishing the same
JP2021527754A (ja) * 2018-06-11 2021-10-14 ザ ユニバーシティー オブ クイーンズランド セルロースナノ繊維を含む材料

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